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WO2019045059A1 - Composition à base de dérivé de fullerène - Google Patents

Composition à base de dérivé de fullerène Download PDF

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Publication number
WO2019045059A1
WO2019045059A1 PCT/JP2018/032420 JP2018032420W WO2019045059A1 WO 2019045059 A1 WO2019045059 A1 WO 2019045059A1 JP 2018032420 W JP2018032420 W JP 2018032420W WO 2019045059 A1 WO2019045059 A1 WO 2019045059A1
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Prior art keywords
group
substituents
fullerene derivative
formula
photoelectric conversion
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Japanese (ja)
Inventor
永井　隆文
洋介 岸川
光信 高橋
誠 辛川
Takayuki KUWABARA (桑原 貴之)
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Daikin Industries Ltd
Kanazawa University NUC
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Daikin Industries Ltd
Kanazawa University NUC
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/58—[b]- or [c]-condensed
    • C07D209/70—[b]- or [c]-condensed containing carbocyclic rings other than six-membered
    • 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 fullerene derivative compositions.
  • An organic thin film solar cell is formed by a coating method from a solution, using an organic compound as a photoelectric conversion material, 1) low cost in device fabrication, 2) It is easy to increase the area, 3) It has various advantages such as a flexible and usable place compared with inorganic materials such as silicon and 4) less concern for resource exhaustion. For this reason, in recent years, development of organic thin film solar cells has been promoted, and in particular, by adopting a bulk heterojunction structure, it becomes possible to greatly improve conversion efficiency, and has drawn wide attention.
  • the active layer of the organic thin film solar cell like the inorganic solar cell, contains a p-type semiconductor which conducts holes as carriers and an n-type semiconductor which conducts electrons as carriers.
  • poly-3-hexylthiophene is particularly known as an organic p-type semiconductor material having excellent performance.
  • P3HT poly-3-hexylthiophene
  • a compound with a structure that can absorb a broad range of wavelengths of sunlight and a structure with an adjusted energy level has been developed (donor-acceptor type ⁇ conjugated polymer), which greatly contributes to performance improvement doing.
  • examples of such compounds include poly-p-phenylenevinylene and 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).
  • PCBM phenyl C61-butyric acid methyl ester
  • PCBM is a fullerene derivative having a three-membered ring portion, and most of the fullerene derivatives reported so far are also fullerene derivatives having a three-membered ring portion like PCBM.
  • fullerene derivatives having a 5-membered ring portion are also known as fullerene derivatives other than fullerene derivatives having a 3-membered ring portion.
  • Non-Patent Document 1 discloses a fullerene derivative having a pyrrolidine ring and having a substituent only at its 1- and 2-positions.
  • Patent Documents 3, 4 and 6 each disclose a fullerene derivative having a pyrrolidine ring and having a substituent at the 1-position thereof.
  • Patent Document 5 discloses a fullerene derivative having two or more pyrrolidine rings.
  • Non-Patent Document 2 discloses that a fullerene derivative having a pyrrolidine ring and having a phenyl group at the 1-position thereof is effective as an n-type semiconductor for an organic thin film solar cell.
  • a photoelectric conversion layer that converts light energy into electric energy in a solar cell is composed of two components, a p-type semiconductor and an n-type semiconductor. Primarily, p-type semiconductors absorb light energy, and it becomes possible to extract electric energy through excited state (exciton) formation, charge separation, charge transfer to the electrode.
  • phase separation spacing in bulk heterojunction structures that is effective in this regard is generally considered to be 10-20 nm.
  • the phase separation shape here is formed by the aggregation of the respective semiconductors, and depends on the crystallinity of each component and the surface energy.
  • the fullerene derivative has higher surface energy and stronger aggregation than a general planar conjugated compound. Due to the inherent nature of this fullerene, a bulk heterojunction is likely to be formed in the photoelectric conversion layer. This is why fullerene derivatives have been widely used as n-type semiconductors in organic thin film solar cells.
  • the crystallinity and surface energy of the donor-acceptor type polymer material which can be expected to have high conversion efficiency as a p-type semiconductor are different from those of existing p-type semiconductors (eg, P3HT).
  • phase separation structure control additive As the phase separation structure control additive to be used here, low polar high boiling point solvents such as diiodo ocnan and octane dithiol, polycyclic aromatic compounds, and compounds having aggregation property in a plane having liquid crystallinity are used.
  • Examples thereof include the novel phase separation structure control additive of Non-Patent Document 3, the mixture of C60 fullerene derivative and C70 fullerene derivative of Non-Patent Document 4, and the cross-linked structure formation in the photoelectric conversion layer of Non-Patent Document 5.
  • none of these approaches has reached the sufficient ease of device fabrication and the expression of sufficient function.
  • an object of the present invention is to provide a fullerene derivative composition and the like which can contribute to the improvement of the power generation performance and the structural stability of the photoelectric conversion layer, and can contribute to the production of an organic thin film solar cell device excellent in durability. .
  • the inventor has accumulated data on fullerene derivative structure and solubility. A correlation is observed between solubility and cohesion, and the cohesion of the fullerene derivative itself can be controlled by adjusting the chain length of the alkyl group to be introduced and the structure. In this case, among fullerene derivatives having different aggregation properties, a bulk heterojunction structure can be stably formed with various p-type semiconductors even though the above additives are hardly used in a certain combination of structures. Found out. Based on such findings, the present inventors Formula (1): [In the formula, R 11 represents an organic group, R 12 represents an organic group, and ring A represents a fullerene ring.
  • the present invention includes the following aspects.
  • Item 1 [In the formula, R 11 represents an organic group, R 12 represents an organic group, and ring A represents a fullerene ring. ] Fullerene derivative (1) represented by and formula (2): [In the formula, R 21 represents an organic group, R 22 represents an organic group, R 23 represents an organic group, and ring A represents a fullerene ring. ] Fullerene derivatives (2) A fullerene derivative composition containing Item 2. The mass ratio of the fullerene derivative (1) and the fullerene derivative (2) is In the range of 1:99 to 99: 1, Item 2. The fullerene derivative composition according to Item 1. Item 3.
  • R 11 is An aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents, Item 3.
  • R 11 is It is a phenyl group which may have one or more substituents, Item 4.
  • R 12 is An aryl group which may have one or more substituents, An alkyl group which may have one or more substituents, The fullerene derivative composition according to any one of Items 1 to 4, which is an ether group which may have one or more substituents, or an ester group which may have one or more substituents.
  • Item 6. In the formula (1), Item 6. The fullerene derivative composition according to Item 5, wherein R 12 is a phenyl group or an alkyl group. Item 7. In the formula (2), R 21 is An aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents, Item 7. The fullerene derivative composition according to any one of Items 1 to 6. Item 8. In the formula (1), 8. The fullerene derivative composition according to any one of Items 1 to 7, wherein R 21 is a phenyl group which may have one or more substituents. Item 9.
  • R 22 is An aryl group which may have one or more substituents, An alkyl group which may have one or more substituents, 9.
  • Item 10 10.
  • R 23 is An aryl group which may have one or more substituents, An alkyl group which may have one or more substituents, 11.
  • the content of at least one additive for controlling phase separation structure selected from the group consisting of diiodooctane, octanedithiol, chloronaphthalene, trimethylbenzene, nitrobenzene, and a liquid crystalline substance having a triphenylene structure or an allylaldimine structure is
  • the photoelectric conversion layer according to Item 15 which is 1 part by mass or less with respect to 100 parts by mass of the total amount of the fullerene derivative (1) and the fullerene derivative (2).
  • the photoelectric conversion element provided with the photoelectric conversion layer of Claim 15 or 16.
  • a light sensor comprising the photoelectric conversion layer according to item 15 or 16.
  • An organic thin film solar cell comprising the photoelectric conversion element according to Item 17.
  • Item 13 A perovskite solar cell comprising an electron transport layer containing the composition according to any one of Items 1 to 12.
  • the present invention contributes to the improvement of the power generation performance and the structural stability of the photoelectric conversion layer, and can contribute to the production of an organic thin film solar cell device excellent in durability.
  • 7 is an AFM image of the power generation layer of Example 1.
  • 7 is an AFM image of a power generation layer of Example 2.
  • 7 is an AFM image of a power generation layer of Comparative Example 1;
  • examples of “halo (group)” can include fluoro (group), chloro (group), bromo (group) and iodo (group).
  • examples of “halogen (atom)” can include fluorine (atom), chlorine (atom), bromine (atom), and iodine (atom).
  • organic group means a group containing one or more carbon atoms (or a group formed by removing one hydrogen atom from an organic compound).
  • An example of the "organic group” is A hydrocarbon group which may have one or more substituents, A heterocyclic group which may have one or more substituents, Cyano group, Aldehyde group, Ether group (eg, R r O-), An acyl group (eg, R r CO-), R r SO 2- , Ester group (eg, R r OCO-), and R r OSO 2- (In these formulas, R r is independently It is a hydrocarbon group which may have one or more substituents, or a heterocyclic group which may have one or more substituents) Can be included.
  • examples of the "hydrocarbon group” include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group and an aralkyl group, and two or more of them. Include groups to which is attached.
  • the carbon number of the “hydrocarbon group” is, for example, 1 to 100, 1 to 80, 1 to 60, 1 to 40, 1 to 30, 1 to 20, or 1 to 10 (Example: 2, 3, 4, 5, 6, 7, 8, 9, 10).
  • examples of the “substituent” in the “hydrocarbon group which may have one or more substituents” are halo group, nitro group, cyano group, oxo group, thioxo group, sulfo group, A sulfamoyl group, a sulfinamoyl group, a sulfenamoyl group, a heterocyclic group, and a group in which two or more of these are linked are included.
  • the number of the substituents can be in the range from 1 to the maximum number of substitutable (for example, 1, 2, 3, 4, 5, 6).
  • alkyl group examples are methyl, ethyl, propyl (e.g. n-propyl, isopropyl), butyl (e.g. n-butyl, isobutyl, sec-butyl, tert- Butyl), pentyl (eg n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl), hexyl, heptyl, octyl, nonyl and decyl etc., linear or branched , C 1 -C 10 alkyl groups.
  • alkenyl group examples are vinyl, 1-propen-1-yl, 2-propen-1-yl, isopropenyl, 2-buten-1-yl, 4- Linear or branched C 2 -C 10 alkenyl groups such as penten-1-yl and 5-hexen-1-yl can be included.
  • alkynyl group examples are ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, 5-hexyne Linear or branched C 2 -C 10 alkynyl groups, such as 1-yl, can be included.
  • examples of the “cycloalkyl group” can include C 3 -C 7 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.
  • examples of the “cycloalkenyl group” can include C 3 -C 7 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and the like.
  • examples of the "cycloalkadienyl group” are cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononadienyl And C 4 -C 10 cycloalkadienyl groups such as cyclodecadienyl and the like.
  • the "aryl group” can be monocyclic, bicyclic, tricyclic or tetracyclic.
  • the “aryl group” can be, for example, a C 6 -C 18 aryl group, a C 6 -C 14 aryl group, or a C 6 -C 10 aryl group.
  • examples of the “aryl group” can include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl and 2-anthryl.
  • the “aralkyl group” can be, for example, a C 7 -C 20 aryl group, a C 7 -C 16 aryl group, or a C 7 -C 12 aryl group.
  • examples of the "aralkyl group” are benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4- Phenylbutyl, 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, and 4-biphenylylmethyl can be included.
  • heterocyclic group examples include non-aromatic heterocyclic group and heteroaryl group.
  • the “heterocyclic group” can be, for example, 5-18, 5-14 or 5-10 members, and in the present specification, “one or more”.
  • the “substituent” in the “optionally substituted heterocyclic group” are halo, nitro, cyano, oxo, thioxo, sulfo, sulfamoyl, sulfinamoyl, sulfenamoyl, carbonized A hydrogen group, a heterocyclic group, and a group in which two or more of these are linked are included.
  • the “non-aromatic heterocyclic group” can be monocyclic, bicyclic, tricyclic or tetracyclic.
  • the “non-aromatic heterocyclic group” is, for example, 1 to 4 selected from an oxygen atom, a sulfur atom and a nitrogen atom in addition to carbon atoms as a ring constituting atom It can be a non-aromatic heterocyclic group containing a heteroatom.
  • the "non-aromatic heterocyclic group” can be saturated or unsaturated.
  • non-aromatic heterocyclic group examples include tetrahydrofuryl, oxazolidinyl, imidazolinyl (e.g. 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridinyl (e.g.
  • azetidinyl eg: 1-azetidinyl, 2-azetidinyl
  • pyrrolidinyl eg: 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl
  • piperidinyl eg: 1-piperidinyl, 2-piperidinyl, 3-Piperidinyl
  • azepanyl eg: 1-azepanyl, 2-azepanyl, 3-azepanyl, 4-azepanyl
  • azocanyl eg: 1-azocanil, 2-azocanil, 3-azocanil, 4-azocanyl
  • piperazinyl eg : 1,4-piperazin-1-yl, 1,4-pipe Gin-2-yl
  • diazepinyl e.g.
  • Diazocanyl eg, 1,4-d
  • heteroaryl group examples include monocyclic aromatic heterocyclic groups (eg, 5- or 6-membered monocyclic aromatic heterocyclic groups), and aromatic fused rings. Heterocyclic groups (eg, 5- to 18-membered aromatic fused heterocyclic groups) can be included.
  • examples of the “5- or 6-membered monocyclic aromatic heterocyclic group” are pyrrolyl (eg: 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (eg : 2-furyl, 3-furyl), thienyl (example: 2-thienyl, 3-thienyl), pyrazolyl (example: 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (example: 1-imidazolyl, 2- Imidazolyl, 4-imidazolyl), isoxazolyl (eg, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), oxazolyl (eg, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (eg, 3-isothiazolyl, 4 -Isothiazolyl, 5-isothiazo
  • examples of “a 5- to 18-membered aromatic fused heterocyclic group” are isoindolyl (eg: 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5- Iso-in-drill, 6-iso-in-drill, 7-iso-in-drill), in-drill (eg: 1-in-drill, 2-in-drill, 3-in-drill, 4-in-drill, 5-in-drill, 5-in-drill, 6-in-drill, 7-in-drill), benzo [b] furanyl ( Example: 2-benzo [b] furanyl, 3-benzo [b] furanyl, 4-benzo [b] furanyl, 5-benzo [b] furanyl, 6-benzo [b] furanyl, 7-benzo [b] furanyl) , Benzo [c]
  • ether group means a group having an ether bond (-O-).
  • ether groups include polyether groups.
  • polyether groups are Formula: R a- (O-R b ) n -or Formula: R a- (O-R b ) n -O- (In the formula, R a is an alkyl group, R b is the same or different at each occurrence, is an alkylene group, and n is an integer of 1 or more.)
  • R a is an alkyl group
  • R b is the same or different at each occurrence, is an alkylene group
  • n is an integer of 1 or more.
  • a group represented by The alkylene group is a divalent group formed by removing one hydrogen atom from the alkyl group.
  • ether groups also include hydrocarbyl ether groups.
  • the hydrocarbyl ether group means a hydrocarbon group having one or more ether bonds.
  • the “hydrocarbyl group having one or more ether bonds” can be a hydrocarbyl group in which one or more ether bonds are inserted. Examples include the benzyloxy group.
  • hydrocarbon group having one or more ether bonds examples include alkyl groups having one or more ether bonds.
  • the "alkyl group having one or more ether bonds” can be an alkyl group into which one or more ether bonds are inserted. Such groups may be referred to herein as alkyl ether groups.
  • RCO 2- wherein R is an alkyl group
  • R a -CO 2 -R b- wherein R a is an alkyl group
  • R b is an alkylene group.
  • Fullerene Derivative Composition The fullerene derivative composition of the present invention is Formula (1): [In the formula, R 11 represents an organic group, R 12 represents an organic group, and ring A represents a fullerene ring. ] Fullerene derivative (1) represented by and formula (2): [In the formula, R 21 represents an organic group, R 22 represents an organic group, R 23 represents an organic group, and ring A represents a fullerene ring. ] Fullerene derivatives (2) Contains
  • the mass ratio of the fullerene derivative (1) and the fullerene derivative (2) is Preferably in the range of 1:99 to 99: 1, More preferably, it is in the range of 5:95 to 95: 5, more preferably, in the range of 10:90 to 90:10, Still more preferably, it is in the range of 20:80 to 80:20, Particularly preferably, it is in the range of 30:70 to 70:30, and more particularly in the range of 40:60 to 60:40.
  • the fullerene derivative (1) can be an additive to the fullerene derivative (2).
  • the fullerene derivative (2) can be an additive to the fullerene derivative (1).
  • R 11 is preferably It is an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents.
  • R 11 is more preferably It is a phenyl group which may have one or more substituents.
  • the position of the substituent may be ortho, para or meta.
  • R 11 is more preferably It is a phenyl group which may have one or more substituents selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group and a cyano group.
  • R 11 is It is a phenyl group.
  • R 12 is preferably An alkyl group which may be substituted by one or more substituents, An aryl group which may be substituted by one or more substituents, It is an ether group which may be substituted by one or more substituents, or an ester group which may be substituted by one or more substituents.
  • each “substituent” in the group include a fluorine atom, an alkyl group which may be substituted with one or more fluorine atoms, an alkoxy group which may be substituted with one or more fluorine atoms, an ester group, and cyano Groups.
  • the number of the substituents may be one or more and the maximum number of substitutable or less, and is preferably, for example, 1 to 4, 1 to 3, 1 to 2, or 1.
  • R 12 is An alkyl group having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, still more preferably 5 to 8), One or more substituents selected from a fluorine atom, an alkyl group which may be substituted by one or more fluorine atoms, an alkoxy group which may be substituted by one or more fluorine atoms, an ester group, and a cyano group
  • An aryl group (preferably a phenyl group) which may be substituted by Ether group (preferably alkyl ether group) having 1 to 12 carbons (preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6), or 2 to 12 carbons (preferably 2 to 10) More preferably, it is an ester group of 2 to 8, more preferably 2 to 6).
  • R 12 is An alkyl group having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, still more preferably 5 to 8), An ether group having 1 to 12 carbons (preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6), or 2 to 12 carbons (preferably 2 to 10, more preferably 2 to 8) More preferably, it is an ester group of 2 to 6).
  • R 12 is still more preferably an alkyl group having 1 to 8 carbon atoms or an ether group having 5 to 6 carbon atoms.
  • R 12 is particularly preferably methyl, hexyl, 2-ethylhexyl, CH 3- (CH 2 ) 2 -O-CH 2- , or CH 3 -O- (CH 2 ) 2 -O- (CH 2 ) 2 ) 2 -O-CH 2- .
  • R 12 is a phenyl group or an alkyl group.
  • R 12 is preferably A phenyl group, or linear or branched, having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, still more preferably 5 to 10, and still more preferably 5 to 8) Is an alkyl group of
  • R 21 is preferably It is an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents.
  • R 21 is preferably It is a phenyl group which may have one or more substituents.
  • the position of the substituent may be ortho, para or meta.
  • R 21 is It is a phenyl group which may have one or more substituents selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group and a cyano group.
  • R 21 is more preferably It is a phenyl group.
  • R 22 is preferably An alkyl group which may be substituted by one or more substituents, An aryl group which may be substituted by one or more substituents, It is an ether group which may be substituted by one or more substituents, or an ester group which may be substituted by one or more substituents.
  • R 22 "Alkyl group optionally substituted with one or more substituents", "Aryl group which may be substituted by one or more substituents", “Ether group optionally substituted with one or more substituents”, and “ester group optionally substituted with one or more substituents”
  • substituent in each "substituent” in the group are a fluorine atom, an alkyl group which may be substituted with one or more fluorine atoms, an alkoxy group which may be substituted with one or more fluorine atoms, and an ester group And cyano groups.
  • the number of the substituents may be one or more and the maximum number of substitutable or less, and is preferably, for example, 1 to 4, 1 to 3, 1 to 2, or 1.
  • R 22 is An alkyl group having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, still more preferably 5 to 8), One or more substituents selected from a fluorine atom, an alkyl group which may be substituted by one or more fluorine atoms, an alkoxy group which may be substituted by one or more fluorine atoms, an ester group, and a cyano group
  • An aryl group (preferably a phenyl group) which may be substituted by Ether group (preferably alkyl ether group) having 1 to 12 carbons (preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6), or 2 to 12 carbons (preferably 2 to 10) More preferably, it is an ester group of 2 to 8, more preferably 2 to 6).
  • R 22 is An alkyl group having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, still more preferably 5 to 8), An ether group having 1 to 12 carbons (preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6), or 2 to 12 carbons (preferably 2 to 10, more preferably 2 to 8) More preferably, it is an ester group of 2 to 6).
  • R 22 is still more preferably an alkyl group having 1 to 8 carbon atoms, or an ether group having 5 to 6 carbon atoms.
  • R 22 is particularly preferably methyl, hexyl, 2-ethylhexyl, CH 3- (CH 2 ) 2 -O-CH 2- , or CH 3 -O- (CH 2 ) 2 -O- (CH 2 ) 2 ) 2 -O-CH 2- .
  • R 22 is or an alkyl group.
  • R 22 is preferably A linear or branched alkyl group having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, still more preferably 5 to 10, and still more preferably 5 to 8) carbon atoms is there.
  • R 23 is preferably An alkyl group which may be substituted by one or more substituents, An aryl group which may be substituted by one or more substituents, It is an ether group which may be substituted by one or more substituents, or an ester group which may be substituted by one or more substituents.
  • R 23 "Alkyl group optionally substituted with one or more substituents", "Aryl group which may be substituted by one or more substituents", “Ether group optionally substituted with one or more substituents”, and “ester group optionally substituted with one or more substituents”
  • substituent in each "substituent” in the group are a fluorine atom, an alkyl group which may be substituted with one or more fluorine atoms, an alkoxy group which may be substituted with one or more fluorine atoms, and an ester group And cyano groups.
  • the number of the substituents may be one or more and the maximum number of substitutable or less, and is preferably, for example, 1 to 4, 1 to 3, 1 to 2, or 1.
  • R 23 is An alkyl group having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, still more preferably 5 to 8), One or more substituents selected from a fluorine atom, an alkyl group which may be substituted by one or more fluorine atoms, an alkoxy group which may be substituted by one or more fluorine atoms, an ester group, and a cyano group
  • An aryl group (preferably a phenyl group) which may be substituted by Ether group (preferably alkyl ether group) having 1 to 12 carbons (preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6), or 2 to 12 carbons (preferably 2 to 10) More preferably, it is an ester group of 2 to 8, more preferably 2 to 6).
  • R 23 is An alkyl group having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, still more preferably 5 to 8), An ether group having 1 to 12 carbons (preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6), or 2 to 12 carbons (preferably 2 to 10, more preferably 2 to 8) More preferably, it is an ester group of 2 to 6).
  • R 23 is still more preferably an alkyl group having 1 to 8 carbon atoms, or an ether group having 5 to 6 carbon atoms.
  • R 23 is particularly preferably methyl, hexyl, 2-ethylhexyl, CH 3- (CH 2 ) 2 -O-CH 2- , or CH 3 -O- (CH 2 ) 2 -O- (CH 2 ) 2 ) 2 -O-CH 2- .
  • R 23 is or an alkyl group.
  • R 23 is preferably A linear or branched alkyl group having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, still more preferably 5 to 10, and still more preferably 5 to 8) carbon atoms is there.
  • Ring A is preferably a C60 fullerene ring A.
  • composition of the present invention may contain other components such as a surfactant as long as the effects of the present invention are not significantly lost.
  • the fullerene derivative of the present invention can be produced by mixing the fullerene derivative (1) and the fullerene derivative (2) in a desired ratio.
  • the mixing may be carried out using a conventional method based on common technical knowledge. Specifically, for example, these can be introduced into an organic solvent capable of dissolving or dispersing the fullerene derivative (1) and the fullerene derivative (2), and stirred.
  • organic solvent examples include carbon disulfide, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene and the like. These solvents may be mixed and used in appropriate proportions.
  • the fullerene derivative (1) and the fullerene derivative (2) can each be produced by a known method. As the said method, each method of the said patent document 3, 4 and 6 is mentioned.
  • the fullerene derivative composition of the present invention can be suitably used as an n-type semiconductor material, in particular, an n-type semiconductor material for a photoelectric conversion element such as an organic thin film solar cell or an optical sensor.
  • the fullerene derivative composition of the present invention can also be used as an electron transport material in transistors, perovskite solar cells, and the like. These uses can be implemented based on technical common sense.
  • the fullerene derivative composition of the present invention can be used for the electron transport layer in combination with the perovskite layer.
  • the fullerene derivative composition of the present invention is used as an n-type semiconductor material, it is usually used in combination with an organic p-type semiconductor material (organic p-type semiconductor compound).
  • organic p-type semiconductor material for example, poly-3-hexylthiophene (P3HT), poly-p-phenylenevinylene, poly-alkoxy-p-phenylenevinylene, poly-9,9-dialkylfluorene, poly-p- Phenylene vinylene is exemplified.
  • donor-acceptor ⁇ -conjugated polymers have a donor unit and an acceptor unit, and have a structure in which they are alternately arranged.
  • Examples of the donor unit used herein include benzodithiophene, dithienosilole, N-alkylcarbazole, and examples of the acceptor unit include benzothiadiazole, thienothiophene, thiophenepyrroledione and the like.
  • poly (thieno [3,4-b] thiophene-co-benzo [1,2-b: 4,5-b ′] thiophene) PTBx series
  • poly (bi (bi) [3,4-b] thiophene) which is a combination of these units
  • Polymer compounds such as dithieno [1,2-b: 4,5-b '] [3,2-b: 2', 3'-d] silole-alt- (2,1,3-benzothiadiazoles) Is illustrated.
  • a more preferable example is a PTB compound having a fluorine atom at the 3-position of thieno [3,4-b] thiophene as an acceptor unit, and as a particularly preferable example, PBDTTT-CF and PTB7 are exemplified. Be done.
  • a photoelectric conversion layer prepared using the fullerene derivative composition of the present invention as an n-type semiconductor material in combination with an organic p-type semiconductor material can exhibit high conversion efficiency.
  • the fullerene derivative composition of the present invention exhibits good solubility in various organic solvents, so when it is used as an n-type semiconductor material, preparation of a photoelectric conversion layer by a coating method is possible, and a large area is obtained. The preparation of the photoelectric conversion layer is also easy.
  • the fullerene derivative composition of the present invention has good compatibility with the organic p-type semiconductor material and has appropriate self-aggregation property. Therefore, a photoelectric conversion layer having a bulk junction structure is easily formed by using the fullerene derivative composition as an n-type semiconductor material (organic n-type semiconductor material). By using this photoelectric conversion layer, it is possible to obtain an organic thin film solar cell having high conversion efficiency, an optical sensor or the like.
  • the fullerene derivative composition of the present invention as an n-type semiconductor material, it is possible to produce an organic thin film solar cell having excellent performance at low cost.
  • the photoelectric conversion layer containing (or consisting of) the n-type semiconductor material of the present invention there is an image sensor for a digital camera.
  • the problem of reduced sensitivity has been pointed out for existing image sensors made of silicon semiconductors.
  • it is expected that high sensitivity and high definition can be achieved by an image sensor made of an organic material with high light sensitivity. Materials that construct the light receiving unit of such a sensor are required to absorb light with high sensitivity and generate electrical signals with high efficiency.
  • the photoelectric conversion layer containing (or consisting of) the n-type semiconductor material of the present invention can efficiently convert visible light into electrical energy, and therefore, as a material for the light receiving portion of the image sensor, It can express high function.
  • n-Type Semiconductor Material contains the composition of the present invention.
  • the n-type semiconductor material of the present invention can contain an additive as long as the effects of the present invention are not significantly impaired.
  • Preferred examples of the additive include liquid crystal compounds.
  • Preferred specific examples of the additive include one or more additions selected from the group consisting of diiodooctane, octanedithiol, chloronaphthalene, trimethylbenzene, nitrobenzene, and a liquid crystalline substance having a triphenylene structure or an allyl aldimine structure. Agents can be included.
  • the additive can be for phase separation structure control.
  • examples of the "triphenylene derivative” include hexamethoxytriphenylene.
  • Examples of the "allylaldimine derivative” include 5-octyloxy-2-[ ⁇ 4- (2-methylbutoxy) -phenylimino ⁇ -methyl] phenol.
  • the content of the additive in the n-type semiconductor material of the present invention can be preferably 1 part by mass or less with respect to 100 parts by mass of the total of the fullerene derivative (1) and the fullerene derivative (2).
  • the n-type semiconductor material of the present invention can preferably contain substantially no phase separation structure control additive.
  • the content of the additive for controlling phase separation structure in the n-type semiconductor material of the present invention is preferably 1 part by mass with respect to 100 parts by mass of the total of the fullerene derivative (1) and the fullerene derivative (2). It can be
  • the n-type semiconductor material of the present invention can preferably be for photoelectric conversion, and more preferably for solar cells.
  • the photoelectric conversion layer of the present invention contains the n-type semiconductor material of the present invention. That is, the photoelectric conversion layer of the present invention contains the fullerene derivative composition of the present invention as an n-type semiconductor material (n-type semiconductor compound).
  • the photoelectric conversion layer of the present invention usually contains the organic p-type semiconductor material (organic p-type semiconductor compound) in combination with the fullerene derivative composition of the present invention or the n-type semiconductor material of the present invention.
  • the photoelectric conversion layer of the present invention is usually composed of the n-type semiconductor material of the present invention and the organic p-type semiconductor. In the photoelectric conversion layer of the present invention, preferably, the n-type semiconductor material of the present invention and the organic p-type semiconductor material form a bulk heterojunction structure.
  • the photoelectric conversion device of the present invention is formed from a composition containing a p-type semiconductor material [ie, a composition containing the fullerene derivatives (1) and (2) of the present invention] and an n-type semiconductor material.
  • composition may contain other components such as surfactants, as long as the effects of the present invention are not significantly impaired.
  • the proportion of the n-type semiconductor material in the composition is preferably 10 to 1000 parts by weight, and more preferably 50 to 500 parts by weight with respect to 100 parts by weight of the p-type semiconductor material.
  • the method of mixing the p-type semiconductor material and the n-type semiconductor material is not particularly limited, but after adding these to the solvent in a desired ratio, one or more of heating, stirring, ultrasonic irradiation, etc. Depending on the combination, it may be dissolved in a solvent to prepare a solution.
  • a solvent having a solubility of 1 mg / mL or more at 20 ° C. it is preferable to use a solvent having a solubility of 1 mg / mL or more at 20 ° C. for each of the p-type semiconductor material and the n-type semiconductor material.
  • solvent examples include tetrahydrofuran, 1,2-dichloroethane, cyclohexane, chloroform, bromoform, benzene, toluene, o-xylene, m-xylene, chlorobenzene, bromobenzene, iodobenzene, o-dichlorobenzene, anisole, methoxybenzene , Trichlorobenzene, and pyridine, and combinations of two or more thereof.
  • the additive for controlling a phase separation structure is used.
  • a suitable bulk heterojunction structure of a p-type semiconductor material and an n-type semiconductor material is formed in the film forming process, and a photoelectric conversion element having excellent photoelectric conversion efficiency It is possible to obtain
  • composition of the present invention when used, a photoelectric conversion element having excellent photoelectric conversion efficiency and suppressing deterioration of the performance can be obtained without using such an additive.
  • such an excellent effect of the present invention is to use a fullerene derivative with high aggregation and a fullerene derivative with low aggregation, that is, in the light of the present invention, specifically, fullerene derivatives (1) and aggregations different from each other
  • fullerene derivative (2) in combination is based on the formation of a suitable bulk heterojunction structure without using the additive, but the present invention is based on the principle. It is not limited by things.
  • the height of the cohesiveness can be determined based on the grain size formed by the fullerene derivative in the photoelectric conversion layer formed between PTB7 used as a donor material.
  • the high cohesiveness of the fullerene derivative can mean that the grain size is about 100 nm to 200 nm. High conversion efficiency can not be expected because this material alone does not form an excellent bulk heterojunction with the donor material. On the other hand, low cohesiveness can mean that the grain size is 10 nm or less (preferably 5 to 10 nm).
  • Using a fullerene derivative with high aggregation and a fullerene derivative with low aggregation can mean that the ratio of the aggregation is 5 or more (preferably 10 to 20).
  • the content of the additive is 100 parts by mass of the total of the fullerene derivative (1) and the fullerene derivative (2), Preferably, it can be 1 part by mass or less.
  • the film thickness of the photoelectric conversion layer can be, for example, in the range of 1 nm to 1 ⁇ m, 2 to 1000 nm, 5 to 500 nm, or 20 to 300 nm.
  • the photoelectric conversion layer of the present invention is, for example, a spin coating method, a casting method, a dipping method, an inkjet method, from a solution obtained by dissolving the n-type semiconductor material of the present invention and the organic p-type semiconductor material in an organic solvent. It can be prepared by forming a thin film on a substrate using a known thin film forming method such as a doctor blade method and a screen printing method.
  • the photoelectric conversion layer of the present invention is at least one phase separation structure selected from the group consisting of diiodooctane, octanedithiol, chloronaphthalene, trimethylbenzene, nitrobenzene, and a liquid crystalline substance having a triphenylene structure or an allyl aldimine structure.
  • the content of the control additive is, based on 100 parts by mass of the total of the fullerene derivative (1) and the fullerene derivative (2), It may be preferably 3 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.5 parts by mass or less.
  • the photoelectric conversion layer of the present invention preferably contains substantially no such additive, and more preferably contains substantially no such additive.
  • the fullerene derivative composition of the present invention has good compatibility with an organic p-type semiconductor material (preferably, P3HT or PTB7) and has appropriate self-aggregation properties Therefore, a photoelectric conversion layer containing the fullerene derivative composition of the present invention as the n-type semiconductor material and the organic p-type semiconductor material and having a bulk heterojunction structure can be easily obtained.
  • an organic p-type semiconductor material preferably, P3HT or PTB7
  • the photoelectric conversion layer of the present invention can suitably convert light into electricity.
  • the photoelectric conversion device of the present invention comprises the photoelectric conversion layer of the present invention.
  • the performance deterioration with time is suppressed.
  • the said photoelectric conversion element can be understood by description of this specification based on technical common sense.
  • the photoelectric conversion device of the present invention is at least one additive for phase separation structure control selected from the group consisting of diiodooctane, octanedithiol, chloronaphthalene, trimethylbenzene, nitrobenzene, triphenylene derivative, and arylyl aldimine derivative.
  • a additive for phase separation structure control selected from the group consisting of diiodooctane, octanedithiol, chloronaphthalene, trimethylbenzene, nitrobenzene, triphenylene derivative, and arylyl aldimine derivative.
  • Relative to 100 parts by mass of the total of the fullerene derivative (1) and the fullerene derivative (2) Preferably, it can be 1 part by mass or less.
  • Organic thin-film solar cell of the present invention comprises the photoelectric conversion layer of the present invention described above. For this reason, the organic thin film solar cell of the present invention has high conversion efficiency. In the organic thin film solar cell of the present invention, the performance deterioration with time is suppressed.
  • the organic thin film solar cell of the present invention comprises at least one phase separation selected from the group consisting of diiodooctane, octanedithiol, chloronaphthalene, trimethylbenzene, nitrobenzene, and a liquid crystalline material having a triphenylene structure or an allylaldimine structure.
  • the content of the additive for structure control is 100 parts by mass of the total of the fullerene derivative (1) and the fullerene derivative (2), Preferably, it may be preferably 1 part by weight or less, and more preferably 0.5 part by weight or less.
  • the structure of the organic thin film solar cell is not particularly limited, and may be the same structure as that of a known organic thin film solar cell, and the organic thin film solar cell of the present invention is in accordance with a known method of manufacturing an organic thin film solar cell However, it can be preferably produced without using a phase separation structure control additive.
  • the organic thin film solar cell containing the said fullerene derivative composition for example, on a board
  • the solar cell of the laminated structure can be illustrated.
  • the organic power generation layer is preferably a semiconductor thin film layer (that is, a photoelectric conversion layer) having a bulk heterojunction structure, containing an organic p-type semiconductor material and the fullerene derivative composition of the present invention as an n-type semiconductor material. .
  • known materials can be appropriately used.
  • examples of the material of the electrode include aluminum, gold, silver, copper, indium oxide (ITO) and the like.
  • examples of the material of the charge transport layer include PFN (poly [9,9-bis (3 '-(N, N-dimethylamino) propyl-2,7-fluorene) -alt-2,7- (9,9) -Dioctyl fluorene)]) and MoO 3 (molybdenum oxide) etc. are illustrated.
  • the photoelectric conversion layer obtained by the present invention effectively functions as a light receiving portion for an image sensor in a high performance product of a digital camera.
  • a light sensor is constructed of a silicon substrate, an electrode, a light receiving unit including a photoelectric conversion layer, a color filter, and a microlens.
  • the thickness of the light receiving portion can be about several hundred nm, and can be configured to be a fraction of the thickness of a conventional silicon photodiode.
  • the used AMF device has the following configuration. ⁇ Device configuration> System: SPI3800N (SII Nanotechnology Inc.) Unit: SPA400 (SII Nanotechnology Inc.) Note that Measurement mode: DFM (tapping mode), and cantilever: SI-DF3 (SII Nanotechnology Inc.) Was adopted and measured.
  • the RMS (root mean square) value described in the figure is a value automatically calculated from measurement data by software attached to the apparatus at the time of AMF measurement. Light irradiation was continuously performed for 2 hours, and the conversion efficiency was measured at intervals of 30 minutes. The table shows data of conversion efficiency for the first and after 2 hours.
  • the figure shows the AFM image and the RMS value of the power generation layer of each example.
  • RMS means root mean square.
  • One side of each AFM image is 2 ⁇ m.
  • the description such as 0/100 indicates the ratio of Compound 1 / Compound 2.
  • RMS was measured by the following method and conditions. ⁇ RMS analysis method and analysis conditions>
  • Example 1 The combination of the compound 1 and the compound 2 which showed the structure below was used as an acceptor. The mixing ratio was changed to study changes in conversion efficiency. The results are summarized in Table 1.
  • the conversion efficiency was higher when Compound 2 was added to Compound 1 than when Compound 1 was used alone. That is, when an active layer was constructed only from compound 1 and PTB7, it was difficult to obtain a phase separation structure (bulk heterostructure) suitable for photoelectric conversion, and a sufficiently high function could not be expressed. On the other hand, the addition of the compound 2 improves the phase separation structure, so that the numerical value of the conversion efficiency is improved. In particular, when the ratio of compounds 1 and 2 was 25:75 and 50:50, better performance was obtained than when used alone respectively.
  • the results of atomic force microscopy (AFM) measurement of the active layer (FIG. 1) confirmed that the active layer formed of the donor material and the acceptor material forms a proper grain phase separation. Furthermore, when two types of fullerene derivatives were mixed, it was observed that the decrease in conversion efficiency under light irradiation for two consecutive hours was suppressed, and the effect of improving not only conversion efficiency but durability was obtained by mixing. .
  • Example 2 In the same manner as Example 1, except that the combination of the compound 3 and the compound 2 was used as the acceptor, the mixing ratio was changed to examine the difference in the change in conversion efficiency with time. The results are summarized in Table 2. Similar to Example 1, when Compound 2 was added to Compound 3, improvement in conversion efficiency was observed. Moreover, the tendency of the durability improvement by continuous light irradiation was also confirmed.
  • Comparative Example 1 In the same manner as Example 1, except that the combination of Compound 1 and Compound 4 was used as the acceptor, the mixing ratio was changed to examine the difference in the change with time in conversion efficiency. At any mixing ratio, the performance was worse than when it was used in Compound 1, and no improvement in durability performance at continuous light irradiation for 2 hours was observed.

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Abstract

La présente invention aborde le problème de la fourniture d'une composition à base de dérivé de fullerène qui contribue à des améliorations de la performance de génération d'énergie, et de la stabilité structurelle de couches destinées à la conversion photoélectrique, et qui peut contribuer à la production de dispositifs de cellule solaire à couche mince organique ayant une excellente durabilité. La présente invention concerne une composition à base de dérivé de fullerène qui comprend un dérivé de fullerène (1) représenté par la formule (1) [dans laquelle R11 représente un groupe organique, R12 représente un groupe organique, et l'anneau A représente un anneau de fullerène] et un dérivé de fullerène (2) représenté par la formule (2) [dans laquelle R21 représente un groupe organique, R22 représente un groupe organique, R23 représente un groupe organique, et l'anneau A représente un anneau de fullerène].
PCT/JP2018/032420 2017-09-01 2018-08-31 Composition à base de dérivé de fullerène Ceased WO2019045059A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011030411A1 (fr) * 2009-09-09 2011-03-17 株式会社 東芝 Cellule solaire à couche mince organique
JP2012089538A (ja) * 2010-10-15 2012-05-10 Daikin Ind Ltd 有機薄膜太陽電池用ｎ型半導体材料
EP2905277A1 (fr) * 2014-02-07 2015-08-12 LANXESS Deutschland GmbH Fulleropyrrolidines 1',2',5'-trisubstitués
JP2017007973A (ja) * 2015-06-19 2017-01-12 ダイキン工業株式会社 組成物
WO2017061543A1 (fr) * 2015-10-06 2017-04-13 ダイキン工業株式会社 DÉRIVÉ DE FULLERÈNE ET MATÉRIAU DE SEMI-CONDUCTEUR DE TYPE n

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Publication number Priority date Publication date Assignee Title
WO2011030411A1 (fr) * 2009-09-09 2011-03-17 株式会社 東芝 Cellule solaire à couche mince organique
JP2012089538A (ja) * 2010-10-15 2012-05-10 Daikin Ind Ltd 有機薄膜太陽電池用ｎ型半導体材料
EP2905277A1 (fr) * 2014-02-07 2015-08-12 LANXESS Deutschland GmbH Fulleropyrrolidines 1',2',5'-trisubstitués
JP2017007973A (ja) * 2015-06-19 2017-01-12 ダイキン工業株式会社 組成物
WO2017061543A1 (fr) * 2015-10-06 2017-04-13 ダイキン工業株式会社 DÉRIVÉ DE FULLERÈNE ET MATÉRIAU DE SEMI-CONDUCTEUR DE TYPE n

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