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    公开号:ES2875962T9
    申请号:ES14786142T
    申请日:2014-09-26
    公开日:2022-01-21
    发明作者:Andre Weiss；Olga Gerdes；Dirk Hildebrandt；Roland Fitzner；Gunter Mattersteig；Daniel D'souza；Martin Pfeiffer；Peter Bäuerle；Amaresh Mishra；Hannelore Kast；Astrid Vogt；Christoph Wenzel；Christopher Steck；Popovic Dusko
    申请人:Universitat Ulm；Heliatek GmbH；ULM, University of；
    IPC主号:
    专利说明:

    [0001] Photoactive organic material for optoelectronic components
    [0002] Optoelectronic components are based on the optical and electronic properties of materials and currently have a wide application in everyday life, such as solar cells, LED's, TFT's. In general, these comprise all the products and procedures that enable the transformation of electronically generated data and energy into light emission, or light emissions into energy.
    [0003] Optoelectronic components that transform light emission into energy include photodiodes that are operated as photovoltaic installations or are used as photosensitive sensors or photometers in various products, such as digital cameras, CD players, photoelectric barriers.
    [0004] Optoelectronic components made of organic materials are mostly known for applications such as LEDs (OLEDs) and photovoltaic installations (OPVs). The organic materials used fulfill different tasks in these optoelectronic components, such as charge transport, light emission or light absorption. In this case, the organic materials in optoelectronic components can be polymers or reduced molecules, and processed in solution or emulsion by wet chemical processes, such as coating or printing, or in a vacuum, for example by sublimation, to give thin layers.
    [0005] A solar cell converts light energy into electrical energy. In this sense, the concept "photoactive" is understood as the transformation of light energy into electrical energy. In contrast to inorganic solar cells, in the case of organic solar cells free charge carriers are not generated directly by light, but excitons are formed first, i.e. electrically neutral excited states (electron-hole pairs). linked).
    [0006] Therefore, recombinant exciton diffusion and active interphase play a critical role in organic solar cells. Therefore, to contribute to the photoelectric current, in a good organic solar cell, the exciton diffusion length must exceed the typical penetration depth of the light so that the predominant part of the light can be used.
    [0007] If the absorbing layer is a mixed layer, only one of the components or even both take on the task of absorbing light. The advantage of mixed layers is that the generated excitons have only a short path to travel until they reach a domain boundary, where they separate. The transport of electrons, or holes, is carried out separately in the respective materials. Since the materials are in contact with each other everywhere in the mixed layer, it is decisive in this concept that the separate charges have a long lifetime in the respective material and that percolation paths for both types of charge-bearing are present from anywhere. for the respective contact.
    [0008] An important factor in the improvement of the solar cells mentioned above is the improvement of the organic layers. For absorbent layers, especially in the field of reduced molecules, few new materials have been disclosed in the last 5 years. Document WO2006092134A1 discloses compounds that have an acceptor-donor-acceptor structure, the donor block having an extended n-system.
    [0009] Thienothiophene derivatives which form an n-system with other aromatic compounds and are surrounded by alkyl groups on both sides and their use in organic semiconductors are disclosed in DE60205824T2.
    [0010] EP2400575A1 discloses a 5-membered heterocyclic ring donor with a size of at most 9 conjugated double bonds in an acceptor-donor-acceptor oligomer. Document EP2483267A1 describes as a donor block in the acceptor-donor-acceptor oligomer a combination of condensed 5- or 6-ring aromatic rings and individual 5- or 6-ring rings.
    [0011] WO2009051390 discloses thiophene-based acceptor-donor dyes for use in dye-sensitive solar cells.
    [0012] WO 002008145172A1 presents new phthalocyanines for use in solar cells. US7655809B2 discloses series condensed carbon ring compounds and their use as organic semiconductors.
    [0013] In WO2006111511A1 and WO2007116001A2 rylenetetracarboxylic acid derivatives for use as active layer in photovoltaics are disclosed.
    [0014] On the contrary, various polymers for use as active layers in organic photovoltaics are known, for example disclosed in documents WO 2008088595A2, EP2072557A1 or US20070112171A1. In general, these are not evaporable, but are processed in liquid form to give thin layers.
    [0015] A. Yassin et al. "Evaluation of bis-dicyanovinyl short-chain conjugated systems as donor materials for organic solar cells" Solar Energy Materials and Solar Cells, volume 95, no. 23-09-2010, pages 462-468, disclose an optoelectronic component with a photosensitive layer, the organic photosensitive layer containing a dithienopyrrole derivative.
    [0016] EP 2696351 A2 (publication date 02-12-2014) discloses an optoelectronic component with a photosensitive layer, the organic photosensitive layer referring to acceptor-donor-acceptor type compounds with a fully condensed donor central block.
    [0017] The invention is based on the task of overcoming the drawbacks of the state of the art and indicating improved photoactive components.
    [0018] The task is solved by independent claim 1. Embodiments of the invention can be found in the dependent claims.
    [0019] According to the invention, the task is solved by a photoactive component with an electrode and a counter electrode and at least one photosensitive organic layer between the electrode and the counter electrode, characterized in that the photosensitive organic layer contains a compound of the general formula I
    [0020] EWG-Vn-D-Vo-EWG (I)
    [0021] where EWG has electroattracting properties against D
    [0022] V, independently of each other, -CR1=CR2- or -C=C- with R1 and R2 selected from H, C1-C10 alkyl, OC1-C10 alkyl, SC1-C10 alkyl, where R1 and R2 may form a ring , yny
    [0023] or are 0 or 1 independently of each other, and
    [0024] D a donor block extended from at least 5 fused heterocyclic aromatic 5-membered rings and/or heterocyclic and homocyclic aromatic 6-membered rings, where a linear sequence of conjugated double bonds is present between both EWGs, provided that they are excluding the following structures:
    [0027] X1 to X5 being the same or different and being, independently of each other, CRr CR2', SiR3'R4', NR5', oxygen (O) or selenium (Se), R1' to R5' being the same or different and being, independently of each other yes, hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 20 aryl group, a substituted or unsubstituted C 3 to C 20 heteroaryl group, and combination of these.
    [0028] In the following application, by "fused" it is meant that 2 heterocyclic or homocyclic aromatic rings share two ring atoms.
    [0029] In one embodiment of the invention, the extended donor block of general Formula I is made up of heterocyclic aromatic 5-membered rings selected from thiophene, selenophene, furan or pyrrole.
    [0030] Preferably, at least one of the heterocyclic aromatic 5-membered rings of the extended donor block is not thiophene. More preferably, at least one of the heterocyclic aromatic 5-membered rings of the extended donor block is a pyrrole.
    [0031] In an embodiment of the invention, the extended D donor block of general Formula I is selected from
    [0035] where Y, in each occurrence independently of one another, is S or NR3, with R3 selected from C1-C10 alkyl, C5-C10 cycloalkyl, C6-C10 aryl.
    [0036] In one embodiment of the invention, the extended donor block D of general Formula I is selected from a maximum of 7 heterocyclic aromatic 5-membered rings and/or heterocyclic or homocyclic aromatic 6-membered rings.
    [0037] In one embodiment of the invention, in the extended donor block D of general Formula I there are 1 or 2 homocyclic aromatic 6-membered rings. In homocyclic aromatic 6-membered rings there are preferably two O-alkyls, which point in an opposite spatial direction.
    [0038] In one embodiment of the invention, at least one doped transport layer is present, which is arranged between the electrode or the counter electrode and at least one light-absorbing layer.
    [0039] An individual cell, a tandem cell or a multiple cell is also an object of the present invention. In the present application, tandem cell is understood as the fact that two functional cells are stacked one on top of the other and connected in series, it being possible for an intermediate layer to be arranged between the cells. Likewise, by a multiple cell is meant the fact that two or more functional cells are stacked one on top of the other and connected in series, it being possible for an intermediate layer to be arranged between the cells. The component preferably consists of nip, ni, ip, pnip, pni, pip, nipn, nin, ipn, pnipn, pnon or pipn structures, in which several independent combinations containing at least one layer i are stacked on top of one another. In this connection, n or p means an n or p doping which leads to an increase in the density of free electrons or holes in the thermal equilibrium state. In this sense, such layers should be understood primarily as transport layers. Instead, the name layer i denotes an undoped layer (intrinsic layer). In this case, one or more layer(s) i can consist of both one material and a mixture of two or more materials (so-called interpenetrating networks).
    [0040] In addition, the object of the present invention is an organic solar cell with a photoactive zone that has at least one organic donor material in contact with at least one organic acceptor material, the donor material and the acceptor material forming a donor-acceptor heterotransition and containing the photoactive zone at least one compound of Formula I, as defined above.
    [0041] According to a preferred embodiment of the present invention, the photoactive component is selected from an organic solar cell, an electroluminescence device, a photodetector, and an organic field effect transistor. The device is in particular an organic solar cell.
    [0042] In an embodiment of the invention, the photoactive component is a tandem solar cell with 2 donor-acceptor heterotransitions, at least one material of the first donor-acceptor heterotransition being different from both major components of the second donor-acceptor heterotransition.
    [0043] They are typical EWG electroattraction groups:
    [0048] with R1 = H, CN and R2 = H, CH3, CN,
    [0052] where D represents the point of attachment to the D-extended donor block and R a substituent selected from C1-C8-branched or straight chain alkyl.
    [0053] In one embodiment of the invention, V is a cyclohexene and my/uo is 1. The following compound is shown by way of example:
    [0056] Cyclohexene as a linking group between the donor block and the electrowithdrawing groups offers the advantage of easy production of pure cis-trans stereoisomeric compounds. In this case, other substituents on the hexene may be present on the hexane.
    [0058] In one embodiment of the invention, n and or are 0. Typical compounds are:
    [0059]
    [0061] In one embodiment of the invention, n and/or o are 1. They are typical compounds.
    [0063]
    [0066] The compounds of the formula I used according to the invention are distinguished by at least one of the following properties:
    [0067] Stannyl-free synthesis procedure
    [0068] High thermal stability
    [0069] Steep absorption edges, especially at the longer wavelength end
    [0070] Very high extinction coefficients
    [0071] The content of the compound of the formula I in the photoactive zone is preferably 10 to 90% by weight, particularly preferably 25 to 75% by weight, based on the total weight of the semiconductor material (p and n semiconductor) in the photoactive zone.
    [0073] The production of condensed D-donor blocks can be accomplished through a variety of procedures known in the literature. In this case, a chain construction of individual heterocycles or condensed smaller fragments and subsequent cyclization takes place.
    [0079] Hex Hox
    [0080] The introduction of terminal acceptor groups can be effected, for example, by methods known to those skilled in the art, such as Gattermann, Gattermann-Koch, Houben-Hoesch, Vilsmeier/Vilsmeier-Haack, Friedel-Crafts acylation or after lithiation by a reaction with an acid derivative or a carbonylation reagent.
    [0081] Other acceptor groups can be produced by refunctionalizing the carbonyl function C(O)R described above, for example by Knoevenagel condensation.
    [0085] The introduction of terminal acceptor groups can be carried out, for example, with BuLi and tetracyanoethylene (Cai et al, J. Phys. Chem. B 2006, 110, 14590).
    [0089] Alternatively, the reaction can also be performed without BuLi in DMF (Pappenfus et al, Org. Lett. 2008, 10, 8, 1553).
    [0090] Cyclohexenyl as terminal acceptor group can be effected, for example, by coupling reactions known in the literature (eg Stille, Suzuki, Negishi, ...).
    [0095] Compounds with different terminal acceptor groups can in principle be produced with the same methods.
    [0098] Compounds of Formula (I) where n and/or o are equal to 1 can be synthesized by reacting D with POCI3 and dimethylaminoacrolein. Alternatively, D can be deprotonated with base and subsequently reacted with dimethylaminoacrolein (Theng et al. Chem. Mater. 2007, 19, 432-442). The vinylaldehyde obtained in this way can be converted into a dicyanovinyl compound in a subsequent Knoevenagel reaction.
    [0100]
    [0103] Surprisingly, it was found that the compounds according to the invention have a very high quenching value. This can be justified not only with increasing number of multiple bonds in the molecule, as the following table shows.
    [0106] In this case, V-1 represents a comparative compound not according to the invention and 1 to 3 are compounds according to the invention of different length.
    [0111] In Figure 2 there is a comparison of the absorption spectra of Compounds 1 according to the invention, once with R = hexyl and once with R = propyl and 2 with R = hexyl compared to compound V-3 not corresponding to the invention with the same number of multiple bonds.
    [0114] The absorption spectrum is clearly more structured for the compounds according to the invention, as well as more closely shifted to the shorter wavelength range. This is a significant difference that makes it possible to arrive at an improved photoactive component, for example in a tandem or multiple cell, in combination with another photoactive material with absorption in the longer wavelength region.
    [0116] The production of a photoactive component according to the invention can be completely or partially produced by precipitation under vacuum with or without carrier gas, by printing, spinning, grafting, coating or other common techniques for processing dissolved or suspended materials into thin layers.
    [0118] In one embodiment of the invention, the production of the photoactive donor heterotransition is effected by gas phase precipitation. In this case, the compound of the general formula I and a suitable acceptor material, for example from the class of fullerenes, can be precipitated in the direction of co-sublimation as a mixed layer or as single layers successively as planar heterotransition . The precipitation is carried out in a high vacuum at a pressure in the range of about 10-2 to 10-8 mbar. The precipitation rate is usually in a range from about 0.01 to 10 nm/s.
    [0120] The temperature of the substrate in the precipitation is preferably 50 to 150°C.
    [0122] Suitable substrates for organic solar cells are, for example, oxidic materials, polymers, and combinations of these. Preferred oxidic materials are selected from glass, ceramic, SiO2, quartz, etc. Preferred polymers are selected from polyolefins (such as polyethylene and polypropylene), polyesters (such as polyethylene terephthalate and polyethylene naphthalate), fluorinated polymers, polyamides, polyurethanes, polyalkyl (meth)acrylates, polystyrenes, polyvinyl chlorides, and mixtures and compositions of these.
    [0124] In principle, metals, semiconductors, metal alloys, semiconductor alloys and combinations of these, so-called DMD's, but also silver nanotubes or special graphites are suitable as electrodes (cathode, anode). Preferred metals are those from groups 2, 9, 10, 11 or 13 of the periodic system (PES), for example the alkaline earth metals (group 2) Mg, Ca and Ba, from group 10 of the PES such as Pt, from group 11 of the PES as Au, Ag and Cu, and from PES group 13 as Al and In. Metal alloys, for example based on Pt, Au, Ag, Cu, etc., and special Mg/Ag alloys, but otherwise also alkali metal fluorides, such as LiF, NaF, KF, RbF and CsF, are preferred. and mixtures of alkali metal and alkali metal fluorides.
    [0126] Appropriate acceptor materials are preferably selected from the group fullerenes and fullerene derivatives, polycyclic aromatic hydrocarbons and their derivatives, especially naphthalene and its derivatives, rylenes, especially perylene, terrylene and quaterrylene and their derivatives, azenes, especially anthracene, tetracene, in particular rubrene, pentacene and its derivatives, pyrene and its derivative, quinones, quinondimethanes and their derivatives, phthalocyanines, subphthalocyanines and their derivatives, porphyrins, tetraazoporphyrins, tetrabenzoporphyrins and their derivatives, thiophenes, oligo-thiophenes, condensed/annelated thiophenes, such as thienothiophene and bitienothiophene and their derivatives, thiadiazoles and their derivatives, carbazoles and triarylamines and their derivatives, indanthrones, violantrones and flavantones and their derivatives, and fulvalenes, tetrathiafulvalenes and tetraselenfulvalenes and their derivatives.
    [0128] The acceptor material is preferably one or more fullerenes and/or fullerene derivatives. Appropriate fullerenes are preferably selected from C60, C70, C76, C80, C82, C84, C86, C90 and C94. Appropriate fullerene derivatives are preferably selected from methyl C61-phenyl butyrate ([60]PCBM), methyl C71-phenyl butyrate ([71]PCBM), methyl C84-phenyl butyrate ([84]PCBM) , butyl phenyl-C61-butyrate ([60]PCBB), octyl-phenyl-C61-butyrate ([60] p C b O), and methyl-thienyl-C61-butyrate ([60]ThCBM). C60, [60]PCBM and mixtures of these are particularly preferred.
    [0130] In addition to the donor-acceptor heterotransition layers, the photoactive component may contain other layers, which serve, for example, as transport layers and usually absorb incident light only at a wavelength below 450 nm, so-called wide-gap materials. Transport layers can have hole-conducting or electron-conducting properties and be undoped or doped.
    [0131] Suitable layers with hole-conducting properties preferably contain at least one material with a low ionization energy relative to the vacuum level, i.e. the layer with hole-conducting properties has a lower ionization energy and a lower electron affinity relative to the vacuum level. vacuum than the layer with electron-conducting properties. The materials can be organic or inorganic materials. Organic materials suitable for use in a layer with hole-conducting properties are preferably selected from poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS), Ir-DPBIC (tris-N,N'-diphenylbenzimidazole -2-ylidene-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-methoxyphenylamin)-9,9'-spirobifluorene
    [0132] (spiro-MeOTAD), 9,9-Bis (4- (N,N-bis-biphenyl-4-yl-amino)phenyl)-9H-fluorene (BPAF), N,N-diphenyl-N,N-bis (4-(N,N-bis(naphth-I-yl)-amino)-biphenyl-4-yl)-benzidine (DiNPB) etc. and mixtures of these.
    [0133] Suitable layers with electron conducting properties preferably contain at least one material whose LUMO relative to the vacuum level is more energetic than the LUMO of the material with hole conducting properties. The materials can be organic or inorganic materials. Materials suitable for use in a layer with electron conducting properties are preferably selected from fullerenes and fullerene derivatives as defined above, 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 Suitable fullerenes and fullerene derivatives are preferably selected from
    [0134] C60, C70, C84, methyl phenyl-C61-butyrate ([60]PCBM), methyl phenyl-C71-butyrate ([71]PCBM), methyl-phenyl-C84-butyrate ([84]PCBM), phenyl- C61-butyl butyrate ([60]PCBB), phenyl-C61-octyl butyrate ([60]PCBO), thienyl-C61-methyl butyrate ([60]ThCBM), and mixtures of these. C60, [60]PCBM and mixtures of these are particularly preferred. Very particularly preferably, the layer with electron-conducting properties contains C60.
    [0135] In another embodiment, the transport layer system p contains a donor p, this donor being p
    [0136] F4-TCNQ, a p-donor as described in DE10338406, DE10347856, DE10357044, DE102004010954, DE102006053320, DE102006054524 and DE102008051
    [0137] 737 or a transition metal oxide (VO, WO, MoO, etc.).
    [0138] In another embodiment, the n-transport layer system contains an n-donor, this n-donor being a TTF derivative (tetrathiafulvalene derivative) or a DTT derivative (dithienothiophene), an n-donor as described in DE10338406 , DE10347856, DE10357044, DE102004010954, DE102006053320, DE102006054524 and DE102008051
    [0139] 737 or Cs, Li or Mg.
    [0140] The invention is explained in more detail in some subsequent exemplary embodiments and corresponding figures, without being limited to these.
    [0141] show
    [0142] Figure 1 a component according to the invention. In this case, 1 represents the substrate, 2 an optional transport layer system consisting of one or more layers, 3 a stack of photoactive layers with at least one compound 5 according to the invention, another transport layer system consisting of one or more several layers and 6 a counter electrode,
    [0143] FIG. 2 a comparison of film absorption spectra of 3 compounds according to the invention with a compound not according to the invention,
    [0144] Figure 3 a curve
    [0146]
    [0148] 10.71 mmol of thienothiophene 7 are dissolved in 30 ml of chloroform and 32.14 mmol of bromine in 20 ml of chloroform are slowly added dropwise under ice-cooling. The reaction mixture is stirred for 16 h at room temperature. It is hydrolyzed with concentrated NaOH solution and the precipitate is dissolved in chloroform. The organic phase is separated and washed with water and saturated NaCl solution. The organic phase is dried over sodium sulfate and filtered. The solvent is distilled off and the residue is recrystallized from a mixture of n-hexane and chloroform. 9.42 mmol (88%) of product 8 are obtained as a colorless solid. GC-MS: m/z 378 (100%) (M+).
    [0149] Thienothiophene Monobromide 9:
    [0150] 5.5 mmol of tribromothienothiophene 8 are dissolved in 25 ml of hot acetic acid. 28.0 mmol of zinc dust are carefully added in portions and the mixture is heated under reflux for 1 h. After cooling to room temperature, 100 ml of water are added and the aqueous phase is extracted three times with diethyl ether. The combined organic phases are washed with saturated sodium carbonate solution until the aqueous phase is neutral. The organic phase is dried over sodium carbonate and filtered. The solvent is distilled off and the residue is purified by gas chromatography (SiO 2 , n-hexane, Rr = 0.50). 4.1 mmol (74%) of product 9 are obtained as a colorless solid. GC-MS: m/z 220 (100%) (M+).
    [0151] Thienothiophene Dimer 10:
    [0152] 6.76 mmol of monobromothienothiophene 9 are dissolved in 10 ml of anhydrous THF and cooled to -70°C. 4.13 ml of a 1.8 M LDA solution are added and the mixture is stirred at -70°C for 30 min. The reaction mixture is warmed to -30°C and 14.88 mmoles of CuCb are added. Stir for 1 h at -30°C and then allow the reaction mixture to warm to room temperature overnight. It is mixed with 2N HCl solution and extracted with dichloromethane (DCM). The organic phase is washed with water and NaCl solution and dried over sodium sulfate. It is filtered and the solvents are distilled off. The solvent is sublimed under high vacuum at 180°C. The sublimation product is recrystallized from chloroform/n-hexane and 1.40 mmol (41%) of product 10 are obtained as slightly yellow solid. GC-MS: m/z 436 (100%) (M+).
    [0153] Bis-thienothiophene-pyrrole 11:
    [0154] 0.69 mmol of thienothiophene dimer 10 are dissolved in 5 ml of toluene. 0.28 mmol of BINAP and 1.66 mmol of NaOtBu are added and the mixture is stirred for 30 min under an argon atmosphere. 0.14 mmol of Pd(dba) 2 and 0.79 mmol of hexylamine are added and the reaction mixture is heated for 3 days at 110°C. The reaction mixture is filtered through a short silica gel column (eluent: DCM/n-hexane (1:1)). The solvents of the filtrate are distilled off and the residue is purified by gas chromatography (SiO 2 , DCM/n-hexane (1:4), Rf = 0.55). 0.21 mmol (30%) of product 11 are obtained as a yellow solid. GC-MS: m/z 375 (100%) (M+).
    [0155] Dialdehyde 12:
    [0157] 3.31 mmol of POCh and 3.41 mmol of DMF are dissolved in 6 ml of 1,2-dichloroethane (DCE) and the mixture is stirred at room temperature for 2 h. This solution is added to a solution of 0.41 mmol of bis-thienothiophene-pyrrole 11 in 10 ml of DCE and stirred for 40 h at 80°C. The suspension formed is added to a 1N NaOH solution and DCM and methanol are added until the solid material has dissolved. This mixture is stirred for 1 h at room temperature and then 20 ml of saturated sodium carbonate solution are added. It is stirred for a further 1.5 h at room temperature and the phases are then separated. The aqueous phase is extracted three times with DCM and combined with the organic phase. The organic phase is dried over sodium sulfate and filtered. The solvents are distilled off and the residue is purified by chromatography (SiO 2 , DCM/acetone (80:1), Rf (DCM) = 0.64). 0.30 mmol (74%) of product 12 are obtained as a red solid. 1H-NMR (CDCh): 9.96 ppm (s, 2H), 7.97 (s, 2H), 4.40 (dd, 2H), 1.99 (m, 2H), 1.44 (m, 2H), 1.30 (m, 4H), 0.85 (t, 3H).
    [0159] Dicyanovinyl Compound 13:
    [0161] 0.30 mmol of dialdehyde 12 and 2.41 mmol of malodinitrile are dissolved in 40 ml of DCE. 0.03 mmol of piperidine are added and the mixture is heated under reflux for 24 h. The solvent is distilled off and refluxed with 20 ml of water for 2 h under reflux. Filter and wash with hot methanol. The residue is dried and recrystallized using a Soxhlet extractor from chlorobenzene. 0.12 mmol (39%) of product 13 are obtained as a black solid. 1H-NMR (TCE-d2, 375 K): 8.07 ppm (s, 2H), 7.84 (s, 2H), 4.53 (dd, 2H), 2.12 (m, 2H), 1 0.56 1.40 (m, 6H), 0.95 (t, 3H).
    [0163] Production of compound 2:
    [0168] Compound 14 was produced as described in the literature (Donaghey, Jenny E. et al, Journal of Materials Chemistry, 21(46), 18744-18752; 2011).
    [0170] Dialdehyde 15:
    [0172] 4.84 mmol of POCl3 and 4.99 mmol of DMF are dissolved in 9 ml of 1,2-dichloroethane (DCE) and the mixture is stirred at room temperature for 2 h. This solution is added to a solution of 0.6 mmol of bisthienopyrrolo-indole 14 in 15 ml of DCE and stirred at 80°C for 40 h. The suspension that forms is added to a 1N NaOH solution and DCM and methanol are added until the solid material dissolves. This mixture is stirred for 1 h at room temperature and then 20 ml of saturated sodium carbonate solution are added. It is stirred for a further 1.5 h at room temperature and the phases are then separated. The aqueous phase is extracted three times with DCM and combined with the organic phase. The organic phase is dried over sodium sulfate and filtered. Solvents are distilled and the residue is purified by chromatography (SIO 2 , DCM, Rf (DCM) = 0.39). 0.24 mmol (43%) of product 15 are obtained as a red solid. Dicyanovinyl Compound 16:
    [0173] 0.24 mmol of dialdehyde 15 and 1.95 mmol of malodinitrile are dissolved in 5 ml of DCE. 0.03 mmol of piperidine are added and the mixture is heated under reflux for 24 h. The solvent is distilled off and the residue is heated with 20 ml of water for 2 h under reflux. Filter and wash with hot methanol. The residue is dried and recrystallized using a Soxhlet extractor from toluene. 0.04 mmol (17%) of product 16 are obtained as a black solid. MALDI m/z, 588.4 [M].
    [0174] Embodiment example 3:
    [0175] Component with compound 1a
    [0176] In another exemplary embodiment, an MIP component is produced on a glass sample with ITO transparent cover contact by successive precipitation of the following sequence of layers in vacuo: 15 nm of C60, 20 nm of a 1:1 mixture by coprecipitation of compound 1a and C60, the substrate being heated to 90°C, 10nm BPAPF, 45nm p-doped BPAPF and a gold counter electrode.
    [0180] Figure 3 shows the current-voltage curve of the MIP component with compound 1a. In this case, the dashed line shows the course of current density versus voltage without light, and the solid line under illumination. The most important parameters for the evaluation of the MIP component show a well-functioning solar cell with the load factor of 63.2%, the short-circuit current of 7.2 mA/cm2 and the open-circuit voltage of 0.9 V. .
    [0181] Embodiment example 4:
    [0182] Component with compound 13
    [0183] In another exemplary embodiment, an MIP component is produced on a glass sample with ITO transparent cover contact by successive precipitation of the following sequence of layers in vacuo: 15 nm of C60, 20 nm of a 1:1 mixture by coprecipitation of compound 13 and C60, the substrate being heated to 90°C, 5nm BPAPF, 50nm p-doped BPAPF and a gold counter electrode.
    [0187] Figure 4 shows the current-voltage curve of the MIP component with compound 13. In this case, the dashed line shows the course of current density versus voltage without light, and the solid line under illumination. The most important parameters for the evaluation of the MIP component show a well-functioning solar cell with the load factor of 51.6%, the short-circuit current of 8.1 mA/cm2 and the open-circuit voltage of 0.9 V. .
    [0188] Embodiment example 5:
    [0189] Component with compound 2a
    [0190] In another exemplary embodiment, an MIP component is produced on a glass sample with ITO transparent cover contact by successive precipitation of the following sequence of layers in vacuo: 15 nm of C60, 20 nm of a 2:1 mixture by coprecipitation of compound 1a and C60, the substrate being heated to 90°C, 10nm BPAPF, 45nm p-doped BPAPF and a gold counter electrode.
    [0194] Figure 5 shows the current-voltage curve of the MIP component with Compound 2a. In this case, the dashed line shows the course of current density versus voltage without light, and the solid line under illumination. The most important parameters for the evaluation of the MIP component show a well-functioning solar cell with a load factor of 51.4%, a short circuit current of 9.3 mA/cm2 and an open circuit voltage of 0.9 V. .
    [0195] List of reference signs
    [0196] 1 substrate
    [0197] 2 electrode
    [0198] 3 Transport Layer System (ETL, or HTL)
    [0199] 4 Photoactive layer stack
    [0200] 5 Transport layer system (ETL, or HTL)
    [0201] 6 counter electrode
    权利要求:
    Claims (11)
    [1]
    1.- Photoactive component with an electrode (2) and a counter electrode (6) and at least one photosensitive organic layer (4) between the electrode (2) and the counter electrode (6), characterized in that the photosensitive organic layer (4) contains a compound of the general Formula I
    EWG-Vn-D-Vo-EWG (I)
    where
    EWG has electroattracting properties against D
    V -CR1=CR2- or -C=C- with R1 and R2 selected from H, C1-C10 alkyl, OC1-C10 alkyl, SC1-C10 alkyl, where R1 and R2 may form a ring, and n and or are 0 or 1 independently of each other, and characterized in that
    D is a donor block extended from at least 5 fused heterocyclic aromatic 5-membered rings and/or heterocyclic and homocyclic aromatic 6-membered rings, with the proviso that the following structures are excluded:

    [2]
    2. Component according to claim 1, characterized in that the extended donor block of general Formula I is made up of rings with 5 heterocyclic aromatic members selected from thiophene, selenophene, furan or pyrrole.
    [3]
    3. Component according to claim 2, characterized in that at least one of the 5-membered aromatic heterocyclic rings is selected from selenophene, furan or pyrrole.
    [4]
    4. Component according to one of claims 1 to 3, characterized in that the extended donor block D of general Formula I is selected from

    [5]
    5. Component according to claim 1, characterized in that the extended donor block D consists of a maximum of seven condensed heterocyclic aromatic 5-membered rings and/or heterocyclic or homocyclic aromatic 6-membered rings.
    [6]
    6. Component according to claim 1, characterized in that the extended donor block D of general Formula I comprises one or two homocyclic aromatic 6-membered rings.
    [7]
    7. Component according to one of claims 1 to 6, characterized in that n and/or o is 1.
    [8]
    8. Component according to one of claims 1 to 4, the compound of the photosensitive organic layer being selected from the group of the following compounds:

    [9]
    9. Component according to one of claims 1 to 8, characterized in that at least one doped transport layer is present, which is arranged between the electrode or the counter electrode and at least one light-absorbing layer.
    [10]
    10. Component according to one of claims 1 to 9, characterized in that it is a single cell, a tandem cell or a multiple cell.
    [11]
    11.- Organic solar cell with a photoactive zone that has at least one organic donor material in contact with at least one organic acceptor material, the donor material and the acceptor material containing a donor-acceptor heterotransition and the photoactive zone at least one organic compound. Formula I, as defined in claims 1 to 8.
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    同族专利:
    公开号 | 公开日
    DK3050134T3|2021-08-02|
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    ES2875962T3|2021-11-11|
    EP3050134A1|2016-08-03|
    EP3050134B9|2021-10-27|
    KR102233924B1|2021-03-30|
    EP3050134B1|2021-05-05|
    KR20160065885A|2016-06-09|
    WO2015044377A1|2015-04-02|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE102013110693.5A|DE102013110693A1|2013-09-27|2013-09-27|Photoactive, organic material for optoelectronic devices|
    PCT/EP2014/070671|WO2015044377A1|2013-09-27|2014-09-26|Photoactive organic material for optoelectronic components|
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