TW201213232A - Method for producing fullerene derivatives - Google Patents

Abstract

The present invention describes an improved method for producing halogenated fullerenes, represented by a reaction of fullerene with at least one halogen atom. The invention contains a production method for obtaining a halogenated fullerene selectively and at the same time isolating the halogenated fullerene produced thereby. The invention contains a production method with which relatively large quantities of materials can be reacted and simultaneously isolated. The invention describes the use of the fullerene C60F36 as the p-dopant for hole transport layers in semiconductive organic components with a layer arrangement including an electrode and a counter electrode as well as a series of organic layers arranged between the electrode and the counter electrode.

Description

201213232 VI. Description of the Invention: [Technical Field of the Invention] [0001] [Prior Art] [The efficacy and service life of organic semiconductor components such as organic light-emitting diodes (OLEDs) and organic solar cells in recent years Significant improvements have been made. A decisive criterion is the increased conductivity of charge-conducting layers composed of organic materials [K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Rev. 107, 1233 (2007)]. The concept of p-doping and n-doping of the charge-conducting layer is relevant for this purpose. The doping of the molecules increases the charge carrier density in the matrix and this compensates for the poor internal carrier charge mobility of the matrix. The concept of molecular doping allows the conductivity of the conductive layer to increase the strength of the order [material. (61! at 6]:,1 (.1^〇, again.2匕〇11,夂5·

Huang, M. Hofmann, A. fferner, J. Blochwitz-

Nimoth, Org. Electron. 4, 89 (2003)]. This results in a significant increase in performance because the operating voltage in the 〇LED is reduced and the series resistance in the organic solar cell is reduced. The charge energy barrier of the charge carrier is reduced and the formation of the depletion region can be easily overcome by the charge carrier via the tunneling process [J. Blochwitz, T, Fritz, M. Pfeiffer, K.

Leo, D. M. Alloway, P. A. Lee, N. R. Am- strong, Org. Electron 2, 97 (2001)]. The most effective monochrome available today [R. Meerheim, R. Nitscht 1L Leo, Appl. Phys. Lett. 93, 04331 0 (2008)] and white [S. Reineke, F. Lindner, G. Schwartz, N. Seidler , K. Walzer, B. Lussera, K. Leo, 100133011 Form No. A0101 Page 4 of 26 innq 201213232

Nature 459, 234 (2009)] ribbed and organic solar cells [press release from Heliatek GmbH: ht-tp://heliatek.de/, April 2〇1〇] use this doped layer. Doping can be achieved by simultaneously evaporating the two materials. The dopant in the gas phase is mixed with the substrate in a low ratio and deposited on the surface. in? An example of doping (hole transport) is that the matrix may contain the formula *ν,ν,ν,,ν,_tetra-u-methoxyphenyl)benzidine (Me0_TPD)). In order for doping to be possible, the substrate must have an ionization potential equal to (+/_〇·3 eV) or lower than the electron affinity of the dopant. P-dopant (fullerene derivative) The ferrocene (Fc / Fc+) should have a reduction potential greater than or equal to about _〇3 ,, preferably greater than or equal to about 〇. 〇v, more preferably greater than Or equal to about 0.24 V. Doped molecules should be able to be introduced evenly into the matrix and • should have a low tendency to diffuse. Some p with high electron affinity (E)

A doped molecules are known, such as relatively weak electron acceptors (tetracyanobenzene diterpene (TCNQ)) [M. Maitrot, G. Guillaud, B. Boudjema, JJ Andre, J. Simon, J . Appl.

Phys. 60, 2396 (1986); R. C. Wheland, J. L 0

Gillson, J. Am. Chem. Soc. 98, 3916 (1976)] or a fluorinated modification (3,6-difluoro-2, 5, 7, 7, 8, 8-hexacyanobenzidine dimethane (F2-HCNQ)) [ZQ Gao, BX Mi, GZ Xu, YQ Wan, ML Gong, KW Cheah, CH Chen, Chem. Commun., 1 17 (2008)] and often used 2,3,5,6 -tetrafluoro-7,7,8,8-tetrachloro alum methane (卩4-1^) [J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett. 73, 729 (1998); WY Gao and A. Kahn, Appl. Phys. Lett. 79, 4040 100133011 Form No. A0101 Page 5 of 26 1003451854-0 201213232 (200 1 )]. Because of its low molecular weight, this material type has a high vapor pressure and tends to cause uncontrolled contamination of the therapeutic gas deposition chamber, thus also causing the subsequent deposition of the layer. In this example, contamination of the layers in the assembly can cause excitons to be suppressed and thus impair the performance of the assembly [Βχ·Mi, Z.Q. Gao, K.W. Cheah, C. H. Chen, Appl. Phys. Lett. 94, 073507 (2009)]. Layers doped with this material type can also have low thermal stability [Ρ·WeUmann, M. Hofmann, 0. Zeika, A. Werner, J. Birnstock, R. Meer-heim, G. He, K. Walzer , M. Pfeiffer, K. Leo, J. Soc. Inf. Disp. 13, 393 (2005)]. This reduces the life of the component. Perfluorinated fullerenes also have comparable electron affinities of approximately 5 eV [N. Liu, Y. Morio, F. Okino, H. Touhara, 0. V. Boltalina, V.K. Pavlovich, Synth.

Metals 86, 2289 (1997)]. Perfluorinated fullerene CF has been studied as a p-dopant in a polymer layer before 60 36. This polymer layer was deposited in a solution-based process [0. Solomeshch, YJ Yu, AA Goryunkov , LN Sidorov, RF Tuk-tarov, DH Choi, J.-Il Jin, N. Tessler,

Adv. Mater. 21, 4456 (2009)]. This document includes a few published reports on the manufacture of fluorinated fullerenes. Boltalina et al. use various fluorochemical salts [P. A. Tro shin, 0. V. Boltalina, NV Polykova, ZE Klink-ina, J. Fluor Chem. 110, 157, (2001)], lanthanides Fluoride [AA Goryunkov, Z. Mazej, B. emva, SH Strauss, 0.V. Boltalina, Mendeleev 100133011 Form No. A0101 Page 6 of 26 1003451854-0 201213232

Commun. 16' 1 59 (2006)] or transition metal fluoride combined with fluorine gas [NS Chilingarov, AV Nikitin, J. y. Rau, IV Golyshevsky, AV Kepraan, FM Spiridonov, LN Sidorov, J. Fluor Chem. 113, 219 (2002)] to synthesize fluorinated fullerene. All of the methods cited above are based on the use of molecular fluorine during fluorination or during the fluorination of synthetic suitable reagents. Fluorine is classified as highly toxic and corrosive to many commonly used materials in instrument settings. The necessary workplace safety precautions are considered to be highly impractical and overly expensive. At the same time, this method only shows good selectivity for c F ordinary 60 3 6 and very low to normal yield (less than 3〇%).

Boltalina et al. disclose a different version of 60 3 6 for the synthesis of ρ without the use of fluorine gas, in which a nickel tube with one end closed is filled with powder of manganese fluoride (ΙΠ) and C6() [〇. Boltalina, A. Borschevskii, L. Sidrov, J. Street, R. Taylor, Chem.

Comm., 529 (1 996)]. Place the filled nickel tube in a glass sublimation tube. The glass tube was heated to 33 (TC) in a tube furnace under pressure for 3 minutes, and maintained at this temperature for 24 h. During this time, various fluorinated fullerenes were mixed. Condensed on a cold glass wall. According to mass spectrometry, this mixture consisted of 51% C6〇F36, 33%C (unreacted fullerenes), 8% C6〇F34, and 15% C6〇F32. All described methods There is a disadvantage that it cannot be upgraded to the scale of millimolar. [Invention] [0003] It is therefore an object of the present invention to present an improved method for producing a fullerene derivative of 1003451854-0. The patent scope is described in the third paragraph and the phase 100133011 Form No. A0101, page 7 / 26 pages 201213232 shall be solved by the manufacturing method of the subordinate patent application scope. In the method for manufacturing a rich derivative, in the opposite , fullerene reacts with a self-reagent, wherein at least - additional chemical elements are also added to the reactor. Advantages of this method include the use of fluorine gas in the manufacture, higher yields, and the materials produced Higher purity. The Fuller The dilute is preferably selected from the group consisting of molecular gases wherein m is selected from the group consisting of 36, 6 〇, 7 〇, 76 78 80 82 ' 84 ' 86, 9 〇, 94 or any other integer capable of forming such a spherical molecule. Preferably, m = 60, 70, 76, 80, 82, 84 '86, 90 or 94. It is preferred that the dentate is selected from the group consisting of F, C1 and Br 1. Preferably, the halogen is a metal ion-salt compound. It is used in the form of (referred to as a dentate compound in this context). The metal ion may be selected from the group consisting of chromium (Cr), 猛 ()η), nail (Ru), 翻 (M〇), iron (Fe) , 嫣 (W), 姑 (Co), money (Rh), silver (Ir), recorded (Ni), put (Pd), turn (Pt), copper (Cu), silver (Ag), gold (Au) , Ming (τι), Tin (Sn), Sb (Sb), 碲 (Te), Lead (10), Qian (Bi), Rotten (La), 钸 (Ce), 镨 (pr), Syria (M),钐 (Sm), 铕 (Eu), 釓 ((4), 铽 (several), 镝 (Dy), 鈥 (Ho), oblique (Er), ϋ (Τπι), 镱 (Yb), 镏 (Lu). The preferred compound is MnF. 3 The extra chemical elements are used in the form of wires, scraps or powders of any size. They can be introduced in pure form and become Alloy or mixture. The additional chemical elements are preferably selected from the group consisting of titanium (Ti), niobium (Zr), hunger (v), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (M〇), tungsten ( w ), Mn (Μη), 铢 (Re), iron (Fe), 钌 (Ru), 锇 (100133011 1003451854-0 Form No. A0101 Page 8 of 26 201213232 〇s), Ming (c〇), |^(Rh), silver (Ir), recorded (Ni), put (Pd), l6 (Pt), copper (Cu), silver (Ag), gold (An), zinc (Zn), edit (Cd) Ήμ), marry (Ga), steel (1)), snake (τι), 锗 (Ge), tin (Sn), ship (pb), arsenic...), recorded (Sb), ^ (Bi), 砸 (Se) , 碲 (Te), steel (

La), Ce (Ce), 镨 (Pr), Syria (Nd), #(Sm), money (EU), 釓 (Gd), 铽 (Tb), (Dy), 鈥 (H〇),

A group consisting of oblique (Er), _ (Tm), 镱 (Yb), and (Lu). Nickel (Ni) is particularly preferred. The presene-halogen derivative preferably has the formula C^n, wherein n can be from 1 to m. C6〇F36 (m = 60, η = 36) and C6〇F34 to 48 (m = 60, n = 34) 〇 In a specific embodiment of the invention, fullerene is added to the 之前 before the reaction Chemical elements are mixed. Fullerenes, at least one additional chemical element, and a pixel compound are preferably mixed prior to the reaction.

The reactor is a chemical reactor that is close to the environment (e.g., the atmosphere) during the reaction. The chemical reactor can be a boiler, a transfer pipe or, for example, some other container. Some connected containers can also be used. In an advantageous configuration of the invention, the reactor is an elongated vessel, such as a sublimation tube, wherein the manufacture takes place via sublimation and simultaneous separation. It is assumed that a fullerene derivative is used in an organic semiconductor layer. The fullerene derivative can form an organic semiconductor layer. 100133011 Also in accordance with the present invention, the organic semiconductor layer is a fullerene derivative comprising an organic hole transport semiconductor material as a host and a doped layer as a p-dopant. Doped semiconductors having an increased charge carrier density and effective charge carrier mobility can be fabricated by performing the method according to the present invention. Form No. A0101 Page 9 of 26 1003451854-0 201213232 Body material. The fullerene derivative is advantageously an organic diode, and the component of the organic photoactive component is 'special' a component of a solar cell, a photodetector or a light emitting diode. An assembly containing at least one organic semiconductor layer is considered to be an organic component. For the purposes of the present invention, fullerenes and derivatives thereof are also included herein. The organic semiconductor layer also contains an organic molecule called a "small molecule" or an organic polymer, which is a single layer or a mixture mixed with other organic substances (for example, as described in US Pat. No. 5, No. 11-9). The organic molecules and organic polymers in those or in organic materials have semiconductor or metal-like properties. Organic light-emitting diodes are typically constructed from a number of different organic material layers, at least one layer (light-emitting layer) containing an electroluminescent material that can be induced to emit light when a voltage is applied thereto (Tang, US 4, 76 9, 292 ). For example, high efficiency 〇led is described in US 7,074,500. The construction of solar cells is known to those of ordinary skill in the art, see Epi 861 886 and EP 1859494. A particularly preferred component is a doping component as described by Walzer et al. [Chem. Rev. 107, 1 233 (2007)]. The fullerene derivative advantageously forms part of a battery, preferably a cathode [N, Liu, H. Touhara, F. Okino, S. Kawasaki, Y. Nakacho, J. Electrochem. Soc. 143, 2267 (1996)] . [Embodiment] [0004] 100133011 An example of synthesizing C6()F36 is at 1 (Γ3 mbai·pressure and 2〇(Γ(:temperature, within 24 h from MnF3 (ABCR, 98%) for synthesis) Trace traces of water and oxygen. Purify from the form number A0101, page 10 of 26 inn, a chemical supplier (eg American Dye Source), and purify it by secondary sublimation. In a nitrogen environment The fullerene ς 6〇 (1·00 g; 1. 388 mraol) and MnF3 (5 59 g; 6〇·15 mmol) were completely ground in a sanding disc. Nickel powder (6.6 1%) was added to In a mixture of nickel crucibles, and place the filled nickel crucible in a sublimation device as shown in Figure 1. The sublimation tube is heated to a temperature of 330 ° C up to 24 at a pressure of 4 x 1 〇 -4 mbar h, during which the fluorinated reaction product condenses on the cooler portion of the sublimation tube in the form of a yellow-white solid (〇76 g). The ring loaded with condensate undergoes a further sublimation step in which Finally, a product of 〇·75 g (0 534 mmol, 38% theoretical yield) was isolated. To analyze the residue of the sublimation product, the sample was finished. Yue stupid dissolved in and completely evaporated in a mass spectrometer. All measured total ion current, and 2 are shown in FIG. Present in the sample

The strength ratios of all compounds correspond to the following compositions: 84% C F 60 36 , 14% c6QF34, and 2% c6De Process Example 1 Description of the contamination behavior of the dopant compared to L-TCNQ. 4 01) 〇〇 The purpose of this is to verify the volatilization of doped *F4-TCNQ and C6QF36, and to provide evidence that does not show any chamber contamination unlike F4-TCNQ, c6()f36. The volatility of the dopants F4-TCNQ and C6QF36 in the undoped Me〇-TPD layer was examined using X-ray photoelectron spectroscopy (XPS), reference dopants F4-TCNQ, and CenFQC fluorine signals. Figure 4 shows a comparison of the Is fluorine core signals obtained in XPS measurements on a 10 nm thick internal Me〇-TPD layer. These are created in a chamber that does not contain the dopants or contains one of the two dopants in the unheated source. Form No. A0101 Page 11 of 26201213232 In the cavity to the middle of f "tcnq, only 689. 5eV beam If% of the significant fluorine signal can be observed on the layer undergoing evaporation. In the ultraviolet photoelectron spectroscopy ( _ In this layer, the layer also exhibits a doping effect in the form of a significant displacement toward the Fermi energy (eb = 0eV) of the highest occupied molecular orbital ( _ 〇 ) of Me 〇 TpD. Relative to (;; (6), There is a sample of τ undergoing evaporation, which confirms the contamination of the F4*~tcnq molecule. In the sample from the chamber with Ce〇F36, no fluorine signal was observed in xps, and there was no HOMO displacement in the UPS. That is to say, no contamination is observed in the MeO-TPD layer. Considering the treatment of the hole conducting layer, the very low volatility of 'C6〇F36' represents a significant advantage compared to F4_tcnq. Process Example 2 FrT (10), a description of the thermal stability of a hole conducting layer doped with c6Gf36. The purpose is to present the thermal stability of the hole conduction doped with C60f36. To test the thermal stability, because the matrix material N, N, _ ((二笨基_ N,N'-double) 9,9,-two High glass transition temperature (TG = 160 ° C) (US20020171358 A1) 'The substrate material N, N, - ((diphenyl-N, N,-bis) 9,9,-monomethyl-burial-2-yl)-biphenylamine (BF-DPB). Its conductive behavior depending on the temperature at which TG is reached is therefore attributable to the dopant. With a ratio of 26 mol% F-TCNQ and 21 mol% CF, the two layers exhibit comparable conductivity of 3 · 1 〇_6 S era-1 at room temperature (Fig. 6). In this context 'The lower doping with C6〇F36 is a higher doping efficiency of the dopant. Since the LUM0 of F4-TCNQ is very close to the HOMO level of BF-DPB according to UPS (-5. 23 eV) The same, the charge transfer generated in this system is inefficient. Because 100133011 Form No. A0101 Page 12 of 26 1003451854-0 201213232 It can be assumed that CuFu has stronger electron affinity than F plant TCNQ. When the temperature is 60 36 4 When lifting, the conductivity of the two layers increases, f4—tcnQ activation energy 265meV and CenFQe activation energy 692meV reach the maximum, and if the temperature increases by 60 〇b, further The conductivity is not disintegrated. At 145 ° C, a lower stability is observed in the BF-DPB/F4-TCNQ layer, and there is a decrease in conductivity. In the layer of BF_DPB/CF, the layer collapses before 18 (TC). Will occur and therefore be high in the matrix material. The decline in conductivity is therefore not directly attributable to

G c60f36 dopant. Process Example 3 说明 A description of the hole conducting layer doped with C6〇F36 in an OLED compared to F4-TCNQ. Phosphorescent p_i_n 0LEDs with orange-red illumination are used to compare dopants in the assembly. The layer structure of the fabricated assembly is depicted in Figure 7. The organic layer was placed on a glass substrate between a 9 Å thick indium tin oxide (ITO) anode and a 1 〇〇 thick silver covered joint. As a hole conducting layer (HTL) with 1% by weight of F4-TCNQ or 8 weight percent doped 60 nm thick MeO-TPD layer, a conductivity of about 2.1〇_5S cm_1 was achieved with the hole conducting layer. . The 65 nm doped planer 4,7-diphenyl-1,10-phenanthrenequinone (BPhen) acts as an electron conducting layer (ETL) and provides similar conductivity. In order to concentrate the charge injected in the luminescent layer (EML), 2, 2', 7, 7'-tetra-(N, N-diphenylamino)_9,9 _ is included on either side of the EML. Spiro_TAD and BPhen's 10 nm thick electrons and hole barriers (EBL, HBL). 20 nm thick EML consists of 10 weight percent triplet bis(2-methyldibenzo-[f,h]〇|; whistle 0 acetylpyruvyl pyruvate (III) (Ir(MDQ) ( Acac)) doped yttrium, Ν'-bis(naphthalen-2-yl)-indole, Ν'-diphenyl- phenylideneamine (a_NpD) 100133011 Form No. A0101 Page 13 of 26 1003451854-0 201213232 Composition. As shown in Figure 8, 'two LEDs show the same electroluminescence spectrum that prevents c F from sending 6 0 3 6 ~ ^. The current-voltage curves of the two comparison components are similar (9th Figure), although the I (V) characteristic curve with c ^ Fm_ dopant is steep, indicating that hole injection is better for equal layer conductivity. Larger hole injection increases charge carrier density and offset The charge carrier balance in EML leads to higher efficiency of C60F36〇LED (Fig. 10) Process Example 4 Compared to F4-TCNQ, doping c F is used in organic solar cells.

60 36 J Description of the hole conducting layer. The service life measurement of the assembly thus obtained shows the stability of the use of the assembly using a hybrid layer of zinc hydride (ZnPc) and C60 as a provider-receiver-absorber pair. The layer structure of the assembly thus produced is shown in Figure U. A 60 nn^Me〇_ TPD layer doped with 2% by weight of F4-TCNQ or 8 weight percent of CsqF36 was used as the hole conducting layer (JJTL). C6〇 and ZnPc (1:1) 30 nm hybrid layer act as an absorption layer, which is close to 3〇(10) thick internal c 60s. Electron transport was ensured by a 15 nm thick C6() layer doped with 3 weight percent of 3,6-bis(dimethylamino)acridine (AOB). The reflective cathode is formed from a 100 nm thick aluminum layer. As shown in Figure 12, the two solar cells are comparable in terms of all parameters and exhibit only the smallest differences that fall within the range of measurement uncertainty. The open-end voltage (V) is not affected by the \J V»/ dopant. The (:6{^36 doping caused a very slight decrease in series resistance. Too% of the battery was aged at 50 °C and under illumination from a white LED with a 500 mW cm-2 turn. Figure 13 depicts The difference in durability of organic solar cells. Because of the low glass transition temperature of f4-tcnq, there is less than one solar cell with 10013311 Form No. A0101 Page 14/26 Page 1003451854-0 201213232 〇[0005] The use of a hundred hours of life Ρ ' makes this material completely unsuitable for commercial use. Conversely, batteries containing c have fixed battery parameters of more than 500 hours. Field & 6 <) 36 W, the stability of these batteries The properties are significantly greater than the use of F4~TCNQ cell stabilizers for their use as Pin OLEDs and p-substitutes in organic solar cells'. It can therefore be concluded that replacing FfTCNQ is associated with improved components and better component stability. In addition, the low of ' Ce()F36 dopant: Barometric pressure means that the chamber will not be contaminated during the manufacturing process. ~ [Simple description of the diagram] Fig. 1: Schematic diagram of equipment for manufacturing c60f36 on a millimolar scale. Figure 2: Mass spectrometer analysis of the reaction product. Figure 3: ORTEP image of the molecular structure of the p-dopant C6〇F36 and the structure of the p-doping plant TCNQ and MeO-TPD. Figure 4: Measurement of the contamination behavior of p-dopants F, -TCNQ and C F 4 60 36 using UPS and XPS. Figure 5: Structure of BF-DPB. Ο δ: Thermal stability of the hole transport layer containing #F4-TCNQ or C6qF36 0 100133011 Figure 7: Layer construction and composition of OLED, as well as Bphen, Spiro-TAD, a-NPIUx & Ir (MDQ ) The structure of 2acac. Figure 8: Comparison of electroluminescence spectra of OLEDs. Figure 9: Comparison of the characteristic I(v) curves of two OLEDs and cold light. Figure 10: Comparison of energy production and external quantum efficiency of OLED. Figure 11 - Layer construction and composition of organic solar cells, and structure of ZnPc. Figure 12: Two organic solar cells in the solar simulator (AM1.5) Form No. AG1G1 Page 15 of 26 1003451854-0 201213232 Illumination and feature I ( v ) curves in the dark and characteristic performance parameters Comparison. Figure 13: Comparison of characteristic parameters of aging in chronological order. [Explanation of main component symbols] [0006] a-NPD Ν, Ν' _ bis(naphthalen-2-yl)-n, N,-diphenyl-benzidine Α0Β 3,6-bis(didecylamino) Bite BF-DPB N, Ν'-((diphenyl-N,N' _bis) 9,9-dimethyl- -2-phenylbenzidine BPhen 4, 7-di-phenyl-1, ι 〇-o-phenanthroline F4_TCNQ 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano styrene> dimethyl sulphide Ir(MDQ) 2acac triple illuminant bis (2-A Base two stupid-[f, h] quinoxaline) silver acetyl phthalate (Π I) ITO indium tin oxide

MeO-TPD Ν,Ν,Ν’,Ν’-tetra-(4-methoxyphenyl)benzidine

Spiro-TAD 2, 2',7, 7,-tetra-(N,N-diphenylamino)-9, 9'-spirobis UPS UV photoelectron spectroscopy XPS X-ray photoelectron spectroscopy

ZnPc zinc cyanide 100133011 Form No. A0101 Page 16 of 26 1003451854-0

Claims (1)

201213232 VII. Patent application scope: A method for producing a fullerene derivative, wherein a fullerene is reacted with at least one halogen atom in a reactor, characterized in that at least - additional chemical elements are added To the reactor. The method for producing a fullerene derivative as described in claim 1 is characterized in that at least one halogen atom is selected from the group consisting of F, C1, and Β. The method for producing a fullerene derivative according to any one of the preceding claims, wherein the fullerene is a spherical carbon having a molecular formula 镇 town' where m is selected from 36, 60, 70, 76, 78, 80, 82, 84 or any other natural number suitable for forming such spherical molecules. The method for producing a Fullerene derivative according to any one of the preceding claims, wherein the functional atom is used in the form of at least one salt or a mixture of salts, wherein the salt contains a metal ion. , by ion selection, Mn, Ru, Mo, Fe, [co'Rh, 'IrrN^ Pd'Pt, CU, Ag, AU, Tl, Sn, Sb, Te, Pb, Bi, La, Ce, Pr, Nd, Sm 'Eu, Gd, Tb, Dy, H〇' Er, Tm, Yb, Lu. The method for producing a Fullerene derivative 7 according to the scope of the patent, wherein the at least the additional chemical elements may be Ti, r, V, Nb, Ta, Cr. , M〇, w, Mn, Re, Fe, Ru, 〇s, C0, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, cdAi, Ga, In, T1, Ge, Sn, Pb , AS, Sb, Bi, Se, Te, La Ce ' Pr, Nd, such as, Eu, Gd, flutter, ^, n, the 'Yb' Ub any size of metal wire, car scrap or powder form elements a mixture. 100133011 Form No. A0101 * 17 pages/total 26 pages 1003451854-0 201213232 6. A method for producing a fullerene derivative according to any one of the claims, wherein the additional chemical element is nickel. 7. A method for making a Fuller-backed creature as described in any one of the claims, wherein the manufacturing occurs simultaneously with the separation via sublimation. An organic semiconductor layer is characterized in that it contains a material which has been produced in a process as described in any one of the above-mentioned claims. A doped organic semiconductor layer characterized by being contained in the scope of the aforementioned patent application! An organic hole transport semiconductor material and a fullerene derivative which have been fabricated in the process described in any of the items of the seventh item. The doped organic semiconductor layer according to claim 9 is characterized in that the Fuller compound is a p-dopant for the organic hole material. 11 12 - a multi-layered organic diode, an organic photoactive component, in particular a solar cell, a light-emitting device or a light-emitting device, wherein at least one of the plurality of layers contains any of the materials according to the scope of the aforementioned patent application A fullerene derivative has been produced. A fullerene derivative battery which is produced by the process described in the above-mentioned Patent Application Nos. 1 to 7. 100133011 Form NumberΑ0101 Page 18 of 26 1003451854-