DE102010046040A1 - Preparing fullerene derivatives useful e.g. as organic semiconductor layers of organic diodes and photo detectors, comprises reacting fullerene with halogen atom in reactor, where an additional chemical element is added to reactor - Google Patents

Abstract

Preparing fullerene derivatives, comprises reacting fullerene with at least one halogen atom in a reactor, where at least one additional chemical element is added to the reactor. Independent claims are also included for: (1) an organic semiconductor layer comprising the fullerene derivatives prepared by the above method; (2) a doped organic semiconductor layer comprising an organic hole-transporting semiconductor material and the fullerene derivative prepared by the above method; (3) an organic diode, organic photoactive component, preferably solar cell, photo detector or light emitting diode, which are constructed of several layers, where at least one of the layers comprises the fullerene derivative prepared by the above method; and (4) a battery comprising the fullerene derivative prepared by the above method.

Description

The invention relates to a process for the preparation of fullerene derivatives according to the features of claim 1.

State of the art

The performance and lifetime of organic semiconducting devices such as organic light emitting diodes (OLEDs) and organic solar cells (OSZs) have improved significantly in recent years. A key criterion is the increase in the conductivity of charge-transporting layers consisting of organic materials [ K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Rev. 107, 1233 (2007) ]. To this end, the concept of p- and n-doping of the charge transport layers is used. The molecular doping achieves an increase in the charge carrier density in the matrix, which compensates for the poor intrinsic charge carrier mobility of the matrix. Due to the concept of molecular doping, the conductivity of the transport layers can be increased by several orders of magnitude [ M. Pfeiffer, K. Leo, X. Zhou, JS Huang, M. Hofmann, A. Werner, J. Blochwitz-Nimoth, Org. Electron. 4, 89 (2003) ]. This achieves a significant increase in performance, since the operating voltage in OLED is reduced or the series resistance in OSZ is lowered. The injection barrier for charge carriers is lowered and a depletion zone is formed, which can easily be overcome by charge carriers through a tunneling process [ J. Blochwitz, T. Fritz, M. Pfeiffer, K. Leo, DM Alloway, PA Lee, NR Amstrong, Org. Electron. 2, 97 (2001) ]. The most efficient monochrome [ R. Meerheim, R. Nitsche, K. Leo, Appl. Phys. Lett. 93, 043310 (2008) ] and white [ Reineke, F. Lindner, G. Schwartz, N. Seidler, K. Walzer, B. Lüssem, K. Leo, Nature 459, 234 (2009) ] OLED, as well as OSZ [ Press release Heliatek GmbH: http://heliatek.de/, April 2010 ], use such doped layers. Doping can be achieved by simultaneously evaporating two materials. The dopant is mixed in a low ratio with the matrix in the gas phase and deposited on a surface. In the case of p-type doping (hole transport), such a matrix may include, for example, N, N, N ', N'-tetrakis (4-methoxyphenyl) benzidine (MeO-TPD). Prerequisite for the dopability is an equal (+/- 0.3 eV) or lower ionization potential of the matrix in relation to the electron affinity of the dopant. The p-dopant (fullerene derivative) should have a reduction potential which is greater than or equal to about -0.3 V, preferably greater than or equal to about 0.0 V, more preferably greater than or equal to about 0, compared to ferrocene (Fe / Fc ⁺ ). 24V is. The doping molecules should be uniform in the matrix and have a low tendency to diffuse. Some high electron affinity (E _A ) p-doping molecules are known, such as. B. the relatively weak electron acceptor tetracyanoquinodimethane (TCNQ) [ M. Maitrot, G. Guillaud, B. Boudjema, JJ André, J. Simon, J. Appl. Phys. 60, 2396 (1986) ; RC Wheland, JL Gillson, J. Am. Chem. Soc. 98, 3916 (1976) ] or the fluorinated modification 3,6-difluoro-2,5,7,7,8,8-hexacyanoquinodimethane (F ₂ -HCNQ) [ ZQ Gao, BX Mi, GZ Xu, YQ Wan, ML Gong, CH Cheah, CH Chen, Chem. Commun., 117 (2008) ] and the commonly used 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F ₄ -TCNQ) [ J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett. 73, 729 (1998) ; WY Gao and A. Kahn, Appl. Phys. Lett. 79, 4040 (2001) ]. This class of materials has a high vapor pressure due to the low molecular weight and tends to uncontrolled contamination of the vapor deposition chamber and thus the subsequent vapor deposited layers. Here, the contamination of the layers in the component can lead to an extinction of excitons, resulting in a reduction in the performance of the components [ BX Mi, ZQ Gao, KW Cheah, CH Chen, Appl. Phys. Lett. 94, 073507 (2009) ]. Furthermore, the layers doped with this material class have a low thermal stability [ Wellmann, M. Hofmann, O. Zeika, A. Werner, J. Birnstock, R. Meerheim, G. He, K. Walzer, M. Pfeiffer, K. Leo, J. Soc. Inf. Disp. 13, 393 (2005) ]. The consequence is a shortened service life of the component.

Perfluorinated fullerenes also have a comparable electron affinity of about 5 eV [ N. Liu, Y. Morio, F. Okino, H. Touhara, OV Boltalina, VK Pavlovich, Synth. Metals 86, 2289 (1997) ]. In polymer layers, which were applied by solution-based processes, the perfluorinated fullerene C ₆₀ F _{36 has} already been investigated as a p-dopant [ O. Solomeshch, YJ Yu, AA Goryunkov, LN Sidorov, RF Tuktarov, DH Choi, J.-Il Jin, N. Tessler, Adv. Mater. 21, 4456 (2009) ].

Few published reports on the production of fluorinated fullerenes are found in the literature. Boltalina et al. Synthesized Fluorinated Fullerenes Using Different Fluoroplants [ PA Troshin, OV Boltalina, NV Polykova, ZE Klinkina, J. Fluor. Chem. 110, 157, (2001) ], Lanthanide-series fluorides [ AA Goryunkov, Z. Mazej, B. Žemva, SH Strauss, OV Boltalina, Mendeleev Commun. 16, 159 (2006) ] or transition metal fluorides in combination with fluorine gas [ NS Chilingarov, AV Nikitin, JV Rau, IV Golyshevsky, AV Kepman, FM Spiridonov, LN Sidorov, J. Fluor. Chem. 113, 219 (2002) ]. All of the above methods are based on the use of molecular fluorine gas during fluorination or in the synthesis for fluorination of suitable reagents. Fluorine is classified as highly toxic and affects many materials commonly used in apparatus engineering corrosive. The required occupational safety measures make these production examples very impractical and cost-intensive. The methods showed only moderate good selectivity with respect to C ₆₀ F ₃₆ at very low to moderate yields of less than 30%. Boltalina et al. published a fluorine gas-free variant for the synthesis of C ₆₀ F ₃₆ in which a trituration of manganese (III) fluoride and C _{60 was} filled into a nickel tube sealed at one end [ O. Boltalina, A. Borschevskii, L. Sidrov, J. Street, R. Taylor, Chem. Comm., 529 (1996) ]. The filled nickel tube was placed in a glass sublimation tube. At a pressure of 10 ^-2 mbar, the glass tube was heated in a tube furnace within 30 min at 330 ° C and held for 24 h at this temperature. During this time, a mixture of different fluorinated fullerenes separated on the cold glass wall. This mixture consisted by mass spectrometric analysis of 51% C ₆₀ F ₃₆ , 33 C ₆₀ % (unreacted fullerene), 8% C ₆₀ F ₃₄ and 15% C ₆₀ F ₃₂ . All of the cited methods have the disadvantage of not being scalable to a millimolar scale.

It is therefore an object of the present invention to provide an improved process for producing a fullerene derivative. The object is solved by the method for the production according to claim 1 and corresponding dependent claims.

In the process for producing fullerene derivatives, fullerene is reacted in a reactor with at least one halogen, with at least one additional chemical element being added to the reactor.

Advantages of this process is the fluorine gas-free production, the higher yield and greater purity of the materials produced.

The fullerene is preferably selected from the formula C _m , where m is selected from 36, 60, 70, 76, 78, 80, 82, 84, 86, 90, 94 or any other natural number suitable for such a spherical one Molecule to form. Preferably m = 60, 70, 76, 80, 82, 84, 86, 90, or 94.

The halogen is selected from F, Cl, Br, with F being preferred. It is preferred that the halogen be used in the form of a halometalionic salt compound (referred to herein as a halogen compound). The metal ion can be selected from: chromium (Cr), manganese (Mn), ruthenium (Ru), molybdenum (Mo), iron (Fe), tungsten (W), cobalt (Co), rhodium (Rh), iridium (Ir ), Nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), thallium (Tl), tin (Sn), antimony (Sb), tellurium (Te ), Lead (Pb), bismuth (Bi), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb ), Dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu). Preferred compound is MnF ₃ .

The additional chemical element is used in the form of wire, chips or powder of any size. It can be used in pure form, as an alloy or as a mixture.

The additionally added chemical element is preferably selected from titanium (Ti), zirconium (Zr), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), aluminum (Al), gallium (Ga), indium (In), thallium (Ti), germanium (Ge), tin (Sn), lead (Pb), arsenic (As), antimony (Sb), bismuth (Bi), selenium (Se), tellurium (Te), lanthanum (La), cerium (Ce), praseodymium (Pr), Neodymium (Nd), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb), lutetium (Lu). More preferred is nickel (Ni).

The fullerene-halogen derivative preferably has the formula C _m F _n , where n = 1 to m. Particularly preferred are C ₆₀ F ₃₆ (m = 60 with n = 36) and C ₆₀ F ₃₄ to 48 (m = 60 with n = 34).

In one embodiment of the invention, the fullerene is mixed before the reaction with at least one additional chemical element. Preferably, the fullerene, at least one additional chemical element and the halogen compound is mixed prior to the reaction.

The reactor is a chemical reactor which is separated from the environment (e.g., air) during the reaction. The chemical reactor can, for. As a boiler, a pipe, or another vessel. Several linked vessels can also be used.

In an advantageous embodiment of the invention, the reactor is an elongated vessel, such. B. a sublimation tube, wherein the production takes place with simultaneous isolation by sublimation.

It is envisaged that the fullerene derivative is used in an organic semiconductor layer. The fullerene derivative may form an organic semiconductor layer.

It is also within the meaning of the invention that the organic semiconductor layer is a doped layer comprising an organic hole-transporting semiconductor material, as a matrix, and the fullerene Derivative, as p-dopant. By a method according to the invention, a doped organic semiconductor material with increased charge carrier density and effective charge carrier mobility can be produced.

Suitably, the fullerene derivative is part of an organic diode, an organic photoactive component, in particular solar cell, photodetector or light emitting diode.

As organic components are components that contain at least one organic semiconductor layer. Fullerenes and their derivatives are also to be understood here as organic. The organic semiconductor layers contain, inter alia, organic molecules, so-called "small molecules", or else organic polymers, the organic molecules and the organic polymers being used as a single layer or as a mixture with other organic (eg US2005 0110009 described) or inorganic materials have semiconductor or metal-like properties. Organic light-emitting diodes typically consist of various layers of organic materials, wherein at least one layer (emission layer) contains an electroluminescent substance which can be brought to emit light by applying a voltage (Tang, US 4,769,292 ). Highly efficient OLEDs are z. In US 7,074,500 described. The structure of organic solar cells is known to the person skilled in the art, see EP1861886 and EP1859494 , Particularly preferred components are doped components according to Walzer et al. [Chem. Rev. 107, 1233 (2007)] ,

Suitably, the fullerene derivative is part of a battery, preferably as a cathode [ N. Liu, H. Touhara, F. Okino, S. Kawasaki, Y. Nakacho, J. Electrochem. Soc. 143, 2267 (1996) ]

The invention will be explained in more detail with reference to exemplary embodiments. Show it:

a schematic representation of the apparatus for the production of C ₆₀ F ₃₆ in the millimolar scale

a mass spectrometric study of the reaction product

a molecular structure of p-dopants F ₄ -TCNQ and C ₆₀ F ₃₆ , as well as structure of MeO-TPD

Measurements of the contamination behavior of p-dopants F ₄ -TCNQ and C ₆₀ F ₃₆ using UPS and XPS.

a structure of BF-DPB.

a representation of the thermal stability of the F ₄ -TCNQ or C ₆₀ F _36- containing hole transport layers

Layer structure and composition of the OLED, as well as structures of Bphen, Spiro-TAD, α-NPD and Ir (MDQ) ₂ acac

a comparison of the electro-luminescence spectra of the OLED.

a comparison of the characteristic I (V) characteristics and the luminescence of both OLEDs.

a comparison of the energy yield and the external quantum efficiency of the OLED

Layer structure and composition of the OSZ, as well as structure of ZnPc.

a comparison of the characteristic I (V) curves of both OSZs under illumination with a solar simulator (AM1.5) and in the dark, as well as all characteristic performance parameters.

a comparison of the characteristic parameters over the course of aging.

Synthesis Example C ₆₀ F ₃₆

The MnF ₃ used for the synthesis (ABCR, 98%) was removed within 24 h at a pressure of 10 ^-3 mbar and at a temperature of 200 ° C traces of water and oxygen. Fullerene C ₆₀ was purchased from a chemical supplier (eg, American Dye Source) and purified by sublimation three times. The fullerene C ₆₀ (1.00 g, 1.388 mmol) and MnF ₃ (5.59 g, 60.15 mmol) were well triturated in a nitrogen atmosphere in a mortar. Nickel powder was added to the mixture in a nickel crucible (6.6 g, 10%) and the filled nickel crucible became corresponding used in the sublimation apparatus. The sublimation tube was heated at a pressure of 4 × 10 ^-4 mbar for 24 h to a temperature of 330 ° C, wherein the fluorinated reaction products condensed on the colder parts of the sublimation tube in the form of a white-yellowish solid (0.76 g). The rings coated with the condensate were subjected to further sublimation to complete 0.75 g (0.534 mmol, 38% of the theoretical yield) of the product could be isolated. For analysis of the additionally sublimed product, a sample was completely dissolved in toluene and completely evaporated in a mass spectrometer. The total ion flow was measured and is in shown. The ratios of the intensities of all compounds contained in the sample corresponds to the Composition 84% C ₆₀ F ₃₆ , 14% C ₆₀ F ₃₄ and 2% C ₆₀ .

Embodiment 1

Documentation of the contamination behavior of the dopant C ₆₀ F ₃₆ compared to F ₄ -TCNQ. The aim here is to investigate the volatility of the dopant F ₄ -TCNQ and C ₆₀ F ₃₆ and to demonstrate that C ₆₀ F _36, in contrast to F ₄ -TCNQ, shows no chamber contamination.

The volatility of the dopants F ₄ -TCNQ and C ₆₀ F ₃₆ was investigated by X-ray photoelectron spectroscopy (XPS) based on their fluorine signals in undoped MeO-TPD layers. Figure 1 shows the comparison of XPS measurement 1s fluorine core signals to 10 nm intrinsic MeO-TPD layers. These were made in chambers in which either none of the dopants was, or either in an unheated source. A significant fluorine signal at a binding energy of 689.5 eV is observed only in the layer that was vaporized in the chamber in the presence of F ₄ -TCNQ. Furthermore, this layer exhibits a doping effect in ultraviolet photoelectron spectroscopy (UPS) in the form of a significant shift of 0.53 eV of the highest occupied molecular orbital (HOMO) of the MeO-TPD in the direction of the Fermi energy (E _B = 0 eV). , This contamination demonstrates the contamination potential of F ₄ -TCNQ molecules, as opposed to a sample that was vaporized in the presence of C ₆₀ F ₃₆ . For samples from the chamber with C ₆₀ F ₃₆ , no fluorine signal in the XPS or a HOMO shift in the UPS, ie no contamination of the MeO-TPD layers is observed. The very low volatility of C ₆₀ F ₃₆ in comparison with F ₄ -TCNQ represents a major advantage in the processing of hole transport layers.

Embodiment 2

Documentation of the temperature stability with C ₆₀ F ₃₆ doped hole transport layers in comparison to F ₄ -TCNQ. The temperature stability of hole transport layers doped with C ₆₀ F ₃₆ should be demonstrated.

In order to investigate the temperature stability, the matrix material N, N '- ((diphenyl-N, N'-bis) 9,9, -dimethyl-fluoren-2-yl) -benzidine (BF-DPB) was used because of the high glass transition temperature ( T _G = 160 ° C) ( US20020171358 A1 ). The behavior of the conductivity as a function of the temperature up to the T _G is therefore due to the dopants. At ratios of 26 mol% for F ₄ -TCNQ and 21 mol% for C ₆₀ F ₃₆ , both layers show a comparable conductivity of 3 × 10 ^-6 S cm ^-1 at room temperature ( ). The lower doping with C ₆₀ F _{36 shows} the higher doping efficiency of the dopant. Since the LUMO of F ₄ -TCNQ is approximately the same as the UPS-determined HOMO level of BF-DPB (-5.23 eV), this system results in an inefficient charge transfer. Therefore, it can be assumed that C ₆₀ F _{36 has} a higher electron affinity compared to F ₄ -TCNQ. With increasing temperature, the conductivity of both layers increases with activation energies of 265 meV and 692 meV for F4-TCNQ and C ₆₀ F ₃₆ up to the maximum, with further temperature increase the conductivity breaks down. For the BF-DPB / F ₄ -TCNQ layer, lower conductivity is observed with the conductivity drop at 145 ° C. In the BF-DPB / C ₆₀ F ₃₆ layer, the collapse occurs only at 180 ° C and is thus higher than the T _{G of} the matrix material. The conductivity drop can therefore not be assigned directly to the dopant C ₆₀ F ₃₆ .

Embodiment 3

Documentation of the use of C ₆₀ F ₃₆ doped hole transport layers in OLED compared to F ₄ -TCNQ. For the comparison of the dopants in components phosphorescent pin OLED are used with orange-red emission.

The layer structure of the components produced is in shown. The organic layers are located between a 90 nm thick indium tin oxide (ITO) anode on a glass substrate and a 100 nm thick silver cover contact. As hole transport layer (HTL), serve 60 nm thick MeO-TPD layers doped with 1 wt% F ₄ -TCNQ or 8 wt% C ₆₀ F ₃₆ resulting in conductivities of about 2 · 10 ^-5 S cm ^-1 . As an electron transport layer (ETL) act 65 nm cesium-doped 4,7-diphenyl-1,10-phenanthroline (BPhen) with comparable conductivity. To concentrate the injected charges in the emission layer (EML), 10 nm thick electron and hole blocking layers (EBL, HBL) are made of 2,2 ', 7,7'-tetrakis- (N, N-diphenylamino) -9,9 Spirobifluorene (spiro-TAD) and BPhen are inserted around the EML. The 20 nm thick EML consists of N, N'-di (naphthalen-2-yl) -N, N'-diphenylbenzidine (α-NPD) doped with 10 wt% of the triplet emitter iridium (III) bis (2) methyldibenzo [f, h] quinoxaline) acetylacetonate (Ir (MDQ) ₂ (acac)). Both OLEDs show accordingly , identical electroluminescence spectra, which precludes parasitic absorption of C ₆₀ F ₃₆ . The current-voltage curves of both comparison components are similar ( ), where the I (V) curves with the C ₆₀ F ₃₆ dopant are steeper, indicating better hole injection with the same layer conductivity. The higher hole injection increases the charge carrier density, or shifts the charge carrier balance in the EML resulting in increased efficiencies of the C ₆₀ F ₃₆ -OLED ( ).

Embodiment 4

Documentation of the use of C ₆₀ F ₃₆ doped hole transport layers in OSZ compared to F ₄ -TCNQ. The lifetime measurements of the components obtained show the stability of the component using mixed layers of zinc phthalocyanine (ZnPc) and C ₆₀ as donor-acceptor absorber pair.

The layer structure of the produced component is in shown. The hole transport layer (HTL) used is a 60 nm thick MeO-TPD layer doped with 2 wt% F ₄ -TCNQ or 8 wt% C ₆₀ F ₃₆ . A 30 nm mixed layer of C ₆₀ and ZnPc (1: 1) acts as an absorber layer, followed by a 30 nm thick layer of intrinsic C ₆₀ . The electron transport is made possible by a 15 nm thick layer C ₆₀ doped with 3 wt% 3,6-bis (dimethylamino) acridine (AOB). The reflective cathode is formed by a 100 nm thick layer of aluminum. Both solar cells are according to are comparable with respect to all parameters and show only minimal differences which lie in the range of measurement uncertainty. The open terminal voltage (V _OC ) is not affected by the dopants. The doping with C ₆₀ F ₃₆ leads to a slightly smaller series resistance.

The solar cells were aged at 50 ° C and illuminated with white LEDs at a power of 500 mW cm ^-2 . illustrates the different lifetimes of the OSZ. Due to the low glass transition temperature of F ₄ -TCNQ, the solar cells with this dopant have a lifetime of less than one hundred hours, making commercial use of this material impossible. In contrast, cells containing C ₆₀ F ₃₆ show constant cell parameters over a period of 500 hours. The stability of these cells is therefore significantly greater than cells containing F ₄ -TCNQ.

With regard to the application as a p-dopant in pin OLED and OSZ, it can be concluded that the replacement of F ₄ -TCNQ leads to improved performance of the components and furthermore leads to a higher stability of the components. Furthermore, the low vapor pressure of the C ₆₀ F ₃₆ dopant does not result in any chamber contamination during the manufacturing process.

QUOTES INCLUDE IN THE DESCRIPTION

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Cited patent literature

• US 20050110009 [0019]
• US 4769292 [0019]
• US 7074500 [0019]
• EP 1861886 [0019]
• EP 1859494 [0019]
• US 20020171358 A1 [0039]

Cited non-patent literature

• K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Rev. 107, 1233 (2007) [0002]
• M. Pfeiffer, K. Leo, X. Zhou, JS Huang, M. Hofmann, A. Werner, J. Blochwitz-Nimoth, Org. Electron. 4, 89 (2003) [0002]
• J. Blochwitz, T. Fritz, M. Pfeiffer, K. Leo, DM Alloway, PA Lee, NR Amstrong, Org. Electron. 2, 97 (2001) [0002]
• R. Meerheim, R. Nitsche, K. Leo, Appl. Phys. Lett. 93, 043310 (2008) [0002]
• Reineke, F. Lindner, G. Schwartz, N. Seidler, K. Walzer, B. Lüssem, K. Leo, Nature 459, 234 (2009) [0002]
• Press release Heliatek GmbH: http://heliatek.de/, April 2010 [0002]
• M. Maitrot, G. Guillaud, B. Boudjema, JJ André, J. Simon, J. Appl. Phys. 60, 2396 (1986) [0002]
• RC Wheland, JL Gillson, J. Am. Chem. Soc. 98, 3916 (1976) [0002]
• ZQ Gao, BX Mi, GZ Xu, YQ Wan, ML Gong, CH Cheah, CH Chen, Chem. Commun., 117 (2008) [0002]
• J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett. 73, 729 (1998) [0002]
• WY Gao and A. Kahn, Appl. Phys. Lett. 79, 4040 (2001) [0002]
• BX Mi, ZQ Gao, KW Cheah, CH Chen, Appl. Phys. Lett. 94, 073507 (2009) [0002]
• Wellmann, M. Hofmann, O. Zeika, A. Werner, J. Birnstock, R. Meerheim, G. He, K. Walzer, M. Pfeiffer, K. Leo, J. Soc. Inf. Disp. 13, 393 (2005) [0002]
• N. Liu, Y. Morio, F. Okino, H. Touhara, OV Boltalina, VK Pavlovich, Synth. Metals 86, 2289 (1997) [0003]
• O. Solomeshch, YJ Yu, AA Goryunkov, LN Sidorov, RF Tuktarov, DH Choi, J.-Il Jin, N. Tessler, Adv. Mater. 21, 4456 (2009) [0003]
• PA Troshin, OV Boltalina, NV Polykova, ZE Klinkina, J. Fluor. Chem. 110, 157, (2001) [0004]
• AA Goryunkov, Z. Mazej, B. Žemva, SH Strauss, OV Boltalina, Mendeleev Commun. 16, 159 (2006) [0004]
• NS Chilingarov, AV Nikitin, JV Rau, IV Golyshevsky, AV Kepman, FM Spiridonov, LN Sidorov, J. Fluor. Chem. 113, 219 (2002) [0004]
• O. Boltalina, A. Borschevskii, L. Sidrov, J. Street, R. Taylor, Chem. Comm., 529 (1996) [0004]
• Walzer et al. [Chem. Rev. 107, 1233 (2007)] [0019]
• N. Liu, H. Touhara, F. Okino, S. Kawasaki, Y. Nakacho, J. Electrochem. Soc. 143, 2267 (1996) [0020]

Claims (12)

A process for the preparation of fullerene derivatives, wherein a fullerene in a reactor reacts with at least one halogen atom, characterized in that at least one additional chemical element is added to the reactor. Process for the preparation of fullerene derivatives according to claim 1, characterized in that at least one halogen atom is selected from F, Cl, Br. Process for the preparation of fullerene derivatives according to one of the preceding claims, characterized in that the fullerenes are spherical carbon clusters of the formula C _m , where m is selected from 36, 60, 70, 76, 78, 80, 82, 84 or any other natural number suitable for forming such a spherical molecule. Process for the preparation of fullerene derivative according to one of the preceding claims, characterized in that the halogen atom is used as at least one salt or salt mixture, wherein the salt contains a metal ion and wherein the metal ion is selected from Cr, Mn, Ru, Mo, Fe , W, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Ti, Sn, Sb, Te, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy , Ho, Er, Tm, Yb, Lu. Process for the preparation of fullerene derivative according to one of the preceding claims, characterized in that the at least one additional chemical element Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co , Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Ti, Ge, Sn, Pb, As, Sb, Bi, Se, Te, La, Ce, Pr , Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or a mixture of these elements in the form of wire, chips or powder of any size. Process for the preparation of fullerene derivatives according to one of the preceding claims, wherein the additional chemical element is nickel. Process for the preparation of fullerene derivatives according to one of the preceding claims, wherein the preparation takes place with simultaneous isolation by sublimation. Organic semiconductor layer, characterized in that a material produced by a method according to one of the preceding claims 1 to 7, is contained. Doped organic semiconductor layer, characterized in that an organic hole-transporting semiconductor material and a fullerene derivative, prepared by a method according to at least one of claims 1 to 7, is contained. Doped organic semiconductor layer according to claim 9, characterized in that the fullerene derivative for the organic hole-transporting semiconductor material is a p-type dopant. Organic diode, organic photoactive component, in particular solar cell, photodetector or light-emitting diode, which is composed of several layers, wherein at least one of the layers contains a fullerene derivative prepared by the method according to one of the preceding claims. Battery with a fullerene derivative prepared by a method according to any one of the preceding claims 1 to 7.

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