EP2329539A1 - Utilisation du dibenzotetraphenylperiflanthene dans des cellules solaires organiques - Google Patents

Utilisation du dibenzotetraphenylperiflanthene dans des cellules solaires organiques

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Publication number
EP2329539A1
EP2329539A1 EP09783163A EP09783163A EP2329539A1 EP 2329539 A1 EP2329539 A1 EP 2329539A1 EP 09783163 A EP09783163 A EP 09783163A EP 09783163 A EP09783163 A EP 09783163A EP 2329539 A1 EP2329539 A1 EP 2329539A1
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European Patent Office
Prior art keywords
layer
electron
cell
organic solar
donor
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EP09783163A
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German (de)
English (en)
Inventor
Martin KÖNEMANN
Jae Hyung Hwang
Gabriele Mattern
Christian DÖRR
Peter Erk
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BASF SE
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BASF SE
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Priority to EP09783163A priority Critical patent/EP2329539A1/fr
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K99/00—Subject matter not provided for in other groups of this subclass
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the use of dibenzoetraphenylperiflanthene as electron donor material in an organic solar cell.
  • Photovoltaic means the direct conversion of radiant energy, mainly solar energy, into electrical energy.
  • the voltage at idle ie when the current is zero, is highest. The more current that is drawn, the lower the voltage and reaches the value 0 in the short circuit.
  • the solar cell does not emit any power either in idle or short circuit. Between idle and short circuit exists a point on the characteristic curve (current as a function of voltage) of the solar cell, in which the output power is maximum (mpp, maximum power point).
  • Organic solar cells consist of a sequence of thin layers, which typically have a thickness between 1 nm to 1 ⁇ m, and which consist at least partly of organic materials, which are preferably vapor-deposited in vacuo or from a solution. to be brought.
  • the electrical contacting is usually carried out by metal layers and / or transparent conductive oxides (TCOs).
  • organic solar cells In contrast to inorganic solar cells, organic solar cells do not directly generate free charge carriers by the light, but excitons are initially formed, ie. 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 based on the exciton separation at photoactive interfaces
  • organic donor-acceptor interfaces or inorganic semiconductor interfaces This requires that excitons generated in the bulk of the organic material can diffuse to this photoactive interface.
  • One of the contact metals used has a large and the other a small work function, so that with the organic layer, a Schottky barrier is formed.
  • a layer contains two or more types of organic pigments that have different spectral characteristics.
  • BHJ bulk heterojunction
  • 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 cells.
  • Dibenzotetraphenylperiflanthen is also mentioned here. However, this document does not teach the use of this compound to prepare an organic solar cell with photoactive 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.
  • dibenzotetraphenylperiflanthene are particularly advantageously suitable as electron donor material for the production of organic solar cells with photoactive donor-acceptor transitions in the form of a bulk heterojunction.
  • a first subject of the invention is therefore the use of Dibenzotetraphenylperiflanthen (DBP) of the formula
  • Another object of the invention is an organic solar cell comprising at least one photoactive donor-acceptor transition in the form of a bulk heterojunction, wherein Dibenzotetraphenylperiflanthen is used as electron donor material.
  • FIG. 1 shows a solar cell with a normal structure which is suitable for the use of dibenzoetraphenylperiflanthene.
  • FIG. 2 shows a solar cell with inverse structure.
  • FIG. 3 shows the structure of a tandem cell.
  • Figure 4 shows a bulk heterojunction with large donor-acceptor interface and uninterrupted transport paths to the electrodes.
  • Organic solar cells are generally layered and typically include at least the following layers: anode, photoactive layer and cathode. It is an essential feature of the invention that the organic solar cell has a mixed layer containing dibenzotetraphenylperiflanthene as electron donor material and at least one electron acceptor material. According to the invention, the mixed layer has donor-acceptor transitions in the form of a bulk heterojunction.
  • Dibenzotetraphenylperiflanthene is prepared by standard methods known to those skilled in the art (e.g., J.D. Debad, J.C. Morris, V. Lynch, P. Magnus and A.J. Bard J. Am. Chem. Soc., 1996, 118, pp. 2374-2379).
  • the dibenzotetraphenylperiflanthene Prior to use in an organic solar cell, the dibenzotetraphenylperiflanthene may 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.
  • 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 example 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.
  • chromatography it is also possible to use a gradient of at least two different solvents, for example 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 dibenzotrapraphenylperiflanthene.
  • 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. Preferred is e.g. a so-called three-zone inflating device. Another method and apparatus for fractional sublimation is described in US 4,036,594.
  • An organic solar cell according to the invention usually comprises a substrate.
  • the substrate is often coated with a transparent, conductive layer as an electrode.
  • Suitable substrates for organic solar cells are z.
  • Oxidic materials such as glass, ceramics, SiO 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.
  • Electrodes are in principle metals (preferably the
  • Groups 2, 8, 9, 10, 11 or 13 of the Periodic Table e.g. Pt, Au, Ag, Cu, Al, In, Mg, Ca
  • semiconductors e.g, doped Si, doped Ge, indium tin oxide (ITO), fluorinated tin oxide (FTO), gallium indium).
  • Tin oxide GITO
  • zinc indium tin oxide ZITO
  • metal alloys eg based on Pt, Au, Ag, Cu, etc., especially Mg / Ag alloys
  • semiconductor alloys e.g. Pt, Au, Ag, Cu, Al, In, Mg, Ca
  • 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 contact is usually done by metal layers and / or transparent conductive oxides (TCOs). This preferably includes ITO, FTO, ZnO, TiO 2 , Ag, Au, Pt.
  • the light-facing layer 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 metal films, preferably of 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 layer comprises dibenzotetraphenylperiflanthene as electron donor material (p-type semiconductor).
  • dibenzotetraphenyl periflanthene is used as the sole electron donor material.
  • the photoactive layer is configured as a mixed layer and, in addition to DBP, comprises at least one electron acceptor material (n-type semiconductor).
  • Fullerenes and fullerene derivatives preferably selected from C ⁇ o, C70, Cs 4, phenyl C ⁇ i-Butyrklaremethylester ([6O] PCBM), phenyl-C7i-Butyrklaremethylester ([7I] PCBM), phenyl-C 8 4-Butyrklamethylester ([84JPCBM) Phenyl ceric butyrylbutyl ester ([6O] PCBB), phenyl C 6- i-butyryl octoyl ester ([6O] PCBO), methyl thiocyanate ([6O] ThCBM) and mixtures thereof. Especially preferred are C ⁇ o, [6O] PCBM and mixtures thereof.
  • Phthalocyanines e.g. are suitable as acceptors due to their substituents. These include hexadecachlorophthalocyanines and hexadecafluorophthalocyanines, such as hexadecachloro copper phthalocyanine, hexadecachlorozinc phthalocyanine, metal-free hexadecachlorophthalocyanine, hexadecafluoro copper phthalocyanine, hexadecafluoro zinc phthalocyanine or metal-free hexadecafluorophthalocyanine.
  • hexadecachlorophthalocyanines and hexadecafluorophthalocyanines such as hexadecachloro copper phthalocyanine, hexadecachlorozinc phthalocyanine, metal-free hexadecachlorophthalocyanine, hexadecafluoro copper phthalocyanine, hex
  • 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
  • one of the radicals Z 1 and Z 2 may also 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 stand, and
  • one of the radicals Z 3 and Z 4 may also represent NR d , where the radicals R b and R d together represent a bridging group having 2 to 5 atoms between the flanking bonds stand. Suitable rylenes are z.
  • WO2007 / 074137, WO2007 / 093643 and WO2007 / 1 16001 PCT / EP2007 / 053330, to which reference is hereby made.
  • donor semiconductor materials e.g. in a tandem cell, as described below, can be used in a further subcell instead of DBP:
  • Phthalocyanines which are non-halogenated or halogenated include metal-free or divalent metals or phthalocyanines containing metal atom-containing groups, in particular those of titanyloxy, vanadyloxy, iron, copper, zinc, chloroaluminum etc.
  • Suitable phthalocyanines are in particular copper phthalocyanine, zinc phthalocyanine, chloroaluminum phthalocyanine and metal-free phthalocyanine.
  • a halogenated phthalocyanine is used. These include:
  • 2,6,10,14-tetrafluorophthalocyanines e.g. Chloroaluminum-2,6,10,14-tetrafluorophthalocyanine, 2,6,10,14-tetrafluoro copper phthalocyanine and 2,6,10,14-
  • Tetrafluorzinkphthalocyanin 1, 5,9,13-Tetrafluorphthalocyanine, z. Chloroaluminum-1, 5,9,13-tetrafluorophthalocyanine, 1,5,9,13-tetrafluoro copper phthalocyanines and 1,5,9,13-
  • Porphyrins such as.
  • Tetrabenzoporphyrins which, like the compound dibenzotetraphenylpran- flanthene used in accordance with the invention, are processed as soluble precursors from solution and are converted on 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.
  • electron-donating substituents eg, alkyl, alkoxy, ester, carboxylate or thioalkoxy
  • electron-withdrawing substituents eg, halogen, nitro, or cyano
  • substituents eg, halogen, nitro, or cyano
  • Suitable substituted Pentacenes are described in US 2003/0100779 and US 6,864,396, which is incorporated herein by reference.
  • a preferred acen is rubrene.
  • Liquid-crystalline (LC) materials for example coronene, such as hexabenzocoronene (HBC-PhCl 2), coronene diimides, or triphenylenes, such as 2,3,6,7,10,1-hexahexylthiouriphenylene (HTT ⁇ ), 2,3,6 , 7,10,1 1-hexakis (4-n-nonylphenyl) -triphenylene (PTPg) or 2,3,6,7,10,1-hexakis- (undecyloxy) -triphenylene (HATu).
  • coronene such as hexabenzocoronene (HBC-PhCl 2)
  • coronene diimides coronene diimides
  • triphenylenes such as 2,3,6,7,10,1-hexahexylthiouriphenylene (HTT ⁇ ), 2,3,6 , 7,10,1 1-hexakis (4-n-nonyl
  • oligothiophenes are quaterthiophenes, quinquethiophenes, sexithiophenes, ⁇ , ⁇ -di (Ci-C8) -alkyloligothiophenes, such as ⁇ , ⁇ -Dihexylquaterthiophene, ⁇ , ⁇ -Dihexylquinquethiophene and ⁇ , ⁇ -Dihexylsexithiophene, poly (alkylthiophene), such as poly (3 -hexylthiophene), bis (dithienothiophenes), anthradithiophenes and dialkylanthra- dithiophenes such as dihexylanthradithiophene, phenylene-thiophene (PT) -oligomers and derivatives thereof, especially ⁇ , ⁇ -alkyl-sub
  • DCV5T 3-bis (2,2-dicyanovinyl) quinquethiophen
  • PCPDTBT Poly [2,6- (4,4-bis (2-ethylhexyl) -4 H -cyclo-penta [2.1b; 3,4b '] -dithiophene) -4,7- (2,1,3 -benzothiadiazol).
  • 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
  • Triarylamines Polyanilines, ie aniline-containing oligomers and polymers. Triarylamines, polytriarylamines, polycyclopentadienes, polypyrroles, polyfurans, polysiols, polyphospholes, TPD, CBP, spiro-MeOTAD.
  • DBP and at least one fullerene or fullerene derivative are particularly preferably used in the organic solar cells according to the invention in the photoactive layer.
  • the semiconductor mixture used in the photoactive layer consists of DBP and C ⁇ o.
  • the content of Dibenzotetraphenylperiflanthen in the photoactive layer is preferably 10 to 90 wt .-%, particularly preferably 25 to 75 wt .-%, based on the total weight of the semiconductor material (p- and n-type semiconductor) in the photoactive layer.
  • the photoactive layer is made to be sufficiently thick to cause maximum light absorption but thin enough to efficiently extract the generated charge carriers.
  • the thickness of the layer is preferably in a range of 5 to 200 nm, more preferably 10 to 80 nm.
  • the organic solar cell may have one or more further layers.
  • Electron conductive layer ETL
  • exciton (and possibly hole) blocking layers EBL
  • Suitable layers with hole-conducting properties preferably comprise at least one material with a low ionization energy in relation to the vacuum level, ie the layer with hole-conducting properties has a lower ionization energy and a lower electron affinity, based on the vacuum level, than the layer with electron-conducting properties.
  • 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.
  • PEDOT-PSS poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate)
  • Ir DPBIC Tris-N, N '-Diphenylbenzimid
  • the organic materials may be doped with a p-type dopant which has a LUMO which is in the same range or lower than the HOMO of the hole-conducting material.
  • Suitable dopants are, for example, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ), WO 3, MoO 3, etc.
  • Suitable inorganic materials for use in a layer with hole-conducting properties preferably selected from WO3, Mo ⁇ 3, etc.
  • 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.
  • Suitable layers with electron-conducting properties preferably contain at least one material whose LUMO, based on the vacuum level, is higher in energy than the LUMO of the material with hole-conducting properties.
  • the materials may be organic or inorganic materials.
  • Suitable organic materials for use in a layer having electron-conducting properties 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.
  • organic materials may be doped with an n-type dopant having a HOMO that is in the same range or lower than the LUMO of the electron-conductive material.
  • Suitable dopants are e.g. CS2CO3, pyronin B (PyB), rhodamine B, cobaltocenes, etc.
  • Suitable inorganic materials for use in a layer having electron-conducting properties are preferably selected from ZnO, etc. Particularly preferably, the layer having electron-conducting properties contains C ⁇ o.
  • the thickness of the layers with electron-conducting properties is preferably in a range of 5 to 200 nm, particularly preferably 10 to 100 nm.
  • Suitable excitons and holes blocking layers are for. As described in US 6,451, 415. Suitable materials for Excitonenblocker harshen are z. 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), polyethylene dioxythiophene (PEDOT), etc. It is preferred to use a material which at the same time is well suited for electron transport , Preferred are BCP, Bphen and BPY-OXD.
  • the thickness of the layers having exciton blocking properties is preferably in the range of 1 to 50 nm, more preferably 2 to 20 nm.
  • the heterojunction is embodied as a bulk heterojunction or interpenetrated donor-acceptor network (compare, for example, BCJ Brabec, NS Sariciftci, JC Hummelen, Adv. Funct. Mater., 11 (1), 15 (2001). .).
  • the solar cells according to the invention thus obtained surprisingly have advantageous properties compared with solar cells in which the heterojunction is flat (smooth).
  • For the construction of solar cells with flat heterojunctions for example, 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. Cryst., 252, 243-258 (1994).
  • the preparation of the photoactive donor-acceptor transitions in the form of a bulk heterojunction by a vapor deposition process (Physical Vapor Deposition, PVD).
  • PVD Physical Vapor Deposition
  • Suitable methods are e.g. in US 2005/0227406, to which reference is hereby made.
  • dibenzotetraphenylperiflanthen and at least one electron acceptor 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 the range of about 10 " 5 to 10" 7 mbar.
  • the deposition rate is preferably in a range of about 0.01 to 10 nm / sec.
  • the temperature of the substrate in the deposition is preferably in a range of about -100 to 300 ° C, more preferably -50 to 250 ° C.
  • the deposition can be carried out under an inert atmosphere, for. B. under nitrogen, argon or helium.
  • the production of the other, the solar cell-forming layers can be carried out by conventional methods known in the art. These include vapor deposition in a vacuum or inert gas atmosphere, laser ablation or solution or dispersion processing methods such as spin coating, doctoring, casting, spraying, dip coating or printing (eg inkjet, flexo, offset, gravure, gravure, nanoimprint).
  • vapor deposition in a vacuum or inert gas atmosphere laser ablation or solution or dispersion processing methods such as spin coating, doctoring, casting, spraying, dip coating or printing (eg inkjet, flexo, offset, gravure, gravure, nanoimprint).
  • laser ablation or solution or dispersion processing methods such as spin coating, doctoring, casting, spraying, dip coating or printing (eg inkjet, flexo, offset, gravure, gravure, nanoimprint).
  • dip coating or printing eg inkjet, flexo, offset, gravure, gravure, nanoimprint.
  • the production of the entire solar cell is preferably carried
  • the photoactive layer (mixed layer) can be subjected to a thermal treatment directly after its production or after the 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 it has been prepared or after the preparation of further layers forming the solar cell.
  • saturated solvent vapors are used in air at ambient temperature. Suitable solvents are toluene, xylene, chloroform, N-
  • Methyl pyrrolidone 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 can be present as a single cell with a normal structure.
  • such a cell has the following layer structure
  • first electrode front electrode, anode
  • hole-conducting layer a mixed layer of DBP and at least one electron acceptor in the form of a bulk heterojunction, electron-conducting layer, an exciton-blocking / electron-conducting layer
  • second electrode back electrode, Cathode
  • FIG. 1 shows a solar cell according to the invention with a normal structure.
  • the solar cells according to the invention can also be present as a single cell with inverse structure.
  • such a cell has the following layer structure
  • first electrode front electrode, cathode
  • exciton-blocking / electron-conducting layer electron-conducting layer
  • electron-conducting layer a mixed layer of DBP and at least one electron acceptor in the form of a bulk heterojunction
  • second electrode back electrode, Anode
  • FIG. 2 shows a solar cell according to the invention with inverse structure.
  • the solar cells according to the invention can also be configured as a tandem cell.
  • the basic structure of tandem cell is described, for example, by P. Peumans, A. Yakimov, SR Forrest in J. Appl. Phys. 93 (7), 3693-3723 (2003) and US 4,461,922, US 6,198,091 and US 6,198,092.
  • a tandem cell consists of two or more than two (e.g., 3, 4, 5, etc.) sub-cells.
  • a single subcell, a subset of cells or all subcells may have photoactive donor-acceptor transitions in the form of a bulk heterojunction based on dibenzotetraphenylperiflanthene.
  • at least one of the sub-cells contains DBP and at least one fullerene or fullerene derivative.
  • the semiconductor mixture used in the photoactive layer of at least one subcell consists of DBP and C ⁇ o.
  • 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. usually only cells with normal structure or only cells with inverse structure are combined with each other.
  • FIG. 3 shows the basic structure of a tandem cell according to the invention.
  • Layer 21 is a transparent conductive layer. Suitable materials are those previously mentioned for the individual cells.
  • Layers 22 and 24 represent sub-cells.
  • Sub-cell refers to a cell, as previously defined, without cathode and anode.
  • the subcells may be e.g. either all have DBP-C60 bulk heterojunction or other combinations of semiconductor materials, e.g. B C60 with Zn phthalocyanine, C60 with oligothiophene (such as DCV5T).
  • individual sub-cells can also be designed as a dye-sensitized solar cell or polymer cell. In all cases, a combination of materials is preferred which cover different regions of the spectrum of incident radiation, e.g. of natural sunlight.
  • DBP-C60 mainly in the range of 400 nm to 600 nm.
  • Zn phthalocyanine C60 cells absorb mainly 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 nm absorb.
  • the used spectral range should expand.
  • 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.
  • tandem cell has at least one subcell in which the photoactive donor-acceptor transition is in the form of a flat heterojunction is present.
  • the aforementioned semiconductor materials can be used, which may additionally be doped. Suitable dopants are z. B. pyronin B and rhodamine derivatives.
  • Layer 23 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 0.5-5 nm. In the case of highly n- and p-doped layers, the layer thickness is preferably in a range of 5 - 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 26 is the top electrode.
  • the material depends on the polarity of the sub-cells.
  • low work function metals such as Ag, Al, Mg, Ca, etc. are preferably used.
  • 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. For this reason, the thickness of each subcell should be optimized so that all subcells have substantially the same current intensity.
  • the high purity crystalline fraction is subjected to three-zone sublimation to produce solar cells.
  • DBP was purified by Dreizonensublimation at 2-3 x10 "6 mbar, wherein the first zone 450 0 C was obtained. The sublimed at 250 ⁇ 50 0 C the product was used. From 821 mg loading was obtained after 48 hours of sublimation of 553 mg (67 %) sublimated product.
  • DBP purified by three-zone sublimation (once) as previously described.
  • C60 from Alfa Aesar, grade (purity + 99.92%, sublimed), used without further purification.
  • Bphen used by Alfa Aesar, without further purification.
  • ITO ITO was sputtered onto the glass substrate.
  • the thickness of the ITO film was 140 nm, the resistivity was 200 ⁇ cm, and the root mean square roughness (RMS roughness) was less than 5 nm.
  • the substrate was allowed to stand for 20 minutes before deposition of the organic material UV irradiation "ozonized" (UV ozone cleaning).
  • Bilayer cells bilayer cells
  • BHJ cells bulk heterojunction cells
  • high vacuum pressure ⁇ 10 " 6 mbar.
  • the donor-acceptor transition is flat (smooth), in contrast
  • the BuIk heterojunction cell there is an interpenetrated donor-acceptor network.
  • the bilayer cell (ITO / DBP / C60 / Bphen / Ag)
  • DBP and C60 were vapor-deposited successively on the ITO substrate.
  • the deposition rate for both layers was 0.2 nm / sec.
  • the deposition temperature was 410 0 C and 400 0 C.
  • Bphen and then 100 nm Ag was evaporated as a top contact.
  • the arrangement had an area of 0.03 cm 2 .
  • BHJ cell ITO / DBP: C60 (1: 1) / C60 / Bphen / Ag
  • DBP and C60 were deposited on the ITO substrate by coevaporation at the same rate (0.1 nm / sec) that the DBP-C60 volume ratio in the mixed th layer was 1: 1.
  • the deposition of the Bphen and Ag layer was carried out as described for the bilayer cell.
  • the solar simulator used was an AM 1.5 simulator from Solar Light, USA, with a xenon lamp (Model 16S-150 V3).
  • the UV region below 415 nm was filtered and current-voltage measurements were made at ambient conditions.
  • the intensity of the solar simulator was calibrated with a monocrystalline FZ (float zone) silicon solar cell (Fraunhofer ISE). By calculation, the mismatch factor was approximately 1.0.

Abstract

La présente invention concerne l'utilisation de dibenzotétraphénylpériflanthène de formule (I) comme matériau donneur d'électrons dans une cellule solaire organique à transitions photoactives donneur-accepteur sous la forme d'une hétérojonction volumique.
EP09783163A 2008-09-19 2009-09-18 Utilisation du dibenzotetraphenylperiflanthene dans des cellules solaires organiques Withdrawn EP2329539A1 (fr)

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