EP1476881A2 - Doped organic semiconductor material and method for production thereof - Google Patents

Abstract

The invention relates to a doped organic semiconductor material with increased charge carrier density and more effective charge carrier mobility, which may be obtained by doping an organic semiconductor material with a chemical compound comprising one or several organic molecular groups (A) and at least one further compound partner (B). The desired doping effect is achieved after cleavage of at least one organic molecular group (A) from the chemical compound by means of at least one organic molecular group (A) or by means of the product of a reaction of at least one molecular group (A) with another atom or molecule. A method for production thereof is disclosed.

Description

Doped organic semiconductor material and process for its production

description

The invention relates to doped organic semiconductor material with increased charge carrier density and effective charge carrier mobility according to claim 1, a method for producing the doped organic semiconductor material according to claim 48 and the use of the semiconductor material.

Since the demonstration of organic light-emitting diodes and solar cells in 1989 [C.W. Tang et al., Appl. Phys. Lett. 51 (12), 913 (1987)] are components of organic thin films which are the subject of intensive research. Such layers have advantageous properties for the applications mentioned, such as efficient electroluminescence for organic light-emitting diodes, high absorption coefficients in the range of visible light for organic solar cells, inexpensive manufacture of materials and manufacture of components for the simplest electronic circuits, among others The use of organic light-emitting diodes for display applications is already of commercial importance.

The performance characteristics of (opto) electronic multilayer components are determined, among other things, by the ability of the layers to transport the charge carriers. In the case of light-emitting diodes, the ohmic losses in the charge transport layers during operation are related to the conductivity, which on the one hand has a direct influence on the required operating voltage, but on the other hand also determines the thermal load on the component. Furthermore, depending on the charge carrier concentration of the organic layers, there is a band bending in the vicinity of a metal contact, which facilitates the injection of charge carriers and can thus reduce the contact resistance. Similar considerations for organic solar cells lead to the conclusion that their efficiency is also determined by the transport properties for charge carriers.

By doping hole transport layers with a suitable acceptor material (p-doping) or electron transport layers with a donor material (n-doping), the charge carrier density in organic solids (and thus the conductivity) can be increased considerably. In addition, in analogy to the experience with inorganic semiconductors, applications are expected that are based on the use of p- and n-doped Layers are based in a component and would not otherwise be conceivable. US Pat. No. 5,093,698 describes the use of doped charge carrier transport layers (p-doping of the hole transport layer by admixing acceptor-like molecules, n-doping of the electron transport layer by admixing donor-like molecules) in organic light-emitting diodes.

The following approaches are known for improving the conductivity of organic vapor-deposited layers:

1. Increasing the mobility of the charge carriers through a) use of electron transport layers consisting of organic radicals (US Pat. No. 5,811,833), b) generation of highly ordered layers which allow an optimal overlap of the pi orbitals of the molecules,

2. Increasing the density of the mobile charge carriers by a) cleaning and careful treatment of the materials in order to avoid the formation of charge carrier traps, b) doping of organic layers by means of aa) inorganic materials (gases, alkali atoms patent US Pat. No. 6,013,384 (J. Kido et al. ); J. Kido et al., Appl. Phys. Lett. 73, 2866 (1998)), bb) organic materials (TNCQ (M. Maitrot et al., J. Appl. Phys., 60 (7), 2396 -2400 (1986)), F4TCNQ (M. Pfeiffer et al., Appl. Phys. Lett., 73 (22), 3202 (1998)), BEDT-TTF (A. Nollau et al., J. Appl. Phys ., 87 (9), 434Ö (2000)))

Doped organic charge transport layers have already been successfully used to improve organic light-emitting diodes. By doping the hole transport layer with the acceptor material F4TCNQ, the operating voltage of the light-emitting diode is drastically reduced (X. Zhou et al, Appl. Phys. Lett., 78 (4), 410 (2001).). A similar success can be achieved by doping the electron-transporting layer with Cs or Li (J. Kido et al., Appl. Phys. Lett., 73 (20), 2866 (1998); J.-S. Huang et al. , Appl. Phys. Lett., 80, 139 (2002)).

The electrical doping with inorganic materials suffers from the lack that the atoms or molecules used are easy in the component due to their small size can diffuse and thus complicate a defined production, for example, sharp transitions from p-doped to n-doped regions. In contrast, diffusion plays a subordinate role when large organic molecules are used as dopants. However, their use is impaired by the fact that potential doping molecules must be characterized by extreme values of the electron affinity for the p-doping or the ionization potential for the n-doping. This is accompanied by a decreasing chemical stability of the molecules.

The object of the invention is now to provide a solution for overcoming the chemical instability of efficient doping molecules mentioned and the production of layers doped therewith.

According to the invention the object is achieved by the features mentioned in claim 1. Advantageous refinements are the subject of dependent claims.

The object is further achieved by a method with the features mentioned in claim 48. Advantageous variants of the method are the subject of dependent claims.

In the invention, organic molecules are used which, although unstable in the neutral state, are stable as a charged cation or anion or in connection with a covalent connecting partner. These charged molecules are made in situ from a precursor compound that is converted into the desired charged molecule before, during, or after the vapor deposition process. Without limitation, such a connection may e.g. an organic salt or a metal complex. The unstable dopant can also be generated in situ from a stable precursor.

So far, the doping molecule used has been introduced into the layer to be doped in the neutral state, in order to then be present as an anion or cation after a charge transfer to the matrix. The use of the neutral molecule is therefore only an intermediate step in bringing about the charge transfer. The associated stability problems already described can be avoided according to the invention by using an already ionized, stable molecule as dopant.

If necessary, other methods are used to support the dissociation of the precursor compound. These conduct the necessary energy to split the connection to, or cause a chemical reaction with the undesirable remainder of the precursor compound so that it does not get into the layer or is easier to remove from it, or does not impair the electrical properties of this layer. An advantageous solution according to the invention is, for example, the use of a laser for the evaporation of rhodamine B chloride, which leads to the predominant production of rhodamine B cations.

Even if the previous description is based on splitting off an already charged molecular group according to claim 1, the purpose of the invention can also be achieved if a neutral radical is first generated from the compound according to claim 1, which is sufficiently stable in situ to be able to Layer to be installed, and this in the layer is subject to a transfer of the radical electron to the matrix or a recording of another electron from the matrix.

No. 5,811,833 describes an electron transport layer consisting of free radicals, in particular pentaphenylcyclopentadienyl, for use in organic light-emitting diodes. US Pat. No. 5,922,396 shows that such a layer can be produced from organometallic compounds, in particular from decaphenylgermanocen or decaphenylplumbocen (see also M. L Heeg, J. Organometallic Chem., 346, 321 (1988)). US Pat. No. 5,811,833 and US Pat. No. 5,922,396 lead to layers with increased microscopic charge carrier mobility (or the transfer rates in the hopping process), since a negatively charged pentaphenylcylclopentadienyl molecule has an aromatic character, and thus the electron transfer to an adjacent neutral pentaphenylcyclopentadienyl molecule due to the electron overlap of the pi orbitals the phenyl groups of the molecules involved is improved. The increase in conductivity is achieved by increasing the microscopic mobility of the charge carriers (or the transfer rates in the hopping process). In contrast, the equilibrium charge carrier density is increased according to the invention in order to increase the conductivity. Discrimination is possible, for example, through time-of-flight (measurement of charge carrier mobility), the Seebeck effect or the field effect (measurement of charge carrier density).

The invention further relates to the use of the doping molecules in mixed layers which additionally contain materials in order to achieve a further purpose. These purposes can, for example, change the layer growth, the production of interpenetrating Networks (CJ Brabec et al., Adv. Mater., 11 (1), 15 (2001)), or in organic light-emitting diodes to improve the quantum efficiency of light emission or change the color of the emitted light by adding a luminescent dye substance.

Furthermore, it is within the meaning of the invention that, by suitable selection of the doping molecule used, such purposes can be achieved by adding the doping molecules to the layer. For example, cationic dyes such as rhodamine B often have a high luminescence quantum yield, which enables use as luminescence dyes in organic LEDs.

Finally, this invention also encompasses the use of molecules from claim 1 for doping polymer layers. Such layers are typically produced by a spin coating process by deposition from the solution. In contrast to the already known electrochemical doping, in which the anions and cations of a salt are drawn to the respective contacts by the applied voltage and are therefore movable, the present invention enables the polymer layers to be doped with large, non-mobile molecules.

An exemplary embodiment to illustrate the invention consists in the use of the dye molecule rhodamine B chloride as dopant. If a mixed layer of naphthalene tetracarboxylic acid dianhydride (NTCDA) and rhodamine B in the ratio (150: 1) is produced, the conductivity is le-5 S / cm at room temperature, which corresponds to an increase of 4 orders of magnitude compared to a pure NTCDA layer. The physical explanation for this is that Rhodamine B chloride molecules disintegrate into positively charged Rhodamine B molecules and negatively charged chloride ions during heating in the cuvette. The charged rhodamine B molecules are built into the mixed layer. The electrons required to maintain the charge neutrality of the entire layer remain on the NTCDA molecules, since the electron affinity of NTCDA is higher than that of rhodamine B (3.2 eV, H. Meier, "Organic Semiconductors", Verlag Chemie Weinheim, 1974, p. These electrons fill the lowest unoccupied orbitals of the NTCDA and thus increase the conductivity. The increased density of the charge carriers can be determined, for example, by measurements of the Seebeck coefficient and the field effect. Field effect measurements on a sample made of NTCDA doped with pyronin B (50: 1 ) confirms the presence of electrons as majority carriers with a concentration of 10 ¹⁷ cm ^"3 . From Seebeck measurements This system also follows an n-line, with a Seebeck coefficient of -1.1 mN / K and thus a higher charge carrier concentration than was previously possible with doped NTCDA (A. Nollau et al, J. Appl. Phys., 87 (9), 4340 (2000)).

If a layer of C60 (fullerene) (50: 1) doped with Rhodamine B is prepared with an increased substrate temperature, the conductivity is 6e-3 S / cm. This is two orders of magnitude larger than a sample produced at room temperature (5e-5S / cm). The heat supplied during the vapor deposition leads to an increased breakdown of the rhodamine B.

The doping effect of rhodamine B was also used for matrices made of MePTCDI (perylene-3,4,9,10-tetracarboxylic acid-N, N'-dimethyl-diimide) and PTCDA (3,4,9,10-

Perylenetetracarboxylic acid dianhydride) and is therefore independent of the concrete chemical structure of the matrix.

A strong known organic donor, tetrathiafulvalene (TTF), has an oxidation potential of +0.35 V against SCE (Y. Misaki et al., Adv. Mater. 8, 804 (1996)). Stronger donors, i.e. Dopants with a lower oxidation potential are unstable in air (GC Papavassiliou, A. Terzis, P. Delhaes, in: HS Nalwa (Ed.) Handbook of conductive molecules and polymers, Vol. 1: charge-transfer salts, fillers and photoconductors, John Wiley & Sons, Chichester, 1997). Rhodamine B has a reduction potential of -0.545 V versus NHE (M. S. Chan, J. R. Bolton, Solar Energy, 24, 561 (1980)), i.e. -0.79 V against SCE. The reduction potential of the organic salt rhodamine B is determined by the reduction potential of the rhodamine B cation. This value is equal to the oxidation potential of the neutral Rhodamine B radical. As a result, the rhodamine B radical is a stronger donor than TTF. In the chemical compound rhodamine B chloride, however, this strong donor rhodamine B is stable. So far it has been possible to use donors with an oxidation potential greater than +0.35 V against SCE, but the invention described here allows doping with donors whose oxidation potential is less than +0.35 V against SCE.

Chemically stable compounds within the meaning of claim 1 are, for example, ionic dyes. These are used in photography to sensitize AgBr, for example. The electron affinity of AgBr is 3.5eV. Dyes which can sensitize AgBr by electron transfer are also suitable as chemically stable compounds for use in doping organic semiconductor materials within the meaning of claim 1. A subclass of the ionic dyes are the di- and triphenylmethane dyes and their known analogues of the general structure T 2 and T 2

+ or -

T l T 2 where X CR ⁴ , SiR ⁴ , GeR ⁴ , SnR ⁴ , PbR ⁴ , N, P and Rl, R2, R3 and R ^{4 are} suitable, known substituents, for example in each case one or more: hydrogen; Oxygen; Halogens, for example fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, for example diphenylaminyl, diethylaminyl; Aliphatics with 1 to 20 carbon atoms, for example methyl, ethyl, carboxyl; Alkoxyl, for example: methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl having 3 to 25 carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. One or more p-position substitutions of the phenyl groups can often be found (M 3 to M 6).

T 3 T 4

T 5 T 6 where X CR8, SiR8, GeR8, SnR8, PbR8, N, P and Rl to R7 and R8 are suitable known substituents, e.g. one or more each: hydrogen; Oxygen; Halogens, e.g. Fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, e.g. Diphenylaminyl, diethylaminyl; Aliphates with 1 to 20 carbon atoms, e.g. Methyl, ethyl, carboxyl; Alkoxyl e.g. methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl of 3 to 25 carbon atoms, e.g. Are phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. Examples of diphenylmethane dyes are Auramin O (CI 655) or Auramin G (CI 656). Examples of triphenylmethane dyes are malachite green (CI 657), turquoise blue (CI 661), fluorescein (CI 45350) or patent blue V (CI 712).

The representative of the triphenylmethane dyes malachite green chloride produces a conductivity of 4-10 ^"4 S / cm in an NTCDA matrix with a doping ratio of 1: 122. Malachite green is therefore a compound in the sense of claim 11 and in particular in the sense of subclaims 12 to 22 This property is brought about by the valence structure of the central carbon atom (main group 4), and other known compounds of this type of structure with atoms of the main group 4 as central atom (triarylsilyl, germyl, stannyl, plumbyl) are accordingly likewise suitable as a compound in the sense of claims 1, 12 to 22. Compounds in which there is a direct bond between 2 carbon atoms of each phenyl ring of the di- or triphenylamine are contained in claims 23 to 25.

The doping effect also occurs when using the leuco forms (T 7 T 8) of the ionic dyes. Rhodamine B base has a doping effect on a PTCDA matrix, for example a conductivity of 7 * 10-5 S / cm for a 1:70 doping.

M 7 M 8

Another group of ionic dyes are the xanthene dyes. The Rhodamine B listed above is a representative of this class. Pyronin B, Rhodamine 110 and Rhodamine 3B as further representatives of this class of materials also have a doping effect. The xanthene dyes are similar the pyran, thiopyran, indamine, acridine, azine, oxazine and thiazine dyes, which differ in substitutions in the multinuclear heterocycle. Because of the otherwise identical structure, these dye classes (T 9) are also suitable compounds in the sense of claims 1, 23 to 26.

M 9

Dyes on a polymethine structure

+ or

based also act as dopants.

In an NTCDA matrix, N, N'-diethyl-cyanine and N.N'-diethyl-thiacarbocyanine increase the conductivity to 3-10 ^"5 S / cm (1:11 doping ratio) or 5-10 ^{" 5} S / cm (1:47 doping ratio). These two dyes are each a representative of the polymethm dyes with a specific choice of X and Z. The leuco bases of ionic dyes are also suitable compounds in the sense of claims 1, 12 to 26. For example, rhodamine B base in NTCDA gives a conductivity of 3-10 ^"5 S / cm (1:70 doping ratio).

Since the doping effect does not depend on the dye property of the ionic dyes, but rather on their character as an organic salt, other organic salts also act as a compound within the meaning of claim 11. Organic salts are often based on suitable heterocycles (e.g. pyridinium, pyrrolium, pyrylium, thiazolium , Diazininium, thininium, diazolium, thiadiazolium or dithiolium etc. individually or as part of a multinuclear heterocycle) or suitable groups (eg ammonium, sulfonium, phosphonium, iodonium etc.).

Mass spectrometric studies in the case of pyronine B chloride show that evaporation of pyronine B produces, inter alia, HCl and a protonated form of pyronine B with a mass number of 324. Apparently, the chlorine radicals and neutral pyronin B radicals generated during the decomposition of pyronine B chloride are saturated by a proton. These protons are supplied by other pyronin B molecules in the vaporising substance. An evaporated layer of pyronine B chloride is initially colorless. This proves the formation of the neutral pyronine B. Under the influence of oxygen, the vapor deposition layer turns red again, which corresponds to the formation of the pyronine B cation, i.e. the vaporized substance is oxidized under the influence of oxygen. This process also takes place in a mixed layer of matrix and dopant. Evaporation mixed layers of pyronine B chloride and tetracyanoquinodimethane are immediately colored red, and the presence of tetracyanoquinodimethane anions can be detected by UV / VIS and FTIR spectroscopy.

Claims

claims 1. Doped organic semiconductor material with increased charge carrier density and effective charge carrier mobility, obtainable by doping an organic semiconductor material with a chemical compound consisting of one or more organic molecular groups A with at least one further compound partner B, the desired doping effect after splitting off at least one organic molecular group A from which the chemical compound is obtained by at least one organic molecular group A or by the product of a reaction of at least one molecular group A with another atom or molecule. 2. Doped organic semiconductor material according to one of claims 1, in which at least one of the further connecting partners B is the same molecular group as A. 3. Doped organic semiconductor material according to one of claims 1 to 2, in which the further connecting partner B is a molecular group, an atom or an ion. 4. Doped organic semiconductor material according to one of claims 1 to 3, in which the molecular group A is present in the chemical compound as a single or multiply charged cation or anion. 5. Doped organic semiconductor material according to one of claims 1 to 4, in which the molecular group A is based on one or more pyridinium units. 6. Doped organic semiconductor material according to claim 5, in which one or more pyridinium units occur as part of one or more multinuclear heterocycles. 7. Doped organic semiconductor material according to one of claims 5 and 6, in which the molecular group A on the structure is based, wherein: Rl, R2, R3 and R4, for example, each one or more: hydrogen; Oxygen; Halogens, for example fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, for example diphenylaminyl, diethylaminyl; Aliphatics with 1 to 20 carbon atoms, for example methyl, ethyl, carboxyl; Alkoxyl, for example: methoxy; cyano; Sulfonic acid and its salts; Aryl having 3 to 25 carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 8. Doped organic semiconductor material according to one of claims 1 to 4, in which the molecular group A is based on one or more pyrrolium, pyrylium, thiazolium, diazininium, thininium, diazolium, thiadiazolium, tetrazolium or dithiolium units. 9. Doped organic semiconductor material according to claim 5, in which one or more pyrrolium, pyrylium, diazininium, thininium, diazolium, thiazolium, thiadiazolium, tetrazolium or dithiolium units occur as part of one or more multinuclear heterocycles. 10. Doped organic semiconductor material according to one of claims 1 to 4, in which the molecular group A is based on one or more borate benzene units. 11. Doped organic semiconductor material according to claim 10, in which one or more boratabenzene units occur as part of one or more multinuclear heterocycles. 12. A doped organic semiconductor material according to any one of claims 1 to 11, wherein the molecular group A is a cationic dye, an anionic dye or another organic salt. 13. Doped organic semiconductor material according to one of claims 1 to 12, in which the molecular group A on the structure A 1 or the corresponding leuco base A 2 AIA 2 is based, where: X CR ⁴ , SiR ⁴ , GeR ⁴ , SnR ⁴ , PbR ⁴ , N, P and Rl, R2, R3 and R ^4, for example, each one or more: hydrogen; Oxygen; Halogens, for example fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, for example diphenylaminyl, diethylaminyl; Aliphatics with 1 to 20 carbon atoms, for example methyl, ethyl, carboxyl; Alkoxyl, for example: methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl having 3 to 25 carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 14. Doped organic semiconductor material according to one of claims 1 to 13, in which the molecular group A on the structure A 3 or the corresponding leuco base A 4 A 3 A 4 based, where: X CR ⁸ , SiR ⁸ , GeR ⁸ , SnR ⁸ , PbR ⁸ , N, P and Rl, R2, R3, R4, R5, R6, R7, R ^8, for example in each case one or more: hydrogen; Oxygen; Halogens, e.g. Fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, e.g. diphenylaminyl, Diethylaminyl; Aliphates with 1 to 20 carbon atoms, e.g. Methyl, ethyl, carboxyl; Alkoxyl e.g. methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl from 3 to 25 Are carbon atoms, for example phenyl, pyridyl or naphthyl or ^' those atoms which form a condensed ring. 15. Doped organic semiconductor material according to one of claims 1 to 14, in which the molecular group A on the structure A 5 or the corresponding leuco base A 6 A 5 A 6 is based on: X CR ⁴ , SiR ⁴ , GeR ⁴ , SnR ⁴ , PbR ⁴ , N, P, S and Rl, R2, R3, R ^4, for example, each one or more: hydrogen; Oxygen; Halogens, for example fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, for example diphenylaminyl, diethylaminyl; Aliphatics with 1 to 20 carbon atoms, for example methyl, ethyl, carboxyl; Alkoxyl, for example: methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl having 3 to 25 carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 16. Doped organic semiconductor material according to one of claims 1 to 15, in which the molecular group A on the structure A 7 or the corresponding leuco base A 8 A 7 A 8 is based on: X C, Si, Ge, Sn, Pb, S and Rl, R2, R3 and R4, for example, each one or more: hydrogen; Oxygen; Halogens, for example fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, for example diphenylaminyl, diethylaminyl; Aliphatics with 1 to 20 carbon atoms, for example methyl, ethyl, carboxyl; Alkoxyl, for example: methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl having 3 to 25 carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 17. Doped organic semiconductor material according to one of claims 1 to 16, in which the molecular group A on the structure A 9 or the corresponding leuco base A 10 A 9 A 10 is based, whereby: X C, Si, Ge, Sn, Pb and Rl, R2, R3, R4, R5, R6, R7 and R8 e.g. one or more each: hydrogen; Oxygen; Halogens, e.g. Fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, e.g. diphenylaminyl, Diethylaminyl; Aliphates with 1 to 20 carbon atoms, e.g. Methyl, ethyl, carboxyl; Alkoxyl e.g. methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl from 3 to 25 Carbon atoms, e.g. Are phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 18. Doped organic semiconductor material according to one of claims 1 to 17, in which the molecular group A on the structure A 11 or the corresponding leuco base A 12 A ll A 12 based, where: X C, Si, Ge, Sn, Pb and R1, R2, R3, R4 e.g. one or more each: hydrogen; Oxygen; Halogens, e.g. Fluorine, Chlorine, bromine or iodine; hydroxyl; Aminyl, e.g. Diphenylaminyl, diethylaminyl; Aliphate with 1 to 20 carbon atoms, e.g. Methyl, ethyl, carboxyl; Alkoxyl e.g. methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl of 3 to 25 carbon atoms, e.g. Are phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 19. Doped organic semiconductor material according to one of claims 11 to 18, in which the chemically stable compound CI. Basic Yellow 37 (CI. 41001) or another diphenylmethane dye with a known counter anion. 20. Doped organic semiconductor material according to one of claims 11 to 18, wherein the chemically stable compound CI. Basic Green 4 (CI. 42000) or another diamino derivative of triphenylmethane dyes with a known counter anion. 21 .Doped organic semiconductor material according to one of claims 11 to 18, in which the chemically stable compound CI. Basic Red 9 (CI 42500) or another triamino derivative of triphenylmethane dyes with a known counter anion. 22. Doped organic semiconductor material according to one of claims 11 to 18, in which the chemically stable compound is phenylene blue (CI. 49400) or another indamine dye with a known counter anion. 23. Doped organic semiconductor material according to one of claims 11 to 18, in which the molecular group A on the structure A 13 or the corresponding leuco base A 14 A 13 A 14 is based on: X and Z are each CR ⁴ , O, S, N, NR ⁵ or a direct bond between the two Phenyl rings of the compound mean without another atom, and Rl, R2, R3, R ⁴ and R ⁵ , for example each one or more: hydrogen; Oxygen; Halogens, for example fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, for example diphenylaminyl, diethylaminyl; Aliphates with 1 to 20 carbon atoms, e.g. Methyl, ethyl, carboxyl; Alkoxyl, e.g .: methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl of 3 to 25 carbon atoms, e.g. Are phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 24. Doped organic semiconductor material according to one of claims 11 to 23, in which the molecular group A on the structure A 15 or the corresponding leuco base A 16 A 15 A 16 based, where: X and Z are each CR ⁸ , O, S, N, NR ⁹ or a direct bond between the two Phenyl rings of the compound mean without another atom, and Rl, R2, R3, R4, R5, R6, R7, R ⁸ and R ^9, for example each one or more: hydrogen; Oxygen; Halogens, e.g. Fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, e.g. Diphenylaminyl, diethylaminyl; Aliphates with 1 to 20 carbon atoms, e.g. Methyl, Ethyl, carboxyl; Alkoxyl e.g. methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl with 3 to 25 carbon atoms, e.g. Are phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 25. Doped organic semiconductor material according to one of claims 11 to 24, in which the molecular group A on the structure A 17 or the corresponding leuco base A 18 based, where: X and Z are each CR ⁴ , O, S, N, NR ⁵ or are a direct bond between the two phenyl rings of the compound without another atom, and Rl, R2, R3, R ⁴ and R ^5, for example, each one or more: hydrogen; Oxygen; Halogens, for example fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, for example diphenylaminyl, diethylaminyl; Aliphatics with 1 to 20 carbon atoms, for example methyl, ethyl, carboxyl; Alkoxyl, for example: methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl having 3 to 25 carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 26. Doped organic semiconductor material according to one of claims 11 to 22, in which the molecular group A on the structure A 19 or the corresponding leuco base A 20 A 19 A 20 based, where: X and Z each CR ⁶ , O, S, N, NR ⁷ and Rl, R2, R3, R4, R5, R ⁶ and R ⁷ each, for example, one or more: hydrogen; Oxygen; Halogens, e.g. Fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, e.g. diphenylaminyl, Diethylaminyl; Aliphates with 1 to 20 carbon atoms, e.g. Methyl, ethyl, carboxyl; Alkoxyl e.g. methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl from 3 to 25 Are carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 27. Doped organic semiconductor material according to one of claims 23 to 26, in which X where R is hydrogen; Oxygen; Halogens, for example fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, for example diphenylaminyl, diethylaminyl; Aliphatics with 1 to 20 carbon atoms, for example methyl, ethyl, carboxyl; Alkoxyl, for example: methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl having 3 to 25 carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 28. Doped organic semiconductor material according to one of claims 11 to 27, in which the chemically stable compound pyronine B (CI. 45010), CI. Basic Red 11 (CI. 45050), Sacchareϊn (CI. 45070), Rosamine (CI. 45090), Rhodamine B (CI. 45175) or another diamino derivative of the xanthene dyes is substances with a known counter anion. 29. Doped organic semiconductor material according to one of claims 11 to 27, in which the chemically stable compound Coeruleϊn B (CI. 45500) or another dihydroxy derivative of the xanthene dyes is substances with a known counterion. 30. Doped organic semiconductor material according to one of claims 11 to 27, in which the chemically stable compound is acriflavine (CI. 46000) or another diamino derivative of acridine with a known counterion. 31. Doped organic semiconductor material according to one of claims 11 to 27, in which the chemically stable compound is phenosafranine (CI. 50200) or another azine dye with a known counterion. 32. Doped organic semiconductor material according to one of claims 11 to 27, in which the chemically stable compound is C.I. Basic Blue 3 (CI. 51004) or another oxazine dye with a known counterion. 33. Doped organic semiconductor material according to one of claims 11 to 27, in which the chemically stable compound Lauth's Violet (CI. 52000) or another thiazine dye with a known counter ion. 34. Doped organic semiconductor material according to one of claims 11 to 12, wherein the molecular group A on the structure based, where n is a natural number, X and Z each NR ¹ , S or BR ² as a hetero atom in a mono- or polynuclear Heterocycle Xn each N or CR ³ and R ¹ , R ² , R ³ , Rn, for example in each case one or more: hydrogen; Oxygen; Halogens, e.g. fluorine, Chlorine, bromine or iodine; hydroxyl; Aminyl, e.g. Diphenylaminyl, diethylaminyl; Aliphate with 1 to 20 carbon atoms, e.g. Methyl, ethyl, carboxyl; Alkoxyl e.g. methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl of 3 to 25 carbon atoms, e.g. Are phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 35. Doped organic semiconductor material according to claim 34, in which X and Z are each individually on an element of the group are based on XI each CR ⁴ R ⁵ , NR ⁶ , O or S and Rl, R2, R3, R ⁴ , R ⁵ , R ^6, for example, each one or more: hydrogen; Oxygen; Halogens, for example fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, for example diphenylaminyl, diethylaminyl; Aliphates with 1 to 20 carbon atoms, e.g. Methyl, ethyl, carboxyl; Alkoxyl, e.g .: methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl having 3 to 25 carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which are a condensed ring form. 36. Doped organic semiconductor material according to one of claims 11 to 35, in which the chemically stable compound is N, N'-dialkyl cyanine or N, N'-dialkyl thiacarbocyanine or another methine or polymethine dye with a known counterion. 37. Doped organic semiconductor material according to one of claims 11 to 12, in which the molecular group A on the structure based, where n is a natural number, X and Z are each O, C (CN) ₂ , N-CN and Rn e.g. each one or more: known electron-withdrawing groups, hydrogen; Oxygen; Halogens, e.g. Fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, e.g. Diphenylaminyl, diethylaminyl; Aliphates with 1 to 20 carbon atoms, e.g. Methyl, Ethyl, carboxyl; Alkoxyl, for example: methoxy; cyano; Nitro _. ; Sulfonic acid and its salts; Aryl having 3 to 25 carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 38. Doped organic semiconductor material according to one of claims 11 to 12, in which the molecular group A on the structure rests with X, XI, Z and ZI are each S or Se and R e.g. in each case one or more: known electron-donating groups, hydrogen; Oxygen; Halogens, for example fluorine, chlorine, bromine or iodine; hydroxyl; Aminyl, e.g. Diphenylaminyl, diethylaminyl; Aliphatics with 1 to 20 carbon atoms, for example methyl, ethyl, carboxyl; Alkoxyl, for example: methoxy; cyano; nitro; Sulfonic acid and its salts; Aryl having 3 to 25 carbon atoms, for example phenyl, pyridyl or naphthyl or those atoms which form a condensed ring. 39. Doped organic semiconductor material according to one of claims 1 to 4, in which the organic molecular group A on the structure is based, where X is C, N, Si or P and n is 3 for X = C or Si or n = 2 for X = N or P. 40. Doped organic semiconductor material according to one of claims 1 to 4, in which the organic molecular group A on the structures Ä 21 or A 22nd A 21 A 22 is based. 41.Doped organic semiconductor material according to one of claims 1 to 40, wherein the compound formally positively charged nitrogen (azoηia, ammonium), oxygen (oxonia, oxonium), phosphorus (phosphonia, phosphonium), sulfur (thionia, sulfonium) and / or contains formally negatively charged boron (boranuida, borate). 42. Doped organic semiconductor material according to one of claims 1 to 41, in which the compound is a metal complex compound. 43. Doped organic semiconductor material according to one of claims 1 to 42, in which one or more molecular groups A with one or more diazo groups - N = N are connected. 44. Doped organic semiconductor material according to one of claims 1 to 43, in which one or more molecular groups A contain one or more -SO ₃ ^" groups. 45. Doped organic semiconductor material according to one of claims 1 to 43, in which one or more molecular groups A contain one or more ammonium, immonium, sulfonium, hydrazinium or thiouronium groups. 46. Doped organic semiconductor material according to one of claims 1 to 42, in which the complex of an organic molecule A and a molecule B is such that B does not form a trap in the matrix M to be doped for the desired majority charge carriers. 47. Doped organic semiconductor material according to one of claims 1 to 46, in which the semiconductor material to be doped is itself a material mixture. 48. Process for the production of doped organic semiconductor materials with increased charge carrier density and increased effective charge carrier mobility, characterized in that a chemical connection of one or more organic molecular groups A with at least one further connection partner B by evaporation in a vacuum or in an inert atmosphere, either by simultaneous Evaporation is deposited with the organic semiconductor material or by successive evaporation and subsequent diffusion of the dopant, the desired doping effect being achieved by splitting off at least one organic molecular group A from that of the chemical compound, caused by at least one molecular group A or by the product of a reaction of the Connection partner A with another atom or molecule is obtained. 49. The method according to claim 48, characterized in that the splitting of the chemical compound into components A and B takes place only after introduction into the semiconductor material to be doped. 50. The method according to any one of claims 48 and 49, characterized in that the splitting of the chemical compound in the prepared layer and / or the removal of component B from the prepared layer is supported. 51. The method according to any one of claims 48 to 50, characterized in that the splitting of the chemical compound and / or the removal of component B is supported by the application of heat. 52. The method according to any one of claims 48 to 50, characterized in that the splitting of the chemical compound and / or the removal of component B is supported by optical excitation in the absorption region of the layer. 53. The method according to any one of claims 48 to 50, characterized in that the splitting of the chemical compound and / or the removal of component B is supported by exposure of the layer to molecular or atomic hydrogen or hydrogen ions or molecular or atomic oxygen or oxygen ions. 54. The method according to any one of claims 48 to 50, characterized in that the splitting of the chemical compound and / or the removal of component B by supplying a further reaction partner, which reacts in the layer with component B in such a way that the reaction product is more volatile is. 55. The method according to any one of claims 48 to 50, characterized in that the component B in the layer reacts with a third substance or a molecule of the matrix such that the reaction product forms an antitrap for the desired majority charge carriers or is easily removable from the layer , 56. The method according to claim 48, characterized in that the splitting of the chemical compound and / or the removal of component B is supported by treatment of the chemical compound in the gas phase during evaporation. 57. The method according to any one of claims 48 and 56, characterized in that the splitting of the chemical compound and / or the removal of component B is supported by optical excitation. 58. The method according to any one of claims 48 and 56, characterized in that the chemical compound is split and / or the component B is removed by deflecting a charged component B or the charged component B by an electric or magnetic field. 59. The method according to any one of claims 48 and 56, characterized in that the splitting of the chemical compound and / or the removal of component B is carried out by a strong electric field during the evaporation process. 60. The method according to claim 48, characterized in that the splitting of the chemical compound and / or the removal of component B in the solid phase is supported in the vapor deposition source. 61. Method according to one of claims 48, 56 and 60, characterized in that the decomposition of the chemical compound and / or the removal of component B is supported by heat supplied during the vapor deposition process, the supply of heat either in the solid or liquid state of the chemical compound and / or takes place in the gas phase. 62. The method according to any one of claims 48 and 60, characterized in that the splitting of the chemical compound and / or the removal of component B is supported by optical excitation. 63. The method according to any one of claims 48, 56 and 60, characterized in that the splitting of the chemical compound and / or the removal of component B is supported by adsorption of the vapor on a reactive surface and subsequent re-desorption. 64. The method according to any one of claims 48, 56 and 60, characterized in that the splitting of the chemical compound and / or the removal of component B is supported by adsorption of the steam on a catalytic surface and subsequent re-desorption. 65. The method according to any one of claims 48 and 60, characterized in that the splitting of the chemical compound and / or the removal of component B is supported by illuminating the compound with intense laser light. 66. The method according to any one of claims 48, 56 and 60, characterized in that the splitting of the chemical compound and / or the removal of component B is supported by the action of a plasma during the vapor deposition process. 67. The method according to any one of claims 48 and 60, characterized in that the chemical compound in an evaporator source reacts with a third substance, and one or more of the reaction products is used for doping. 68. The method according to any one of claims 48 and 60, characterized in that the chemical compound in an evaporator source is brought into interaction with a catalyst. 69. The method according to any one of claims 48 and 60, characterized in that the splitting of the chemical compound in an evaporator source is supported by an electrochemical process on a suitable electrode. 70. Use of a doped organic semiconductor material, having an increased charge carrier density and effective charge carrier mobility, obtained by doping an organic semiconductor material with a chemical compound of one or more organic molecular groups A with at least one further compound partner B, the desired doping effect being achieved by elimination of at least one organic molecular group Group A is obtained from that of the chemical compound, caused by the molecular group A or by the product of a reaction of the connecting partner A with another atom or molecule, characterized in that the organic semiconductor material as a functional layer in organic solar cells, in organic light-emitting diodes , is used in organic field effect transistors, in integrated organic circuits and in organic lasers.