WO2018166232A1 - Molécule conjuguée à base de polyquinane, son procédé de synthèse et son application - Google Patents

Molécule conjuguée à base de polyquinane, son procédé de synthèse et son application Download PDF

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WO2018166232A1
WO2018166232A1 PCT/CN2017/111587 CN2017111587W WO2018166232A1 WO 2018166232 A1 WO2018166232 A1 WO 2018166232A1 CN 2017111587 W CN2017111587 W CN 2017111587W WO 2018166232 A1 WO2018166232 A1 WO 2018166232A1
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formula
group
hexyl
absent
membered ring
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占肖卫
王伟
严岑琪
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北京大学
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the field of organic and perovskite solar cells and photodetectors, in particular to a multi- and five-membered ring conjugated molecule and a preparation method and application thereof.
  • organic solar cells have developed rapidly, and have attracted extensive attention from academia and industry due to their advantages of light weight, good flexibility, simple processing, large-area preparation, and low cost.
  • Translucent organic solar cells are considered to be the most promising application direction in the field of organic solar cells due to their great potential in applications such as photovoltaic building integration.
  • Perovskite solar cells have received great attention from academia and industry in recent years due to the rapid increase in efficiency.
  • organic photodetectors are also an important direction in organic electronics research. At present, the photoelectric conversion efficiency of organic solar cells prepared by blending polymer donors with fullerene receptors has exceeded 11%. This shows a huge application prospect of organic solar cells.
  • polymers Due to its high molar extinction coefficient and wide solar spectrum absorption, the polymer material has higher photoelectric conversion efficiency of photovoltaic devices.
  • polymers also have disadvantages such as uncertain molecular structure, polydisperse molecular weight distribution, difficult batch repeatability, and difficulty in purification.
  • organic fused-ring small molecules and macromolecular semiconductor materials have a certain molecular structure and molecular weight, as well as batch stability, simple purification and high purity, making organic fused ring small molecules and macromolecular solar cells research. It tends to be hot.
  • PC 61 BM and PC 71 BM become acceptor materials due to their large enough electron affinity, isotropic electron transport properties, and matched electronic energy levels.
  • the star molecule has always occupied a dominant position.
  • PCBM also has many shortcomings, such as weak visible light absorption, difficult energy level regulation, and complicated and complicated purification process.
  • the novel organic poly-fused-ring macromolecule has near-infrared absorption properties, and is particularly suitable as a photovoltaic material for a translucent organic solar cell or a near-infrared photodetector. Since its energy level is easy to control, it can also be used as a modification layer of a perovskite solar cell.
  • the electron transport layer or the light trap layer is doped with a component. Therefore, the synthesis of new receptor materials is still very necessary.
  • the present invention provides a poly- and five-membered ring conjugated molecule which is a compound represented by the following formula (1):
  • the two groups A are independently selected from the following structures:
  • Each group B and group C independently represent 1-10 thiophene conjugated fused ring structures
  • Each of R 3 to R 13 is each independently selected from the group consisting of H, F, a C1-C30 alkyl group, a C1-C30 alkoxy group, a C1-C30 alkylthio group, and a C6-C30 aryl group.
  • a method for preparing the above-described multi- and five-membered ring conjugated molecule comprising:
  • a compound represented by the following formula (2) and a compound represented by the formula (a) are subjected to a dehydration condensation reaction in the presence of a basic compound in an organic solvent to obtain a compound represented by the formula (1);
  • Formula (a) is selected from one or more of the following compounds:
  • a third aspect of the invention provides a photovoltaic material or photodetecting material comprising one or more of the above-described multi- and five-membered ring conjugated molecules.
  • a fourth aspect of the invention provides a solar cell comprising a multi- and five-membered ring conjugated molecule in a photovoltaic material.
  • a fifth aspect of the invention provides a method for preparing the above solar cell, the method comprising: disposing the poly- and five-membered ring conjugated molecules in a layer containing a photovoltaic material.
  • a sixth aspect of the invention provides a photodetector comprising a light-trapping active layer, wherein the electron-trapping material and/or the electron acceptor material in the light-trapping active layer contains the above-described multi- and five-element One or more of the conjugated molecules of the ring.
  • a seventh aspect of the present invention provides a method of producing a photodetector, wherein the method comprises an electron donor material and/or an electron acceptor material containing one or more of the above-described multi- and five-membered ring conjugated molecules.
  • An active layer for forming light trapping is provided.
  • the multi- and five-membered ring conjugated molecules provided by the invention have strong light absorption, high charge transport performance and suitable electronic energy level, and are suitable for use as photovoltaic materials or light detecting materials for preparing solar cells or light detecting. In the device.
  • Example 1 is an ultraviolet-visible absorption spectrum of a poly5-membered ring conjugated molecule of the formula (1-6-2) obtained in Example 1 of the present invention, wherein a solution refers to a solution prepared using chloroform as a solvent. (10 -6 mol/L), the film refers to a film (100 nm thickness) spin-coated with a chloroform solution.
  • Fig. 2 is a cyclic voltammetry curve of a polycyclic five-membered ring conjugated molecule of the formula (1-6-2) obtained in Example 1 of the present invention.
  • Example 3 is an I-V curve of the solar cell obtained in Example 10.
  • Example 4 is an I-V curve of the solar cell obtained in Example 11.
  • Fig. 5 is an I-V curve of the translucent solar cell obtained in Example 12.
  • Example 6 is a light transmittance curve of the translucent solar cell obtained in Example 12.
  • Fig. 7 is an I-V curve of the solar cell obtained in Example 13.
  • each group is independently selected from the group consisting of, when each group appears simultaneously and in multiple places in the compound, they are independently selected, may be the same, or may be different, for example, although There are four R 13 in the group shown, but the four R 13 can be independently selected and may be the same or different.
  • the dotted line in the structure with a dotted connection key indicates the connection site, indicating the connection key;
  • a solid line other than the parentheses in the structure with a solid-line bond that is not connected to any group or atom also indicates a connection site, indicating a link.
  • the inclusion The group indicates that the case where F is obtained on the left and right sides of the -F interspersed key, for example, the following formula (1-6-F1) actually means that the A groups on both sides are the group A-3.
  • the present invention provides a poly- and five-membered ring conjugated molecule which is a compound represented by the following formula (1):
  • each group B and group C independently represent 1-5 thiophene conjugates.
  • a fused ring structure each Z is independently selected from C, N and Si; each X, each X' and each Y are each independently selected from O and S; m is an integer from 0 to 4; n is an integer from 0 to 4 ; p is an integer from 0 to 4; each R 3 to R 13 are each independently selected from the group consisting of H, F, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C24 Aryl.
  • each group B and group C each independently represent from 1 to 4 thiophene conjugated fused ring structures; each R 3 -R 13 is independently selected from H, F, C1-C10 alkyl, C1 a C10 alkoxy group, a C1-C10 alkylthio group and a C6-C12 aryl group.
  • n 0, and R 2 is considered to be absent, and the group A is directly bonded to the fused ring unit main body of the compound represented by the formula (1) to form a conjugated structure.
  • Specific examples of the alkyl group of C1-C10 may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-glycol. Base, n-octyl, n-decyl, n-decyl, 2-ethylhexyl, and the like.
  • alkyl groups of the present invention may also be selected from this specific example depending on the circumstances.
  • specific examples of the C1-C10 alkoxy group may be, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a t-butoxy group, and a positive Pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, 2-ethylhexyloxy and the like.
  • alkylthio group of C1-C10 may be, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, and Butylthio, n-hexylthio, n-heptylthio, n-octylthio, n-decylthio, n-decylthio, 2-ethylhexylthio and the like.
  • aryl group of C6-C12 may be, for example, a phenyl group, a benzyl group, a p-tolyl group or the like.
  • two groups B located on both sides of the structure of the compound (1) are understood to constitute a conjugated structure together with the central structure of the compound (1), wherein each independently represents a 1-10 thiophene conjugated fused ring structure
  • the group B is a thiophene conjugated fused ring structure
  • one thiophene group on each side has a basic structure of a conjugated macromolecule with a central structure
  • the group B is a conjugated fused ring of two or more thiophenes Structure
  • Alternate conjugate connection as shown in the structural formula
  • the two carbon atoms connected by the dotted line are shared between the two rings to form a structural formula.
  • a fused fused ring structure of thiophene if it is a ring of 3 thiophenes, then you can continue to connect a No. 2 structure on the left side of No. 1 structure in the same way, or connect No. 1 structure on the right side of No. 2 structure to form Such a positive and negative alternating thiophene conjugated fused ring structure of 1-2-1.
  • the group C located in the middle of the structure of the compound (1) should be understood to constitute a conjugated structure together with other moieties of the central conjugated structure of the compound (1), wherein the group C also represents 1-10 thiophene conjugated fused ring structures,
  • the understanding of the thiophene conjugated fused ring structure is as described for group B.
  • the poly- and five-membered ring conjugated molecule is one of the compounds shown in the formula:
  • the group A has a strong tensile electron effect, and the group A is located at both ends of the fused ring unit to enable the obtained conjugated macromolecule to have strong visible light absorbing ability, high charge transporting property, and suitable electron energy level. It is suitable for use as a photovoltaic material for the preparation of organic solar cells; it is also suitable for use as a light detecting material in photodetectors.
  • the group A is selected from one or more of the following groups: the group A-1 is Group A-2 is Group A-3 is Group A-4 is Group A-5 is Group A-6 is Group A-7 is Group A-8 is Group A-9 is Group A-10 is Group A-11 is Group A-12 is Group A-13 is
  • the poly-and five-membered ring conjugated molecule of the present invention is preferably one of the compounds represented by the following formula:
  • Formula (1-6-1) In the formula (1-6), Z is C, A is a group A-1, R 2 is absent, and R 1 is a n-hexyl group; In the formula (1-6), Z is C, A is a group A-1, R 2 is absent, and R 1 is And R 9 is n-hexyl; formula (1-6-3): in formula (1-6), Z is C, A is a group A-1, R 2 is absent, and R 1 is And R 11 is n-hexyl; formula (1-6-4): in formula (1-6), Z is C, A is a group A-2, R 2 is absent, and R 1 is n-hexyl; Formula (1-6-5): In the formula (1-6), Z is C, A is a group A-2, R 2 is absent, and R 1 is And R 9 is n-hexyl; formula (1-6-6): in formula (1-6), Z is C, A is a group A-2, R 2 is absent, and R 1 is And R 11 is n-hexyl
  • R 2 does not exist, R 1 is And R 9 is n-hexyl;
  • Formula (1-7-1) In the formula (1-7), Z is C, A is a group A-1, R 2 is absent, and R 1 is n-hexyl; formula (1-7-2) In the formula (1-7), Z is C, A is a group A-1, R 2 is absent, and R 1 is And R 9 is n-hexyl; formula (1-7-3): in formula (1-7), Z is C, A is a group A-1, R 2 is absent, and R 1 is And R 11 is n-hexyl; formula (1-7-4): in formula (1-7), Z is C, A is a group A-2, R 2 is absent, and R 1 is n-hexyl; Formula (1-7-5): In the formula (1-7), Z is C, A is a group A-2, R 2 is absent, and R 1 is And R 9 is n-hexyl; formula (1-7-6): in formula (1-7), Z is C, A is a group A-2, R 2 is absent, and R 1 is And R 11 is n-hex
  • Formula (1-8-1) In the formula (1-8), Z is C, A is a group A-1, R 2 is absent, and R 1 is n-hexyl; formula (1-8-2) In the formula (1-8), Z is C, A is a group A-1, R 2 is absent, and R 1 is And R 9 is n-hexyl; formula (1-8-3): in formula (1-8), Z is C, A is a group A-1, R 2 is absent, and R 1 is And R 11 is n-hexyl; formula (1-8-4): in formula (1-8), Z is C, A is a group A-2, R 2 is absent, and R 1 is n-hexyl; Formula (1-8-5): In the formula (1-8), Z is C, A is a group A-2, R 2 is absent, and R 1 is And R 9 is n-hexyl; formula (1-8-6): In the formula (1-8), Z are both C, A are a group A-2, R 2 does not exist, R 1 are And R 11 is n-
  • a compound represented by the following formula (2) and a compound represented by the formula (a) are subjected to a dehydration condensation reaction in the presence of a basic compound in an organic solvent to obtain a compound represented by the formula (1);
  • Formula (a) is selected from one or more of the following compounds:
  • the compound represented by the formula (2) can be selected according to the structure of the poly- and five-membered ring conjugated molecule in the above, and preferably, the compound represented by the formula (2) is one or more of the following formulas:
  • Formula (2-6-1) In the formula (2-6), Z is C, R 2 is absent, and R 1 is n-hexyl; Formula (2-6-2): Formula (2-6) , Z is C, R 2 is not present, R 1 is And R 9 is n-hexyl; formula (2-6-3): in formula (2-6), Z is C, R 2 is absent, and R 1 is And R 11 is n-hexyl; formula (2-7-1): in formula (2-7), Z is C, R 2 is absent, R 1 is n-hexyl; formula (2-7-2): In the formula (2-7), Z is C, R 2 is absent, and R 1 is And R 9 is n-hexyl; formula (2-7-3): in formula (2-7), Z is C, R 2 is absent, and R 1 is And R 11 is n-hexyl; formula (2-8-1): in formula (2-8), Z is C, R 2 is absent, R 1 is n-hexyl; formula (2-8-2): In formula (2-8), Z is C
  • the compound represented by the formula (2) may be a commercially available product, or may be produced by a conventional method in the art, for example, by an aldehyde group on a butyllithium reaction.
  • the compound represented by the formula (a) can be appropriately selected depending on the group A.
  • specific examples of the compound represented by the formula (a) may include:
  • the compound represented by the formula (a) may be a commercially available product, or may be produced by a conventional method in the art, and will not be further described herein.
  • the aldehyde group attached to both ends of the compound represented by the formula (2) can be dehydrated and condensed with the compound represented by the formula (a) to form a compound represented by the formula (1), wherein
  • the amount of the compound represented by the formula (2) and the compound represented by the formula (a) is not particularly limited as long as the compound represented by the formula (1) can be obtained, and preferably, the formula (2) is shown.
  • the molar ratio of the compound to the compound represented by the formula (a) is from 1:2 to 100, more preferably from 1:4 to 10.
  • the reaction is carried out in the presence of a basic compound to provide an alkaline environment for the reaction system
  • the basic compound may be, for example, one or more of piperidine, pyridine and triethylamine.
  • the amount of the basic compound to be used is not particularly limited as long as it can provide an alkaline environment and contribute to the progress of the dehydration condensation reaction, for example, with respect to 1 mmol of the compound represented by the formula (2), the basic compound
  • the amount used is from 0.1 to 1000 mmol, more preferably from 1 to 50 mmol.
  • the organic solvent is, for example, chloroform and/or dichloromethane.
  • the organic solvent may be used in an amount of, for example, 20 to 500 mL (preferably 40 to 400 mL) based on 1 mmol of the compound represented by the formula (2).
  • the conditions of the dehydration condensation reaction include a temperature of 20 to 100 ° C (for example, 50 to 100 ° C) for a time of 10 min to 48 h (for example, 10 to 20 h). More preferably, the conditions of the dehydration condensation reaction include a temperature of 60-80 ° C and a time of 10-15 h.
  • the method further comprises maintaining the reaction system under an inert atmosphere before the reaction, for example, after the raw materials are added, the reaction system is introduced with an inert gas for 20-40 minutes to remove air.
  • the inert gas may be, for example, argon gas, helium gas, nitrogen gas or the like.
  • the method further comprises a post-treatment step such as dehydration condensation reaction product with methanol (relative to the total volume of the reaction liquid of 100 mL, for example, the amount of methanol, for example It can be mixed with 200-1000mL), then subjected to solid-liquid separation.
  • methanol relative to the total volume of the reaction liquid of 100 mL, for example, the amount of methanol, for example It can be mixed with 200-1000mL
  • the obtained solid phase is a silica gel column (200-300 mesh silica gel can be used, and the eluent can be petroleum ether and dichloride in a volume ratio of 1:0.2-3).
  • the methane mixture was subjected to chromatographic separation.
  • a third aspect of the invention provides a photovoltaic material or photodetecting material comprising one or more of the above-described multi- and five-membered ring conjugated molecules.
  • the photovoltaic material is not particularly limited as long as it contains the above-described poly- and five-membered ring conjugated molecules of the present invention, and the photovoltaic material preferably refers to electrons in the active layer of light trapping in a solar cell. a bulk material and/or an electron acceptor material; or a photovoltaic material in an electron transport layer and/or a modification layer (for example for a perovskite solar cell).
  • the electron donor polymer material PTB7-Th or PBnDT-FTAZ may be combined with the conjugated molecules provided by the present invention in a weight ratio of 0.5-4:1 as the photovoltaic material, particularly as a solar cell.
  • the active layer material is captured, and among them, particularly, the multi-membered five-membered ring conjugated molecule provided by the present invention is preferably used as an electron acceptor material.
  • the structural unit of the polymer material PTB7-Th is as follows: Wherein -C 4 H 9 represents n-butyl.
  • the polymer material PTB7-Th was purchased from Belleville.
  • the structural unit of the polymer material PBnDT-FTAZ is as follows:
  • -C 6 H 13 represents n-hexyl group and -C 4 H 9 represents n-butyl group.
  • the preparation of the polymer material PBnDT-FTAZ can be carried out, for example, by the method in the literature (J. Am. Chem. Soc. 2011, 133, 4625), and the present invention will not be repeated here.
  • the photodetecting material is not particularly limited as long as it contains the above-described polypentacyclic conjugated molecule of the present invention.
  • a fourth aspect of the invention provides a solar cell comprising a multi- and five-membered ring conjugated molecule in a photovoltaic material.
  • the configuration of the solar cell of the present invention is not particularly limited as long as the photovoltaic material used therein contains the poly- and five-membered ring conjugated molecules of the present invention, so that the photoelectric conversion efficiency of the solar cell can be effectively improved.
  • the solar cell is an organic solar cell, a translucent solar cell, a perovskite solar cell, or the like.
  • the electron donor material and/or the electron acceptor material in the light-trapped active layer contains the poly- and five-membered ring conjugated molecules One or more.
  • the electron donor material and/or the electron acceptor material in the light-trapping active layer contains one of the multiple and five-membered ring conjugated molecules kind or more.
  • the battery is a perovskite solar cell including an electron transport layer, a perovskite light-trapping layer, and a modification layer
  • the light-trapping layer and/or the electron transport layer and/or the modification layer contains the multi- and five-membered One or more of the conjugated molecules of the ring.
  • the conjugated molecules of the present invention are preferably combined as an electron acceptor material with other electron donor materials to form a light-trapping active layer of a solar cell.
  • an electron donor material for example, may be a polymer material PTB7-Th or PBnDT-FTAZ, as defined above.
  • the polymer material PTB7-Th or PBnDT-FTAZ may be combined with the conjugated macromolecule provided by the present invention in a weight ratio of 0.5-4:1 to form a light-trapped active layer.
  • a fifth aspect of the invention provides a method for preparing the above solar cell, the method comprising: disposing the poly- and five-membered ring conjugated molecules in a layer containing a photovoltaic material.
  • the preparation process of the solar cell is not particularly limited and can be carried out by a method conventional in the art.
  • the layer containing the photovoltaic material may be a light-trapping active layer.
  • the layer containing the photovoltaic material may be a light-trapping active layer.
  • the photovoltaic-containing layer can be a light-harvesting layer and/or an electron-transporting layer and/or a finishing layer.
  • the preparation process of the organic solar cell may include, for example, a reverse structure device: coating a ZnO layer as a cathode modification layer on a conductive glass (for example, indium tin oxide glass, ITO) as a cathode (thickness may be, for example, 20-50nm), after drying, the ZnO layer is coated with a mixture of the polymer material PTB7-Th and the conjugated macromolecule provided by the present invention as an active layer, and after drying, vacuum-deposited molybdenum oxide (thickness) For example, it may be 5-10 nm) and Ag (thickness may be 50-100 nm, for example) as an anode.
  • a reverse structure device coating a ZnO layer as a cathode modification layer on a conductive glass (for example, indium tin oxide glass, ITO) as a cathode (thickness may be, for example, 20-50nm), after drying, the ZnO layer is coated with a mixture of
  • a polymer layer formed, for example, by a combination of polymers of poly 3,4-ethylenedioxythiophene-polystyrene sulfonate is used instead of the ZnO layer, poly 3 , 4-ethylenedioxythiophene-polystyrene sulfonate also means PEDOT:PSS; metal calcium instead of molybdenum oxide; Al instead of Ag.
  • the preparation process of the translucent solar cell may include, for example, a reverse structure device: coating a ZnO layer as a cathode modification layer on a conductive glass (for example, indium tin oxide glass, ITO) as a cathode (thickness may be, for example, 20-50nm), after drying, the ZnO layer is coated with a mixture of the polymer material PTB7-Th and the conjugated macromolecule provided by the present invention as an active layer, and after drying, vacuum-deposited molybdenum oxide (thickness such as A thin layer of Ag (having a thickness of, for example, 10 to 30 nm) may be used as the anode.
  • a reverse structure device coating a ZnO layer as a cathode modification layer on a conductive glass (for example, indium tin oxide glass, ITO) as a cathode (thickness may be, for example, 20-50nm), after drying, the ZnO layer is coated with a mixture of the polymer
  • the preparation process of the perovskite solar cell may include, for example, cleaning the indium tin oxide (ITO) glass as a cathode with a detergent, followed by ultrasonic cleaning with deionized water, acetone, and isopropyl alcohol, and drying.
  • a layer of about 30 nm thick electron transport layer (for example, SnO 2 ) is spin-coated and annealed for 30 minutes for use.
  • the above poly- and 5-membered ring conjugated molecule is dissolved in DMF (for example, a concentration of 0.25 mg/mL), and then an appropriate amount of PbI 2 is added, and then the uniformly mixed solution is spin-coated on the above electron transport layer at 70 ° C.
  • a mixed solution of iodonium (FAI) / methyl iodide (MAI) 2:1) was spin-coated thereon, and annealed at 150 ° C for 15 minutes to obtain the above-mentioned five-membered ring conjugated molecule-doped calcium.
  • Titanium ore layer spin-coated 80mg/mL of 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-
  • the OMeTAD acts as a hole transport layer.
  • Metal Ag having a thickness of about 150 nm was vapor-deposited on the active layer under vacuum (absolute pressure: 2 ⁇ 10 -5 Pa) as an anode of the solar cell.
  • the conjugated molecule provided by the invention has strong absorption peaks in visible light and near-infrared region, for example, has a strong absorption peak in a wavelength range of 600-900 nm; the conjugated molecule has good thermal stability and can withstand a temperature of about 340 ° C. Without decomposition; cyclic voltammetry test results show that its HOMO level and LUMO level can match the energy level of most common electron donor materials, and it has good ability to accept electrons or holes, which is very beneficial Photovoltaic materials for solar cells, in particular electron acceptors and/or electron donor materials, especially as electron acceptor materials.
  • a sixth aspect of the invention provides a photodetector comprising a light-trapping active layer, wherein the electron-trapping material and/or the electron acceptor material in the light-trapping active layer contains the above-described multi- and five-element One or more of the conjugated molecules of the ring.
  • the present invention is not particularly limited in the configuration of the photodetector, and a conventional configuration in the art can be employed as long as it includes the above-described multi- and five-membered ring conjugated molecules of the present invention, so that an excellent light detecting effect can be obtained.
  • a seventh aspect of the present invention provides a method of producing a photodetector, wherein the method comprises an electron donor material and/or an electron acceptor material containing one or more of the above-described multi- and five-membered ring conjugated molecules.
  • An active layer for forming light trapping is provided.
  • the present invention is not particularly limited in the preparation process of the photodetector, and the preparation process of the photodetector in the art can be employed as long as it includes the above-described multi- and five-membered ring conjugated molecules of the present invention, so that excellent results can be obtained. Light detection effect.
  • C 6 H 13 in the molecular formula is n-hexyl.
  • 1 H NMR was measured using a nuclear magnetic resonance apparatus of the Bruker AVANCE 400/300 model.
  • MS (MALDI) was measured using a mass spectrometer of the Bruker Daltonics Biflex III MALDI-TOF Analyzer model.
  • the UV-visible absorption spectrum and the visible light transmission spectrum were measured using an ultraviolet-visible spectrophotometer of the Jasco V-570 spectrophotometer model.
  • the cyclic voltammetry curve was measured using a cyclic voltammetry tester of the CHI660C electrochemical workstation model.
  • the IV curve is measured by the B2912A Precision Source/Measure Unit (Agilent Technologies).
  • the polymer donor material PTB7-Th was purchased from the company, and the preparation of the polymer material PBnDT-FTAZ can be carried out, for example, by the method in the literature (for example, J. Am. Chem. Soc. 2011, 133, 4625).
  • This preparation example is for explaining the preparation method of the compound represented by the formula (2-6-1).
  • the compound represented by the formula IH-C6 120 mg, 0.18 mmol; synthesized by the method of Energy & Environmental Science 2013, 6(1), 139-147), tetrahydrofuran (20 mL) was added to the reaction as shown in the above reaction formula.
  • the vessel was argon-gased and stirred at -78 ° C for 1 h.
  • the n-butyllithium (0.42 mL, 0.60 mmol, 1.6 M in n-hexane) was slowly added dropwise, stirred at -78 ° C for 2 h, and then N,N-dimethylformamide (65.9 mg, 0.9 mmol) was added.
  • This preparation example is for explaining the preparation method of the compound represented by the formula (2-6-2).
  • n-butyllithium ie, n-BuLi, 0.28 mL, 0.45 mmol, 1.6 M in n-hexane
  • N,N-dimethylformamide ie DMF, 58.6 Mg, 0.8 mmol
  • This preparation example is for explaining the preparation method of the compound represented by the formula (2-6-3).
  • the compound represented by the formula IH-Th (150 mg, 0.15 mmol; synthesized by the method of Energy & Environmental Science 2013, 6(1), 139-147), tetrahydrofuran (i.e., THF, 20 mL) is shown in the above reaction formula. It was added to a reaction vessel, and argon gas was passed, and the mixture was stirred at -78 ° C for 1 h.
  • n-butyllithium ie, n-BuLi, 0.35 mL, 0.56 mmol, 1.6 M in n-hexane
  • N,N-dimethylformamide ie DMF, 58.6 Mg, 0.8 mmol
  • This preparation example is for explaining the preparation method of the compound represented by the formula (2-8-2).
  • This preparation example is for explaining the preparation method of the compound represented by the formula (2-7-2).
  • This preparation example is for explaining the preparation method of the compounds represented by the formulae (a-2-3) and (a-2-4).
  • 5-fluoro-1,3-indanedione 820 mg, 5 mmol; purchased from Ark
  • malononitrile 660 mg, 10 mmol
  • ethanol 30 mL
  • the gas was stirred at 25 ° C for 30 minutes.
  • Sodium acetate (492 mg, 6 mmol) was added slowly, stirred at 25 ° C for 2 h, water (40 mL) was added and stirred for 1.5 h.
  • This preparation example is for explaining the preparation method of the compound represented by the formula (a-2-6).
  • This preparation example is for explaining the preparation method of the compound represented by the formula (a-8-1).
  • This example is intended to illustrate the conjugated molecules of the present invention and methods for their preparation.
  • the ultraviolet-visible absorption spectrum of the above poly- and five-membered ring conjugated molecule represented by the formula (1-6-2) is shown in Fig. 1, wherein a strong absorption peak and a maximum molar ratio are in the wavelength range of 650 to 900 nm.
  • the extinction coefficient is 1.6 ⁇ 10 5 M –1 ⁇ cm ⁇ 1 , and the film absorbs most strongly at about 796 nm; the maximum absorption peak of the film is 48 nm reddish in solution.
  • the cyclic voltammetry curve is shown in Fig. 2.
  • the HOMO level is -5.45 eV
  • the LUMO level is -3.93 eV
  • the band gap is 1.52 eV, indicating the above-mentioned multi- and five-element shown in formula (1-6-2).
  • Cyclic conjugated molecules have good electron acceptability and can be matched to most common electron donor material levels.
  • This example is intended to illustrate the conjugated macromolecule of the present invention and a process for its preparation.
  • the ultraviolet-visible absorption of the mixture of the above three kinds of poly- and five-membered ring conjugated molecules represented by the formula (1-6-F1) indicates that it has a strong absorption peak in the wavelength range of 650-1000 nm, and the maximum molar extinction coefficient is 1.9 ⁇ 10 5 M –1 ⁇ cm –1 , the film absorbs most strongly at around 798 nm; the maximum absorption peak of the film is 40 nm redshifted in solution.
  • the HOMO level was -5.50 eV
  • the LUMO level was -3.98 eV
  • the band gap was 1.52 eV by cyclic voltammetry, indicating that the above three kinds of multiple and five-membered rings are represented by the formula (1-6-F1).
  • the mixture of conjugated molecules has good electron acceptability and can be matched to most common electron donor material levels.
  • This example is intended to illustrate the conjugated molecules of the present invention and methods for their preparation.
  • the ultraviolet-visible absorption spectrum of the above polypentacyclic conjugated molecule represented by the formula (1-6-17) indicates that it has a strong absorption peak in the wavelength range of 650-1000 nm, and the maximum molar extinction coefficient is 2.3 ⁇ 10. 5 M –1 ⁇ cm –1 , the film absorbs most strongly at around 800 nm; the maximum absorption peak of the film is 38 nm redshifted in solution.
  • Cyclic voltammetry showed a HOMO level of -5.54 eV, a LUMO level of -4.02 eV, and a band gap of 1.52 eV, indicating that the above poly- and five-membered ring conjugated molecules represented by formula (1-6-17) have Better electron acceptability can match the energy levels of most common electron donor materials.
  • This example is intended to illustrate the conjugated molecules of the present invention and methods for their preparation.
  • This example is intended to illustrate the conjugated molecules of the present invention and methods for their preparation.
  • This example is intended to illustrate the conjugated molecules of the present invention and methods for their preparation.
  • This example is intended to illustrate the conjugated molecules of the present invention and methods for their preparation.
  • This example is intended to illustrate the conjugated macromolecule of the present invention and a process for its preparation.
  • This example is intended to illustrate the conjugated molecules of the present invention and methods for their preparation.
  • This embodiment is for explaining the solar cell of the present invention.
  • ITO Indium tin oxide
  • cathode purchased from Shenzhen CSG Float Glass Co., Ltd.
  • ITO Indium tin oxide
  • the solar light source was simulated with an AM1.5 filter (XES-70S1 model of SAN-EI ELECTRIC Co., Ltd.), and the device was tested for photovoltaic performance at a light intensity of 100 mW/cm 2 , and the light intensity passed through a standard single crystal. Silicon solar cells (purchased from VLSI Standards Inc) are calibrated. The resulting IV curve was measured using a B2912A Precision Source/Measure Unit (Agilent Technologies) and controlled by a computer using Labview software.
  • the obtained IV curve is shown in FIG. 3. It can be seen from the IV curve shown in FIG. 3 that the open circuit voltage V oc of the solar cell is 0.75 V, the short circuit current J sc is 19.6 mA ⁇ cm -2 , and the fill factor FF is 71.7%.
  • the photoelectric conversion efficiency PCE was 10.51%.
  • This embodiment is for explaining the solar cell of the present invention.
  • a 30 nm thick poly 3,4-ethylenedioxythiophene-polystyrene sulfonate PEDOT:PSS was spin-coated on the ITO glass (weight ratio 1: 1)
  • PBnDT-FTAZ replaces PTB7-Th
  • metal Ca replaces MoO 3
  • Al replaces Ag
  • a solar cell is prepared and tested.
  • the obtained IV curve is as shown in FIG. 4, and the IV curve shown in FIG. 4 shows that the open circuit voltage V oc of the solar cell is 0.79 V, the short-circuit current J sc is 16.8 mA ⁇ cm -2 , and the fill factor FF is 62.7%.
  • the photoelectric conversion efficiency PCE was 8.34%.
  • This embodiment is used to describe the translucent solar cell of the present invention.
  • metal Ag of about 20 nm is used as the anode of the solar cell.
  • the obtained IV curve is shown in FIG. 5. It can be seen from the IV curve shown in FIG. 5 that the open circuit voltage V oc of the translucent solar cell is 0.75 V, the short circuit current J sc is 19.0 mA ⁇ cm -2 , and the fill factor FF is 68.1. %, the photoelectric conversion efficiency PCE was 9.77%.
  • the transmittance curve of the visible light region of the obtained device is shown in Fig. 6. From the transmittance curve, the visible light transmittance of the translucent solar cell was 36%.
  • This embodiment is for explaining the solar cell of the present invention.
  • ITO indium tin oxide
  • the indium tin oxide (ITO) glass as a cathode is first washed with a detergent, then ultrasonically washed with deionized water, acetone, and isopropyl alcohol in sequence, and then dried and spin-coated with a layer of SnO 2 electron transport layer of about 30 nm thick, 150 Anneal at °C for 30 minutes and set aside.
  • the above polycyclic five-membered ring conjugated molecule represented by the above formula (1-6-2) is dissolved in DMF at a concentration of 0.25 mg/mL, and an appropriate amount of PbI 2 is further added thereto so as to have a concentration of 500 mg/mL, and then mixed.
  • the uniformly solution was spin-coated on the above SnO 2 layer, annealed at 70 ° C for 20 minutes, and after cooling, a FAI/MAI (2:1) mixed solution was spin-coated thereon, and annealed at 150 ° C for 15 minutes to obtain the above formula (
  • the five-membered ring conjugated molecule-doped perovskite layer shown in 1-6-2) was finally spin-coated with a 80 mg/mL spiro-OMeTAD solution.
  • Metal Ag having a thickness of about 150 nm was vapor-deposited on the active layer under vacuum (absolute pressure: 2 ⁇ 10 -5 Pa) as an anode of the solar cell.
  • the solar light source was simulated with an AM1.5 filter (XES-70S1 model of SAN-EI ELECTRIC Co., Ltd.), and the device was tested for photovoltaic performance at a light intensity of 100 mW/cm 2 , and the light intensity passed through a standard single crystal. Silicon solar cells (purchased from VLSI Standards Inc) are calibrated. The resulting IV curve was measured using a B2912A Precision Source/Measure Unit (Agilent Technologies) and controlled by a computer using Labview software.
  • the obtained IV curve is shown in FIG. 7.
  • the IV curve shown in FIG. 7 shows that the open circuit voltage V oc of the solar cell is 1.065 V, the short-circuit current J sc is 23.39 mA ⁇ cm -2 , and the fill factor FF is 79.1%.
  • the photoelectric conversion efficiency PCE was 19.7%.

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Abstract

La présente invention concerne une molécule conjuguée à base de polyquinane répondant à la formule (I), son procédé de synthèse et son application dans le domaine des cellules solaires. La molécule conjuguée présente de fortes capacités d'absorption de lumière visible et d'absorption de lumière proche infrarouge, de bonnes propriétés de transport de charge et un niveau d'énergie électronique approprié, est adaptée en tant que matériau photovoltaïque ou matériau de couche de transport d'électrons/couche de modification pour la préparation d'une cellule solaire, et est également adaptée en tant que matériau de détection de lumière destiné à être utilisé dans un détecteur de lumière.
PCT/CN2017/111587 2017-03-17 2017-11-17 Molécule conjuguée à base de polyquinane, son procédé de synthèse et son application WO2018166232A1 (fr)

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