WO2016195305A1 - Polymère et élément électronique organique le comprenant - Google Patents

Polymère et élément électronique organique le comprenant Download PDF

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WO2016195305A1
WO2016195305A1 PCT/KR2016/005478 KR2016005478W WO2016195305A1 WO 2016195305 A1 WO2016195305 A1 WO 2016195305A1 KR 2016005478 W KR2016005478 W KR 2016005478W WO 2016195305 A1 WO2016195305 A1 WO 2016195305A1
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group
substituted
unsubstituted
formula
polymer
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PCT/KR2016/005478
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English (en)
Korean (ko)
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임보규
이재철
최두환
강성경
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주식회사 엘지화학
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Priority claimed from KR1020160060910A external-priority patent/KR101732310B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/562,116 priority Critical patent/US10312445B2/en
Priority to EP16803660.6A priority patent/EP3305826B1/fr
Priority to CN201680022327.6A priority patent/CN107531888B/zh
Publication of WO2016195305A1 publication Critical patent/WO2016195305A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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 specification relates to a polymer and an organic electronic device including the same.
  • the organic electronic device refers to a device that requires charge exchange between an electrode and an organic material using holes and / or electrons.
  • the organic electronic device can be divided into two types according to the operating principle. First, excitons are formed in the organic material layer by photons introduced into the device from an external light source, and the excitons are separated into electrons and holes, and these electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). It is a form of electric element.
  • the second type is an electronic device in which holes and / or electrons are injected into an organic semiconductor forming an interface with the electrodes by applying voltage or current to two or more electrodes, and operated by the injected electrons and holes.
  • Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic transistor, and the like, all of which require a hole injection or transport material, an electron injection or transport material, or a light emitting material for driving the device.
  • the organic solar cell will be described in detail.
  • a hole injection or transport material, an electron injection or transport material, or a light emitting material functions on a similar principle.
  • An object of the present specification is to provide a polymer and an organic electronic device including the same.
  • the present specification provides a polymer including a unit represented by the following Chemical Formula 1.
  • X1 and X2 are the same as or different from each other, and each independently CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te,
  • R and R ' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substi
  • [Push] is a structure in which one or two or more of the following structures are bonded,
  • a is an integer from 1 to 4,
  • b and b ' are each an integer of 1 to 3
  • X10 to X22 are the same as or different from each other, and each independently CRaRb, NRa, O, SiRaRb, PRa, S, GeRaRb, Se, or Te,
  • Y10 and Y11 are the same as or different from each other, and each independently CRc, N, SiRc, P, or GeRc,
  • Ra, Rb, Rc and R100 to R113 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstitute
  • [Pull 1 ] and [Pull 2 ] is a group acting as an electron acceptor is the same or different from each other, each independently represented by the following formula (2) or (3),
  • X3 to X7 are the same as or different from each other, and each independently CR15R16, NR15, O, SiR15R16, PR15, S, GeR15R16, Se, or Te,
  • Y1 to Y4 are the same as or different from each other, and each independently CR17, N, SiR17, P, or GeR17,
  • n1 is an integer of 0 or 1
  • n2 to n4 are each an integer of 0 to 3
  • n2 to n4 are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other,
  • R1 to R17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substi
  • the present specification is a first electrode; Second electrode; And one or more organic material layers provided between the first electrode and the second electrode.
  • At least one layer of the organic material layer provides an organic electronic device comprising the polymer described above.
  • the polymer according to one embodiment of the present specification includes an electron acceptor in a side chain, so that electrons are localized in the side chain of the polymer.
  • the dielectric constant may increase.
  • the polymer according to the exemplary embodiment of the present specification is provided with an electron acceptor in the side chain to facilitate contact with the n-type material of the device, for example, PCBM, so that the electrons can be easily transferred to the n-type material.
  • an electron acceptor in the side chain to facilitate contact with the n-type material of the device, for example, PCBM, so that the electrons can be easily transferred to the n-type material.
  • the organic electronic device including the condensed ring derivative according to the exemplary embodiment of the present specification may exhibit excellent characteristics such as increase in open voltage and short circuit current and / or increase in efficiency.
  • Condensed ring derivative according to one embodiment of the present specification can be used alone or mixed with other materials in an organic electronic device, and can be expected to improve the life of the device due to the improvement of efficiency, the thermal stability of the compound, etc. have.
  • FIG. 1 illustrates an organic solar cell according to an exemplary embodiment of the present specification.
  • FIG. 9 is a diagram showing the current density by voltage of the organic solar cell manufactured in Experimental Example 2.
  • the present specification includes a polymer represented by a unit represented by Chemical Formula 1.
  • [Pull 1 ] and [Pull 2 ] are each independently a group serving as an electron acceptor, and [Push] is a group serving as an electron donor.
  • the main chain of the polymer according to one embodiment of the present specification is composed of a structure that acts as an electron donor
  • the side chain of the polymer is composed of a structure acting as an electron acceptor
  • the charge carrier mobility in the organic material has the fastest mobility in the intramolecular direction, and the charge transfer in the pi-pi direction is dominant. Therefore, in order to cause rapid movement of holes and electrons, it is necessary to quickly separate excitons, and holes and electrons must be moved through respective paths to minimize high recombination of electrons and holes.
  • p-type polymers which are electron donor materials, are alternately or randomly bonded to an electron-donating unit (push) rich in electrons and an electron-withdrawing unit (pull) lacking electrons.
  • Intra charge transfer (ICT) has been provided to cause low bandgap.
  • ICT Intra charge transfer
  • the main chain of the polymer according to one embodiment of the present specification is composed of a structure that acts as an electron donor, and the side chain of the polymer is composed of a structure acting as an electron acceptor, so that electrons are relatively localized. Therefore, an increase in permittivity and minimization of recombination of electrons and holes can be expected, and high mobility of holes and electrons can be expected.
  • the side chain of the polymer of the present specification is composed of an electron acceptor unit (pull: electron-withdrawing unit) (pull) is easy to contact with an electron acceptor material, such as n-type, for example, PCBM can be easily transferred to the electron transfer.
  • pulse electron-withdrawing unit
  • the [Pull 1 ] and [Pull 2 ] is reduced in the electrochemical measurement (cyclic voltammetry (CV)).
  • X1 and X2 are S.
  • [Pull 1 ] and [Pull 2 ] are the same or different from each other, and each independently a heteroaryl group serving as an electron acceptor.
  • the heteroaryl group may be monocyclic or polycyclic, and may be a group in which one or two or more heteroaryl groups are connected.
  • X3 is S.
  • X4 is S.
  • X5 is S.
  • Y1 is N.
  • Y2 is N.
  • X6 is S.
  • X7 is S.
  • Y3 is N.
  • Y4 is N.
  • [Pull 1 ] and [Pull 2 ] represented by Formula 2 or Formula 3 are represented by the following Formula 2-1 or Formula 3-1.
  • R1 to R14 are the same as defined in the formula (2) and (3).
  • substituted means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
  • substituted or unsubstituted is deuterium; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted aryl group; And it is substituted with one or more substituents selected from the group consist
  • a substituent to which two or more substituents are linked may be a biphenyl group. That is, the biphenyl group may be an aryl group and can be interpreted as a substituent to which two phenyl groups are linked.
  • carbon number of an imide group is not specifically limited, It is preferable that it is C1-C30. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
  • the amide group may be substituted with one or two of the nitrogen of the amide group is hydrogen, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 50.
  • Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-o
  • the cycloalkyl group is not particularly limited, but preferably 3 to 60 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. Do not.
  • the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C20. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like It may be, but is not limited thereto.
  • the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.
  • the aryl group is a monocyclic aryl group
  • carbon number is not particularly limited, but preferably 6 to 25 carbon atoms.
  • the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.
  • the aryl group is a polycyclic aryl group
  • carbon number is not particularly limited. It is preferable that it is C10-24.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
  • the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.
  • the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Si, Se, and S, and the like. have.
  • carbon number of a heterocyclic group is not specifically limited, It is preferable that it is C2-C60.
  • heterocyclic group examples include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridil group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthro
  • the amine group is not particularly limited, but is preferably 1 to 30.
  • the amine group may be substituted with an N atom, such as an aryl group, an alkyl group, an arylalkyl group, and a heterocyclic group.
  • Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group and phenylamine.
  • the aryl group in the aryloxy group, arylthioxy group, and aryl sulfoxy group is the same as the examples of the aryl group described above.
  • the aryloxy group phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphenoxy, 3-biphenyl Oxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl Oxy, 9-anthryloxy, 1-phenanthryloxy, 3-phenanthryloxy, 9-phenanthryloxy, and the like.
  • arylthioxy group examples include a phenylthioxy group, 2-methylphenylthioxy group, and 4-tert-butylphenyl.
  • Thioxy groups and the like, and aryl sulfoxy groups include, but are not limited to, benzene sulfoxy groups and p-toluene sulfoxy groups.
  • the alkyl group in the alkyl thioxy group and the alkyl sulfoxy group is the same as the example of the alkyl group mentioned above.
  • the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, an octyl thioxy group
  • the alkyl sulfoxy group includes mesyl, ethyl sulfoxy, propyl sulfoxy and butyl sulfoxy Etc., but is not limited thereto.
  • the polymer includes a unit represented by any one of the following Formulas 1-1 to 1-4.
  • a is an integer from 1 to 4,
  • n is a repetition number of units and is an integer of 1 to 1,000
  • n1 and n1 ' are integers of 0 or 1
  • n2 to n4 and n2 'to n4' are each an integer of 0 to 3
  • n2 to n4 and n2 'to n4' are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other,
  • R1 to R14, R1 'to R14', R104, R105, R112 and R113 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted sily
  • n1 and n1 ' are zero.
  • n2 and n2 ' are 1.
  • n3 and n3 ' are 1.
  • n4 and n4 ' are 1.
  • R1 is hydrogen
  • R2 is hydrogen
  • R3 and R4 are the same as or different from each other, and are each independently hydrogen or a halogen group.
  • R3 is hydrogen
  • R3 is a halogen group.
  • R3 is fluorine
  • R4 is hydrogen
  • R4 is a halogen group.
  • R4 is fluorine
  • R5 is hydrogen
  • R6 is hydrogen
  • R7 is a substituted or unsubstituted alkyl group.
  • R7 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
  • R7 is a substituted or unsubstituted 2-octyldodecanyl group.
  • R7 is a 2-octyldodecanyl group.
  • the a is 1.
  • the a is 2.
  • a is three.
  • the side chain between the unit and the unit causes excellent interdigitation, and the rotation of the side chain is minimized, so that the pie-pie packing between the units ( It is more preferable to be able to increase the packing and to produce a dense film.
  • the unit represented by Chemical Formula 1 may be represented by the following units, but is not limited thereto.
  • the number average molecular weight of the polymer is preferably 5,000 g / mol to 1,000,000 g / mol.
  • the polymer may have a molecular weight distribution of 1 to 10.
  • the polymer has a molecular weight distribution of 1-3.
  • the number average molecular weight is preferably 100,000 or less in order to have a certain solubility or higher so that the solution coating method is advantageous.
  • Polymers according to the present disclosure can be prepared by multistage chemical reactions. Monomers are prepared through alkylation reactions, Grignard reactions, Suzuki coupling reactions, and Still coupling reactions, followed by carbon-carbon coupling reactions such as steel coupling reactions. Can be prepared. When the substituent to be introduced is a boronic acid or boronic ester compound, it may be prepared through Suzuki coupling, and the substituent to be introduced is tributyltin or trimethyltin. ) Compound may be prepared through a steel coupling reaction, but is not limited thereto.
  • first electrode a first electrode
  • Second electrode And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the polymer described above.
  • the organic electronic device is an organic light emitting device; Organic solar cells; And organic transistors.
  • the organic electronic device may be an organic light emitting device.
  • an organic light emitting device including a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one layer of the organic layer is It provides an organic electronic device comprising a polymer.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes the polymer.
  • the organic material layer includes a hole injection layer or a hole transport layer, and the hole injection layer or hole transport layer comprises the polymer.
  • the organic material layer includes an electron injection layer or an electron transport layer, and the electron injection layer or the electron transport layer includes the polymer.
  • the organic electronic device may be an organic transistor.
  • an organic transistor including a source, a drain, a gate, and one or more organic material layers, and at least one of the organic material layers provides an organic electronic device including the polymer.
  • the organic electronic device may be an organic solar cell.
  • the organic electronic device includes a first electrode; Second electrode; And at least one organic material layer including a photoactive layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the polymer.
  • the principle of an organic solar cell is that the p-type semiconductor forms an exciton where electrons and holes are paired by photo excitation, and the exciton is separated into electrons and holes at the p-n junction.
  • the separated electrons and holes move to the n-type semiconductor thin film and the p-type semiconductor thin film, respectively, and they are collected by the first electrode and the second electrode, respectively, so that they can be used as electrical energy from the outside.
  • FIG. 1 is a diagram illustrating an organic solar cell according to an exemplary embodiment of the present specification.
  • a substrate 101, a first electrode 102, a hole transport layer 103, a photoactive layer 104, and a second electrode 105 are included.
  • the organic solar cell according to the exemplary embodiment of the present specification is not limited to the structure and the material of FIG. 1, and additional layers may be provided, and each layer may be configured using various materials.
  • the organic solar cell may further include an additional organic material layer.
  • the organic solar cell may reduce the number of organic material layers by using an organic material having several functions at the same time.
  • the organic material layer includes a photoactive layer and an organic material layer provided between the photoactive layer and the first electrode or the second electrode, and the photoactive layer and the first electrode or the second electrode.
  • the organic material layer provided between includes the polymer.
  • the organic material layer includes a photoactive layer
  • the photoactive layer has a bilayer structure including a n-type organic material layer and a p-type organic material layer
  • the p-type organic material layer includes the polymer.
  • the organic material layer includes a photoactive layer
  • the photoactive layer is a bulk heterojunction structure including an electron donor material and an electron acceptor material
  • the electron donor material includes the polymer
  • Bulk heterojunction means that the electron donor material and the electron acceptor material are mixed with each other in the photoactive layer.
  • the bulk heterojunction in which the electron donor material and the electron acceptor material are mixed with each other, has a large donor-rich part, an acceptor-rich part, and the electron donor and the electron acceptor coexist ( mixed phase).
  • the exciton formed in the photoactive layer is dissociated into holes and electrons at the portions where the electron donor and the electron acceptor coexist with each other and where the electron donor and the electron acceptor are in contact with each other.
  • the molecules of the donor material are moved to the first electrode or the second electrode, respectively.
  • the polymer according to an exemplary embodiment of the present specification is composed of an electron donating unit (push) in the main chain and an electron-withdrawing unit (pull) in the side chain to recombine electrons and holes.
  • an electron donating unit push
  • an electron-withdrawing unit pull
  • the polymer which acts as an electron donor material in the photoactive layer, has a side chain composed of an electron acceptor unit, and thus easily contacts with the electron acceptor material, thereby facilitating transfer of electrons to the electron acceptor material.
  • the organic compound included in the electron acceptor material is fullerene, fullerene derivative (PCBM ((6,6) -phenyl-C61-butyric acid-methylester) or PCBCR ((6, 6) -phenyl-C61-butyric acid-cholesteryl ester), perylene (perylene) PBI (polybenzimidazole), and PTCBI (3,4,9,10-perylene-tetracarboxylic bis-benzimidazole) 1 or Two or more compounds.
  • PCBM ((6,6) -phenyl-C61-butyric acid-methylester) or PCBCR ((6, 6) -phenyl-C61-butyric acid-cholesteryl ester)
  • perylene (perylene) PBI polybenzimidazole
  • PTCBI 3,4,9,10-perylene-tetracarboxylic bis-benzimidazole
  • the organic solar cell according to the exemplary embodiment of the present specification includes a first electrode, a photoactive layer, and a second electrode.
  • the organic solar cell may further include a substrate, a hole transport layer, and / or an electron transport layer.
  • the first electrode is an anode
  • the second electrode is a cathode
  • the first electrode is a cathode and the second electrode is an anode.
  • the organic solar cell may be arranged in the order of cathode, photoactive layer and anode, and may be arranged in the order of anode, photoactive layer and cathode, but is not limited thereto.
  • the organic electronic device has a normal structure.
  • the normal structure may mean that an anode is formed on a substrate.
  • the first electrode formed on the substrate may be an anode.
  • the organic electronic device has an inverted structure.
  • the inverted structure may mean that a cathode is formed on a substrate.
  • the first electrode formed on the substrate may be a cathode.
  • the organic solar cell has a normal structure, and the organic material layer includes a photoactive layer; And an organic material layer provided between the photoactive layer and the second electrode, wherein the organic material layer provided between the photoactive layer and the second electrode includes the polymer, and the first electrode is an anode electrode and the second electrode. Is a cathode electrode.
  • the organic electronic device has an inverted structure
  • the organic material layer includes an organic material layer provided between the photoactive layer and the first electrode, and between the photoactive layer and the first electrode.
  • the organic material layer provided in the polymer includes the polymer
  • the first electrode is a cathode electrode
  • the second electrode is an anode electrode
  • the organic electronic device may further include an additional organic material layer.
  • the organic electronic device may reduce the number of organic material layers by using an organic material having several functions at the same time.
  • the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto, and the substrate may be any substrate that is commonly used in organic solar cells. Specifically, there are glass or polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC). It is not limited to this.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PP polypropylene
  • PI polyimide
  • TAC triacetyl cellulose
  • the anode electrode may be a transparent and excellent conductive material, but is not limited thereto.
  • Metals such as vanadium, chromium, copper, zinc and gold or alloys thereof;
  • Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SNO 2 : Combination of metals and oxides such as Sb;
  • Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the method of forming the anode electrode is not particularly limited, but is applied to one surface of the substrate or coated in a film form using, for example, sputtering, E-beam, thermal deposition, spin coating, screen printing, inkjet printing, doctor blade or gravure printing. It can be formed by.
  • the anode electrode When the anode electrode is formed on the substrate, it may be subjected to cleaning, water removal, and hydrophilic modification.
  • the patterned ITO substrate is sequentially cleaned with a detergent, acetone, isopropyl alcohol (IPA), and then dried in a heating plate for 1 to 30 minutes at 100 to 150 ° C., preferably at 120 ° C. for 10 minutes to remove moisture.
  • IPA isopropyl alcohol
  • the surface of the substrate is modified to be hydrophilic.
  • the bonding surface potential can be maintained at a level suitable for the surface potential of the photoactive layer.
  • Pretreatment techniques for the anode electrode include a) surface oxidation using parallel plate discharge, b) oxidation of the surface through ozone generated using UV ultraviolet light in a vacuum state, and c) oxygen generated by plasma. And oxidation using radicals.
  • One of the above methods can be selected depending on the state of the anode electrode or the substrate. In any case, however, it is desirable to prevent oxygen escape from the surface of the anode electrode or the substrate and to minimize the residual of moisture and organic matter in common. At this time, the substantial effect of the pretreatment can be maximized.
  • a method of oxidizing a surface through ozone generated using UV may be used.
  • the patterned ITO substrate is baked on a hot plate and dried well, then put into a chamber, and a UV lamp is activated to cause oxygen gas to react with UV light.
  • the patterned ITO substrate can be cleaned.
  • the surface modification method of the patterned ITO substrate in this specification does not need to be specifically limited, Any method may be used as long as it is a method of oxidizing a substrate.
  • the cathode electrode may be a metal having a small work function, but is not limited thereto.
  • metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; LiF / Al, LiO 2 / Al, LiF / Fe, Al: Li, Al: BaF 2 , Al: BaF 2
  • It may be a material of a multi-layer structure such as, but is not limited thereto.
  • the cathode electrode is 5x10 - may be formed is deposited on the internal heat evaporator showing a degree of vacuum of less than 7 torr, not limited to this method.
  • the hole transport layer and / or electron transport layer material plays a role of efficiently transferring electrons and holes separated in the photoactive layer to the electrode, and the material is not particularly limited.
  • the hole transport layer material may be PEDOT: PSS (Poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid)), molybdenum oxide (MoO x ); Vanadium oxide (V 2 O 5 ); Nickel oxide (NiO); Tungsten oxide (WO x ), and the like, but is not limited thereto.
  • PSS Poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid)
  • MoO x molybdenum oxide
  • V 2 O 5 Vanadium oxide
  • NiO Nickel oxide
  • WO x Tungsten oxide
  • the electron transport layer material may be electron-extracting metal oxides, specifically, a metal complex of 8-hydroxyquinoline; Complexes including Alq 3 ; Metal complexes including Liq; LiF; Ca; Titanium oxide (TiO x ); Zinc oxide (ZnO); And cesium carbonate (Cs 2 CO 3 ), and the like, but is not limited thereto.
  • metal oxides specifically, a metal complex of 8-hydroxyquinoline; Complexes including Alq 3 ; Metal complexes including Liq; LiF; Ca; Titanium oxide (TiO x ); Zinc oxide (ZnO); And cesium carbonate (Cs 2 CO 3 ), and the like, but is not limited thereto.
  • the photoactive layer may be formed by dissolving a photoactive material, such as an electron donor and / or an electron acceptor, in an organic solvent and then spin coating, dip coating, screen printing, spray coating, doctor blade, brush painting, or the like. It is not limited to the method.
  • a photoactive material such as an electron donor and / or an electron acceptor
  • Dissolve compound of formula 1-A (4.23 g, 7.1 mmol) and tributyltin thiophene (2.69 g, 7.2 mmol) in 60 ml toluene, tris (dibenzylideneacetone) dipalladium (0) (Pd 2 dba 3 )
  • a catalyst (0.23 g, 0.25 mmol) and triphenylphosphine (PPh 3 ) ligand (0.26 g, 1 mmol) were added thereto, and the mixture was stirred at 110 ° C. for 48 hours.
  • the obtained gel was precipitated in methanol, the solid obtained was dissolved in chloroform, mixed with an aqueous solution of ethylenediaminetetraacetic acid (EDTA), and stirred at 120 ° C for 2 hours.
  • the reaction solution was precipitated in methanol, and the obtained solid was soxhlet in order of methanol, acetone, hexane, petroleum ether, dichloromethane (DCM) and chloroform, and the final dissolved air in chloroform was precipitated.
  • Union 1-E was obtained.
  • HOMO highest occupied molecular orbital
  • LUMO lowest unoccupied molecular orbital
  • band gap of Compound A and Compound B below were included in the Gaussian 09 program in the B3PW91 category. Measurements were made using a functional and 6-31G * basis set.
  • the prepared polymer is used as an electron donor and PC 70 BM is used as an electron acceptor, but the compounding ratio is 1: 3 (w / w ratio), and dissolved in dichlorobenzene (DCB: diposite solution).
  • DCB dichlorobenzene
  • the concentration was adjusted to 2.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al.
  • ITO-coated glass substrates were ultrasonically cleaned with distilled water, acetone and 2-propanol, ozonated the ITO surface for 10 minutes, and spin-coated PEDOT: PSS (AI4083) at 4000 rpm for 40 seconds to 45 nm to 235 Heat treatment was carried out for 5 minutes at °C.
  • Compound-PC 70 BM composite solution was filtered with a 0.45 ⁇ m PP syringe filter and then spin coated, using a thermal evaporator under a 3 ⁇ 10 -8 torr vacuum to a thickness of 100 nm. Al was deposited to prepare an organic solar cell.
  • Voc is the open voltage
  • Jsc is the short-circuit current
  • FF is the fill factor
  • PCE is the energy conversion efficiency.
  • the open-circuit and short-circuit currents are the X- and Y-axis intercepts in the four quadrants of the voltage-current density curve, respectively. The higher these two values, the higher the efficiency of the solar cell.
  • the fill factor is the area of the rectangle drawn inside the curve divided by the product of the short circuit current and the open voltage. By dividing these three values by the intensity of the emitted light, the energy conversion efficiency can be obtained, and higher values are preferable.
  • FIG. 9 is a diagram showing the current density by voltage of the organic solar cell manufactured in Experimental Example 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne un polymère qui comprend un groupe fonctionnel accepteur d'électrons sur une chaîne latérale et qui est représenté par la formule chimique 1, ainsi qu'un élément électronique organique le comprenant.
PCT/KR2016/005478 2015-06-03 2016-05-24 Polymère et élément électronique organique le comprenant WO2016195305A1 (fr)

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US15/562,116 US10312445B2 (en) 2015-06-03 2016-05-24 Polymer and organic electronic element comprising same
EP16803660.6A EP3305826B1 (fr) 2015-06-03 2016-05-24 Polymère et élément électronique organique le comprenant
CN201680022327.6A CN107531888B (zh) 2015-06-03 2016-05-24 聚合物和包含其的有机电子元件

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CN110178241A (zh) * 2017-05-11 2019-08-27 株式会社Lg化学 光活性层和包括其的有机太阳能电池

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CN110178241A (zh) * 2017-05-11 2019-08-27 株式会社Lg化学 光活性层和包括其的有机太阳能电池
CN108034042A (zh) * 2017-12-11 2018-05-15 华南协同创新研究院 一种主链给体-侧链受体型共轭聚合物及其制备和应用
CN108034042B (zh) * 2017-12-11 2019-12-03 华南协同创新研究院 一种主链给体-侧链受体型共轭聚合物及其制备和应用

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