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WO2011000939A1 - Utilisation de périflanthènes substitués dans des piles solaires organiques - Google Patents

Utilisation de périflanthènes substitués dans des piles solaires organiques Download PDF

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WO2011000939A1
WO2011000939A1 PCT/EP2010/059453 EP2010059453W WO2011000939A1 WO 2011000939 A1 WO2011000939 A1 WO 2011000939A1 EP 2010059453 W EP2010059453 W EP 2010059453W WO 2011000939 A1 WO2011000939 A1 WO 2011000939A1
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substituted
organic solar
solar cell
unsubstituted
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Martin KÖNEMANN
Jae Hyung Hwang
Jianqiang Qu
Jan SCHÖNEBOOM
Gabriele Mattern
Regina HÖH
Torsten Noe
Gerd Weber
Christian DÖRR
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BASF SE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/52—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of six-membered aromatic rings being part of condensed ring systems
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    • C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
    • C09B3/14—Perylene derivatives
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H10K30/211—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions comprising multiple junctions, e.g. double heterojunctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/54—Ortho- or ortho- and peri-condensed systems containing more than five condensed rings
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
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    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/611—Charge transfer complexes
    • 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 an organic solar cell having a photoactive region comprising at least one organic donor material in contact with at least one organic acceptor material, the donor material and the acceptor material having a donor-acceptor heterojunction (donor acceptor heterojunction) and wherein the photoactive region contains at least one substituted periflanthene.
  • Photovoltaic means the direct conversion of radiant energy, mainly solar energy, into electrical energy.
  • inorganic solar cells in organic solar cells the light does not directly generate free charge carriers, but excitons are initially formed, ie. H. electrically neutral excitation states in the form of electron-hole pairs. These excitons can only be separated by very high electric fields or at suitable interfaces. In organic solar cells, sufficiently high fields are not available, so that all previous concepts for organic solar cells on the exciton separation based on photoactive interfaces (organic donor-acceptor interfaces or interfaces to an inorganic semiconductor).
  • the first organic solar cell with percent efficiency was developed by Tang et al. Tang et al., Appl. Phys. Lett., 48, 183 (1986)). It consisted of a two-layer copper phthalocyanine (CuPc) system p-type semiconductor and perylene-3,4: 9,10-tetracarboxylic bisimidazole (PTCBI) as
  • the z. B. by using pin structures with doped transport layers large band gap can be further improved.
  • mixed layers of donors and acceptors can be used, forming an interpenetrating network, in which internal donor-acceptor heterojunctions are possible.
  • an organic solar cell obtained by vacuum deposition of CuPc / C ⁇ o, resulting in a special form of the mixed layer in the form of a donor acceptor bulk heterojunction (BHJ).
  • BHJ donor acceptor bulk heterojunction
  • the advantage of such a mixed layer is that the generated excitons only have to travel a very short distance until they reach a domain boundary where they are separated.
  • a critical point of bulk heterojunction (BHJ) is to find suitable materials and fabrication processes that result in blend layers that have closed transport paths for both electrons and holes to their respective contacts. Since the individual materials each fill only a part of the mixed layer, in many cases the transport properties for the charge carriers deteriorate markedly in comparison to the pure layers.
  • there are classes of substances such. B.
  • JP 2008-135540 describes the use of perylene derivatives of the general formula
  • R 1 and R 2 are condensed rings which may be substituted by alkyl, alkenyl, aryl, aralkyl or heterocyclyl and AR 1 - AR 8 may be alkyl, alkenyl, aryl, aralkyl or heterocyclyl, as electron donor material for the production of organic solar panels.
  • AR 1 - AR 8 may be alkyl, alkenyl, aryl, aralkyl or heterocyclyl, as electron donor material for the production of organic solar panels.
  • exclusively dibenzotetraphenyl periflanthene is used to prepare an organic solar cell with photoactive donor-acceptor transitions in the form of a flat heterojunction.
  • the use of differently substituted periflanthenes is not proven, nor is the production of organic solar cells with donor-acceptor transitions in the form of a bulk heterojunction.
  • the object of the invention is to provide an organic solar cell in which the efficiency of energy conversion is improved.
  • substituted periflanthenes are particularly advantageously suitable as semiconductor material for the production of organic solar cells with photoactive donor-acceptor transitions, in particular with photoactive donor-acceptor transitions in the form of a bulk heterojunction. They serve specifically as donor material (p-type semiconductor).
  • a first aspect of the invention is an organic solar cell having a photoactive region comprising at least one organic donor material in contact with at least one organic acceptor material, wherein the donor material and the acceptor material form a donor-acceptor heterojunction and wherein the photoactive region is at least one substituted periflanthene of the formula (I)
  • X is independently selected from hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl and unsubstituted or substituted ON-go (het) aryl,
  • Y is independently selected from unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, and unsubstituted or substituted oligo (het) aryl, each having at least two adjacent radicals selected from X and Y together with the carbon atoms of the benzene nucleus to which they are attached may also stand for a fused ring system having 1, 2, 3, 4, 5, 6, 7 or 8 further rings.
  • Exempted from the subject invention are organic solar cells, wherein the photoactive region Dibenzotetraphenylperiflanthen of the formula
  • the compounds of formulas 4 to 18 specifically disclosed in paragraphs [0020] to [0034] in JP 2008-135540 are preferably not used in the organic solar cells according to the invention.
  • FIG. 1 shows a solar cell with a normal structure which is suitable for the use of substituted periflanthenes.
  • FIG. 2 shows a solar cell with inverse structure which is suitable for the use of substituted periflanthenes.
  • Figure 3 shows the structure of a suitable for the use of substituted periflanthenes solar cell with normal structure and with a donor-acceptor interface in the form of a bulk heterojunction.
  • Figure 4 shows the structure of a for the use of substituted periflanthene solar cell with inverse structure and with a donor-acceptor interface in the form of a bulk heterojunction.
  • FIG. 5 shows the structure of a tandem cell.
  • FIG. 6 shows the structure of a solar cell with a donor-acceptor interface in the form of a bulk heterojunction, which is designed as a gradient.
  • unsubstituted or substituted alkyl, aryl, heteroaryl or oligo (het) aryl is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl or unsubstituted or substituted oligo (het) aryl.
  • alkyl includes straight-chain or branched alkyl.
  • Alkyl is preferably C 1 -C 30 -alkyl, in particular C 1 -C 20 -alkyl and very particularly preferably C 1 -C 12 -alkyl.
  • alkyl groups are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.
  • R a is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • Substituted alkyl groups may have one or more (eg, 1, 2, 3, 4, 5 or more than 5) substituents depending on the length of the alkyl chain. These are preferably selected independently from among cycloalkyl, heterocycloalkyl, aryl, heteroaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO 3 H, sulfonate, sulfamino , Sulfamide, amidino, NE 1 E 2 , wherein E 1 and E 2 are independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • E 1 and E 2 are independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • Carboxylate and sulfonate represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid ester or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function.
  • Cycloalkyl, heterocycloalkyl, aryl and heteroaryl substituents of the alkyl groups may themselves be unsubstituted or substituted; suitable substituents are the substituents mentioned below for these groups.
  • Aryl substituted alkyl (“aralkyl”) groups have at least one unsubstituted or substituted aryl group as defined below.
  • R b is preferably water hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • Arylalkyl is preferably phenyl-Ci-Cio-alkyl, particularly preferably phenyl-Ci-C4-alkyl, for.
  • benzyl 1-phenethyl, 2-phenethyl, 1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut-1 -yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl , 1- (phenmeth) eth-1-yl,
  • Halogen-substituted alkyl groups include a straight-chain or branched alkyl group in which at least one or all of the hydrogen atoms are replaced by halogen.
  • the halogen atoms are preferably selected from fluorine, chlorine and bromine, in particular fluorine and chlorine.
  • haloalkyl groups are, in particular, chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,
  • 2,2,2-trifluoroethyl 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3, 3-trichloropropyl, -CH 2 -C 2 F 5 , -CF 2 -C 2 F 5 ,
  • cycloalkyl denotes a cycloaliphatic radical having preferably 3 to 10, particularly preferably 5 to 8 , Carbon atoms.
  • Examples of cycloalkyl groups are in particular cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Substituted cycloalkyl groups may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the ring size. These are preferably selected independently from among alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl , SO 3 H, sulfonate, sulfamino, sulfamide, amidino, NE 3 E 4 , wherein E 3 and E 4 are independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • the cycloalkyl groups carry in the case of substitution preferential one or more, for example one, two, three, four
  • Ci-C ⁇ -alkyl groups are, in particular, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 2-, 3- and 4-propylcyclohexyl, 2-, 3- and
  • bicycloalkyl preferably comprises bicyclic hydrocarbon radicals having 5 to 10 C atoms, such as bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl,
  • aryl in the context of the present invention comprises mono- or polynuclear aromatic hydrocarbon radicals having preferably 6 to 14, particularly preferably 6 to 10, carbon atoms.
  • aryl are in particular phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, etc., and especially phenyl or naphthyl.
  • Substituted aryls may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the number and size of their ring systems. These are preferably selected independently from among alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcar - bonyloxy, carbamoyl, SO3H, sulfonate, sulfamino, sulfamide, amidino, NE 5 E 6 , wherein E 5 and E 6 are independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • E 5 and E 6 are independently hydrogen, alkyl, cycloalkyl, heterocycloalky
  • the alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl and heteroaryl substituents on the aryl may in turn be unsubstituted or substituted. Reference is made to the substituents previously mentioned for these groups.
  • the substituents on the aryl are preferably selected from alkyl, alkoxy, haloalkyl, haloalkoxy, aryl, fluorine, chlorine, bromine, cyano and nitro.
  • Substituted aryl is particularly preferably substituted phenyl, which generally carries 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents.
  • Substituted aryl is preferably substituted by at least one alkyl group aryl ("alkaryl").
  • alkaryl groups may have one or more (for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more than 9) alkyl substituents.
  • the alkyl substituents may be unsubstituted or substituted.
  • the alkaryl groups have exclusively unsubstituted alkyl substituents.
  • Alkaryl preferably represents phenyl which carries 1, 2, 3, 4 or 5, preferably 1, 2 or 3, particularly preferably 1 or 2, alkyl substituents.
  • Aryl which carries one or more radicals is, for example, 2-, 3- and
  • unsubstituted or substituted aryl also apply to unsubstituted or substituted aryloxy and unsubstituted or substituted arylthio.
  • aryloxy are phenoxy and naphthyloxy.
  • heterocycloalkyl in the context of the present invention comprises non-aromatic, unsaturated or fully saturated, cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms.
  • cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms.
  • 1, 2, 3, 4 or more than 4 of the ring carbon atoms are replaced by heteroatoms or heteroatom-containing groups over the corresponding cycloalkyl groups.
  • R c is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • heterocycloalkyl groups are in particular pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, dihydro-2-yl, tetrahydrofuranyl, Dihydrofuran-2-yl, tetrahydropyranyl, 1, 2-oxazolin-5-yl, 1, 3-oxazolin-2-yl and dioxanyl.
  • Substituted heterocycloalkyl groups may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the ring size. These are preferably selected independently of one another from alkyl, alkoxy, alkylamino no, alkylthio, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO3H, sulfonate, sulfamino, Sulfamide, amidino, NE 7 E 8 , wherein E 7 and E 8 are independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • the heterocycloalkyl groups in the case of a substitution preferably carry one or more, for example one, two,
  • heteroaryl in the context of the present invention encompasses heteroaromatic, mononuclear or polynuclear groups. These have in addition to the ring carbon atoms 1, 2, 3, 4 or more than 4 of the ring heteroatoms.
  • the heteroatoms are preferably selected from oxygen, nitrogen, selenium and sulfur.
  • the heteroaryl groups preferably have 5 to 18, e.g. B. 5, 6, 8, 9, 10, 11, 12, 13 or 14 ring atoms.
  • Monocyclic heteroaryl groups are preferably 5- or 6-membered heteroaryl groups, such as 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2-thienyl (thiophen-2-yl), 3-thienyl ( Thiophen-3-yl), selenophen-2-yl, selenophen-3-yl, 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, pyrrol-1-yl, imidazol-2-yl, imidazole 1-yl, imidazol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl , 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl
  • Polycyclic heteroaryl has 2, 3, 4 or more than 4 fused rings.
  • the fused rings may be aromatic, saturated or partially unsaturated.
  • Examples of polycyclic heteroaryl groups are quinolinyl, isoquinolinyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzoxadiazolyl; Benzothiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, benzotriazinyl, benzoselenophenyl, thiethiophenyl, thienopyrimidyl, thiazolothiazolyl, dibenzopyrrolyl (carbazolyl), dibenzofuranyl, dibenzothiophenyl, naphth
  • Substituted heteroaryls may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the number and size of their ring systems. These are preferably selected independently from among alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, fluorine, Chlorine, bromine, hydroxy, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO 3 H, sulfonate, sulfamino, sulfamide, amidino, NE 9 E 10 , where E 9 and E 10 are independent each other is hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • E 9 and E 10 are independent each other is hydrogen, alkyl, cycloalkyl, heterocycl
  • Halogen substituents are preferably fluorine, chlorine or bromine.
  • the substituents are preferably selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxy, carboxy, halogen and cyano.
  • oligo (het) aryl denotes unsubstituted or substituted groups having at least two repeating units.
  • the repeating units may all have the same meaning, some of the repeating units may have mutually different meanings, or all repeating units may have mutually different meanings.
  • the repeating unit is selected from aryldiyl groups, heteroaryldiyl groups and combinations thereof.
  • the aryldiyl group is a divalent group derived from a flavor, preferably a group derived from benzene or naphthalene, such as 1, 2-phenylene (o-phenylene), 1, 3-phenylene (m-phenylene),
  • the heteroaryldiyl group is a heteroaromatic derived divalent group, preferably a thiophene or furan derived group
  • the terminal group of the oligo (het) aryl groups is a monovalent group. This is preferably also derived from the aforementioned repeating units.
  • the oligo (het) aryl groups may be unsubstituted or substituted.
  • Substituted oligo (het) aryls may have one or more (eg 1, 2, 3, 4, 5, 6, 7, 8, 9 or more than 9) substituents depending on the number and size of their ring systems. These substituents are preferably independently selected from unsubstituted alkyl, haloalkyl, fluorine or chlorine.
  • Suitable repeating units are the following:
  • radicals R a independently of one another are unsubstituted alkyl, haloalkyl, fluorine or chlorine, w is 0, 1, 2, 3 or 4 and x is 0, 1 or 2.
  • Preferred oligoaryl groups are biphenylyl, terphenylyl, quaterphenylyl or quinquephenylyl. Examples thereof are o-biphenylyl, m-biphenylyl, p-biphenylyl, p-terphenylyl, m-terphenylyl, o-terphenylyl, p-quaterphenylyl or p-quinquephenylyl.
  • Preferred oligohetaryl groups are biphenylyl, terphenylyl, quaterphenylyl or quinquephenylyl. Examples thereof are o-biphenylyl, m-biphenylyl, p-biphenylyl, p-terphenylyl, m-terphenylyl, o-terphenylyl, p-quaterphenylyl or p-quinquephenylyl.
  • Preferred oligohetaryl groups
  • n is an integer from 1 to 20, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Sulfomethyl 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl; 2-hydroxyethyl, 2- and 3-hydroxypropyl, 3- and 4-hydroxybutyl and 8-hydroxy-4-oxo-octyl;
  • Carbamoyl methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl,
  • Aminosulfonyl N-dodecylaminosulfonyl, N, N-diphenylaminosulfonyl, and
  • 2-dioxanyl 1-morpholinyl, 1-thiomorpholinyl, 2- and 3-tetrahydrofuryl, 1-, 2- and 3-pyrrolidinyl, 1-piperazyl, 1-diketopiperazyl and 1-, 2-, 3- and 4-piperidyl;
  • Preferred fluorine-containing radicals X, Y, R 1 , R 2 , R 3 and R 4 are the following: 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluoroethyl, 2, 2,3,3,4,4,4-heptafluorobutyl, 2,2,3,3,3-pentafluoropropyl, 1H, 1H-pentadecafluorooctyl, 3-bromo-3,3-difluoropropyl, 3, 3,3-trifluoropropyl, 3,3,3-trifluoropropyl, 1H, 1H, 2H, 2H-perfluorodecyl, 3- (perfluorooctyl) propyl, 4,4-difluorobutyl, 4,4,4-trifluorobutyl, 5, 5,6,6,6-pentafluorohexyl, 2,2-difluoropropy
  • 2,6-Difluorophenethyl 4- (4-fluorophenyl) phenethyl, 3,5-di (trifluoromethyl) phenethyl, pentafluorophenethyl, 2,4-di (trifluoromethyl) phenethyl, 2-nitro-4- (trifluoromethyl) phenethyl, (2 Fluoro-3-trifluoromethyl) phenethyl, (2-fluoro-5-trifluoromethyl) phenethyl,
  • a specific embodiment of the invention relates to compounds in which at least one of the radicals X, Y, R 1 and / or R 2 mentioned in formula (I) and the following formulas is a C 1 -C 30 -alkyl radical in the form of a so-called sulfur - tail rest stands.
  • the radicals X, Y, R 1 and R 2 are then preferably a radical of the general formula (II)
  • # stands for a binding site
  • the radicals R d are selected from C 1 to C 28 -alkyl, where the sum of the carbon atoms of the radicals R d is an integer from 2 to 29.
  • the radicals R d are preferably selected from C 1 - to C 12 -alkyl, in particular C 1 - to C 6 -alkyl.
  • Preferred radicals of the formula (II) are, for example: 1-ethylpropyl, 1-methylpropyl, 1-propylbutyl, 1-ethylbutyl, 1-methylbutyl, 1-butylpentyl, 1-propylpentyl, 1-ethylpentyl, 1-methylpentyl, 1-pentylhexyl, 1-butylhexyl,
  • 1-nonyltetracosanyl 1-octyltetracosanyl, 1-heptyltetracosanyl, 1-hexyltetracosanyl, 1-pentyltetracosanyl, 1-butyltetracosanyl, 1-propyltetracosanyl, 1-ethyltetracosanyl, 1-methyltetracosanyl, 1-heptacosanyloctacosanyl, 1 -hexacosanyloctacosanyl, 1-pentacosanyloctacosanyl, 1-tetracosanyloctacosanyl, 1-tricosanyloctacosanyl, 1-docosanyloctacosanyl, 1-nonadecyloctacosanyl, 1 - Octadecyloctacosanyl,
  • radicals of the formula (II) are, for example:
  • the groups X may all have the same meaning, or 2, 3 or 4 of the groups X have mutually different meanings. In a specific embodiment, in the compounds of general formula (I), the groups X all have the same meaning.
  • the groups X are independently selected from hydrogen and unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl and unsubstituted or substituted oligo (het) aryl ,
  • the groups X are independently selected from hydrogen, unsubstituted alkyl, aralkyl, unsubstituted aryl, alkaryl, halo-substituted aryl, heteroaryl and oligo (het) aryl.
  • the groups X are particularly preferably selected, independently of one another, from hydrogen and unsubstituted or substituted C 1 - to C 30 -alkyl, unsubstituted or substituted C 1 - to C 30 - Alkyl, unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, and unsubstituted or substituted anthracenyl.
  • the groups X are hydrogen.
  • the groups X are all hydrogen.
  • 1, 2, 3 or 4 of the groups X are unsubstituted or substituted C 1 - to C 30 -alkyl.
  • 1, 2, 3 or 4 of the X groups is unsubstituted or substituted d- to C 2 alkyl.
  • 1, 2, 3 or 4 of the groups X are particularly preferably unsubstituted linear C 1 - to C 12 -alkyl, especially unsubstituted linear C 4 - to C 12 -alkyl, such as n-octyl, n-nonyl, n-decyl, n-undecyl , n-dodecyl.
  • all groups X are unsubstituted or substituted C 1 - to C 12 -alkyl, more particularly unsubstituted linear C 1 - to C 12 -alkyl, even more particularly unsubstituted linear C 4 - to C 12 -alkyl, such as n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl.
  • # stands for a binding site
  • the radicals R d are selected from C 1 to C 28 -alkyl, where the sum of the carbon atoms of the radicals R d is an integer from 2 to 29.
  • the alkyl groups when the groups X are substituted alkyl, the alkyl groups, depending on their chain length, are preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more 10 substituents.
  • the substituents of the alkyl radicals are preferably independently selected from aryl, fluorine, chlorine, nitro and cyano.
  • # is the binding site for the periflanthene backbone
  • R 1 are each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, unsubstituted or substituted alkyl, unsubstituted or substituted aryl and unsubstituted or substituted heteroaryl. (The numbering of the aromatic ring systems is used below to indicate the position of the substituents.)
  • radicals R 1 preferably have a meaning other than hydrogen.
  • Monosubstituted groups of the formula (III.1) preferably have a radical R 1 in the 4-position.
  • Disubstituted groups of the formula (III.1) preferably have two radicals R 1 in the 3-position and in the
  • radicals R 1 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (III.2), 0 or 1 of the radicals R 1 have a meaning other than hydrogen.
  • Monosubstituted groups of the formula (III.2.2) preferably have a radical R 1 in the 4-position.
  • radicals R 1 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (III.3), 0 or 1 of the radicals R 1 have a meaning other than hydrogen.
  • radicals R 1 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (III.4), 0 or 1 of the radicals R 1 have a meaning other than hydrogen.
  • radicals R 1 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (III.5.5), 0 or 1 of the radicals R 1 have a meaning other than hydrogen.
  • radicals R 1 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (III.6.6), 0 or 1 of the radicals R 1 have a meaning other than hydrogen.
  • 0, 1 or 2 of the radicals R 1 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (III.7.7), 0 or 1 of the radicals R 1 have a meaning other than hydrogen.
  • radicals R 1 preferably have a meaning other than hydrogen. Particular preference is given in the pen of formula (III.8) 0 or 1 of the radicals R 1 has a meaning other than hydrogen.
  • radicals R 1 are each independently selected from among hydrogen, alkyl, haloalkyl, aryl, fluorine, chlorine, bromine, cyano and nitro.
  • the radicals R 1 are each independently selected from among hydrogen, C 1 - to C 12 -alkyl and C 1 - to C 12 -haloalkyl.
  • radicals R 1 which have a meaning other than hydrogen are selected from unsubstituted C 1 - to C 4 -alkyl groups, such as methyl, ethyl, n- Propyl, isopropyl, n-butyl and tert-butyl.
  • the radicals R 1 which have a meaning other than hydrogen are selected from unsubstituted linear C 5 - to C 12 -alkyl groups, such as n-octyl, n-nonyl , n-decyl, n-undecyl, n-dodecyl.
  • radicals R 1 which have a meaning other than hydrogen are selected from radicals of the general formula (II)
  • R d is a binding site
  • R 1 is a radical of the general formula (II)
  • R d is a radical of the general formula (II)
  • 1, 2, 3 or 4 of the groups X are selected from groups of the general formulas (111.1 a), (111.1 b), (111.1 c), (III.1d), (III .2a), (III.4a), (III.7a), (III. ⁇ a), (III.9a), (III.10a), (111.11a) and (111.12a)
  • X is a group III.1d which carries a C8-C12 linear alkyl group in the 4-position.
  • all groups X are selected from groups of the general formulas (III.1a), (III.1b), (III.1c), (III.1d), (III.2a), (III. 4a), (III.7a), (III. ⁇ a), (III.9a), (III.10a), (111.11a) or (111.12a).
  • all groups X are selected from groups of general formulas (III.1a), (III.1b), (III.1c), (III.1d), (III.2a) and (III. 4a).
  • all groups X have the same meaning.
  • 1, 2, 3 or 4 of the groups X are unsubstituted or substituted heteroaryl.
  • 1, 2, 3 or 4 of the groups X are pyridinyl, quinolinyl or isoquinolinyl, where the 3 latter groups can be unsubstituted or carry 1, 2, 3 or 4 radicals which are selected from unsubstituted or substituted alkyl, unsubstituted or substituted aryl and unsubstituted or substituted heteroaryl.
  • X is preferably pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-8-yl, isoquinoline-4 yl, isoquinolin-5-yl, isoquinolin-6-yl and isoquinolin-8-yl, where the 1 1 last-mentioned groups are unsubstituted or can carry 1, 2, 3 or 4 Ci-C3o-alkyl groups.
  • X is substituted or unsubstituted pyridin-4-yl.
  • pyridinyl, quinolinyl or isoquinolinyl carry 1, 2, 3 or 4 C 1 -C 30 -alkyl groups, these are preferably selected from unsubstituted linear or branched C 1 -C 4 -alkyl and unsubstituted linear C 1 -C 12 -alkyl.
  • pyridinyl, quinolinyl or isoquinolinyl carry 1, 2, 3 or 4 Ci-C3o-alkyl groups, they are preferably selected according to a specific embodiment of the radicals of the general formula (II).
  • the groups Y may all have the same meaning, or 2, 3 or 4 of the groups Y have mutually different meanings. In a specific embodiment, in the compounds of general formula (I), the groups Y all have the same meaning.
  • the groups Y are independently selected from unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl and unsubstituted or substituted oligo (het) aryl.
  • the groups Y are independently selected from unsubstituted alkyl, aralkyl, unsubstituted aryl, alkaryl, halo-substituted aryl, heteroaryl and oligo (het) aryl.
  • 1, 2, 3 or 4 of the groups Y are selected from groups of the general formulas (IV.1) to (IV.12)
  • Each R 2 is independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, unsubstituted or substituted alkyl, unsubstituted or substituted aryl and unsubstituted or substituted heteroaryl.
  • 0, 1 or 2 of the radicals R 2 preferably have a meaning other than hydrogen.
  • Monosubstituted groups of the formula (IV.1) preferably have a radical R 2 in the 4-position.
  • Disubstituted groups of the formula (IV.1) preferably have two radicals R 2 in the 3-position and in the 5-position.
  • radicals R 2 preferably have a meaning other than hydrogen.
  • 0 or 1 of the radicals R 2 particularly preferably have a meaning other than hydrogen.
  • Monosubstituted groups of the formula (IV.2) preferably have a radical R 2 in the 4-position.
  • radicals R 2 preferably have a meaning other than hydrogen.
  • 0 or 1 of the radicals R 2 particularly preferably have a meaning other than hydrogen.
  • radicals R 2 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (IV.4), 0 or 1 of the radicals R 2 have a meaning other than hydrogen.
  • radicals R 2 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (IV.5), 0 or 1 of the radicals R 2 has a meaning other than hydrogen.
  • radicals R 2 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (IV.6), 0 or 1 of the radicals R 2 has a meaning other than hydrogen.
  • 0, 1 or 2 of the radicals R 2 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (IV.7), 0 or 1 of the radicals R 2 has a meaning other than hydrogen.
  • 0, 1 or 2 of the radicals R 2 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formula (IV.8), 0 or 1 of the radicals R 2 have a meaning other than hydrogen. In the groups of the formulas (IV.9) to (IV.12), 0, 1, 2, 3 or 4 of the radicals R 2 preferably have a meaning other than hydrogen. At each thiophene ring, 0, 1 or 2 of the radicals R 2 preferably have a meaning other than hydrogen. Particularly preferably, in the groups of the formulas (IV.9) to (IV.12), 0 or 1 of the radicals R 2 have a meaning other than hydrogen.
  • radicals R 2 are each independently selected from hydrogen, alkyl, haloalkyl, aryl, fluorine, chlorine, bromine, cyano and nitro.
  • radicals R 2 are each independently selected from hydrogen, C 1 - to C 12 -alkyl and C 1 - to C 12 -haloalkyl.
  • the radicals R 2 which have a meaning other than hydrogen, are selected from unsubstituted C 1 - to C 4 -alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
  • the radicals R 2 which have a meaning other than hydrogen are selected from unsubstituted linear C 5 - to C 12 -alkyl groups, such as n-octyl, n Nonyl, n-decyl, n-undecyl, n-dodecyl.
  • radicals R 2 which have a meaning other than hydrogen, are selected from radicals of the general formula (II)
  • # stands for a binding site
  • the radicals R d are selected from C 1 to C 28 -alkyl, where the sum of the carbon atoms of the radicals R d is an integer from 2 to 29.
  • R 2 is a radical of the general formula (II)
  • R d is a radical of the general formula (II)
  • R d is a radical of the general formula (II)
  • 1, 2, 3 or 4 of the groups Y are selected from groups of the general formulas (IV.1 a), (IV.1 b), (IV.1 C), (IV .1 d), (IV.2a), (IV.4a), (IV.7a), (IV.8a), (IV.9a), (IV.10a), (IV.1 1a) and (IV .The 12a)
  • # represents the binding site to the periflanthene backbone.
  • Y is a group IV.1 d which carries a linear C 8 -C 12 -alkyl group in the 4-position.
  • all groups Y are selected from groups of the general formulas (IV.1a), (IV.1b), (IV.1c), (IV.1d), (IV. 2a), (IV.4a), (IV.7a), (IV. ⁇ a), (IV.9a), (IV.10a), (IV.11a) or (IV.12a).
  • all groups Y are selected from groups of general formulas (IV.1a), (IV.1b), (IV.1c), (IV.1d), (IV .2a) and (IV.4a).
  • all groups Y have the same meaning.
  • 1, 2, 3 or 4 of the groups Y are unsubstituted or substituted heteroaryl.
  • 1, 2, 3 or 4 of the groups Y are pyridinyl, quinolinyl or isoquinolinyl, where the 3 latter groups can be unsubstituted or carry 1, 2, 3 or 4 radicals which are selected from unsubstituted or substituted alkyl, unsubstituted or substituted aryl and unsubstituted or substituted heteroaryl.
  • Y is preferably pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-8-yl, isoquinoline-4 yl, isoquinolin-5-yl, isoquinolin-6-yl and isoquinolin-8-yl, where the 1 1 last-mentioned groups are unsubstituted or can carry 1, 2, 3 or 4 Ci-C3o-alkyl groups.
  • X is substituted or unsubstituted pyridin-4-yl.
  • pyridinyl, quinolinyl or isoquinolinyl carry 1, 2, 3 or 4 C 1 -C 30 -alkyl groups, these are preferably selected from unsubstituted linear or branched C 1 -C 4 -alkyl and unsubstituted linear C 5 -C 12 -alkyl.
  • pyridinyl, quinolinyl or isoquinolinyl carry 1, 2, 3 or 4 Ci-C3o-alkyl groups, they are preferably selected according to a specific embodiment of the radicals of the general formula (II).
  • two adjacent radicals Y together with the carbon atoms of the benzene nucleus to which they are attached, stand for a fused ring system having 1, 2, 3 or 4 further rings.
  • two adjacent radicals Y together represent a group which is selected from groups of the general formulas (V.1) to (V.4)
  • R 3 are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, unsubstituted or substituted alkyl, unsubstituted or substituted aryl and unsubstituted or substituted heteroaryl.
  • R 3 preferably have a meaning other than hydrogen.
  • radicals R 3 preferably have a meaning other than hydrogen.
  • the radicals R 3 are each independently selected from hydrogen, alkyl, aralkyl, haloalkyl, aryl, alkaryl, fluorine, chlorine, bromine, cyano and nitro.
  • the radicals R 3 are each independently selected from hydrogen, C 1 - to C 12 -alkyl and C 1 - to C 12 -haloalkyl.
  • the radicals R 3 which have a meaning other than hydrogen, are selected from unsubstituted C 1 - to C 4 -alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
  • the radicals R 3 which have a meaning other than hydrogen, are selected from unsubstituted linear C 4 - to C 12 -alkyl groups, such as n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl.
  • radicals R 3 which have a meaning other than hydrogen, are selected from radicals of the general formula (II)
  • R d stands for a binding site, and the radicals R d are selected from C 1 to C 28 -alkyl, where the sum of the carbon atoms of the radicals R d is an integer from 2 to 29.
  • R 3 is a radical of the general formula (II)
  • suitable and preferred radicals R d reference is made in full to the abovementioned suitable and preferred radicals R d .
  • radicals Y together represent a group of the general formula (V.1) in which all radicals R 3 are hydrogen
  • the two radicals X which are bonded to the same benzene ring as these radicals Y are preferably from Hydrogen different.
  • these radicals X are then both C 1 - to C 30 -alkyl, particularly preferably both are linear C 4 - to C 12 -alkyl, in particular both are n-octyl, n-nonyl, n-decyl, n-undecyl or n- dodecyl.
  • two adjacent radicals Y together represent a group (V.1), (V.2), (V.3) or (V.4) in which the radicals R 3 are all hydrogen.
  • Anellated groups X and Y represent a group (V.1), (V.2), (V.3) or (V.4) in which the radicals R 3 are all hydrogen.
  • two radicals X and two radicals Y which are bonded to the same benzene ring, together with the carbon atoms to which they are attached, stand for a condensed ring system with 3, 4, 5, 6, 7 or 8 further rings.
  • the groups X and the groups Y together then represent a group of the general formula (VI)
  • R 4 are each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, unsubstituted or substituted alkyl, unsubstituted or substituted aryl and unsubstituted or substituted heteroaryl. (The numbering of the aromatic ring systems is used below to indicate the position of the substituents.)
  • radicals R 4 preferably have a meaning other than hydrogen.
  • Particularly preferred positions for radicals R 4 other than hydrogen are positions 3, 6, 9 and / or 12.
  • radicals R 4 are each independently selected from hydrogen, alkyl, aralkyl, haloalkyl, aryl, alkaryl, fluorine, chlorine, bromine, cyano and nitro.
  • radicals R 4 are each independently selected from hydrogen, C 1 - to C 12 -alkyl and C 1 - to C 12 -haloalkyl.
  • radicals R 4 which are one of
  • Hydrogen have various meanings selected from unsubstituted C 1 to C 4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
  • the radicals R 4 which have a meaning other than hydrogen, are selected from unsubstituted linear C 4 - to C 12 -alkyl groups, such as n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl.
  • radicals R 4 which have a meaning other than hydrogen, are selected from radicals of the general formula (II)
  • R d stands for a binding site, and the radicals R d are selected from C 1 to C 28 -alkyl, where the sum of the carbon atoms of the radicals R d is an integer from 2 to 29.
  • R 4 is a radical of the general formula (II)
  • the abovementioned suitable and preferred radicals R d are referred to in their entirety.
  • a specific embodiment is an organic solar cell, wherein the photoactive region comprises at least one substituted periflanthene which is selected from compounds of the formula (A):
  • R 1 are each independently selected from hydrogen, fluorine, chlorine, unsubstituted or substituted alkyl, unsubstituted or substituted aryl and unsubstituted or substituted heteroaryl and
  • R 3 are each independently selected from hydrogen, fluorine, chlorine, cyano, unsubstituted or substituted alkyl, unsubstituted or substituted aryl and unsubstituted or substituted heteroaryl.
  • radicals R 1 preferably have a meaning other than hydrogen.
  • radicals R 3 preferably have a meaning other than hydrogen.
  • the radicals R 1 and R 3 are each independently selected from hydrogen, alkyl, haloalkyl, aryl, fluorine or chlorine.
  • R 1 and R 3 each independently of one another selected from hydrogen, d- to Ci2-alkyl and d- to C12- haloalkyl.
  • the radicals R 1 and R 3 which have a meaning other than hydrogen, are selected from unsubstituted C 1 - to C 4 -alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
  • the radicals R 1 and R 3 which have a meaning other than hydrogen, are selected from unsubstituted linear C 4 - to C 12 -alkyl groups, such as n-octyl, n-nonyl, n -Decyl, n-undecyl, n-dodecyl.
  • the radicals R 1 and R 3 are all hydrogen.
  • the radicals R 1 are all hydrogen, one of the radicals R 3 is cyano and the other radicals R 3 are all hydrogen.
  • the radicals R 1 are all hydrogen, and two of the radicals R 3 are cyano and the other radicals R 3 are all hydrogen.
  • the radicals R 3 which are cyano, are at opposite terminal ends.
  • substituted periflanthenes which are preferably suitable for use in organic solar cells.
  • the substituted periflanthenes used in the solar cells according to the invention can be prepared by customary methods known to the person skilled in the art (for example M. Wehmeier, M. Wagner and K. Müllen, Chem. Eur. J. 2001, 7, No. 10, p. 2197 - 2205).
  • This also includes the construction of the molecular skeleton of a bromoaryl compound with an arylboronic acid derivative under the conditions of a Suzuki coupling, ie in the presence of a platinum metal catalyst and in particular in the presence of a palladium catalyst under known reaction conditions, such as Acc. Chem. Res. 15, pp. 178-184 (1982), Chem. Rev. 95, pp.
  • catalysts are tetrakis (triphenylphosphine) -palladium (O), bis (triphenylphosphine) palladium (II) chloride, bis (acetonitrile) palladium (II) chloride, [1, 1'-bis (diphenylphosphino) ferrocene].
  • the substituted periflaved can be subjected to purification.
  • the purification can be carried out by customary methods known to those skilled in the art, such as separation on suitable stationary phases, sublimation, extraction, distillation, recrystallization or a combination of at least two of these measures.
  • Each cleaning can be configured in one or more stages. Individual cleaning processes can be repeated two or more times. Different cleaning processes can be combined with each other.
  • the purification comprises a column chromatographic method.
  • the starting material present in a solvent or solvent mixture can be subjected to separation or filtration on silica gel.
  • the solvent is removed, for. B. by evaporation under reduced pressure.
  • Suitable solvents are aromatics such as benzene, toluene, xylene, mesitylene, chlorobenzene or dichlorobenzene, hydrocarbons and hydrocarbon mixtures such as pentane, hexane, ligroin and petroleum ether, halogenated hydrocarbons such as chloroform or dichloromethane, and mixtures of the solvents mentioned.
  • a gradient of at least two different solvents can be used, for. As a toluene / petroleum ether gradient.
  • the cleaning comprises a sublimation.
  • This may preferably be a fractional sublimation.
  • a temperature gradient can be used in the sublimation and / or deposition of the substituted periflanthene.
  • the cleaning can be done by sublimation using a carrier gas stream.
  • Suitable carrier gases are inert gases, e.g. As nitrogen, argon or helium.
  • the loaded with the compound gas stream can then be passed into a separation chamber. Suitable separation chambers may have several separation zones that can be operated at different temperatures. Preferably z. For example, a so-called three-zone sublimation device. Another method and apparatus for fractional sublimation is described in US 4,036,594.
  • Organic solar cells are generally layered and typically include at least the following layers: anode, photoactive layer and cathode. These layers are generally applied to a conventional substrate for this purpose.
  • the structure of organic solar cells is z. In US 2005/0098726 and US 2005/0224905.
  • the invention provides an organic solar cell comprising a substrate having at least one cathode and at least one anode and at least one compound of the general formula (I) as defined above, as a photoactive material.
  • the organic solar cell according to the invention comprises at least one photoactive region.
  • a photoactive region may comprise two layers, each having a homogeneous composition and forming a "flat" donor-acceptor heterojunction.
  • a photoactive region may also comprise a mixed layer and form a donor-acceptor heterojunction in the form of donor-acceptor bulk heterojunction.
  • Organic solar cells with photoactive donor-acceptor transitions in the form of a bulk heterojunction are a preferred embodiment of the invention.
  • Suitable substrates for organic solar cells are z.
  • oxidic materials such as glass, ceramic, SiÜ 2 , quartz, etc.
  • polymers eg., Polyethylene terephthalate, polyolefins, such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth) acrylates, polystyrene, Polyvinyl chloride and mixtures and composites thereof.
  • Electrode cathode, anode
  • Metals preferably of groups 2, 8, 9, 10, 11 or 13 of the Periodic Table, for example Pt, Au, Ag, Cu, Al, In, Mg, Ca
  • Semiconductors eg doped Si, doped Ge, indium tin oxide (ITO), fluorinated tin oxide (FTO), gallium indium tin oxide (GITO), zinc indium tin oxide (ZITO), etc .
  • ITO indium tin oxide
  • FTO fluorinated tin oxide
  • GITO gallium indium tin oxide
  • ZITO zinc indium tin oxide
  • Metal alloys eg based on Pt, Au, Ag, Cu, etc., especially Mg / Ag alloys), semiconductor alloys, etc.
  • the material used for the electrode facing the light is a material which is at least partially transparent to the incident light.
  • these include, in particular, glass and transparent polymers, such as polyethylene terephthalate.
  • the electrical contacting is usually carried out by metal layers and / or transparent conductive oxides (TCOs). These include preferably ITO, doped ITO, FOB (fluorine doped tin oxide), AZO (aluminum doped tin oxide), ZnO, TiO 2, Ag, Au, Pt.
  • the light-facing electrode is made to be sufficiently thin to cause only minimal light absorption but thick enough to allow good charge transport of the extracted charge carriers.
  • the thickness of the layer is preferably in a range of 20 to 200 nm.
  • the material used for the electrode remote from the light is a material which at least partially reflects the incident light.
  • these include tallfilme, preferably from Ag, Au, Al, Ca, Mg, In and mixtures thereof.
  • the thickness of the layer is preferably in a range of 50 to 300 nm.
  • the photoactive region comprises or consists of at least one layer which comprises at least one substituted periflanthene of the general formula (I) as defined above.
  • the photoactive region may have one or more others
  • EBLs holes blocking layers
  • the solar cells according to the invention comprise at least one photoactive donor-acceptor heterojunction (donor-acceptor heterojunction).
  • donor-acceptor heterojunction By excitation of an organic material excitons are generated. For a photocurrent to occur, the electron-hole pair must be separated, usually at a donor-acceptor interface between two dissimilar contact materials. At such an interface, the donor material forms a heterojunction with an acceptor material. If the charges are not separated, they can recombine in a process called "quenching,” either radiantly by the emission of light of lower energy than that radiated in, or non-radiant by the generation of heat. Both processes are undesirable.
  • At least one substituted periflanthene of the general formula (I) can be used as a charge generator (donor) or as a hole conductor (HTM).
  • a charge generator donor
  • HTM hole conductor
  • ETM electron acceptor material
  • a rapid electron transfer to the ETM occurs after the radiation excitation.
  • ETMs are z. C60, C70 and other fullerenes, perylene-3,4, 9,10-bis (dicarboximides) (PTCDIs), etc. (as described below).
  • the heterojunction is flat (see: Two layer organic photovoltaic cell, CW Tang, Appl. Phys. Lett, 48 (2), 183-185 (1986) or N. Karl, A. Bauer, J. Holzäpfel, J. Tanner, M. Möbus, F. Stölzle, Mol. Cryst. Liq.
  • the heterojunction is carried out as a bulk heterojunction, also known as an interpenetrating donor-acceptor network. records.
  • Organic photovoltaic cells with a bulk heterojunction are e.g. By CJ Brabec, NS Sariciftci, JC Hummelen in Adv. Funct. Mater., 11 (1), 15 (2001) or by J. Xue, BP Rand, S. Uchida and SR Forrest in J. Appl. Phys. 98, 124903 (2005).
  • Buk heterojunctions are discussed in detail below.
  • the compounds of the formula (I) can be used as photoactive material in cells with MiM, pin, pn, mip or min structure
  • M metal
  • p p-doped organic or inorganic semiconductor
  • n n-doped organic or inorganic semiconductor
  • i intrinsically conductive system of organic layers, see, for example, J. Drechsel et al., Org. Electron., 5 (4), 175 (2004) or Maennig et al., Appl. Phys. 14 (2004)).
  • the compounds of the formula (I) can also be used as photoactive material in tandem cells. Suitable tandem cells are z. From P. Peumans, A. Yakimov, S.R. Forrest in J. Appl. Phys., 93 (7), 3693-3723 (2003) (see also US 4,461,922, US 6,198,091 and US 6,198,092) and will be described in detail below.
  • the compounds of the formula (I) can also be employed as photoactive material in tandem cells which are made up of two or more than two stacked MiM, pin, Mip or Min structures (see DE 103 13 232.5 and J. Drechsel et al. , Thin Solid Films, 451452, 515-517 (2004)).
  • the layer thickness of the M, n, i and p layers is usually in a range from 10 to 1000 nm, particularly preferably from 10 to 400 nm.
  • the layers forming the solar cell can be produced by customary methods known to the person skilled in the art. These include vapor deposition in a vacuum or in an inert gas atmosphere, laser ablation or solution or dispersion processing methods such as spin coating, knife coating, casting, spraying, dip coating or printing (eg inkjet, flexo, offset, engraving, gravure, nanoimprint ). In a specific embodiment, the entire solar cell is produced by a vapor deposition process.
  • a substituted periflanthene of the general formula (I) and a complementary semiconductor material can be subjected to vapor deposition in the sense of cosublimation.
  • PVD processes are performed under high vacuum conditions and include the following steps: evaporation, transport, deposition.
  • the deposition is preferably carried out at a pressure in a range of about 10 " 2 mbar to 10" 7 mbar, z. From 10 ⁇ 5 to 10 ⁇ 7 mbar.
  • the deposition rate of the metal contacts is preferably in a range of 0.01 to 10 nm / sec.
  • the deposition may be carried out in an inert gas atmosphere, e.g. B. under nitrogen, helium or argon.
  • the temperature of the substrate during the deposition is preferably in a range from -100 to 300 ° C., more preferably from -50 to 250 ° C.
  • the photoactive layer (homogeneous layer or mixed layer) can be subjected to a thermal treatment directly after its production or after production of further layers forming the solar cell. Such a tempering can often improve the morphology of the photoactive layer.
  • the temperature is preferably in a range of about 60 ° C. to 300 ° C.
  • the treatment time is preferably in a range of 1 minute to 3 hours.
  • the photoactive layer (mixed layer) can be subjected to a treatment with a solvent-containing gas directly after its preparation or after the production of further layers forming the solar cell.
  • saturated solvent vapors are used in air at ambient temperature.
  • Suitable solvents are toluene, xylene, chloroform, N-methylpyrrolidone, dimethylformamide, ethyl acetate, chlorobenzene, dichloromethane and mixtures thereof.
  • the treatment time is preferably in a range of 1 minute to 3 hours.
  • the solar cells according to the invention are present as a single cell with a normal structure.
  • FIG. 1 shows a solar cell with a normal structure.
  • the cell has the following structure: an at least partially transparent conductive layer (anode) (11)
  • HTL hole transport layer
  • the donor material preferably comprises at least one compound of the formula (I) or consists of a compound of the formula (I).
  • the acceptor material preferably comprises at least one fullerene or fullerene derivative or consists of a fluorene or fullerene derivative.
  • the acceptor material comprises C60 or PCBM ([6,6] -phenyl-C61-butyric acid methyl ester).
  • the acceptor material preferably comprises C70 or [6,6] -phenyl-C71-butyrate, methyl ester.
  • solar cells comprising at least one compound of the formula (I) as donor material and at least one rylene as acceptor material.
  • the substantially transparent (ie translucent) conductive layer (11) (anode) comprises a support substrate, such as glass or a polymer (eg, polyethylene terephthalate), and a conductive material, as described above. These include z. ITO, doped ITO, FTO, ZnO, AZO, etc.
  • the anode material may be subjected to surface treatment, e.g.
  • the layer (11) should be sufficiently thin to allow maximum light absorption, but also thick enough to ensure good charge transport.
  • the layer thickness of the light-transmitting conductive layer (1 1) is preferably in a range of 20 to 200 nm.
  • the solar cell with a normal structure according to FIG. 1 optionally has a hole-conducting layer (HTL). This layer comprises at least one hole-conveying material (hole transport material, HTM).
  • Layer (12) may be a single layer of substantially homogeneous composition or may comprise two or more than two sublayers.
  • Hole-conductive materials (HTM) suitable for forming layers with hole-conducting properties (HTL) preferably comprise at least one material with high ionization energy.
  • the ionization energy is preferably at least 5.0 eV, more preferably at least 5.5 eV.
  • the materials may be organic or inorganic materials.
  • suitable organic materials are preferably selected from poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate) (PEDOT-PSS), Ir-DPBIC (Tris-N, N '-Diphenylbenzimidazol-2- yliden-iridium (III)), N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1, 1'-diphenyl-4,4'-diamine ( ⁇ -NPD), 2,2 ' , 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) -9,9'-spirobifluorene (spiro-MeOTAD), etc., and mixtures thereof.
  • the organic materials may be doped with a p-type dopant having a LUMO that is in the same range or lower than the HOMO of the hole-conductive material.
  • Suitable inorganic materials for use in a layer having hole-conducting properties are preferably selected from WO 3 , MoO 3 , etc. If present, the thickness of the layers with hole-conducting properties is preferably in a range of 5 to 200 nm, more preferably 10 to 100 nm.
  • Layer (13) comprises at least one compound of general formula (I).
  • the thickness of the layer should be sufficient to absorb as much light as possible, but thin enough to allow the charge to dissipate effectively.
  • the thickness of the layer (13) is preferably in a range from 5 nm to 1 .mu.m, particularly preferably from 5 to 80 nm.
  • Layer (14) comprises at least one acceptor material. Suitable and preferred acceptor materials are mentioned below.
  • the thickness of the layer should be sufficient to absorb as much light as possible, but thin enough to allow effective discharge of the charge.
  • the thickness of the layer (14) is preferably in a range from 5 nm to 1 .mu.m, particularly preferably from 5 to 80 nm.
  • the solar cell with a normal structure according to FIG. 1 optionally comprises an exciton-blocking and / or electron-conducting layer (EBL / ETL).
  • EBL / ETL exciton-blocking and / or electron-conducting layer
  • Suitable materials for exciton blocking layers typically have a larger bandgap than the materials of layer (13) and / or (14). On the one hand, they are able to reflect excitons and, on the other hand, enable good electron transport through the layer.
  • the layer (15) preferably contains at least one low LUMO material, e.g. B. of at most 3.5 eV.
  • the materials for the layer (15) may be organic or inorganic materials.
  • Suitable organic materials are preferably selected from the aforementioned fullerenes and fullerene derivatives, 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline (BCP), 4,7-diphenyl-1, 10-phenanthroline (Bphen), 1, 3-bis [2- (2,2-bipyridin-6-yl) -1, 3,4-oxadiazo-5-yl] benzene (BPY-OXD), etc.
  • the organic materials may, if desired, be combined with an Dopant doped having a HOMO, which is in the same range or lower than the LUMO of the electron-conducting material. Suitable dopants are z.
  • Suitable inorganic materials for use in a layer having electron-conducting properties are preferably selected from ZnO, etc.
  • the thickness of the layers having electron-conducting properties is preferably in a range of 5 to 500 nm, more preferably 10 to 100 nm.
  • Layer 16 is the cathode and preferably comprises at least one compound having a low work function, more preferably a metal such as Ag, Al, Mg, Ca, etc.
  • the thickness of the layer (16) is preferably in a range of about 10 nm to 10 ⁇ m , z. B. 10 nm to 60 nm.
  • the solar cells according to the invention are present as a single cell with inverse structure.
  • FIG. 2 shows a solar cell with inverse structure.
  • the cell has the following structure: an at least partially transparent conductive layer (cathode) (1 1)
  • HTL hole transport layer
  • the solar cells according to the invention are present as a single cell with a normal structure and have a bulk heterojunction.
  • FIG. 3 shows a solar cell with bulk heterojunction.
  • the cell has the following structure: an at least partially transparent conductive layer (anode) (21) a hole transport layer (HTL) (22)
  • a mixed layer comprising a donor material and an acceptor material which form a donor-acceptor heterojunction in the form of a bulk heterojunction (23)
  • the layer (23) comprises at least one substituted periflanthene of the general formula (I) as a photoactive material, especially as a donor material.
  • the layer (23) furthermore preferably has at least one fullerene or fullerene derivative as acceptor material.
  • the layer (23) has, in particular, C60 or PCBM ([6,6] -phenyl C61-butter acid methyl ester) as acceptor material.
  • organic solar cells wherein the layer (23) at least one substituted periflanthene of the general formula (I) as donor material and at least one rylene, preferably 1, 6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboximide having as acceptor material.
  • Layer (23) is a mixed layer comprising at least one compound of the general formula (I) as a donor material. Furthermore, layer (23) has at least one acceptor material.
  • the preparation of the layer (23) can be carried out as previously described by co-evaporation or by solution processing using conventional solvents.
  • the mixed layer preferably has from 10 to 90% by weight, particularly preferably from 20 to 80% by weight, of at least one compound of the general formula (I), based on the total weight of the mixed layer.
  • the mixed layer preferably has from 10 to 90% by weight, particularly preferably from 20 to 80% by weight, of at least one acceptor material, based on the total weight of the mixed layer.
  • the thickness of the layer (23) should be sufficient to absorb the highest possible amount of light, but thin enough to allow effective discharge of the charge.
  • the thickness of the layer (23) is preferably in a range from 5 nm to 1 .mu.m, particularly preferably from 5 to 200 nm, in particular from 5 to 80 nm.
  • the solar cell with bulk heterojunction according to FIG. 3 comprises an electron-conducting layer (24) (ETL).
  • This layer contains at least one electron transport material (ETM).
  • Layer (24) may be a single layer of substantially homogeneous composition or may comprise two or more than two sublayers.
  • Suitable materials for electron-conducting layers generally have a low work function or ionization energy. The ionization energy is preferably at most 3.5 eV.
  • Suitable organic materials are preferably selected from the aforementioned fullerenes and fullerene derivatives,
  • the organic materials may, if desired, be doped with an n-type dopant having a HOMO in the same range or lower than the LUMO of the electron-conducting material. Suitable dopants are z. CS2CO3, pyronine B (PyB), rhodamine B, cobaltocenes, etc.
  • the thickness of the layer (23), if present, is preferably in a range of 1 nm to 1 ⁇ m, especially 5 to 60 nm.
  • the solar cell with donor-acceptor heterojunction in the form of a bulk heterojunction can be prepared by a vapor deposition method as described above become.
  • deposition rates, substrate temperature during deposition, and thermal aftertreatment reference is made to the foregoing.
  • the solar cells according to the invention are present as a single cell with inverse structure and have a bulk heterojunction.
  • FIG. 4 shows a solar cell with bulk heterojunction and inverse structure.
  • the solar cell according to the invention is a tandem cell.
  • a tandem cell consists of two or more than two (eg, 3, 4, 5, etc.) subcells.
  • a single subcell, a subset of cells or all subcells may have photoactive donor-acceptor heterojunctions.
  • Each donor-acceptor heterojunction can be in the form of a flat heterojunction or in the form of a bulk heterojunction.
  • at least one of the donor-acceptor heterojunctions is in the form of a bulk heterojunction.
  • the photoactive layer of at least one subcell has a substituted periflanthene of the general formula (I).
  • the photoactive layer of at least one subcell preferably comprises a substituted periflanthene of the general formula (I) and at least one fullerene or fullerene derivative.
  • the semiconductor mixture used in the photoactive layer of at least one subcell consists of a substituted periflanthene of the general formula (I) and C ⁇ o or [6,6] -phenyl-C61-butyrate.
  • the sub-cells forming the tandem cell may be connected in parallel or in series.
  • the sub-cells forming the tandem cell are connected in series.
  • an additional recombination layer is in each case located between the individual subcells.
  • the individual subcells have the same polarity, i. H. usually only cells with normal structure or only cells with inverse structure are combined with each other.
  • FIG. 5 shows the basic structure of a tandem cell according to the invention.
  • Layer 31 is a transparent conductive layer. Suitable materials are those previously mentioned for the individual cells.
  • Layers 32 and 34 represent sub-cells.
  • Sub-cell refers to a cell, as previously defined, without cathode and anode.
  • the sub-cells may, for. Example, either all have a substituted periflanthene of the general formula (I) used in the invention in the photoactive layer (preferably in combination with a fullerene or fullerene derivative, especially C60) or other combinations of semiconductor materials, eg. C60 with Zn phthalocyanine, C60 with oligothiophene (such as DCV5T).
  • individual sub-cells can also be used as dye-sensitized solar cells. Ie or polymer cell be formed.
  • a combination of materials is preferred, the different areas of the spectrum of the irradiated radiation, z. B. of natural sunlight exploit.
  • z. B. of natural sunlight exploits the different areas of the spectrum of the irradiated radiation, z. B. of natural sunlight exploit.
  • Zn phthalocyanine C ⁇ O cells absorb in the range of 600 nm to 800 nm.
  • a tandem cell from a combination of these subcells should have radiation in the range of 400 nm to 800 nm absorb.
  • the optical interference should be considered.
  • sub-cells that absorb at shorter wavelengths should be located closer to the metal top contact than sub-cells with longer-wavelength absorption.
  • Layer 33 is a recombination layer. Recombination layers make it possible to recombine the charge carriers from a subcell with those of an adjacent subcell. Suitable are small metal clusters, such as Ag, Au or combinations of highly n- and p-doped layers. In the case of metal clusters, the layer thickness is preferably in a range of 0.5 to 5 nm. In the case of highly n- and p-doped layers, the layer thickness is preferably in a range of 5 to 40 nm.
  • the recombination layer usually connects the Electron-conducting layer of a subcell with the hole-conducting layer of an adjacent subcell. In this way, additional cells can be combined into a tandem cell.
  • Layer 36 is the top electrode.
  • the material depends on the polarity of the sub-cells. For normal structure subcells, low work function metals such as Ag, Al, Mg, Ca, etc. are preferably used. For inverse structure subcells, high workfunction metals, such as Au or Pt, or PEDOT-PSS are preferably used.
  • the total voltage corresponds to the sum of the individual voltages of all subcells.
  • the total current is limited by the lowest current of a subcell.
  • the thickness of each subcell should be optimized so that all subcells have substantially the same current intensity.
  • donor-acceptor heterojunctions are a donor-acceptor bilayer with a flat heterojunction or the heterojunction is a hybrid planar-mixed heterojunction or gradient bulk heterojunction ) or thermally treated bulk heterojunction.
  • the donor-acceptor heterojunction is in the form of a gradient bulk heterojunction.
  • the donor / acceptor ratio gradually changes.
  • the shape of the gradient may be stepwise ( Figure 6 (a)) or linear ( Figure 6 (b)).
  • layer 01 consists of 100% donor material
  • layer 02 has a donor / acceptor ratio> 1
  • layer 04 has a donor / Acceptor ratio ⁇ 1
  • layer 05 is 100% acceptor material.
  • layer 01 is 100% donor material
  • layer 02 has a decreasing donor / acceptor ratio, i. H. the proportion of donor material decreases linearly in the direction of layer 03
  • layer 03 consists of 100% acceptor material.
  • the various donor-acceptor ratios can be controlled by the deposition rate of each material. Such structures can promote the percolation pathway for charges.
  • the donor-acceptor heterojunction is performed as a thermally-treated bulk heterojunction, see e.g. Nature 425, 158-162, 2003.
  • the method of making such a solar cell comprises an annealing step or annealing step before or after metal deposition. Annealing may cause donor and acceptor materials to separate, resulting in more extensive percolation paths.
  • the organic solar cells are produced by organic vapor deposition with either a planar or a controlled heterojunction architecture. Solar cells of this type are described in Materials, 4, 2005, 37.
  • At least one substituted periflanthene of the general formula (I) is used as the sole electron donor material.
  • the following semiconductor materials are in principle suitable as acceptors for use in the solar cells according to the invention:
  • Fullerenes and fullerene derivatives preferably selected from C ⁇ o, C70, Cs 4 , phenyl-C ⁇ i-butyrate ([6O] PCBM), phenyl-C71But.yrsauremethylest.er
  • Phthalocyanines z. B. are suitable as acceptors due to their substituents. These include Hexadecachlorphthalocyanine and Hexadecafluorphthalocyanine, such as Hexadecachlorkupferphthalocyanin, Hexadeca ⁇ chloro zinc phthalocyanine, metal-free Hexadecachlorphthalocyanin, Hexadecafluonkupferphthalocyanin, Hexadecafluorophthalocyanin or metal-free Hexadefluonphthalocyanin.
  • Hexadecachlorphthalocyanine and Hexadecafluorphthalocyanine such as Hexadecachlorkupferphthalocyanin, Hexadeca ⁇ chloro zinc phthalocyanine, metal-free Hexadecachlorphthalocyanin, Hexadecafluonkupferphthalocyanin, Hexadecafluorophthalocyanin or metal-free Hexadefluonphthalocyanin.
  • Y 1 is O or NR a , where R a is hydrogen or an organyl radical,
  • Y 2 is O or NR b , where R b is hydrogen or an organyl radical, Z 1 , Z 2 , Z 3 and Z 4 are O, wherein in the case where Y 1 is NR a , one of the Radicals Z 1 and Z 2 may represent NR C , wherein the radicals R a and R c together represent a bridging group having 2 to 5 atoms between the flanking bonds, and in the case where Y 2 is NR b , one of the radicals Z 3 and Z 4 can also be NR d , where the radicals R b and R d together represent a bridging group having 2 to 5 atoms between the flanking bonds.
  • Suitable rylenes are z. In WO2007 / 074137, WO2007 / 093643 and
  • Phthalocyanines which are non-halogenated or halogenated. These include phthalocyanines containing metal-free or divalent metals or metal atom-containing groups, in particular those of titanyloxy, vanadyloxy, iron, copper, zinc, etc. Suitable phthalocyanines are in particular copper phthalocyanine, zinc phthalocyanine and metal-free phthalocyanine. In a special embodiment, a halogenated phthalocyanine is used. These include: 2,6,10,14-Tetrafluorphthalocyanine, z. B. 2,6,10,14-Tetrafluorkupferphthalocyanin and
  • 2,3,6,7,10,1,14,15-octafluorophthalocyanine e.g. 2,3,6,7,10,1,1,15,15-octafluoro-copper phthalocyanine and 2,3,6,7,10,11,14,15-octafluoro zinc phthalocyanine;
  • Porphyrins such as.
  • tetrabenzoprophyrins are preferred, which, like the compounds of the formula (I) used according to the invention, are processed from solution as soluble precursors and converted onto the substrate by thermolysis into the pigmentary photoactive component.
  • Acenes such as anthracene, tetracene, pentacene, which may each be unsubstituted or substituted.
  • Substituted acenes preferably comprise at least one substituent selected from electron-donating substituents (eg, alkyl, alkoxy, ester, carboxylate, or thioalkoxy), electron-withdrawing substituents (eg, halogen, nitro, or cyano) and combinations thereof.
  • Liquid-crystalline (LC) materials for example coronene, such as hexabenzocoronene (HBC-PhCl 2), coronodiimide, or triphenylenes, such as 2,3,6,7,10,1-hexahexylthio-biphenylene (HTT 6 ), 2,3, 6,7,10,1 1-hexakis (4-n-nonylophenyl) -triphenylene (PTP 9 ) or 2,3,6,7,10,1-hexakis (undecyloxy) -triphenylene (HATn); Particularly preferred are liquid crystalline materials that are discotic.
  • coronene such as hexabenzocoronene (HBC-PhCl 2)
  • coronodiimide or triphenylenes, such as 2,3,6,7,10,1-hexahexylthio-biphenylene (HTT 6 ), 2,3, 6,7,10,1 1-hex
  • oligothiophenes are quaterthiophenes, quinquethiophenes, sexithiophenes,
  • ⁇ , ⁇ -di (C 1 -C 8) -alkyloligothiophenes such as ⁇ , ⁇ -dihexyl quaterthiophenes
  • alkylthiophenes such as poly (3-hexylthiophene), bis (dithienothiophenes), anthradithiophenes and dialkylanthra-dithiophenes, such as dihexylanthradithiophene, phenylene-thiophene (PT) oligomers and derivatives thereof, especially ⁇ , ⁇ -alkyl-substituted phenylene-thiophene oligomers.
  • DCV5T 2,2-dicyanovinyl quinquimethiophene
  • POPT 3- (4-octylphenyl) -2,2'-bithiophene
  • Paraphenylenevinylene and paraphenylenevinylene-containing oligomers or polymers such as.
  • Phenyleneethynylene / phenylenevinylene hybrid polymers (PPE-PPV).
  • Polyfluorene and alternating polyfluorene copolymers such as.
  • polyfluorene and alternating polyfluorene copolymers such as.
  • polyfluorene-co-benzothio-diazole F 8 BT
  • poly (9,9'-dioctylfluorene-co-bis-N, N '- (4-butyl-phenyl) -bis-N, N'-phenyl-1,4-phenylenediamine PFB
  • Polyanilines d. H. Aniline-containing oligomers and polymers. Triarylamines, polytriarylamines, polycyclopentadienes, polypyrroles, polyfurans, polysilanes, polyphospholes, TPD, CBP, spiro-MeOTAD.
  • the semiconductor mixture used in the photoactive layer consists of at least one substituted periflanthene of the general formula (I) and C ⁇ o.
  • the semiconductor mixture used in the photoactive layer consists of at least one substituted periflanthene of the general formula (I) and C70.
  • the semiconductor mixture used in the photoactive layer consists of at least one substituted periflanthene of the general formula (I) and [6,6] -phenyl C61-butyrate.
  • the semiconductor mixture used in the photoactive layer consists of at least one substituted periflanthene of the general formula (I) and [6,6] -phenyl C71-butyrate.
  • ITO was sputtered onto the glass substrate to a thickness of 100 nm.
  • the specific resistance was 200 ⁇ cm and the root mean squared roughness (RRMS) was less than 5 nm.
  • the substrate was treated with ozone for 20 minutes under ultraviolet light before the deposition of the further layers (UV ozone cleavage). ning). Production of the cells:
  • Bilayer cells were ( ⁇ 10 "6 mbar pressure) produced (cells of the two-layer structure) and bulk heterojunction cells (BHJ ZeIIe) under high vacuum.
  • the bilayer cell was prepared by sequential deposition of the compound of Example 1 and C 6 o on the ITO substrate. The deposition rate was 0.1 nm / second for both layers. The evaporation temperatures of the conjunction of Example 1 was between 330 0 C and 485 0 C. C was o 6 at 410 0 C deposited. After the Bphen layer (layer thickness 6 nm) had been applied, finally a 100 nm thick Ag layer was vapor-deposited as a top electrode. The cell had an area of 0.04 cm 2 .
  • Bilayer cell ITO / MoOs / compound from Example 2 or 3 / Ceo / Bphen / Ag
  • the bilayer cell was prepared by sequential deposition of a compound of Example 2 or 3 and C 60 (layer thickness 40 nm) on MOO3-coated ITO substrate.
  • the deposition rate was 0.1 nm / s for both layers.
  • the evaporation temperature of the compound from Example 2 was 400 ° C. and that of the compound from Example 3 was 450 ° C.
  • BHJ cell (ITO / (compound from Example 1: C 6 o - 1: 1 by weight) / C 6 o / Bphen / Ag): To prepare the BHJ cell, the compound from Example 1 and the C ⁇ o were evaporated together and on the ITO with the same deposition rate of
  • BHJ cell bulk heterojunction cell
  • a compound from Example 2 or Example 3 and C ⁇ o was evaporated together.
  • the deposition of the Bphen and Ag layer was carried out as described for the bilayer cell.
  • the layer thicknesses were 6 nm for BPhen and 100 nm for Ag.
  • the solar simulator used was an AM 1.5 simulator from Solar Light Co. Inc. with xenon lamp (model 16S-150 V3). The UV range below 415 nm was filtered and the current-voltage measurements were taken at ambient conditions. The intensity of the solar simulator was calibrated with a monocrystalline FZ solar cell (Fraunhofer ISE) and the deviation factor was determined to be approximately 1.0.
  • the solar simulator used was an AM 1.5 simulator from Solar Light Co. Inc. with xenon lamp (model 16S-150 V3). The UV region below 380 nm was filtered and the current-voltage measurements were taken at ambient conditions. The intensity of the solar simulator was calibrated with a monocrystalline FZ solar cell (Fraunhofer ISE) and the deviation factor was determined to be approximately 1.0.

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Abstract

La présente invention concerne une pile solaire organique présentant une zone photo-active qui présente au moins une substance organique donneuse (13) en contact avec au moins une substance organique acceptrice (14), la substance donneuse et la substance acceptrice formant une hétéro-transition donneur-accepteur et la zone photo-active présentant au moins un périflanthène substitué.
PCT/EP2010/059453 2009-07-03 2010-07-02 Utilisation de périflanthènes substitués dans des piles solaires organiques Ceased WO2011000939A1 (fr)

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