Oxocarbon-, pseudooxocarbon- and radialene compounds and their use

Abstract

The present invention relates to oxocarbon-, pseudooxocarbon- and radialene compounds as well as to their use as doping agent for doping an organic semiconductive matrix material, as blocker material, as charge injection layer, as electrode material as well as organic semiconductor, as well as electronic components and organic semiconductive materials using them.

Claims

1. An electronic component with an electronically functionally active region, wherein the electronically active region comprises a charge injection layer which consists of at least one oxocarbon, pseudo-oxocarbon, or radialene compound with the following formula: ##STR00013## in which n=1-4; each X.sub.1, X.sub.2, and X.sub.3 is respectively independently selected from the group consisting of C(CN).sub.2, (CF.sub.3)C(CN), (NO.sub.2)C(CN), C(halogen).sub.2, C(CF.sub.3).sub.2, NCN, O, S, NR.sub.1, ##STR00014## ##STR00015## ##STR00016## wherein X.sub.4 and X.sub.5 are respectively independently selected from the group consisting of C(CN).sub.2, (CF.sub.3)C(CN), (NO.sub.2)C(CN), C(halogen).sub.2, C(CF.sub.3).sub.2 NCN, O, S, and NR.sub.1, wherein Y=CN, NO.sub.2, COR.sub.1 or is perhalogenated alkyl; aryl, respectively Ar is a substituted or unsubstituted aromatic hydrocarbon or biaryl, or optionally polycyclic; hetaryl is a substituted or unsubstituted aromatic heterocyclic compound or biheteroaryl, optionally polynucleic or partially or completely hydrated or fluorinated; and R.sub.1-R.sub.8 are independently selected from hydrogen, halogen, CN, NO.sub.2, COR.sub.1, alkyl, alkoxy, aryl, or heteroaryl.

2. The electronic component as claimed in claim 1, wherein Y is perfluoroalkyl.

3. The electronic component as claimed in claim 2, wherein the perfluoroalkyl is CF.sub.3.

4. The electronic component as claimed in claim 1, wherein the aryl is partially or completely fluorinated.

5. The electronic component as claimed in claim 1, wherein the hetaryl is selected from pyridyl, pyrimidyl, triazine, or oxadiazole.

6. The electronic component as claimed in claim 1, wherein R.sub.1-R.sub.8 are independently selected from perhalogenated and/or partially halogenated alkyl groups.

7. The electronic component as claimed in claim 6, wherein R.sub.1-R.sub.8 are independently selected from perfluorinated alkyl groups.

8. The electronic component as claimed in claim 1, in the form of an organic light emitting diode, a photovoltaic cell, an organic solar cell, an organic diode, or an organic field effect transistor.

9. The electronic component as claimed in claim 1, wherein hetaryl is the substituted or unsubstituted aromatic heterocyclic compound or biheteroaryl, and hetaryl is electron-deficient.

Description

DETAILED DESCRIPTION

(1) In the compounds in accordance with the invention the position of the LUMO is so low that further technically interesting hole transport materials can now be efficiently doped for the first time. Due to the extremely low position of the LUMO and to the associated high reduction potential of the compounds even performance efficiencies of solar cells can be significantly improved. In addition, these compounds are extremely diffusion-stable in organic layers on account of their high polarity. The production processes can be better controlled and thus be carried out with lesser expense and in a more reproducible manner by higher evaporation temperature and lower volatility under the same conditions, whereby, by making available oxocarbons, pseudooxocarbons and radialenes as doping agents, these make possible a sufficient electrical conductivity of the organic semiconductive matrix given advantageous electron affinity of the doping agents in the particular components at low diffusion coefficients that ensure a component structure that is uniform in time. Furthermore, the charge carrier injection of contacts into the doped layer can be improved by the doping agents. Furthermore, the doped organic semiconductive material and the resulting electronic component can have an improved long-time stability on account of the compounds used in accordance with the invention. This concerns, e.g., a reduction of the doping concentration over time. This furthermore concerns the stability of the doped layer that is arranged adjacent to non-doped layers of an electro-optical component so that electro-optical components with increased long-time stability of the electro-optical properties such as light yield at a given length, effectiveness of a solar cell or the like result.

(2) The evaporation rate of a substrate with the compound used in accordance with the invention can be determined, e.g., using a quartz thickness monitor, as is customarily used, e.g., in the production of OLEDs. In particular, the ratio of the evaporation rates of matrix materials and doping agent can be measured by independent measurements of them using two separate quartz thickness monitors in order to adjust the doping ratio.

(3) It is understood that the compounds used in accordance with the invention are preferably such that they evaporate more or less or practically non-decomposed. However, if necessary, even purposeful precursors can be used as doping source that release the compounds used in accordance with the invention, e.g., acid addition salts, e.g., of a volatile or non-volatile inorganic or organic acid, or their charge transfer complexes, which acids and/or electron donors are preferably not volatile or only slightly volatile or the charge transfer complex itself acts as doping agent.

(4) The doping agent is preferably selected in such a manner that it generates a conductivity just as high as or preferably higher than F4TCNQ under conditions that are otherwise the same such as, in particular, doping concentration (molar ratio, doping agent:matrix, layer thickness, current strength) at a given matrix material (e.g., zinc phthalocyanine or another matrix material cited further below), e.g., a conductivity (s/cm) greater than/equal to 1.1 times, 1.2 times or greater than/equal to 1.5 times or twice that of F4TCNQ as doping agent.

(5) The doping agent used in accordance with the invention is preferably selected in such a manner that the semiconductive organic material doped with it still has ≥20%, preferably ≥30%, especially preferably ≥50% or 60% of the conductivity (s/cm) of the value at 100° C. after a temperature change of 100° C. to RT (20° C.).

(6) A few preferred oxocarbons, pseudooxocarbons and radialenes will be shown in the following that can be used with advantage for the purposes of the invention:

(7) ##STR00005## ##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010##

(8) Further derivatives of oxocarbon-, pseudooxocarbon- and [6] radialene structures

(9) ##STR00011##
Preparation of the Oxocarbon-, Pseudooxocarbon- and Radialene Structures

(10) The first oxocarbon compound, potassium croconate, was produced by L. Gmelin in 1825 from potash and coal. Oxocarbons and their esters and halogenides preferably react with electron-rich compounds such as aliphatic and aromatic amines, aromatics and heteroaromatics. A. H. Schmidt, Synthesis (1980) 961. The reaction products from tetrachlorocyclopropene and phenols in the presence of Lewis acids or CH-acidic compounds by strong bases, such as, e.g., arylacetonitriles, 1,3-diketones, cyclopentadienes, malonodinitriles, acceptor-substituted diarylmethanes, electron-poor diheteroarylmethanes are especially suitable for applications in accordance with the invention. [3] Radialenes are obtained after oxidation has taken place, R. West et al. J. Org. Chem. (1975) 40 2295; T. Kazuka, T. Shinji J. Chem. Soc. Chem. Commun. (1994) 519; T. Fukunaga et al. JACS (1976) 98 610.

(11) Squaric acid dichloride and phenols, that can subsequently be oxidized to 4 [radialenes] are furthermore also very well-suited, R. West, S. K. Koster J. Org. Chem. (1975) 40 2300; the nucleophilic anion of the CH-acidic melonic acid dinitrile can also be substituted with preference with esters under the splitting off of alcohol to dianionic squaric acid compounds, T. Fukanaga J. Am. Chem. Soc. (1976) 98 610; W. Ziegenbein, H.-E. Sprenger Angew. Chem. (1967) 79 581; G. Seitz et al. Chem. Ber. (1987) 120 1691. The oxidation of these CN-substituted compounds was successful only electrochemically in the past, T. A. Blinka, R. West, Tetrahedron Lett. (1983) 24 1567. [4]Radialenes can also be prepared by thermal dimerization of diquinone ethylenes, R. West, S. K. Koster, JOC (1975) 40 2300.

(12) The first croconic acid derivatives that were substituted with malodinitrile were able to be produced by Fatiadi, J. Org. Chem. (1980) 45 1338, J. Am. Chem. Soc. (1978) 100 2586. The oxidation of these compounds was also examined electrochemically by him, A. J. Fatiadi, L. M. Doane, J. Electroanal. Chem. (1982) 135 193-209.

(13) However, even [6] radialenes are known, H. Hopf, A. K. Wick Helv. Chim. Acta (1961) 46 380-6.

(14) A few later representatives were and/or are used in the electrophotography as electroluminescent material in video screens, as dye, as photoconductors, as organic oxidants, U.S. Pat. No. 4,003,943 (1977), JP 07-168377, JP 2004010703 A (2004), U.S. Pat. No. 4,133,821 (1979).

(15) Preparation of New Cyclic Oxocarbon- and Pseudooxocarbon Derivatives

EXAMPLE

a) 1,3-Bis(dicyanomethylene)indane-2-ylidene-bis(4-oxo-[3,5-di-t-butyl]-2,-5-cyclohexadienylidene)-cyclopropane

(16) 4.75 g bis(4-oxo-[3,5-di-t-butyl]-2,5-cyclohexadienyl)-cyclopropenone, 3,5 g 1,3-bis(dicyanomethylene)-indane as well as 60 mg β-alanine are dissolved in 12 ml acetic anhydride and briefly heated on the reflux under stirring. The mixture is compounded with 60 ml toluene, allowed to cool off and the reddish-brown crystalline solid removed by suction. The mixture is subsequently washed with benzene/toluene and recrystallized.

(17) Yield: 4.6 g

(18) 2.5 g of the reddish-brown crystals are dissolved under argon in 100 ml chloroform and united with a solution of 4.7 g red potassium ferrocyanide and 8.8 g KOH in 150 ml water. After 1 h intensive stirring, the organic phase is dried with Na2SO4 and evaporated to low bulk and the product recrystallized.

(19) Yield: 2.3 g blackish-green crystals fp. >250° C. under decomposition

b) (2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-pentafluor-ophenylacetonitrile)

(20) A solution of 4 g (20 mmol) pentafluorophenylacetonitrile in 10 ml glyme are added dropwise to 1.6 g NaH in 40 ml glyme and cooled with ice water. Subsequently a solution of 0.9 tetrachloro cyclopropene in 10 ml glyme was added dropwise. After stirring for 24 h at room temperature the dark mixture is poured onto ice water and is extracted with CHCl.sub.3. The extracts provide a black solid.

(21) 4 g of the raw intermediate product are dissolved in 50 ml CHCl.sub.3, and to this solution 50 ml water, containing 2 g K.sub.2CO.sub.3, is added. 0.5 ml bromine is added to this dark green 2-phase mixture under stirring. Thereafter, the phases are separated, and the organic phase is evaporated after drying over Na.sub.2SO.sub.4 using a rotatory evaporator. A remaining orange solid is recrystallized using a suitable solvent. Yield: about 70%.

(22) FP: 182° C.

c) (2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-[2′,3′,5′,-6′-tetrafluoropyrid-4′-yl] acetonitrile)

(23) 4.75 g 2,3,5,6-tetrafluoropyridyl actonitile in 10 ml glyme is added dropwise to 0.4 g LiH in 60 ml glyme. Thereafter 1.1 g tetrachlorocyclopropene is added dropwise to the solution and is stirred over night. The mixture is poured onto ice-water and is extracted with EtOAc. After drying the extracts and evaporation 4.6 g of a solid remained.

(24) 2.25 g of the solid is dissolved in 50 ml AcOH, and 5 ml HNO.sub.3 (65%) is added. Water is added to this orange-brown solution, and the precipitate obtained is isolated, washed with water and dried. Yield: 1 g. Fp: 170° C.

d) (2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(2,6-dichloro-3,5-difluoro-4-(trisfluoromethyl)phenyl)acetonitrile)

(25) 0.29 g LiH are suspended in 68 ml glyme, and cooled, and 5 g 2,6-dichloro-3,5-difluoro-4-(trifluoromethyl)phenyl)acetonitrile) in 6 ml glyme are added slowly under argon atmosphere. The mixture is heated to room temperature, and 0.8 g tetrachlorocyclopropene are added dropwise, and the mixture is stirred over night. The solution is poured onto ice-water, the precipitate obtained is isolated and dried. Yield: 4.75 g.

(26) 3.5 g of the product is dissolved in glacial acetic acid, and under cooling 7 ml HNO.sub.3 is dropwise added, subsequently water is added, and the precipitate obtained is isolated. The product is recrystallized utilizing a suitable solvent. Yield: 72%. Fp.: 185° C.

e) (2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(2,3,5,6-tetrafluoro-4-cyano-phenylacetonitrile)(2-2,3,5,6-tetrafluoro-4-trifluoromethyl-phenylacetonitrile)

(27) Internal salt: 2,3-bis(cyano(4-cyano-2,3,5,6-tetrafluorophenyl)methyl)-1-triethylamino)cycloprop-2-ene-1-ide.

(28) 5.34 g tetrachlorocyclopropene and 13.8 g 2,3,5,6-tetrafluoro-4-cyanobenzylcyanid in 300 ml CH.sub.2Cl.sub.2 are cooled, and 17.1 g triethylamine is added. The resultant product is stirred and heated to room temperature. Then water is added, and the yellow solid obtained is removed, washed and dried at air. Yield: 93%.

(29) 1.15 g 2,3,5,6-tetrafluoro-4-(trifluoromethyl)-benzylcyanid in 15 ml THF is dropwise added to 0.46 g LDA in 55 ml THF. The solution is cooled, and a suspension of 2 g of the internal salt in DMPU is added dropwise. The solution is poured into ice-water. The precipitate is removed and washed with water and subsequently dried in vacuo. Yield: 100%.

(30) 2.7 g of the material to be oxidized is dissolved in 70 ml AcOH, and 5.5 ml HNO.sub.3 (65%) is added dropwise. The material to be oxidized is then precipitated with water. After isolation, washing with water and drying in vacuo the product is obtained in a yield of 90%. Fp: >250° C.

f) (2E,2′E,2″E,2′″E)-2,2′,2″,2′″-(cyclopropane-1,2,3,4-tetraylidene)tetrakis(2-2′,3′,5′,6′-tetrafluoro-4′-cyanophenyl)acetonitrile

(31) 1.2 g 1,2-bis-tosyl-3,4-bis-dimethylamino-quadratat is heated with 2.14 g 2,3,5,6-tetrafluoro-4-cyano-benzylcyanid in 20 ml pyridin for 16 h with stirring. The solution is concentrated and given into ice-water. Thereafter it is extracted with EtOAc. Concentrating the dried extracts results in the product which can be recrystallized in a suitable solvent. Fp.: >250° C.

(32) Matrix Materials

(33) The present invention describes suitable doping agents for organic semiconductive materials such as hole transport materials HT that are customarily used in OLEDs or organic solar cells. The semiconductive materials are preferably intrinsically hole-conducting. The following can apply to doping agents of the oxocarbon- and pseudooxocarbon types in accordance with the invention.

(34) The matrix material can consist partially (>10 or >25% by weight) or substantially (>50% by weight or >75% by weight) or totally of a metal phthalocyanine complex, a porphyrine complex, especially metal porphyrine complex, oligothiophene-, oligophenyl-, oligophenylene vinylene- or oligofluorene compound, in which the oligomer preferably comprises 2-500 or more, preferably 2-100 or 2-50 or 2-10 or more monomeric units. The oligomer can also comprise >4, >6 or >10 or more monomeric units, in particular also for the above-indicated ranges, thus, e.g., 4 or 6-10 monomeric units, 6 or 10-100 monomeric units or 10-500 monomeric units. The monomers and oligomers can be substituted or unsubstituted and even block- or mixed polymerizates of the cited oligomers can be present as well as a compound with a triarylamine unit or a spiro-bifluorene compound. The cited matrix materials can also be present in combination with each other, optionally also in combination with other matrix materials. The matrix materials can have electron-donating substitutents such as alkyl- or alkoxy groups that have a reduced ionizing energy or reduce the ionizing energy of the matrix material.

(35) The metal phthalocyanine complexes or porphyrine complexes used as matrix material can have a main group metal atom or subgroup metal atom. The metal atom Me can be coordinated 4-, 5- or 6-fold, e.g., in the form of oxo-(Me=O), dioxo-(O=Me=O) imine-, diimine-, hydroxo-, dihydroxo-, amino- or diamino complexes, without being limited to them. The phthalocyanine complex or porphyrine complex can each be partially hydrogenated, however, the mesomeric ring system is preferably not disturbed. The phthalocyanine can contain, e.g., magnesium, zinc, iron, nickel, cobalt, magnesium, copper or vanadyl (=VO) as central atom. The same or other metal atoms or oxometal atoms can be present in the case of porphyrine complexes.

(36) In particular, such dopable hole transport materials HT can be arylated benzidines, e.g., N,N′-perarylated benzidines or other diamines such as of the type TPD (in which one, several or all of the aryl groups can have aromatic heteroatoms), suitable arylated starburst compounds such as N,N′,N″-perarylated starburst compounds such as the compound TDATA (in which one, several or all of the aryl groups can have aromatic heteroatoms). The aryl groups can comprise phenyl, naphthyl, pyridine, quinoline, isoquinoline, peridazine, pyrimidine, pyrazine, pyrazole, imidazole, oxazole, furan, pyrrole, indole or the like, especially for each of the above-cited compounds. The phenyl groups of the particular compounds can be partially or completely replaced by thiophene groups.

(37) ##STR00012##

(38) The material used preferably consists completely of a metal phthalocyanine complex, a porphyrine complex, a compound with a triarylamine unit or a spiro-bifluorene compound.

(39) It is understood that even other suitable organic matrix materials, in particular hole-conducting materials can be used that have semiconductive properties.

(40) Doping

(41) The doping can take place in particular in such a manner that the molar ratio of matrix molecule to doping agent, or in the case of oligomeric matrix materials the ratio of matrix monomer number to doping agent is 1:100000, preferably 1:10000, especially preferably 1:1 to 1:100000, e.g., 1:5 to 1:1000, e.g., 1:10 to 1:100, e.g., ca. 1:50 to 1:100 or also 1:25 to 1:50.

(42) Evaporation of the Doping Agents

(43) The doping of the particular matrix material (preferably indicated here as hole-conducting matrix material HT) with the doping agents to be used in accordance with the invention can be produced by one or a combination of the following processes:

(44) a) Mixed evaporation in the vacuum with a source for HT and one for the doping agent.

(45) b) Sequential deposition of HT and doping agent with subsequent inward diffusion of the doping agent by thermal treatment

(46) c) Doping of an HT layer by a solution of doping agent with subsequent evaporation of the solvent by thermal treatment

(47) d) Surface doping of an HT layer by a layer of doping agent applied on the surface.

(48) The doping can take place in such a manner that the doping agent is evaporated out of a precursor compound that releases the doping agent under heating and/or irradiation. The irradiation can take place by electromagnetic radiation, especially visible light, UV light or IR light, e.g., by laser light or also by other radiation types. The heat necessary for evaporation can substantially be made available by the irradiation and can also be radiated in a purposeful manner into certain bands of the compounds or precursors or compound complexes such as charge transfer complexes to be evaporated in order to facilitate the evaporation of the compounds by dissociation of the complexes by conversion into excited states. It is understood that the evaporation conditions described in the following are directed to those without irradiation and that uniform evaporation conditions are to be used for purposes of comparison.

(49) For example, the following can be used as precursor compounds:

(50) a) Mixtures or stoichiometric or mixed crystalline compounds of the doping agent and an inert, non-volatile substance, e.g., a polymer, molecular sieve, aluminum oxide, silica gel, and oligomers or another organic or inorganic substance with high evaporation temperature, in which the doping agent is bound primarily by van der Waals forces and/or hydrogen bridge bonding to this substance.
b) Mixture or stoichiometric or mixed crystalline compound of the doping agent and one non-volatile compound V more or less of the electron donor type, in which a more or less complete charge transfer occurs between the doping agent and the compound V as in charge transfer complexes with more or less electron-rich polyaromatics or heteroaromatics or another organic or inorganic substance with high evaporation temperature.
c) Mixture or stoichiometric or mixed crystalline compound of the doping agent and a substance that evaporates together with the doping agent and has the same or higher ionizing energy as the substance HT to be doped, so that the substance does not form a trap for holes in the organic matrix material. According to the invention the substance can also be identical to the matrix material here, e.g., be a metal phthalocyanine or benzidine derivative. Further suitable volatile co-substances such as hydroquinones, 1,4-phenylene diamines or 1-amino-4-hydroxybenzene or other compounds form quinhydrones or other charge transfer complexes.
Electronic Component

(51) A plurality of electronic components or equipment containing them can be produced using the organic compounds in accordance with the invention for producing doped organic semiconductive materials that can be arranged in particular in the form of layers or electrical line paths. In particular, the doping agents in accordance with the invention can be used to produce organic, light-emitting diodes (OLED), organic solar cells, organic diodes, especially those with a high rectification ratio such as 10.sup.3-10.sup.7, preferably 10.sup.4-10.sup.7 or 10.sup.5-10.sup.7 or organic field effect transistors. The conductivity of the doped layers and/or the improvement of the charge carrier injection of contacts into the doped layer can be improved by the doping agents in accordance with the invention. In particular in the case of OLEDs the component can have a pin structure or an inverse structure without being limited to them. However, the use of the doping agents in accordance with the invention is not limited to the advantageous exemplary embodiments cited above.

EXEMPLARY EMBODIMENTS

(52) The invention will be explained in detail with a few exemplary embodiments.

(53) The compounds to be used in accordance with the invention, in particular, the previously indicated exemplary compounds from the previously described substance class of the oxocarbon- and of the pseudooxocarbon compounds will now be used in the following manner as doping agents for different hole conductors that for their part are used for constructing certain microelectronic or optoelectronic components such as, e.g., an OLED. The doping agents can be evaporated at the same time adjacent to one another with the hole transport materials of the matrix in the high vacuum (ca. 2×10.sup.−4 Pa) at elevated temperatures. A typical substrate evaporation rate for the matrix material is 0.2 nm/s (density ca. 1.5 g/cm.sup.3). The evaporation rates for the doping agents can vary between 0.001 and 0.5 nm/s at the same assumed density in accordance with the desired doping ratio.

(54) In the following examples the current measurements were carried out over a current path of the doped HT material 1 mm long and ca. 0.5 mm wide at 1V. under these conditions ZnPc conducts practically no electrical current.

EXAMPLES

Example 1

(55) Doping of ZnPc with dicyanomethylenebis(4-oxo-[3,5-di-t-butyl]-2,5-cyclohexadienylidene)cyclo-propane

(56) Conductivity: 1,5×10.sup.−5 s/cm

Example 2

(57) Doping of spiro-TTP with dicyanomethylenebis(4-oxo-[3,5-di-t-butyl]-2,5-cyclohexadienylidene)cyclo-propane

(58) Conductivity: 3, 6×10.sup.−7 s/cm

Example 3

(59) Doping of ZnPC with 1,3-bis(dicyanomethylene)indane-2-ylidene-bis(4-oxo-[3,5-di-t-butyl]-2,5-cyclohexadienylidene)cyclopropane

(60) Conductivity: 5,8×10.sup.−6 s/cm

Example 4

(61) Doping of spiro-TTP with 1,3-bis(dicyanomethylene)indane-2-ylidene-bis(4-oxo-[3,5-di-t-butyl]-2,5-cyclohexadienylidene)cyclopropane conductivity: 5×10.sup.−7 S/cm

Example 5

(62) Doping of N.sup.4, N.sup.4-(biphenyl-4,4%-diyl)bis(N.sup.4,N.sup.4′,N.sup.4′-triphenylbiphen-yl-4,4′-diamine) with (2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triyliden)tris(2-pentafluoroph-enylacetonitrile 10%. Conductivity: 3.21×10.sup.−6 S/cm

Example 6

(63) Doping of spiro-TTP with (2E,2′E,2″E)-2,2′,2″-cyclopropane-1,2,3-triylidene)tris(2-pentafluoroph-enylacetonitrile) 10%. Conductivity: 1.89×10.sup.−6 S/cm.

Example 7

(64) Doping of 4,4′-bis(10,11-dihydro-5H-dibenzo[b,f]azepine-5-yl)biphenyl with (2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-pentafluorophenylacetonitrile) 10%. Conductivity: 1.55×10.sup.−7 S/cm.

Example 8

(65) Doping of spiro-TTP with (2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-[2′,3′, 5′,6′-tetrafluoropyrid-4′-yl]acetonitrile) 5%. Conductivity: 4.35×10.sup.−5 S/cm.

Example 9

(66) Doping of a-NPD with (2E,2′E,2″E)-2,2′,2″-cyclopropane-1,2,3-triylidene)tris(2-[2′,3′,5′,6′-tetrafluoropyrid-4′-yl]acetonitrile) 5%. Conductivity: 1.28×10.sup.−5 S/cm.

Example 10

(67) Doping of ZnPc with (N,N′,N″,N′″-cyclobutane-1,2,3,4-tetraylidene)tetraaniline 5%. Conductivity: 1.3×10.sup.−6 S/cm.

Example 11

(68) Doping of spiro-TTP with (2E,2′E,2″E,2′″E)-2,2′,2″,2′″-(cyclobutane-1,2,3,4-tetraylidene)N,N′,-N″,N′″-cyclobutane-1,2,3,4-tetraylidene)tetrakis(2-perfluorophenyl)acetonitrile) 5%. Conductivity: 3.3×10.sup.−5 S/cm.

(69) The features of the invention disclosed in the previous description and in the claims can be essential individually as well as in any combination for the realization of the invention in its various embodiments.