KR20120031153A - Method for producing fullerene derivatives - Google Patents

Abstract

PURPOSE: A method for generating fullerene derivatives is provided to omit the use of fluorine gas and to improve yield by generating the halogenated fullerene based on the reaction of one or more halogen elements and fullerene. CONSTITUTION: Fullerene derivatives are generated by reacting fullerene with one or more halogen elements in a reactor. One or more additional chemical elements are added into the reactor. The halogen elements are selected from F, Cl, or Br. The fullerene is a spherical carbon cluster which is represented by chemical formula Cm. In chemical formula, the m is 36, 60, 70, 76, 78, 80, 82, and 84 or is selected from natural numbers which are suitable to form spherical molecules.

Description

Method for producing fullerene derivatives

The present invention provides an improved process for producing fullerene derivatives.

Conventional technology

The performance and lifetime of organic semiconductor components, such as organic light emitting diodes (OLEDs) and organic solar cells, have improved significantly over the years. One crucial point is the increased conductivity of the charge transport layer of organic material [K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem . Rev. 107 , 1233 (2007). For this purpose, the concept of p- and n-doping of the charge transport layer is appropriate. Molecular doping can cause the density of charge carriers to increase in the matrix, which compensates for the poor inherent charge carrier mobility of the matrix. The concept of molecular doping can cause the conductivity of the transport layer to be increased by several powers of ten. [M. Pfeiffer, K. Leo, X. Zhou, JS Huang, M. Hofmann, A. Werner, J. Blochwitz-Nimoth, Org . Electron . 4 , 89 (2003). It also significantly improves performance because the operating voltage in the OLED is reduced and the series resistance in organic solar cells is lowered. The injection barrier for charge carriers is lowered and a depletion zone is formed, which can be easily overcome by charge carriers through the tunnel process [J. Blochwitz, T. Fritz, M. Pfeiffer, K. Leo, DM Alloway, PA Lee, NR Amstrong, Org . Electron . 2 , 97 (2001). The most efficient monochrome available today [R. Meerheim, R. Nitsche, K. Leo, Appl . Phys . Lett . 93 , 043310 (2008) and white [S. Reineke, F. Lindner, G. Schwartz, N. Seidler, K. Walzer, B. Lussem, K. Leo, Nature 459 , 234 (2009)] OLEDs and organic solar cells [press release from Heliatek GmbH: http: // heliatek.de/, April 2010] uses this type of doped layer. Doping may be accomplished by vaporizing both materials simultaneously. Dopants in the gas phase mix with the matrix at a low rate and deposit on the surface. In the case of p-doping (hole transport), such a matrix may contain, for example, N, N, N ', N'-tetrakis- (4-methoxyphenyl) benzidine (MeO-TPD). . To enable doping, the matrix must have an ionization potential equal to (+/- 0.3 eV) or an ionization potential lower than the electron affinity of the dopant. The p-dopant (fullerene derivative) is about -0.3 V or more, preferably 0.0 V or more, more preferably about 0.24 V or more with respect to ferrocene (Fc / Fc ⁺ ). Must have a reduction potential. Doping molecules must be able to be introduced evenly in the matrix and have a low diffusion tendency. Some p-doped molecules with high electron affinity (E _A ), for example, relatively weak electron acceptor tetracyanoquinomethane (TCNQ) [M. Maitrot, G. Guillaud, B. Boudjema, JJ Andre, J. Simon, J. Appl. Phys . 60 , 2396 (1986); RC Wheland, JL Gillson, J. Am . Chem . Soc . 98 , 3916 (1976)], or fluorinated modified 3,6-difluoro-2,5,7,7,8,8-hexacyanodimethane (F ₂ -HCNQ) [ZQ Gao, BX Mi, GZ Xu, YQ Wan, ML Gong, KW Cheah, CH Chen, Chem . Commun ., 117 (2008)] and often used 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinomimethane (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). Because of the low molecular weight, this class of materials has a high vapor pressure and tends to cause uncontrolled contamination of the vapor deposition chamber, thereby eventually leading to contamination of the deposited layer. In this case, contamination of the layers in the device can suppress excitation and, as a result, impair the capacity of the device [BX Mi, ZQ Gao, KW Cheah, CH Chen, Appl . Phys. Lett . 94 , 073507 (2009). Layers doped with this class of material also have low thermal stability [P. 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)]. This shortens the service life of the device.

Perfluorinated fullerenes also have a significant electron affinity of about 5 eV [N. Liu, Y. Morio, F. Okino, H. Touhara, OV Boltalina, VK Pavlovich, Synth . Metals 86 , 2289 (1997). Perfluorinated digested fullerene _{C 60 F 36 (perfluorinated fullerene C} 60 F 36) the solution in the pre-study was a p- dopant in the polymer-based layer deposited in step [O. Solomeshch, YJ Yu, AA Goryunkov, LN Sidorov, RF Tuktarov, DH Choi, J.-Il Jin, N. Tessler, Adv . Mater . 21 , 4456 (2009). The literature includes several public reports on the production of fluorinated fullerenes. Voltalina et al. Include various fluoroplumbates [PA Troshin, OV Boltalina, NV Polykova, ZE Klinkina, J. Fluor . Chem . 110 , 157, (2001)], fluorides of the lanthanoid series [AA Goryunkov, Z. Mazej, B. Zemva, SH Strauss, OV Boltalina, Mendeleev Commun . 16 , 159 (2006)] or transition metal fluorides associated with fluorine gas [NS Chilingarov, AV Nikitin, JV Rau, IV Golyshevsky, AV Kepman, FM Spiridonov, LN Sidorov, J. Fluor . Chem . 113 , 219 (2002)] were used to synthesize fluorinated fullerenes. All methods cited above are based on the use of molecular fluorine gas during fluorination or during synthesis for fluorination of suitable reagents. Fluorine is classified as very toxic and has a corrosive effect on the many materials commonly used in device setup. The required workplace safety measures make these production examples very impractical and too costly. At the same time, such methods showed only moderately good selectivity with respect to C ₆₀ F ₃₆ , with very low to medium yields of less than 30%. Voltalina et al. Have disclosed a method for synthesizing C ₆₀ F ₃₆ without the use of fluorine gas, in which a nickel pipe with a closed end is made of powder of magnesium (III) fluoride and C ₆₀ . Charged [O. Boltalina, A. Borschevskii, L. Sidrov, J. Street, R. Taylor, Chem . Comm . , 529 (1996). The filled nickel pipes were placed in a glass sublimation tube. The glass tube was heated to 330 ° C. within 30 minutes under a pressure of 10 ⁻² mbar in a tube furnace and held at that temperature for 24 hours. During this time, a mixture of various fluorinated fullerenes condensed on the cold glass walls. According to mass spectrometry, this mixture consists of 51% C ₆₀ F ₃₆ , 33% C ₆₀ (unreacted ppufullerene), 8% C ₆₀ F ₃₄ and 15% C ₆₀ F ₃₂ . All the methods described share a disadvantage that cannot be measured on the millimolar scale.

It is therefore an object of the present invention to present an improved method of producing fullerene derivatives. Such an object is solved by a production method according to claim 1 and the corresponding dependent claims.

In the process for producing the fullerene derivative, fullerene is given to the reaction with one or more halogens in the reactor, and one or more additional chemical elements are also added to the reactor.

The advantages of this method include the fact that the production does not involve the use of fluorine gas, the yield is high and the material produced is more pure.

Fullerenes are preferably selected from the formula C _m , where m is 36, 60, 70, 76, 78, 80, 82, 84, 86, 90, 94 or any of those that can form spherical molecules of that kind Other total number. Preferably m = 60, 70, 76, 80, 82, 84, 86, 90, or 94.

Such halogen is selected from F, Cl, and Br, with F being preferred. Halogen is preferably used in the form of a halogen-metal ion-salt compound, referred to herein as a halogen compound. Metal ions are selected from the following metal ions: 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 .

Additional chemical elements are used in the form of wires, turning or powder of any size. It can be introduced in pure form, as an alloy or as a mixture.

Further chemical elements are preferably 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 (Tl), 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) and lutetium (Lu). Nickel (Ni) is particularly preferred.

The fullerene-halogen derivative preferably has the formula C _m F _n , where n can be 1 to m. C ₆₀ F ₃₆ (m = ₆₀ and n = 36) and C ₆₀ F _{34 to 48} (m = 60 and n = 34 to 48).

In one embodiment of the invention, the fullerene is mixed with one or more additional chemical elements prior to the reaction. Fullerenes, one or more additional chemical elements and halogen compounds are preferably mixed before the reaction.

The reactor is a chemical reactor that is closed to the environment (eg atmosphere) during the reaction. The chemical reactor may be, for example, a boiler, a pipe, or some other vessel. Large numbers of connected containers can also be used.

In an advantageous form of the invention, the reactor is an elongated vessel, such as a sublimation tube, wherein the production is carried out through sublimation with simultaneous separation.

It is preferable that a fullerene derivative is used for the organic semiconductor layer. The fullerene derivative may form an organic semiconductor layer.

It is also consistent with the present invention that the organic semiconductor layer is a doped layer comprising an organic hole transport semiconductor material as a matrix and a fullerene derivative as a p-dopant. Doped semiconductor materials with increased charge carrier density and effective charge carrier mobility can be produced by performing the method according to the present invention.

The fullerene derivative may advantageously be an element of an organic diode, an organic photoactive element, in particular a solar cell, photodetector or light emitting diode.

Devices containing at least one organic semiconductor layer are considered to be organic devices. For that purpose, fullerenes and derivatives thereof are also included in the definition of such organics. The organic semiconductor layer also contains organic molecules, so-called "small molecules", or organic polymers, where they are incorporated as a single layer or in a mixture with other organic (eg, those described in US2005 0110009) or inorganic materials. Organic molecules and organic polymers have semiconductor or metal-like properties. Organic light emitting diodes generally consist of layers of many different organic materials, one or more of which (light emitting layers) contain an electroluminescent material that can be induced to emit light when voltage is applied (Tang, US 4,769,292). . Highly efficient OLEDs are described, for example, in US 7,074,500. The construction of solar cells is known to those skilled in the art. In this regard, reference may be made to EP1861886 and EP1859494. Particularly preferred devices are described in Walzer et al., Chem. Rev. 107, 1233 (2007).

Fullerene derivatives advantageously constitute part of the battery, preferably the cathode [N. Liu, H. Touhara, F. Okino, S. Kawasaki, Y. Nakacho, J. Electrochem. Soc . 143 , 2267 (1996).

1 is a schematic of an apparatus for producing millimolar C ₆₀ F ₃₆ .
2 is a diagram showing mass spectrometry of a reaction product.
3 is an ORTEP representation of the molecular structure of p-dopant C ₆₀ F _{36 and} the structure of p-dopant F ₄ -TCNQ and MeO-TPD.
4 shows the measurement of the contamination behavior of p-dopant F ₄ -TCNQ and C ₆₀ F ₃₆ using UPS and XPS.
5 shows the structure of a BF-DPB.
6 is a diagram showing the thermal stability of the hole transport layer containing F ₄ -TCNQ or C ₆₀ F ₃₆ .
FIG. 7 is a diagram showing the layer structure and composition of OLEDs and the structure of Bphen, Spiro-TAD, α-NPD, and Ir (MDQ) ₂ acac.
8 shows a comparison of the electroluminescence spectra of OLEDs.
9 is a diagram comparing the characteristic I (V) curves and luminance of both OLEDs.
10 is a diagram comparing energy output and external quantum efficiency of OLEDs.
11 is a diagram showing the layer structure and composition of an organic solar cell and the structure of ZnPc.
FIG. 12 shows a comparison of characteristic I (V) curves and all characteristic performance parameters of solar electricity both under illumination by a sun simulator (AM1.5) and in the dark.
13 shows a comparison of characteristic parameters in a temporal aging process.

C ₆₀ F ₃₆ To synthesize Example

Traces of water and oxygen were extracted from MnF ₃ (ABCR, 98%) and used for synthesis at a pressure of 10 ⁻³ mbar and a temperature of 200 ° C. within 24 hours. Fullerene C ₆₀ was purchased from a chemical supplier (eg, American Dye Source) and purified by triple sublimation. Fullerene C ₆₀ (1.00 g; 1.388 mmol) and MnF ₃ (5.59 g; 60.15 mmol) were ground completely in a grinding dish under a nitrogen atmosphere. Nickel powder (6.6 g; 10%) was added to the mixture in the nickel crucible and the charged nickel crucible was placed in a sublimation apparatus as shown in FIG. The sublimation tube is heated to a temperature of 330 ° C. for 24 hours under a pressure of 4-10 ⁻⁴ mbar, during which time the fluorinated reaction product is cooled in the form of a yellowish-white solid (0.76 g). Condensed on part. The ring loaded with condensate was sent to a further sublimation step and 0.75 g (0.534 mmol, 38% of theoretical yield) were separated at the end of that sublimation step. To analyze the remainder of the sublimated product, the sample was completely dissolved in toluene and evaporated completely in a mass spectrometer. The total total ion current was measured and shown in FIG. 2. The ratios for the intensities of all compounds present in the samples correspond to the following compositions: 84% C ₆₀ F ₃₆ , 14% C ₆₀ F ₃₄ and 2% C ₆₀ .

fair Example  One

Collection of contamination behavior of dopant C ₆₀ F ₃₆ compared to F ₄ -TCNQ. The purpose of this collection is to test the volatility of the dopants F ₄ -TCNQ and C ₆₀ F ₃₆ and to provide evidence that, unlike F ₄ -TCNQ, C ₆₀ F ₃₆ does not show any chamber contamination.

Volatilities of the dopants F ₄ -TCNQ and C ₆₀ F ₃₆ were tested in undoped MeO-TPD layers using fluorine signals using x-ray photoelectron spectroscopy (XPS). 4 shows a comparison of 1s fluorine core signals obtained by XPS measurements on a 10 nm thick native MeO-TPD layer. These layers were produced in a chamber containing no dopant or containing either in a non-heated source. Significant fluorine signals for a binding energy of 689.5 eV can only be observed in the layer having evaporated in the presence of F ₄ -TCNQ in the chamber. In ultraviolet photoelectron spectroscopy (UPS), this layer also provides a significant 0.53 eV of Fermi energy (EB = 0 eV) of the highest occupied molecular orbital (HOMO) of MeO-TPD. The doping effect is confirmed in the form of movement. This contamination demonstrates the contamination potential of the F ₄ -TCNQ molecule, in contrast to the sample which has evaporated in the presence of C ₆₀ F ₃₆ . In the sample from the chamber containing C ₆₀ F ₃₆ , no fluorine signal was observed in the XPS and there was no HOMO shift in the UPS. That is, no contamination of the MeO-TPD layer was observed. The very low volatility of C ₆₀ F ₃₆ over F ₄ -TCNQ represents a significant advantage in the problem of processing the hole transport layer.

fair Example  2

Collection of thermal stability of C ₆₀ F ₃₆ -doped hole transport layer compared to F ₄ -TCNQ. The purpose is to present the thermal stability of the hole transport layer doped with C ₆₀ F ₃₆ .

To test the thermal stability, the matrix material N, N '-((diphenyl-N, N'-bis) 9,9-dimethyl-fluoren-2-yl) -benzidine (BF-DPB) was chosen. The reason is because of its high glass transition temperature (T _G = 160 ° C.) (US20020171358 A1). Thus, its conductive behavior, which depends on the temperature below T _G , is due to the dopant. At a ratio of ₂₆ mol% for F ₄ -TCNQ and 21 mol% for C ₆₀ F ₃₆ , the two layers exhibit significant conductivity of 3˜10 ⁻⁶ S cm ⁻¹ at room temperature (FIG. 6). In this regard, low doping by C ₆₀ F ₃₆ is evidence of the high doping efficiency of the dopant. Since the LUMO of F ₄ -TCNQ is, in general, the same as the HOMO level of BF-DPB as measured by the UPS, the transfer of generated charges in such a system is inefficient. Thus, C ₆₀ F ₃₆ can be assumed to have stronger electron affinity than F ₄ -TCNQ. As the temperature rises, the conductivity of the two layers increases and the activation energy of 265 meV and 692 meV for F ₄ -TCNQ and C ₆₀ F ₃₆ increases to a maximum, and as the temperature further increases, the conductivity collapses. Low stability is observed in the BF-DPB / F ₄ -TCNQ layer and conductivity is attenuated at 145 ° C. In the BF-DPB / C ₆₀ F ₃₆ layer, it does not collapse to 180 ° C. and is higher than the TG of the matrix material. Thus, the attenuation of conductivity is not directly attributable to the C ₆₀ F ₃₆ dopant.

fair Example  3

Collection for the use of C ₆₀ F ₃₆ -doped hole transport layers in OLEDs compared to F ₄ -TCNQ. Phosphorescent pin OLEDs with orange-red luminescence were used to compare the dopants in the device.

The layer structure of the device produced is illustrated in FIG. 7. The organic layer is located on a glass substrate between a 90 nm thick indium-tin oxide (ITO) anode and a 100 nm thick silver coated contact. 1% by weight of F ₄ -TCNQ or a 60nm thick doped with 8% of C ₆₀ F ₃₆ weight MeO-TPD layer serving as a hole transport layer (HTL), and carries approximately 2? 10 ^-5 S cm ^-1 by Conductivity is achieved. Cesium-doped 4,7-diphenyl-1,10-phenanthroline (BPhen) at 65 nm acts as an electron transport layer (ETL), providing similar conductivity. 2,2 ', 7,7'-tetrakis- (N, N-diphenylamino) -9,9'-spirobifluorene (Spiro-TAD) to accumulate electrons injected into the light emitting layer (EML) And 10 nm thick electron and hole blocking layers (EBL, HBL) of BPhen are included on one of the sides of the EML. 20 nm thick EML was prepared with 10% by weight of triplet emitter iridium (III) bis (2-methyldibenzo- [f, h] quinoxaline) acetylacetone (Ir (MDQ) ₂ (acac)). Doped N, N'-di (naphthalen-2-yl) -N, N'-diphenyl-benzidine (α-NPD). As shown in FIG. 8, both OLEDs exhibit the same electroluminescence spectrum, which prevents dependent absorption of C ₆₀ F ₃₆ . The current-voltage curves of the two comparative elements are similar (FIG. 9), but the characteristic curve I (V) by C ₆₀ F ₃₆ -dopant is steep, indicating that the hole injection is excellent for the same layer conductivity. More hole injection increases the charge carrier density and shifts the charge carrier balance in the EML, leading to greater efficiency of the C ₆₀ F ₃₆ OLED (FIG. 10).

fair Example  4

Collection for use of C ₆₀ F ₃₆ doped hole transport layer in organic solar cells compared to F ₄ -TCNQ. The service life measurement of the device thus obtained shows the stability of the device using hybrid layers of zinc phthalocyanine (ZnPc) and C ₆₀ as donor-acceptor-absorber pair.

The layer structure of the device thus produced is shown in FIG. A 60 nm thick MeO-TPD layer doped with 2 wt% F ₄ -TCNQ or 8 wt% C ₆₀ F ₃₆ serves as the hole transport layer (HTL). A 30 nm hybrid layer of C ₆₀ and ZnPc (1: 1) acts as an absorber layer, adjacent to the unique C ₆₀ layer 30 nm thick. Electron transport is accomplished by a 15 nm thick C ₆₀ layer doped with 3% by weight of 3,6-bis (dimethylamino) acridine (AOB). The reflective cathode is formed by a 100 nm thick aluminum layer. As shown in FIG. 12, the two solar cells are comparable for all parameters and show only minimal differences, which are within the range of measurement uncertainty. Open terminal voltage ( V _OC ) is not affected by the doping material. Doping with C ₆₀ F ₃₆ causes a very small DC resistance reduction.

The solar cells were aged at 50 ° C. and under illumination from white LEDs with an output of 500 mW cm ⁻² . 13 illustrates the difference in durability of the organic solar cell. Because of the low glass transition temperature of F ₄ -TCNQ, solar cells doped with such dopants have a lifetime of less than 100 hours, making such materials at all unsuitable for commercial use. In contrast, cells containing C ₆₀ F ₃₆ have constant cell parameters over a period of 500 hours. Thus, the stability of these batteries is significantly higher than that of batteries containing F ₄ -TCNQ.

Thus, with regard to its use as p-dopants in pin OLEDs and organic solar cells, it can be concluded that the replacement of F ₄ -TCNQ is associated with improved performance of the device and higher stability of the device. In addition, the low vapor pressure of the C ₆₀ F ₃₆ dopant means that the chamber is not contaminated during the production process.

Claims (12)

A method for producing a fullerene derivative wherein fullerene is reacted with one or more halogen atoms in a reactor, characterized in that one or more additional chemical elements are added to the reactor. The method of claim 1, wherein at least one halogen atom is selected from F, Cl, or Br. 3. The method of claim 1, wherein fullerene is a spherical carbon cluster having the formula C _m and m is 36, 60, 70, 76, 78, 80, 82, 84 or such spherical molecules. A method for producing a fullerene derivative, characterized in that it is selected from any other natural water suitable for forming. The method of claim 1, wherein the halogen atoms are used in the form of one or more salts or salt mixtures, the salts contain metal ions, the metal ions being Cr, Mn, Ru, Mo, Fe, W, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Tl, Sn, Sb, Te, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, A process for producing a fullerene derivative, characterized in that it is selected from Er, Tm, Yb, or Lu. The method of claim 1, wherein the one or more additional chemical elements are 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, Tl, Ge, Sn, Pb, As, Sb, Bi, Se, Te, La, Ce, Pr, Nd , Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or a fullerene derivative, characterized in that it may be a mixture of these elements in the form of wire, turning or powder of any size. How to produce. 6. The method of claim 1, wherein the further chemical element is nickel. 7. 7. Process according to any one of the preceding claims, characterized in that the production is carried out with simultaneous separation through sublimation. An organic semiconductor layer, characterized by containing a material produced by the method according to any one of claims 1 to 7. A doped organic semiconductor layer, characterized in that it contains a fullerene derivative and an organic hole transport semiconductor material produced by the method according to any one of claims 1 to 7. 10. The doped organic semiconductor layer of claim 9, wherein the fullerene derivative is a p-dopant for an organic hole transport semiconductor material. An organic diode, organic photoactive device, in particular a solar cell, a photodetector or a light emitting diode, having a multilayer structure, wherein at least one layer contains a fullerene derivative produced according to any one of claims 1 to 10. A battery containing a fullerene derivative produced according to the method according to any one of claims 1 to 7.

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