WO2017217448A1 - Dérivé de fullerène et matériau semi-conducteur de type n - Google Patents

Dérivé de fullerène et matériau semi-conducteur de type n Download PDF

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WO2017217448A1
WO2017217448A1 PCT/JP2017/021933 JP2017021933W WO2017217448A1 WO 2017217448 A1 WO2017217448 A1 WO 2017217448A1 JP 2017021933 W JP2017021933 W JP 2017021933W WO 2017217448 A1 WO2017217448 A1 WO 2017217448A1
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group
atom
fullerene derivative
fullerene
substituents
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PCT/JP2017/021933
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English (en)
Japanese (ja)
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永井　隆文
足達　健二
安蘇　芳雄
家　裕隆
誠 辛川
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ダイキン工業株式会社
国立大学法人大阪大学
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Priority to JP2018523960A priority Critical patent/JP6931891B2/ja
Publication of WO2017217448A1 publication Critical patent/WO2017217448A1/fr

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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions

Definitions

  • the present invention relates to a fullerene derivative, an n-type semiconductor material, and the like.
  • An organic thin film solar cell is formed by using an organic compound as a photoelectric conversion material by a coating method from a solution.
  • poly-3-hexylthiophene (P3HT) is known as an organic p-type semiconductor material having excellent performance.
  • P3HT poly-3-hexylthiophene
  • a compound with a structure that can absorb a wide range of wavelengths of sunlight or a structure in which the energy level is adjusted has been developed aiming at higher functionality (donor acceptor type ⁇ -conjugated polymer), which greatly improves performance.
  • Examples of such compounds include poly-p-phenylene vinylene, 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 is a fullerene derivative having a three-membered ring portion, and most of the fullerene derivatives that have been reported so far are 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, but there are few reports.
  • Non-Patent Document 1 discloses a fullerene derivative having a pyrrolidine ring and having substituents only at the 1-position and 2-position thereof.
  • Patent Document 3 discloses a fullerene derivative having a pyrrolidine ring and having a substituted or unsubstituted phenyl group at the 1-position among the fullerene derivatives having substituents only at the 1-position and 2-position thereof. Has a high conversion efficiency when used as an n-type semiconductor of a solar cell.
  • Patent Document 4 discloses a fullerene derivative having a pyrrolidine ring and having substituents only at the 1-position and the 2-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 is effective as an n-type semiconductor for organic thin-film solar cells.
  • Non-Patent Document 1 achieves higher conversion efficiency than the device using PCBM. This is a special device in which the anode (ITO electrode) current collecting material is removed. It is a comparison in configuration. Thus, a practical organic thin-film solar cell using a fullerene derivative has not yet been developed, and a new fullerene derivative that can be used for n-type semiconductor materials of an organic thin-film solar cell is still available. Development is required.
  • the main object of the present invention is to provide a material having excellent performance as an n-type semiconductor, particularly an n-type semiconductor for a photoelectric conversion element such as an organic thin film solar cell.
  • one of the objects of the present invention is to provide a new fullerene derivative capable of realizing high conversion efficiency.
  • one of the objects of the present invention is to provide a new fullerene derivative that allows easy device fabrication and enables high voltage output. Accordingly, an object of the present invention is to provide a fullerene derivative having high conversion efficiency and enabling high voltage output.
  • the present invention includes the following aspects.
  • Item 1 is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group optionally having one or more substituents, an alkoxy group optionally having one or more substituents, or cyano Represents a group
  • X 1b represents a chlorine atom, a bromine atom, an iodine atom, an alkyl group optionally having one or more substituents, an alkoxy group optionally having one or more substituents, or a cyano group.
  • R 2 represents an aryl group which may have one or more substituents, or a heteroaryl group which may have one or more substituents;
  • R 3 represents a hydrogen atom or an organic group, and
  • ring A represents a fullerene ring.
  • Item 2. The fullerene derivative according to Item 1, wherein X 1a is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a cyano group.
  • Item 3. Item 3.
  • Item 12. Item 12.
  • Item 13. Item 13.
  • a fullerene derivative having high conversion efficiency and enabling high voltage output is provided.
  • room temperature means a temperature within the range of 10 to 40 ° C.
  • the “organic group” means a group containing one or more carbon atoms as its constituent atoms.
  • examples of the “organic group” include a hydrocarbon group.
  • hydrocarbon group means a group containing one or more carbon atoms and one or more hydrogen atoms as its constituent atoms.
  • a hydrocarbon group may be referred to as a hydrocarbyl group.
  • hydrocarbon group includes an aliphatic hydrocarbon group (eg, benzyl group) optionally substituted with one or more aromatic hydrocarbon groups, and one An aromatic hydrocarbon group (aryl group) which may be substituted with the above aliphatic hydrocarbon group is exemplified.
  • aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof.
  • the “aliphatic hydrocarbon group” may be saturated or unsaturated.
  • examples of the “aliphatic hydrocarbon group” include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group.
  • examples of the “alkyl group” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl. And a linear or branched alkyl group having 1 to 10 carbon atoms.
  • alkenyl group examples include vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, -Ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and 5- Examples thereof include straight-chain or branched alkenyl groups having 2 to 10 carbon atoms such as hexenyl.
  • alkynyl group examples include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, Linear or branched alkynyl groups having 2 to 6 carbon atoms, such as 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, and 5-hexynyl Is exemplified.
  • examples of the “cycloalkyl group” include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopentyl group, cyclohexyl group, and cycloheptyl.
  • alkoxy group is, for example, a group represented by RO— (wherein R is an alkyl group).
  • ester group means an organic group having an ester bond (that is, —C ( ⁇ O) —O— or —OC ( ⁇ O) —).
  • ester bond that is, —C ( ⁇ O) —O— or —OC ( ⁇ O) —.
  • 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.
  • ether group means a group having an ether bond (—O—).
  • ether groups include polyether groups.
  • polyether groups are of the formula: R a — (O—R b ) n — (wherein 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).
  • An 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 groups having one or more ether bonds include alkyl groups having one or more ether bonds.
  • the “alkyl group having one or more ether bonds” can be an alkyl group in which one or more ether bonds are inserted. In the present specification, such a group may be referred to as an alkyl ether group.
  • the “acyl group” includes an alkanoyl group.
  • the “alkanoyl group” is, for example, a group represented by RCO— (wherein R is an alkyl group).
  • the “aryl group” may be monocyclic, bicyclic, tricyclic, or tetracyclic. In the present specification, unless otherwise specified, the “aryl group” may be an aryl group having 6 to 18 carbon atoms. In the present specification, unless otherwise specified, examples of the “aryl group” include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl.
  • the “heteroaryl group” is, for example, a monocyclic, bicyclic, or tricyclic or tetracyclic 5- to 18-membered heteroaryl group. Can do.
  • the “heteroaryl group” refers to, for example, 1 to 4 heteroatoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom in addition to a carbon atom as a ring-constituting atom. It is a heteroaryl group to be contained.
  • the “heteroaryl group” may have 3 to 17 carbon atoms, for example.
  • the “heteroaryl group” includes a “monocyclic heteroaryl group” and an “aromatic fused heterocyclic group”.
  • examples of the “monocyclic heteroaryl group” include pyrrolyl (eg, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (eg, 2-furyl, 3 -Furyl), thienyl (eg, 2-thienyl, 3-thienyl), pyrazolyl (eg, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (eg, 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-isothiazolyl) ), Thiazolyl (eg, 3-isothiazo
  • examples of the “aromatic fused heterocyclic group” include isoindolyl (eg, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6- Isoindolyl, 7-isoindolyl), indolyl (eg, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), benzo [b] furanyl (eg, 2-indolyl) 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 ] Furanyl (eg, 1-benzoindolyl, 2-is
  • examples of the “alkyl group” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl. And a linear or branched alkyl group having 1 to 10 carbon atoms.
  • Fullerene derivative of the present invention is a fullerene derivative represented by the following formula (1).
  • X 1a is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group optionally having one or more substituents, an alkoxy group optionally having one or more substituents, or cyano
  • X 1b represents a chlorine atom, a bromine atom, an iodine atom, an alkyl group optionally having one or more substituents, an alkoxy group optionally having one or more substituents, or a cyano group.
  • R 2 represents an aryl group which may have one or more substituents, or a heteroaryl group which may have one or more substituents;
  • R 3 represents a hydrogen atom or an organic group, and ring A represents a fullerene ring.
  • X 1a is preferably a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a cyano group.
  • X 1a is more preferably a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a cyano group.
  • X 1a is more preferably a chlorine atom, a methyl group, a methoxy group, or a cyano group.
  • X 1b is preferably a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a cyano group.
  • X 1b is more preferably a chlorine atom, a bromine atom, a methyl group, a methoxy group, or a cyano group.
  • X 1b is more preferably a chlorine atom, a methyl group, a methoxy group, or a cyano group.
  • X 1a and X 1b are preferably the same or different and are a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a cyano group.
  • X 1a and X 1b are more preferably the same or different and are a chlorine atom, a methyl group, a methoxy group, or a cyano group.
  • Preferred X 1a and preferred X 1b may each be an electron-withdrawing group or an electron-donating group.
  • the fullerene derivative of the present invention can have excellent properties as an n-type semiconductor material, particularly when X 1a and X 1b are such groups. Specifically, for example, when used for an n-type semiconductor for a photoelectric conversion element such as an organic thin film solar cell, a high voltage can be applied.
  • Examples of the substituent in the “aryl group optionally having one or more substituents” represented by R 2 are as follows: (a) a fluorine atom, (b) an alkyl group optionally substituted by one or more fluorine atoms, (c) an alkoxy group optionally substituted by one or more fluorine atoms, (d) an ester group, and (e) Including a cyano group.
  • the number of the substituents is, for example, 0 (unsubstituted), 1, 2, 3, 4, or 5.
  • Examples of the substituent in the “heteroaryl group optionally having one or more substituents” represented by R 2 are as follows: (a) a fluorine atom, (b) an alkyl group optionally substituted by one or more fluorine atoms, (c) an alkoxy group optionally substituted by one or more fluorine atoms, (d) an ester group, and (e) Including a cyano group.
  • the number of the substituents is, for example, 0 (unsubstituted), 1, 2, 3, 4, or 5.
  • R 2 is preferably (a) a fluorine atom, (b) an alkyl group optionally substituted by one or more fluorine atoms, (c) an alkoxy group optionally substituted by one or more fluorine atoms, (d) an ester group, and (e) optionally substituted with one or more substituents selected from the group consisting of cyano groups, An aryl group (preferably a phenyl group).
  • R 2 is a phenyl group having one or more substituents
  • the position of the substituent can be, for example, an ortho position, a meta position, or a para position.
  • R 2 is preferably a phenyl group which may have one or two substituents at the ortho position.
  • R 3 is preferably Hydrogen atom, An alkyl group optionally substituted with one or more substituents, An alkenyl group optionally substituted by one or more substituents, An alkynyl group optionally substituted by one or more substituents, An aryl group optionally substituted with one or more substituents, It is an ether group which may be substituted with one or more substituents, or an ester group which may be substituted with one or more substituents.
  • R 3 "Alkyl group optionally substituted with one or more substituents", "Alkenyl group optionally substituted with one or more substituents”, “Alkynyl group optionally substituted with one or more substituents”, “Aryl group optionally substituted with one or more substituents”, “An ether group which may be substituted with one or more substituents” and “an ester group which may be substituted with one or more substituents”
  • substituent in each “substituent” in are a fluorine atom, an alkyl group optionally substituted with one or more fluorine atoms, an alkoxy group optionally substituted with one or more fluorine atoms, and an ester group And a cyano group.
  • the number of the substituents may be 1 or more and not more than the maximum number that can be substituted, and is preferably 1 to 4, 1 to 3, 1 to 2, or 1, for example.
  • R 3 is more preferably Hydrogen atom, An alkyl group having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, more preferably 5 to 10, and still more preferably 5 to 8), One or more substituents selected from a fluorine atom, an alkyl group optionally substituted with one or more fluorine atoms, an alkoxy group optionally substituted with one or more fluorine atoms, an ester group, and a cyano group An aryl group optionally substituted with (preferably a phenyl group), An ether group (preferably an alkyl ether group) having 1 to 12 carbon atoms (preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6), or 2 to 12 carbon atoms (preferably 2 to 10 carbon atoms). More preferably, it is an ester group of 2 to 8, more preferably 2 to 6).
  • R 3 is more preferably An alkyl group having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10 and even more preferably 5 to 8), An ether group having 1 to 12 carbon atoms (preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6), or 2 to 12 carbon atoms (preferably 2 to 10, more preferably 2 to 8 carbon atoms), More preferred is an ester group 2-6).
  • R 3 is more preferably an alkyl group having 1 to 8 carbon atoms or an ether group having 5 to 6 carbon atoms.
  • R 3 is particularly preferably a methyl group, a hexyl group, a 2-ethylhexyl group, CH 3 — (CH 2 ) 2 —O—CH 2 —, or CH 3 —O— (CH 2 ) 2 —O— (CH 2 ) 2 —O—CH 2 —.
  • R 3 is a hydrogen atom or an alkyl group.
  • R 3 is preferably (1) a hydrogen atom, or (2) Linear or branched chain having 2 to 18 carbon atoms (preferably 3 to 12, more preferably 4 to 10, still more preferably 5 to 10 and even more preferably 5 to 8) It is an alkyl group.
  • Ring A is preferably a, C 60 fullerene ring, or C 70 fullerene ring, more preferably C 60 fullerene ring.
  • Ring A is preferably a, C 60 fullerene ring.
  • Fullerene derivative of the formula (1) is, the fullerene derivative Ring A is C 60 fullerene ring (hereinafter, also referred to as C 60 fullerene derivatives.), And ring A fullerene derivative is C 70 fullerene ring (hereinafter, C 70 fullerene It may also be a mixture of a derivative).
  • the ratio of the content of the C 60 fullerene derivative and the C 70 fullerene derivative in the mixture is, for example, 99.999: 0.001 to 0.001: 99.999, 99.99: 0.01 to molar ratio. 0.01: 99.99, 99.9: 0.1 to 0.1: 99.9, 99: 1 to 1:99, 95: 5 to 5:95, 90:10 to 10:90, or 80 : 20 to 20:80.
  • the ratio of the content of the C 60 fullerene derivative and the C 70 fullerene derivative is preferably 80:20 to 50:50, more preferably 80:20 to 60:40.
  • the content of the C 60 fullerene derivative in the mixture is, for example, 0.001 to 99.999 mass%, 0.01 to 99.99 mass%, 0.1 to 99.9 mass%, 1 to 99 mass%. It can be 5 to 95% by weight, 10 to 90% by weight, or 20 to 80% by weight.
  • the content of the C 60 fullerene derivative can be preferably 50 to 80% by mass, and more preferably 60 to 80% by mass.
  • the content of the C 70 fullerene derivative in the mixture is, for example, 0.001 to 99.999% by mass, 0.01 to 99.99% by mass, 0.1 to 99.9% by mass, 1 to 99% by mass. It can be 5 to 95% by weight, 10 to 90% by weight, or 20 to 80% by weight.
  • the content of the C 70 fullerene derivative can be preferably 20 to 50% by mass, and more preferably 20 to 40% by mass.
  • the mixture can consist of C 60 fullerene derivatives, and C 70 fullerene derivatives.
  • the mixture can be a mixture of C 60 fullerene derivatives, and C 70 fullerene derivatives.
  • C 60 fullerene (ring) is represented by the following structural formula as often performed in the technical field: It may be expressed as
  • X 1a is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a cyano group
  • X 1b is a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a cyano group
  • R 2 is an aryl group that may have one or more substituents, or a heteroaryl group that may have one or more substituents
  • R 3 is a hydrogen atom or an alkyl group
  • ring A is a C 60 or C 70 fullerene ring (preferably a C 60 fullerene ring).
  • X 1a is a chlorine atom, a methyl group, a methoxy group, or a cyano group
  • X 1b is a chlorine atom, a methyl group, a methoxy group, or a cyano group
  • R 2 is a phenyl group
  • R 3 is a hydrogen atom or an alkyl group having 5 to 10 carbon atoms
  • ring A is a C 60 or C 70 fullerene ring (preferably a C 60 fullerene ring).
  • X 1a is a linear or branched alkyl group having 2 to 8 carbon atoms
  • X 1b is a linear or branched alkyl group having 2 to 8 carbon atoms
  • R 2 is an aryl group that may have one or more substituents, or a heteroaryl group that may have one or more substituents
  • R 3 is a hydrogen atom or an alkyl group having 5 to 10 carbon atoms
  • ring A is a C 60 or C 70 fullerene ring (preferably a C 60 fullerene ring).
  • the fullerene derivative of the present invention exhibits sufficient solubility in various organic solvents, it is easy to form a thin film by a coating method. Furthermore, the fullerene derivative of the present invention can easily form a bulk heterojunction structure when an organic power generation layer is prepared using an organic p-type semiconductor material as an n-type semiconductor material.
  • the fullerene derivative of the present invention has a high conversion efficiency and enables a high voltage output.
  • the fullerene derivative of the present invention preferably has a LUMO level value of ⁇ 3.65 eV or more.
  • the LUMO level can be measured by the method described in Karakawa et al., Journal of Materials Chemistry A, 2014, Vol. 2, page 20889.
  • the fullerene derivative of the present invention can be produced by a known production method of a fullerene derivative or a method analogous thereto. Specifically, the fullerene derivative of the present invention can be synthesized, for example, according to the method of the following scheme.
  • the symbols in the scheme have the same meanings as described above, and as will be apparent to those skilled in the art, the symbols in formula (a) and formula (b) correspond to the symbols in formula (1).
  • step A a glycine derivative (compound (b)) is reacted with an aldehyde compound (compound (a)) and a fullerene (compound (c)) to produce a fullerene derivative represented by formula (1) (compound (1)).
  • the amount ratio of the aldehyde compound (compound (a)), the glycine derivative (compound (b)) and the fullerene (compound (c)) is arbitrary, but is generally fullerene (compound (c)) 1 from the viewpoint of increasing the yield.
  • the aldehyde compound (compound (a)) and glycine derivative (compound (b)) are each used in an amount of 0.1 to 10 mol, preferably 0.5 to 2 mol, relative to mol.
  • the reaction is performed without a solvent or in a solvent.
  • the solvent include carbon disulfide, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene and the like. Of these, chloroform, toluene, xylene, chlorobenzene and the like are preferable. These solvents may be mixed and used at an appropriate ratio.
  • the reaction temperature is usually in the range of room temperature to about 150 ° C, preferably in the range of about 80 to about 120 ° C.
  • the room temperature can be preferably in the range of 15 to 30 ° C.
  • the reaction time is usually in the range of about 1 hour to about 4 days, preferably in the range of about 10 to about 48 hours.
  • the obtained compound (1) can be purified by a conventional purification method as necessary.
  • the obtained compound (1) is purified by silica gel column chromatography (the developing solvent is preferably hexane-chloroform, hexane-toluene, or hexane-carbon disulfide, for example), and then further HPLC ( (Preparative GPC) (As the developing solvent, for example, chloroform or toluene is preferable).
  • the aldehyde compound (compound (a)), glycine derivative (compound (b)), and fullerene (compound (c)) used in Step A are known compounds, respectively, and are known methods or similar methods. They are synthesized by methods or are commercially available.
  • the aldehyde compound (compound (a)) can be synthesized, for example, by the following method (a1), (a2) or (a3).
  • R 2 has the same meaning as R 2 in the formula (1) and corresponds to R 2 of the target fullerene derivative.
  • a method using chromic acid, manganese oxide or the like as an oxidizing agent for example, (i) a method using chromic acid, manganese oxide or the like as an oxidizing agent, (ii) For example, swern oxidation using dimethyl sulfoxide as an oxidizing agent, or (iii) oxidation using hydrogen peroxide, oxygen, air or the like in the presence of a catalyst can be applied.
  • a known method such as (i) a metal as a reducing agent A method using a hydride, (ii) a method of reducing hydrogen in the presence of a catalyst, or (iii) a method using hydrazine as a reducing agent can be applied.
  • Method (a3) Carbonylation of a halide represented by R 2 —X (X represents halogen)
  • X represents halogen
  • n-BuLi is used to form an anion from the halide.
  • a method of introducing a carbonyl group can be applied thereto.
  • amide compounds such as N, N-dimethylformamide (DMF); or N-formyl derivatives of piperidine, morpholine, piperazine or pyrrolidine are used.
  • the glycine derivative (compound (b)) can be synthesized, for example, by the following method (b1), (b2) or (b3).
  • R 1 represents a partial structure in formula (1): Represents.
  • Method (b1) Reaction of aniline derivative and halogenated acetic acid
  • the reaction can be carried out using water, methanol, ethanol, or a mixture thereof as a solvent, and if necessary, in the presence of a base.
  • Method (b2) Reaction of aniline derivative and halogenated acetic acid ester, and hydrolysis of glycine derivative ester obtained by the reaction
  • the reaction between the aniline derivative and the halogenated acetate can be performed in the presence of a base such as acetate, carbonate, phosphate, or tertiary amine using, for example, methanol or ethanol as a solvent.
  • the hydrolysis of the glycine derivative ester can be usually performed at room temperature in the presence of a water-soluble alkali.
  • Method (b3) Reaction of aromatic halide with glycine This reaction can be performed, for example, using monovalent copper as a catalyst and in the presence of a bulky amine, amino acid, amino alcohol or the like.
  • a bulky amine amino acid, amino alcohol or the like.
  • the reaction solvent water, methanol, ethanol, or a mixture thereof is preferably used.
  • the reaction temperature is about room temperature to 100 ° C.
  • the fullerene derivative of the present invention can be synthesized by a simple method using a glycine derivative and an aldehyde compound as raw materials in this way, it can be produced at low cost.
  • fullerene derivative of the present invention can be suitably used as an n-type semiconductor material, particularly an n-type semiconductor material for a photoelectric conversion element such as an organic thin film solar cell.
  • the fullerene derivative of the present invention can also be used as an electron transport material for transistors, perovskite solar cells, and the like.
  • the fullerene derivative 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 examples include poly-3-hexylthiophene (P3HT), poly-p-phenylene vinylene, poly-alkoxy-p-phenylene vinylene, poly-9,9-dialkylfluorene, poly-p- Examples include phenylene vinylene. Since these are many examples of studies as solar cells and are easily available, devices with stable performance can be easily obtained.
  • a donor-acceptor type ⁇ -conjugated polymer that enables absorption of long-wavelength light by narrowing the band gap (low band gap) is effective.
  • These donor-acceptor type ⁇ -conjugated polymers have a structure in which donor units and acceptor units are arranged alternately.
  • the donor unit used here include benzodithiophene, dithienosilol, and N-alkylcarbazole
  • examples of the acceptor unit include benzothiadiazole, thienothiophene, and thiophenepyrroldione.
  • PTB compounds having a fluorine atom at the 3-position of thieno [3,4-b] thiophene as the acceptor unit
  • PBDTTTT-CF and PTB7 are particularly preferred examples. Is done.
  • n represents the number of repetitions.
  • n represents the number of repetitions.
  • n represents the number of repetitions.
  • n represents the number of repetitions.
  • n represents the number of repetitions.
  • An organic power generation layer prepared using the fullerene derivative of the present invention as an n-type semiconductor material in combination with an organic p-type semiconductor material can exhibit high conversion efficiency. Since the fullerene derivative of the present invention exhibits good solubility in various organic solvents, when it is used as an n-type semiconductor material, an organic power generation layer can be prepared by a coating method, and a large area organic The power generation layer can be easily prepared.
  • the fullerene derivative of the present invention is a compound having good compatibility with an organic p-type semiconductor material and having appropriate self-aggregation properties. Therefore, an organic power generation layer having a bulk junction structure is easily formed using the fullerene derivative as an n-type semiconductor material (organic n-type semiconductor material). By using this organic power generation layer, an organic thin film solar cell or a photosensor having high conversion efficiency can be obtained.
  • an organic thin film solar cell having excellent performance can be produced at low cost.
  • Another application of the organic power generation layer containing (or consisting of) the n-type semiconductor material of the present invention is an image sensor for a digital camera.
  • an image sensor made of an organic material with high photosensitivity is expected to enable high sensitivity and high definition.
  • a material for constructing the light receiving part of such a sensor is required to absorb light with high sensitivity and to generate an electric signal with high efficiency therefrom.
  • the organic power generation layer containing (or consisting of) the n-type semiconductor material of the present invention can efficiently convert visible light into electrical energy. High function can be expressed.
  • n-type semiconductor material of the present invention comprises the fullerene derivative of the present invention.
  • the organic power generation layer of the present invention contains the fullerene derivative of the present invention as an n-type semiconductor material (n-type semiconductor compound).
  • the organic power generation layer of the present invention can be a light conversion layer (photoelectric conversion layer).
  • the organic power generation layer of the present invention usually contains the organic p-type semiconductor material (organic p-type semiconductor compound) in combination with the fullerene derivative of the present invention, that is, the n-type semiconductor material of the present invention.
  • the organic power generation layer of the present invention is usually composed of the n-type semiconductor material of the present invention and the organic p-type semiconductor.
  • the n-type semiconductor material of the present invention and the organic p-type semiconductor material form a bulk heterojunction structure.
  • the organic power generation layer of the present invention is prepared, for example, by dissolving the n-type semiconductor material of the present invention and the organic p-type semiconductor material in an organic solvent, and from the obtained solution, a spin coating method, a casting method, a dipping method, an inkjet method, It can prepare by forming a thin film on a board
  • the fullerene derivative of the present invention has good compatibility with an organic p-type semiconductor material (preferably P3HT or PTB7) and has appropriate self-aggregation.
  • An organic power generation layer containing the fullerene derivative of the present invention as an n-type semiconductor material and an organic p-type semiconductor material and having a bulk heterojunction structure can be easily obtained.
  • the organic thin film solar cell of the present invention includes the organic power generation layer of the present invention described above. For this reason, the organic thin film solar cell of this invention has high conversion efficiency.
  • the structure of the organic thin film solar cell is not particularly limited, and can be the same structure as a known organic thin film solar cell, and the organic thin film solar cell of the present invention is manufactured according to a known method for manufacturing an organic thin film solar cell. it can.
  • the organic thin film solar cell containing the fullerene derivative for example, a transparent electrode (cathode), a cathode side charge transport layer, an organic power generation layer, an anode side charge transport layer, and a counter electrode (anode) are sequentially laminated on a substrate.
  • a transparent electrode cathode
  • a cathode side charge transport layer an organic power generation layer
  • an anode side charge transport layer an organic power generation layer
  • anode anode
  • a counter electrode anode
  • the organic power generation layer is preferably a semiconductor thin film layer (that is, a photoelectric conversion layer) containing an organic p-type semiconductor material and the fullerene derivative of the present invention as an n-type semiconductor material and having a bulk heterojunction structure.
  • a known material can be appropriately used as a material for each layer other than the organic power generation layer.
  • examples of the material for the electrode include aluminum, gold, silver, copper, and indium oxide (ITO).
  • the material for the charge transport layer for example, PFN (poly [9,9-bis (3 ′-(N, N-dimethylamino) propyl-2,7-fluorene) -alt-2,7- (9,9 -Dioctylfluorene)]), MoO 3 (molybdenum oxide) and the like.
  • the photoelectric conversion layer obtained in the present invention effectively functions as a light receiving portion for an image sensor in a high-functional product of a digital camera.
  • the optical sensor is constructed from a silicon substrate, an electrode, a light receiving part including a photoelectric conversion layer, a color filter, and a microlens.
  • the light receiving portion may have a thickness of about several hundreds of nanometers, and may be configured to be a fraction of the thickness of a conventional silicon photodiode.
  • solar cells were prepared by the method described later and their functions were evaluated.
  • PTB7 is used as the organic p-type semiconductor material
  • PFN poly [9,9-bis (3 ′-(N, N-dimethylamino) propyl-2,7-fluorene) -alt-2, 7- (9,9-dioctylfluorene)]
  • MoO 3 molecular oxide
  • ITO indium tin oxide
  • test solar cell A test solar cell was produced according to the following procedure. 1) Pretreatment of substrate The ITO patterned glass plate was put in a plasma cleaning machine, and the substrate surface was cleaned for 10 minutes by plasma generated while oxygen gas was introduced. 2) Preparation of PFN thin film (cathode-side charge transport layer) Using an ABLE / ASS-301 type spin coat method film forming apparatus, a PFN methanol solution (2% w / v) was used for the pre-treated ITO. A PFN thin film was formed on a glass plate. The film thickness of the formed PFN thin film was about 10 nm.

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Abstract

La présente invention traite le problème de la fourniture d'un matériau ayant d'excellentes propriétés en tant que semi-conducteur de type n, en particulier un semi-conducteur de type n pour un photo-convertisseur d'une batterie solaire organique à couche mince, et analogue. L'invention concerne un dérivé de fullerène représenté par la formule générale (1) [où X 1a est un atome d'hydrogène, un atome de chlore, un atome de brome, un atome d'iode, un groupe alkyle ayant facultativement un ou plusieurs groupes substituants, un groupe alcoxy ayant facultativement un ou plusieurs groupes substituants, ou un groupe cyano; X 1b est un atome de chlore, un atome de brome, un atome d'iode, un groupe alkyle ayant facultativement un ou plusieurs groupes substituants, un groupe alcoxy ayant facultativement un ou plusieurs groupes substituants, ou un groupe cyano; R 2 est un groupe aryle ayant facultativement un ou plusieurs groupes substituants ou un groupe hétéroaryle ayant facultativement un ou plusieurs groupes substituants; R 3 est un atome d'hydrogène ou un groupe organique; et l'anneau A est un anneau de fullerène].
PCT/JP2017/021933 2016-06-14 2017-06-14 Dérivé de fullerène et matériau semi-conducteur de type n WO2017217448A1 (fr)

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