DE10024993A1 - Electrical device, used as sensor, organic field-effective transistor or light-emitting diode, photovoltaic or Shottky cell, antistatic film or battery, has polymer layer containing molecular organic semiconductor with polymerizable group - Google Patents

Abstract

In an electrical device with a layer containing polymer(s) influencing the electrical properties of the device, the polymer contains molecular organic semiconductor(s). n an electrical device with a layer containing polymer(s) influencing the electrical properties of the device, the polymer contains molecular organic semiconductor(s), at least one of which contains polymerizable group(s) through which it is polymerized to the polymer. An independent claim is also included for the production of the device by: (i) providing an electrical conductor; (ii) modifying a molecular organic semiconductor (I) with polymerizable groups; and (iii) electropolymerization of (I) on the conductor.

Description

The invention relates to an electrical component with an electrical Influencing properties of the electrical component, at least one Polymer containing layer.

Such electrical components are known from the prior art. So the article by P. Ingleby et al. "Effect of micro-electrode geometry on response of thin-film poly (pyrrole) and poly (aniline) chemoresistive sensors "in Sensors and Actuators, B57 (1999) 17-27, already a chemoresistive sensor, which is a polymer based on pyrrole or aniline to influence the electrical Contains properties of the component.

The object of the present invention is a component of the aforementioned Art to improve and provide a process for its manufacture.  

This object is achieved by a component of the type mentioned electrical component according to claim 1 solved. At the same time, the invention a method for producing the component according to the invention Claim 18 available.

The advantages of the invention are in particular that due to the insertion of a molecular organic semiconductor the electrical properties of the Polymer layer can be changed specifically. Among molecular organic Semiconductors are understood in the following as molecular groups that are in pure substance work as organic semiconductors. There are already from US Pat. No. 5,120,610 Polymers known by the polymerization of organic semiconductors, such as Phthalocyanine; however, these polymers do not have the additional modification of the molecular organic semiconductors with the help at least one polymerizable group, as is realized in the invention has been. This modification of molecular organic semiconductors with at least a polymerizable group, however, makes it possible in a particularly advantageous manner Way the electrical properties of the component so equipped adjust particularly precisely. Is it electrical, for example? Component around a sensor, so you can select a specific one molecular organic semiconductor, for example by the selection of phthalo cyanine, and through the targeted modification of this molecular organic semicon ters with the help of a polymerizable group, for example aniline, the Eigen Properties of a polymer formed in this way are adjusted so that with the help of a polymer formed in this way, a sensorially active layer of the component is particularly sensitive to a specific wavelength of light, while it is not for other wavelengths. This is only an example guided. Likewise, it is possible due to the invention, one for one tes solvent special sensitivity of the polymer through the choice of molecular organic semiconductor and the polymerizable group, so that the corresponding component is only sensitive to this solvent, while it is almost insensitive to all other solvents.  

The invention thus provides an electrical component, which due to its Polymer layer designed according to the invention in a novel and previously not known manner exactly adjustable to the special needs of the application is. The advantages of the invention are initially only introduced here. In the course of The following description of the invention will reveal a number of others advantageous embodiments of the invention based on their structure, their Properties and their advantages described.

In a preferred embodiment of the invention, the contains at least one molecular organic semiconductors a macrocyclic ligand and / or its Metal complexes, especially substituted and / or unsubstituted phthalocyanines, substituted and / or unsubstituted porphyrins, substituted and / or unsub substituted porphyrazines, substituted and / or unsubstituted naphthalocyanines, substituted and / or unsubstituted biphthalocyanines, and / or substituted and / or unsubstituted chlorine, or a condensed aromatic, ins special substituted and / or unsubstituted perylene dyes and pigments and their derivatives, substituted and / or unsubstituted terry fenes and their Derivatives, substituted and / or unsubstituted quaterrylenes and their derivatives, and / or substituted and / or unsubstituted coronenes and / or their derivatives. It is also possible to use dyes that are semiconducting as the pure substance Have properties such as substituted and / or unsubstituted Merocyanines. The merocyanines mentioned are particularly preferred Embodiment used as a coating for a CD. The can Take advantage of the property of the merocyanines when exposed to laser beams certain wavelengths to change the absorption behavior.

It is particularly preferred if the at least one molecular organic Semiconductor at least one element from the amount of phthalocyanine, hemiporphyra zin, triazole hemiporphyrazine, biphthalocyanine, naphthalocyanine, phorphyrin, perylene, Perylenedicarboxylic anhydride, perylenedicarboximide, perylenetetracarboxylic acid dianhydride, perylene tetracarboxylic acid diimide, perylene tetracarboxylic acid monoanhydride monoimide,  Coronen, Coronendicarbonsäureanhydrid, Coronendicarbonsäureimid, Coronetetracarboxylic acid dianhydride, Coronetetracarboxylic acid diimide, Coronetetra carboxylic acid monoanhydride monoimide, Rubicen, Rubicendicarbonsäureanhydrid, Rubicendicarboximide, Rubicentetracarboxylic Dianhydride, Rubicentetracar bonsäurediimid, Rubicentetracarbonsäuremonoanhydridmonoimid, imidazole, Imidazole dicarboxylic acid anhydride, imidazole dicarboximide, imidazole tetracar bonic acid dianhydride, imidazole tetracarboxylic acid diimide, and imidazole tetracarboxylic acid contains monoanhydride monoimide. These organic semiconductors have proven to be proven particularly advantageous embodiments because they are easy are easy to manufacture and easy to process and secondly the defined one Allow adjustment of certain properties of a polymer constructed in this way. Of course, all other molecular organic semiconductors are also usable according to the invention. Some of the previously listed molecular organic ones Semiconductors will be discussed below regarding their manufacture and their Properties described in more detail.

For a better understanding of the molecular organic semiconductors mentioned In the present invention, these molecular organic semiconductors are as follows juxtaposed inorganic semiconductors or conductors. In addition, in follow the synthesis and properties of preferred molecular organic Semiconductors of the present invention described.

First, the electrical properties of metals and inorganic and organic semiconductors are compared. Fig. 45 shows for this purpose an overview of conductivities of organic and inorganic conductor or semiconductor. In addition, Table 1 below also shows the mobilities and specific conductivities of silicon (Si), an inorganic semiconductor, and of PcCu, an organic semiconductor, each in the undoped state. The table also shows the distances of the atoms or molecules in the respective crystal lattice.

Table 1

Organic semiconductors have significantly lower conductivities than inorganic semiconductors. According to the classic classification, they would be isolators (σ _spec <10 ^-10 S / cm). However, they show the following properties that are characteristic of semiconductors:

• - increase in conductivity with temperature;
• - Increase in conductivity in the presence of foreign substances (i.e. with dots tion);
• - they have a thermal voltage;
• - photoconductivity;
• - Depletion or enrichment boundary layers in contacts → Fotovoltal activity;
• - electrochemical activity
  • a) active as an electrochromic layer, charge storage
  • b) as a catalyst for electrochemical reactions
  • c) Photo-electrochemical activity (photo voltages, photo currents in the electrolyte contact).

Typical examples of organic semiconductors are large-area, π-electron-rich aromatic compounds, such as. B. Phorphyrins, perylenes and Phthalocyani ne. The advantages of these compounds are that they are simple and inexpensive to produce in large quantities and in high purity. Phthalocyanines can be produced, for example, with a purity of 10 ¹⁴ to 10 ¹⁶ traps per cm ³ . In addition, these classes of compounds are thermally and chemically very stable and are only attacked by oxidizing acids. They also have an intensive absorption in the visible range, with extinction coefficients that are in part at 10 ⁵ cm ² mol ^-1 in solution. In contrast to inorganic semiconductors, which are covalently linked in the crystal bond, the organic molecules are only kept in the crystal bond via Van der Waals interactions. The distances between the individual atoms are correspondingly larger. The splitting of the molecular orbitals into broad bands (valence and conduction band), as is the case with inorganic semiconductors, advantageously does not take place in organic semiconductors due to the low interactions. The molecules therefore largely retain the properties of the individual molecules in the solid state. The mobility of the cable carrier in organic semiconductors is generally significantly lower than in inorganic semiconductors. The band model, which is used to explain the conduction mechanism for inorganic semiconductors, plays a subordinate role in charge transport in organic semiconductors. Rather, the transport of charge carriers in organic crystals is mainly explained by hopping mechanisms such as "phonon assisted hopping" and by activated tunnel processes.

In contrast, conductive polymers can also be referred to as electrical conductors or metals (σ _spec <10 S / cm) due to their conductivity in the doped state (more detailed information on the conductive polymers is given below). As with inorganic metals, their conductivity decreases with increasing temperature. These materials show no field effect and no thermal voltage. As with organic semiconductors, the mechanism of charge transport is not described here using the classic band model. The charge transfer takes place via so-called mid-gap states, which arise from the occurrence of solitons. Typical conductive polymers are therefore the polypyrrole, polyaniline, polyphenylene venylidene and polyacetylene, which are explained in more detail below, ie polymers which have a conjugating system along the polymer chain. Here too, a more detailed description of the synthesis and properties of such polymers is made below. A wide range of specific conductivities can advantageously be covered by conductive polymers. This conductivity strongly depends on the doping of the polymer. The doping can thus be used in an advantageous manner to reinforce the properties of the inventive components according to the invention. With low doping, the conductive polymers behave like organic semiconductors. In the undoped state they can be called insulators due to their low conductivity.

In the following there are advantageous embodiments of the invention molecular organic semiconductors based on the synthesis of the same and their Properties described. It also goes directly to the accompanying drawing reference to understanding these preferred embodiments to facilitate.

The phthalocyanines which can advantageously be used in the invention are first described on the basis of their synthesis and properties which are advantageous for the invention. The phthalocyanine can be prepared with or without a central metal. In the case of phthalocyanines with central metal, more than 70 different central metals have been represented in the prior art. The basic structure of the phthalocyanines has also been substituted symmetrically and asymmetrically with different substituents in the prior art. The metal-free phthalocyanine, ie without a central metal, can be prepared from metal-containing phthalocyanines whose central metals are unstable to acids, such as Ca and Li. In addition, the metal-free phthalocyanine can be directly synthesized from 1,3-diiminoisoindolenine 1 in high-boiling solvents. The preparation from 1,2-phthalonitrile 2 in pentanol with DBU as a catalyst proceeds more gently and with greater yields. Fig. 1 gives an overview of the presentation methods for the presentation of metal-free phthalocyanine.

In Fig. 2 preparation methods for the representation of metal-containing Phthalocya nine are shown. However, not every method can be used for substituted dinitriles. On the one hand, phthalocyanine can be prepared with 1,2-cyanobenzoic acid amide 3 and phthalonitrile 4 as starting materials. Other possibilities for preparing phthalocyanine start from phthalic anhydride 5 , from 1,2-bromobenzene 6 , from 1-bromo-2-cyanobenzene 7 and from phthalimide 8 . The synthetic routes for central metal-free phthalocyanines are also suitable for the preparation of metal-containing phthalocyanines.

Phthalocyanines occur in various crystal structures. The three main modifications are referred to as α, β and X. By Evaporation of a phthalocyaninato zinc on a substrate is obtained in vacuo, if the substrate temperature is between 50 ° C and 140 ° C, the α-modification. When the layer is heated to above 210 ° C, the α modification is stored in the β- Modification around. However, if the point of recrystallization is cooled, arise amorphous films.

Fig. 3 shows the exact bond angle in the example of the molecular crystal zinc phthalocyanine. The individual modifications also differ in their conductivity and in their UV-Vis spectra. It is therefore crucial which modification the prepared thin film has.

Furthermore, here are advantageous embodiments of the invention molecular, organic semiconductors the synthesis and properties of perylene and perylene derivatives.

By heating 3,4,9,10-perylene tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid dianhydride (hereinafter referred to as PTCDA) can be synthesized. PTCDA can be used as the starting product for the preparation of the 3,4,9,10-perylene tetracarboxylic acid diimides (hereinafter referred to as PTCDI). PTCDIs can be used advantageously for the invention since they are easily accessible and easy to clean by sublimation or chromatography. The absorption maxi ma of the imides present in solution in monomer differ very little in the UV-Vis spectrum. The position of the absorption maxima is also very little influenced by the solvent used. The bands are at 525 nm, 489 nm and 458 nm. The fluorescence spectra with bands at 540 nm and 575 nm agree with different dyes within 5 nm. Symmetrical PTCDIs can be synthesized by heating PTCDA with an amine and a water-releasing agent (e.g. Zn acetate) in high-boiling solvents (e.g. quinoline). However, only thermally stable amines can be used for this synthetic route. Amines with easily removable second substituents on the alkyl or aryl radical, such as carbon, sulfonic or sulfuric acid groups, can only be reacted under mild conditions. PTCDA can be reacted with glycine in a DMSO / H ₂ O mixture at 100 ° C. In this way, a uniform product can be obtained after about three hours. Fig. 4 schematically illustrates the representation symmetrical perylenes.

The synthesis and properties of phorphyrins are briefly explained as a further preferred molecular organic semiconductor. In contrast to phthalocyanines and perylenes, phorphyrins occur naturally. They take on important biochemical functions in animals and plants. For example, they form the prosthetic group in hemoglobin and myoglobin and are therefore responsible for the oxygen transport in the blood. In the cytochromes, they play a crucial role in electron transport. Phoryphins are produced by cyclocondensation of pyrrole derivatives with aldehydes, preferably in an acidic environment. The conversion of pyrrole with formaldehyde to the unsubstituted porphin gives low yields. However, better yields can be achieved in the reaction with substituted aldehydes, which leads to meso-substituted porphirins. FIG. 5 shows the reaction scheme of the reaction Rothermund the example of 5,10,15,20-tetrakis (p-phenylcarboxylic acid) porphirins. The Zen tralmetallion must be introduced subsequently in the reaction shown in FIG. 5.

Another preferred embodiment of the invention is characterized in that that the group is polymerizable by electropolymerization. At this Embodiment can thus the polymerization and the application of Polymers for example on a substrate of an electrical component with the help electropolymerization.

In preferred embodiments, the groups themselves contain at least one element from the set consisting of aniline, pyrrole, thiophene, ethylene, indole, paraphenylene, aminoanthracene, aminoaphthalene, aminophenol, carbazole, benzoquinone, acrylonitrile, pyrrolidones, phenylenediamine, tetrathiapentalene, acrylic acid and phenols and their derivatives and substituents. These polymerizable groups used to modify the molecular organic semiconductors are described in more detail below with regard to their polymerization. For clarity, the structures of aminophenol aminoanthracene (Fig. 38), Aminoaphthalin (Fig. 39), acrylic acid (Fig. 40), tetrathiapentalene (Fig. 41), carbazole are shown in FIGS. 37-44 (Fig. 37), ( Fig. 42) Phyrrole ( Fig. 43), phenol ( Fig. 44). However, when these polymerizable groups are bound to the molecular organic semiconductors, it is particularly preferred that these groups are not arranged directly on the molecular organic semiconductor, but rather that this is done only indirectly via an interposed molecular chain, a so-called spacer. This spacer preferably contains a molecular chain which contains at least one element from the group consisting of (CH ₂ ) _n , (CFH) _n , (CF ₂ ) _n , OCO (CH ₂ ) _n , OCO (CF ₂ ) _n , OCO (CFH) _n , COO (CH ₂ ) _n , COO (CF ₂ ) _n , COO (CHF) _n , NH (CH ₂ ) _n , NH (CF ₂ ) _n , and NH (CHF) _n , where n = 0 to 20 is.

Another preferred embodiment of the present invention is characterized in that the polymer is electrically conductive. Conductive polymers are derivatives of polyenes, i.e. compounds with extensive conjugated systems. They have excess charges due to oxidation or reduction processes and can also be viewed as polymer salts. In Figs. 6a to 6d are idealized chain structures of the polymers polyacetylene (Fig. 6a), polyvinylidene (Fig. 6b), polypyrrole (Fig. 6c), and polyaniline shown (Fig. 6d). Crosslinking and branching occur during the actual polymerization. Pyrroles even form ring structures. Polyaniline and polypyrrole can be polymerized both chemically and electrochemically from their monomers, aniline and pyrrole, respectively. In both polymers, the electrochemical polymerization takes place at the anode. Hydrogen peroxide and iron (III) chloride are suitable initiators for chemical synthesis. In contrast, polyacetylene and polyvinylidene can only be polymerized chemically. The polymerization of acetylene is carried out on cooled substrates using Ziegler-Natter catalysts. Polyvinylidene is made from a mixture of an oxidizing agent and a Friedel-Crafts catalyst (CuCl ₂ / AlCl ₃ ) from benzene. The high electrical conductivities result from movable positive or negative charge carriers (so-called solitons), which result from doping. The doping can either be carried out electrochemically during the synthesis of the polymers or subsequently by treating the polymers with oxidizing or reducing agents.

The combination of the aforementioned conductive polymers according to the invention and building blocks of molecular organic semiconductors advantageously result in one Combination of their respective properties. By the invention Polymerization of molecular organic semiconductors via those mentioned above Electropolymerizable groups are primarily the conductivity of the so manufactured materials raised. In addition, the invention molecular organic semiconductors redox active centers for catalysis that Electrocatalysis and the sensors of electrical components according to the invention in the highly conductive basic structure of the conductive polymers. The polymers the advantage that they are heterogeneous catalysts from each Can separate reaction mixture. Furthermore, the invention offers combinations of porphyrins and conductive polymers Electron transfer processes.  

It is now an example of further preferred embodiments of the invention with regard to the polymerizable groups. Also be on the synthesis and properties of the groups that can be polymerized and the molecular monomers formed to form the polymer in the organic semiconductor Component according to the invention received. This preferred execution Form the component according to the invention or of the manufacture of the The method used in the device according to the invention are described below also described with reference to figures of the drawing.

First, in this connection, the synthesis of the monomers received. Here are p-type monomers for electropolymerization pyrrole-substituted phthalocyanines interesting, in which the polymerizable A spacer is attached to the steric hindrance during the group To minimize polymerization by the phthalocyanine. The synthesis concept should the possibility of using pyrrole-substituted phthalocyanines include different spacer lengths in order to produce the To determine whether the reactivity of the monomers with the spacer length increases. In addition, the electrical properties of the polymers change, when the phthalocyanines as conjugated systems by longer aliphatic spacers are separated from the pyrroles. Within the scope of the invention, among other things Pyrrol-1-yl alkanol shown. The N-alkylated compounds have the advantage that they are easily synthesized and the length of the alkyl group is simple is to be varied. The hydroxyl group offers possibilities as a functional group Connection to the phthalocyanine. Basically, the connection to the Phthalocyanine can be realized through two synthesis concepts. The one One possibility is to introduce the desired substituent during the synthesis. This usually happens through the synthesis of an appropriately substituted one Phthalonitrile. 4-nitro-phthalonitrile is suitable as a starting substance because the Nitro group can be substituted nucleophilically by aliphatic hydroxyl groups. The another way to introduce the electropolymerizable group is Substitution on phthalocyanines. Here is an esterification of a tetrakis-4-  Carboxy-phenoxy-phthalocyanine preferred. This concept has the advantage that the polymerizable group is not considered to be over the entire course of the synthesis reactive group on the molecule. Tetrakis-4-carboxy-phenoxy-phthalocyanine has however, a low solubility in organic solvents, so that a direct Esterification in organic solvents is not possible. With esterifications About the acid chloride has been shown that the reaction is not quantitative at all Expires. The synthetic route via the 4-nitro-phthalonitrile was therefore preferred because it provides clean, tetrasubstituted phthalocyanines.

The synthesis described in relation to this embodiment can thus be divided into four parts:

• - Synthesis of pyrrol-1-yl alkanols
• - Representation of the dinitriles
• - cyclotetramerization
• - Installation of the central metal ion.

The pyrrol-1-yl alkanol can be prepared from pyrrolyl potassium and the corresponding bromoalkanol by nucleophilic substitution in DMSO / THF. At 71%, this reaction had the highest yield for the preparation of the pyrrol-1-yl alkanols. The reaction is shown schematically in FIG. 7. The alcohol used is in the protolysis equilibrium with pyrrolyl potassium, which is due to the smaller pKa value of 2-bromoethanol on its side. Therefore, double the molar concentration of pyrrolyl potassium, based on the alcohol, is used. A product mixture of pyrrole and the desired pyrrol-1-yl alkanol is formed. However, the required column chromatographic purification is relatively time consuming. In addition, in the test series carried out by the inventors, impurities were still detected in the product. It is therefore preferred for the invention to prepare the desired pyrrol-1-yl alkanols according to a slightly modified procedure. The production of pyrrolyl potassium is dispensed with. Rather, potassium t-butoxide is added for deprotonation. The pyrrolyl potassium is generated in situ in this reaction. The excess of pyrrole can thus be dispensed with in this reaction, so that pyrrole-1-alkanol is the only monomer. In addition, crown ether can be added as a phase transfer catalyst, which means that the reaction can also be carried out successfully in low-boiling solvents. In this preferred variant, the purification is carried out by distillation in an oil pump vacuum via a Vigreux column. In this embodiment of the synthesis method according to the invention, a product mixture was likewise obtained, as in the synthesis explained above. In both syntheses described, a reaction of the unprotected hydroxyl group under the existing basic conditions with bromine-alkanol still present to ether was found.

It is therefore even more preferred for the synthesis of the monomers in the present invention if the representation method shown schematically in FIG. 8 is used. In this synthesis of pyrrol-1-yl alkanol, the aminoalkanol is first esterified with acetic acid before the dimethoxytetrahydro furan is added. The amino group substitutes the oxygen in the dimetoxy tetrahydrofuran and at higher temperatures the metoxy groups are thermally eliminated, so that the ethyl acetate of the pyrrol-1-yl alkanol is formed. This is then split into methanol by adding KOH. The purification is carried out by distillation in an oil pump vacuum over a Vigreux column. The yield of the crude product is around 70%. An advantage of this synthetic route is the problem-free implementation of large batches. This rule can easily be carried out for n = 2.

However, it has been shown that the yield of the pure product due to the high Losses during distillation depend on the batch size. The explained above The rule should be varied for n = 3 and n = 5. It is 2-hydroxyethyl min in the regulation in fourfold excess, based on the dimethoxy tetrahydrofuran used. Since it is a liquid, it can  can be easily added dropwise. 3-hydroxypropyiamine is a highly viscous Liquid and 5-hydroxypenthylamine a solid. 3- was added dropwise Hydroxypropylamine mixed with 30 ml n-propanol and 5-hydroxypenthylamine in n-propanol dissolved. For economic reasons, both amines should be in only a small amount Excess (1.3 or 1.5 times) can be used. Furthermore, it has been shown that with the longer-chain alcohols, the ester cleavage after stirring overnight is not completed. For this reason, the reprocessing should be preferred the ester cleavage can be varied. To make the acetic acid as complete as possible to separate from the acetic acid-ω-pyrrol-1-yl-alcylyl ester, dis are united organic phases three times with saturated potassium hydrogen carbonate solution washed. The reaction time of the subsequent ester cleavage is 20 Hours. The yields are independent of the chain length between 25 and 60%.

The 4- (2-pyrrol-1-yl-ethoxy) -phthalonitrile and the 4- (3-pyrrol-1-yl-propoxy) -phthalenitrile are prepared according to the principle shown schematically in FIG. 9. The representation shown there is a nucleophilic substitution on the aromatic. Due to the -M effect of the cyano groups, the electron density at the C ₄ position in the aromatic system is reduced. Nitrofunctions are good leaving groups and can therefore be substituted by hydroxyl groups. In this substitution reaction, aromatic hydroxyl groups show the highest reactivity. With aliphatic hydroxyl groups, the reactivity decreases with increasing chain length. The ratio of the educts is changed to simplify the processing. In the description described, the alcohol and the nitrophthalonitrile are used in a molar ratio of 1: 1. In order to ensure complete conversion of the nitrophthafonitrile, the alcohol is used in at least a 1.3-fold excess, so that the chromatographic separation of the nitrophthalonitrile can advantageously be dispensed with. When 4- (3-pyrrol-1-yl-propoxy) -phthalonitrile is prepared, the reaction time is additionally increased by 4d. In both cases, the raw products can only be precipitated after careful neutralization. The pyrrole begins to polymerize in acidic solution, which leads to considerable losses in yield, so that acidification should be avoided. The crystals only form in ice-cold solution or after complete removal of impurities. With 4- (3-pyrrol-1-yl-propoxy) phthalonitrile, the crystallization time is about 4 weeks. In the preferred embodiment of the synthesis method according to the invention described here, it is therefore preferred to continue using the product as an oil if the MS and NMR spectra no longer have any impurities. The yield decreases with increasing chain length.

The cyclotetramerization to give 2,9,16,23-tetrakis (pyrrol-1-yl-alkoxy) phthalocyanine is carried out according to the procedure shown schematically in FIG. 10. 0.2 g-0.5 g dinitrile is dissolved in boiling pentanol under nitrogen. A spatula tip of lithium is added and the mixture is stirred for three quarters of an hour. During production it has been shown that increasing the reaction time to one hour increases the yield. After the reaction, the pentanol is first removed completely in vacuo and the remaining oil is added to the methanol / water mixture (volume ratio 1: 1) to precipitate. In tetrakis (pyrrol-1-yl-alkoxy) phthalocyanine, lithium as the central metal is removed by washing with the methanol / water mixture. In order to remove the lithium in tetrakis (pyrrol-1-yl-alkoxy) phthalocyanine, the phthalocyanine is stirred in pH 5 buffer, then filtered off and neutralized with water. Treatment in acetic acid should be avoided as this leads to a high loss due to polymerization. The regulation is modified for the preparation of phthalocyanines containing central metal. The metalation is carried out without working up in pentanol by adding the corresponding metal salt to the cyclotetramerization batch. The product is checked using UV-Vis spectroscopy. Zinc and cobalt have been shown to have strong interactions with the complex. Nickel, on the other hand, can be extracted from the phthalocyanine by washing with water. For this reason, the product is not processed with a methanol / water mixture, but in pure methanol. The yields that can be achieved are well over 80%.

In the case of the perylenes, basic structures are preferred as n-conductors, which - depending on Choice of polymerizable group - both anodic and cathodic polymeric let sieren. As an n-type molecular organic semiconductor, the 3,4,9,10- Perylene tetracarbodiimide is preferred. The polymerizable groups should be like this appropriate that they have no influence on the conjugating system in order not to change the line character. There is a knot on the nitrogen of the diimide in the HOMO and LUMO, the residues attached there vary the electronic ones System properties are not. As a cathodically polymerizable group Hydroxyphenyl substituent preferred. As an anodically polymerizable group selected an aminophenyl substituent.

The syntheses can be broken down as follows:

• - Representation of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarbonsäureanhy drid
• - Presentation of the perylene-3,4,9,10-tetracarbodiimide from diamino compounds
• - Preparation of the perylene-3,4,9,10-tetracarboxylic acid diimides from monoamino connections, the representation of the perylene-3,4,9,10-tetracarbodiimide and the 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarbodiimide according to the same synthesis instructions were carried out.

The 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid anhydride is prepared by chlorinating the anhydride in accordance with the procedure schematically processed in FIG. 11. Chlorosulfonic acid is suitable for introducing chlorine onto aromatics. Iodine acts as a catalyst in this reaction. The reaction achieved a yield of 98%.

The syntheses of the perylene-3,4,9,10-tetracarbodiimide and the 1,6,7,12-tetrachloro-3,4,9,10-perylene tetracarbodiimide are carried out according to FIG. 12. In this specification, the diamino component is used in a 10-fold excess in order to reduce the probability of polycondensation. It is also preferable to largely avoid carcinogenic solvents. For example, toluene or xylene can be used instead of benzene if it is possible due to the solubility of the starting materials. Despite the high excess of the diamonic component, the perylenetetracarboxylic acid dianhydride cannot be completely converted. The anhydride groups of this compound can be converted into two carboxylic acid groups by boiling in potassium hydroxide. The perylene tetracarboxylic acid formed is soluble in potassium hydroxide and can thus be separated off. The resulting products are soluble in formic acid and could thus be separated from the resulting polymers. The products can also be prepared in a two-stage synthesis from the corresponding monoaminon tro compounds by synthesizing the perylene carbodiimides in a first reaction step and then reducing the nitro groups.

Referring to FIG. 13, the perylene-3,4,9,10-tetracarboxylic diimide of monoamino compounds can be represented. The conversion is quantitative for X = H and the yield is 20% for X = Cl. The reactivity of the perylene-3,4,9,10-tetracarboxylic acid diimide is greatly reduced by the introduction of the chlorine atoms. The chlorine atoms do not inhibit reactivity when reacting with diamino components.

In the following, further details of the electropolymerization of the phthalocyanines according to the invention will now be discussed. In order to minimize the educt quantities for electropolymerization, a single compartment cell with a volume of 5 ml is used, in which there is a 1 × 1 cm working electrode made of ITO (indium tin oxide), an equally large platinum mesh as counter electrode and a silver wire as reference electrode . The silver wire serves as a quasi reference electrode and should be calibrated against ferrocene after each measurement. If Hg / HgCl or Ag / AgCl is used as the reference electrode, traces of water can get into the solvent. Because small amounts of contaminants or traces of water can trap the radicals that form on the anode and inhibit the polymerization, a direct reference electrode should not be used. Electropolymerization can take place using two different deposition methods: potentiostatic deposition and potentiodynamic deposition. In the case of potentiostatic deposition, a constant potential is applied between the reference and the working electrode, while in the case of the potentiodynamic deposition, a cyclically varying potential is used. Another separation option consists in the reaction with constant current flow (galvanostatic) or specifically predetermined varying current flow (galvanodynamic mix). The polymerization conditions should be optimized for the maximum achievable layer thickness for both the potentiostatic and the potentiodynamic deposition. In addition to the pyrrole-substituted phthalocyanines, the inventors also used tetraminophthalocyaninato-nickel as a comparison substance. Due to the low solubility of the monomers (3.10 ^-4 to 9.10 ^-4 mol / l), a saturated solution should be used. So that the solution has the same concentration over the entire reaction time, about 10 ^-3 mol / l should be used in each case. The voltages in the cyclic voltamograms shown in the figures are given against SCE.

In cyclic voltammetry, triangular voltages are applied between the working and reference electrodes using a potentiostat. For this purpose, the potential between an initial and a reversal potential is continuously changed over time. The currents flowing between the working and counter electrodes are measured. The current densities are obtained by dividing the currents by the active electrode size. Cyclic voltammograms are the plots of the currents or current densities against the voltages resulting from this measuring technique. Reaction 1 shows a cyclic voltammogram of a substance which can react as follows in solution:

The charges Q picked up or given off by the electrode are obtained by integrating the curve:

q = ∫ idt equation 1

A distinction is made between three limit ranges in cyclic voltammetry:

• - the reversible reaction
• - the quasi-reversible reaction
• - the irreversible reaction.

In the reversible reaction, the distance between the cathodic and anodic peak potential is between 57 and 60 mV. The theoretically calculated value of 59.2 mV is rarely measured because the resistance effects of the solution lead to small distortions. The amounts of charge q _A and q _k are of equal magnitude. The peak potential can be determined using the following formula:

Is the rate of electron transfer slow compared to the time scale (for large Feed speeds) is the thermodynamic equilibrium between A and A 'disturbed. The distance between the peak potentials increases. Just in case the redox potential can no longer be determined exactly. One speaks of one Quasi-reversible reaction. Equation 2 is mostly used to approximate the Redox potentials used.

If the anodic and cathodic reaction peaks no longer overlap, one speaks in the electrochemical sense of an irreversible reaction. The Cyclic voltammograms shown are not irreversible reactions in the elec trochemical sense, but they are irreversible in chemical nature. At no redox potentials can be given for these reactions.  

The figures in the drawing show the changes in the cyclic voltamograms during the potentiodynamic polymerization. The layer thicknesses obtained and the charges absorbed are then discussed in comparison to the potentiostatic polymerizations. Two cyclic voltammograms (CV) are shown for each monomer. The first CV according to FIG. 14 shows the first five cycles to illustrate the changes in the potential between the monomer and the polymer. In the second CV according to FIG. 15, every fifth cycle is plotted to show the saturation of the currents. The individual polymerization parameters are optimized beforehand. The potentiodynamic electro-polymerizations shown here are carried out at a speed of 10 mV / s. Increasing the scanning speed leads to less pronounced oxidation and reduction peaks and to lower film thicknesses after the same deposition time. Acetonitrile, dichloromethane (DCM) and dimethylformamide (DMF) are used as solvents. The pyrrole-substituted phthalocyanines achieve the greatest layer thicknesses from DCM and the tetraamino-phthalocyaninato nickel from DMF. Tetrabuty laminonium tetrafluorophorate (TBABF ₄ ), tetrabutylamonium perchlorad (TBACIO ₄ ) and tetrabutylamonium hexafluorophosphate (TBAPF ₆ ) are investigated as conductive salts, whereby the separation of the tetraaminophthalocyaninato-nickel succeeds optimally from a solution with 0.1 mol / l TBACIO ₄ . In contrast, the pyrrole-substituted phthalocyanines achieve the greatest layer thicknesses when deposited from 0.1 mol / l TBAPF ₆ . The potentiodynamic polymerization is terminated every two hours. The following table is intended to give an overview of the optimized reaction conditions according to the invention:

Table 2

The potentiodynamic electropolymerization of tetraaminophthalocyaninato-nickel is carried out in DMF with 0.1 mol TBACIO ₄ as the conducting salt. The monomer has three oxidation peaks (0.29 V; 0.72 V; 0.98 V) and two reduction peaks (0.55 V; 0.95 V). The position of the oxidation peaks shifts significantly to more positive potentials during the transition from the monomer to the oligomer. The first oxidation peak of the oligomer is 0.55 V and the second is 0.95 V. The third oxidation peak for the oligomer is outside of the voltage range. The second reduction peak does not shift (0.87 V). In contrast, the first reduction peak of the oligomer is slightly shifted to higher voltages at 0.35 V.

In Fig. 15, every fifth cycle is plotted. It can be seen that the oxidation and reduction peaks only increase in intensity, but then decrease from the 20th cycle. The potentiodynamic electropolymerization of tetrakis (2-pyrrol-1-yl-etoxy) phthalocyanine is carried out in DCM as a solvent. 0.1 mol / l TBAPF _{6 is} used as the conductive salt. Fig. 16 shows the corresponding CV. The central metal-free tetrakis (2-pyrrol-1-yl-etoxy) phthalocyanine shows two oxidation peaks (0.79 V; 1.20 V) and a reduction peak (1.03 V). The position of the reduction peak does not change during the polymerization. During the transition from the monomer to the oligomer, the oxidation peaks shift to more positive potentials (1.2 V; 1.38 V). The oxidation and reduction peaks decrease sharply after the first five cycles. The maximum current density at 1.4 V steadily decreases with increasing layer thickness.

Regarding electropolymerization, it should be noted that this belongs to the group of belongs to electro-organic syntheses. Electron-rich aromatics can pass through electrochemical oxidation or reduction are brought to polymerization. Most conductive polymers are polymerized anodically (oxidatively). This The method can also advantageously be used for non-conductive polymers become. The cathodic polymerization of phenol to polyphenylidene oxide is also possible. The advantage of this method is the resulting homogeneous Layers whose thickness can be controlled well over the deposition time. With this technique, it is also advantageously possible to remove the layers during the Doping deposit.

It can optionally be modified by generating radicals Electrodes also carry out a radical polymerization using electricity.  

According to an exemplary embodiment of the invention, the preparation is carried out in a 3-electrode arrangement, as is used for cyclic voltammetry. Alternatively, a 2-electrode arrangement could also be used. Fig. 17 shows a corresponding arrangement according to the invention as a schematic diagram. In this method, a silver wire or a silver wire with a silver chloride coating is used as the quasi-reference electrode (RE). It has the advantage that it does not have to be in contact with aqueous electrolytes, and thus traces of water can be excluded as impurities. However, it must be calibrated against ferrocene after each measurement. 1- and 2-complement cells are used for electroorganic syntheses. The arrangement of FIG. 17 is a 2-Kompatiment cell. In this cell, the anode (AE) is separated from the cathode (GE) by a semi-permeable partition (ST). It has proven to be advantageous for the invention to arrange the electrodes in a special way. Normally, the reference electrode is arranged in the vicinity of the working electrode, while the counter electrode is arranged at a further distance. For the invention, however, it is preferred to arrange the counter electrode as close as possible to the working electrode and to arrange the reference electrode behind the working electrode at a greater distance. The suitability of the cell depends on the monomer and should be tailored to the monomer.

The cell shown in FIG. 17 additionally has two openings for purging inert gases. In order to achieve homogeneous layers, the counter electrode (GE) should have the same geometry and size as the working electrode and be aligned in parallel. The deposition can be carried out according to three different methods: with constant voltage (potentiostatic deposition), constant current (galvanostatic deposition) or with cyclically varying potential (potentiodynamic deposition). The type of deposition then determines the morphology of the layers deposited in this way. It is thus possible, in particular in the case of potentiodynamic deposition, to achieve a higher porosity of the layers, ie an increased pore size. The sensitivity of such a layer is improved in this way, since more gas molecules of a gas to be detected can diffuse into a more porous layer. The mode of operation of the cell shown will be explained using the example of pyrrole. The individual reaction steps are shown in FIGS. 18a to d. First, pyrrole is oxidized to the radical at the anode. This can then react either with another radical or with a pyrrole molecule. The first case is referred to here as radical-radical dimerization, while the second case is referred to here as radical-substrate dimerization, the first reaction path being more probable. In both cases, two protons are split off and one electron is released during the radical-substrate coupling. The progressive reaction gives polypyrrole. The electropolymerization of aniline and amino-substituted aromatics is to be illustrated using the example of the electropolymerization of tetraaminophthalocyaninato-nickel according to FIG. 19. The mechanism of electropolymerization of tetraamine minophthalocyaninato-nickel shown in FIG. 19 is also an anodic polymerization. Radical-radical dimerization is also more likely in this reaction.

The following are the potentiodynamic and potentiostatic deposition be compared with each other.

First, the amounts of charge absorbed during the static and dynamic polymerization of P2 can be compared. For the Calculation of the amount of charge of the potentiostatically deposited polymers the polymerization was terminated after various reaction times and the currents measured during the reaction are integrated against time. To the To determine amounts of charge during the potentiodynamic polymerization, a CV that was recorded over 2 h is broken down into the individual cycles. Then the tensions with the feed rate in times converted. The resulting graphs (current versus time) will be integrated for the calculation of the exempt and dispensed per cycle  Charge. The amounts obtained are subtracted by the amount remaining in the polymer To get charges. To compare the results of the potentiostatic and the Potentiodynamic electropolymerization is the total amount of Charges per cycle determined by adding the previous cycles and plotted against time until the respective cycle.

The results of the calculation are shown in FIG. 20. With the same polymerization time, the layers of tetrakis (2-pyrrol-1-yl-phthalocyanine) produced by potentiodynamics take up 1/3 more charge carriers than the layers produced by potentiostats. The charge absorbed by the polymer saturates as the reaction time progresses in both preparation methods. The following table should allow a comparison of the potentiostatic and the potentiodynamic electropolymerization.

Table 3

In the case of the polymers which reach a layer thickness of more than 1 µm, the absorbed is Charge in the potentiodynamic deposition is significantly larger than in the potentiostatic. The layer thicknesses achieved are in the polymeric phthaloy cyanines with nickel as the central metal in potentiodynamic electropolymeri station thicker. For the other polymer films containing central metal, these are achieved layer thicknesses similarly by both preparation methods. For the rushes of the central metal-free polymers reach the potentiostatically deposited Films with thicker layers. For the invention, layer thicknesses are between 1 µm and 5 µm advantageous.

The monomers, which only have a small layer thickness, have a low charge consumption. However, the charge consumption per layer thickness is different for the individual monomers. The maximum layer thickness depends clearly on the structure of the monomer. In the pyrrole-substituted phthalocyanines, the central metal-free monomers grow significantly to higher layer thicknesses. The extension of the alkyl spacer between the phthalocyanine and the pyrrole substituent leads to greater layer thicknesses after the electropolymerization. The incorporation of the central metal in these compounds leads to lower layer thicknesses with the same polymerization time. The following are the main reasons for the different layer thicknesses achieved:

• - solubility
• - reactivity
• - Conductivity of the resulting polymer
• - electrode kinetics.

The central metal-containing pyrrole-substituted phthalocyanines have a lower solubility than the central metal-free (~ 10 ^-4 : ~ 5.10 ^-4 ). This explains why the central metal-containing monomers achieve lower layer thicknesses. Again, it cannot be explained why the cobalt-containing phthalocyanine achieves greater layer thicknesses than the Zing or. Nickel-containing. This is because the redox-active central metal activates the polymerization. The polymerization behavior of the pyrrole-substituted phthalocyanines differs from that of the tetraamino-substituted phthalocyanines. In the pyrrole-substituted phthalocyanines, the cobalt-containing layer achieves the greatest layer thicknesses, followed by the nickel-containing layer. The zinc-containing monomer grows the worst. In the case of the tetraamino-substituted phthalocyanines, the nickel-containing phthalocyanine grows to the greatest layer thicknesses, the zinc-containing one reaches the second thickest layer thicknesses, and the cobalt-containing layer shows the lowest reactivity. Nickel-containing phthalocyanines show higher spec. Conductivities than other phthalocyanines. For this reason, growing up to high layer thicknesses can be explained. The reason for the different reaction behavior is the electron density of the radical cations. The tetraamino-substituted phthalocyanines have a higher electron density in the aromatic system than the pyrrole-substituted phthalocyanines due to the mesomer-shifting amino groups.

The monomer with the C ₃ spacer between the pyrrole group and the phthalocyanine grows to a greater layer thickness than the monomer with the C ₂ spacer. Since the solubilities are comparable, this reason for different growth behavior is excluded. The slight steric hindrance of the pyrrole group in the monomer with the C ₃ spacer increases the reactivity of the polymerization. The conductivity of the resulting polymers is comparable.

The polymer of amino-substituted phthalocyanine has a significantly higher one Conductivity than the pyrrole-substituted phthalocyanines.

The electrode kinetics are similar for the monomers described here because the The size of the molecules and their polarity do not vary widely. So you can assume that the diffusion constants and the interactions with the Electrode are similar.

The electropolymerization is carried out on the perylenes shown. The hydroxyphenoxy-substituted perylene 16 can be deposited at negative potentials with CaCl ₂ as the conductive salt from DMF on ITO. Electropolymerization in the presence of TBAPF ₆ as the conductive salt is not possible. The redox couple is striking at -0.56 V. Since it does not occur with the electropolymerizable phthalocyanines, it can be assigned to the perylene backbone. The maximum shifts to less negative potentials. The growing polymer is more difficult to reduce than the monomer. In Fig. 21, every fifth cycle of electropolymerization is plotted.

The tetrachlorinated hydroxyphenoxy-substituted perylene 17 can only be deposited in very thin layers under the same conditions. The redox pair of the perylene backbone is 0.3 V and can only be seen during the first cycles. Also, every fifth cycle of potentiody namic deposition is shown in Fig. 22. The current densities decrease rapidly after a few cycles.

The aminophenoxy-substituted perylenes I1-I5 cannot be deposited on ITO in DMF using either CaCl ₂ or TBAPF ₆ as the conductive salt. On the other hand, on platinum electrodes, the polymerization of perylenes with di-aminophenyl ether as substituents (I1, I2) with TBAPF ₆ as the conductive salt begins. However, the films only grow to small layer thicknesses. Fig. 23 shows every fifth cycle of potentiodynamic electropolymerization of I1.

The introduction of chlorine atoms for electropolymerization is also unfavorable here. As can be seen from FIG. 24, the current densities during the potentiodynamic deposition from the chlorinated PTCDI I2 are significantly lower than those of the non-chlorinated derivatives I1. The decrease in the current densities with the cycle number is significantly greater with the chlorinated PTCDI derivative (I2).

In general, the PTCDA, which are reacted with di-amino-diphenyl ether (I1, I2) the highest reactivity among the amino substituted perylenes 11-15. The steric hindrance can thus be caused by a longer spacers can be reduced. The increase in electron density in the attacking aromatics favored by the oxygen as a heteroatom Polymerization in addition. Substitution of the PTCDA with methylene para diaminodiphenyl (I3) does not increase the reactivity. The steric Obstacle during electropolymerization is also in this case discontinued, but the electron density in the reacting aromatic did not increase. On Difference in reactivity between the meta- and para-di-aminophenyl sub PTCDA's (I4 and I5) are not available.

The polymerization parameters should be optimized for the p-di-amino-substituted PTCDA (I4). The reactivity of the electropolymerization can be increased by adding perchloric acid as a catalyst. Potentiodynamic separation from I4 to ITO succeeds. Fig. 25 shows each fifth cycle of the electropolymerization of I4 in DMF with TBAPF ₆ as conducting salt with two drops of perchloric acid as a catalyst. The reaction starts at more positive potentials compared to NiPc [NH ₂ ] ₄ A1 (1.4 V at 14 and 1.1 V at NiPC [NH ₂ ] ₄ A1), with the maxima of the oxidation and reduction for the PTCDI I4 shifts to lower positive potentials. One reason for the potential shift is the protonation of the I4.

Since the electropolymerization is catalyzed by acids, the use of acidic electrolytes is generally recommended during the reaction. The use of anhydrous acids such as HBF ₄ etherate complexes also leads to a further increase in reactivity.

Another preferred embodiment of the component according to the invention contains a preferably electrically conductive substrate, which is further preferred in the Form of interdigital electrodes can be microstructured. Is on this substrate the layer containing the polymer is preferably polymerized. The digital electronics Trodes are preferably designed as fingers, which also face each other can be nested in a comb-like manner. It is preferred if the distance between the digital electrodes of a comb is between 1 µm and 2 µm lies. A small distance between the digital electrodes is advantageous because then the subsequently applied polymer layer is definitely closed Layer can be applied.

In a further embodiment of the invention, the electrodes of the Component according to the invention by electroplating another one Metal are changed. For example, only a part of the electrodes of the Component according to the invention by electroplating a further metal be changed so that two or more are different available in a microstructured manner on the component according to the invention be put. The can then on these different electrodes Polymer layer are polymerized. This can also be a heterogeneous one Polymer layer, as described below, can be used to the properties of the component according to the invention for example  tune the detecting gas.

In a further preferred embodiment of the invention, the component is a sensor for measuring the at least presence, preferably the concentration tration of substances in gases and / or liquids and / or solids, preferably of gases in air, the layer for measuring the presence, preferably the concentration that is sensorially active. The trained according to the invention The th layer thus forms the central section of a sensor. Such sensors can also be used as an array, i.e. H. connected in series, for quantitative and qualitative Detection of gases and / or liquids can be used. These sensors can be used, for example, for non-specific measurements in air quality monitoring in a motor vehicle, in the sensor-controlled ventilation of closed Rooms, for example in a bathroom, and in food quality inspections gene, used for example in fruit / meat departments and warehouses become. The polymer sensor according to the invention can be used advantageously several different bases at the same time, which are caused by the ripening process of the food arise, grasp. It is possible, for example, to use different polymers to integrate in a single polymer layer, so that the properties of the appropriate sensors targeted to those to be detected or monitored Food can be matched. But also leave with only one polymer different gases capture because the polymer with different gases too reacted differently. These different reactions can then then in a computer unit with certain calibration values the gases are compared, so that these gases then by Assignment of the recorded values to the calibration values can be determined.

In further preferred embodiments, the one according to the invention can Combination of a polymer and a molecular organic semiconductor layer also contains an antistatic film, an organic field effect transistor (OFET), an organic light emitting diode (OLED), a photovoltaic cell, a Schottky cell and / or a battery. The following are some of these  Areas of application explained.

The largest industrial application of conductive polymers is that electromagnetic shielding of electronic components. Antistatic foils are mainly made from poly-3,4-ethylenedioxythiophene (PEDOT).

The other application that is already ready for production is OLEDs. Fig. 26 shows the schematic structure.

A reactive metal such as calcium or magnesium is used as the cathode. Typical organic layers as luminescent or emitting layers are PPV or Alq ₃ . With OLEDs, PEDOT is used on the one hand to smooth the substrate and on the other hand as a hole conductor layer. A typical anode material is indium tin oxide (ITO). It has a high conductivity and is transparent. However, conductive polymers can also be used, so that flexible OLEDs are formed. The principle of operation is identical to the inorganic LEDs. holes are injected through the anode and electrons through the cathode. Both migrate through the applied field into the luminescent layer, where they recombine with the emission of electromagnetic radiation.

OLEDs are the physical reversal of the photovoltaic cell in which electricity is generated by the radiation of electromagnetic radiation. For organic photovoltaic cells, an organic n-semiconductor (e.g. Me-PTCDI) and an organic p-semiconductor (e.g. ZnPc) are combined. It is also possible to manufacture Schottky cells from an organic semiconductor and a conductive polymer as a metal substitute. Fig. 27 shows typical structures of an organic photovoltaic cell and a Schottky cell.

While organic light-emitting diodes can compete with inorganic LEDs in terms of both lifetime and light intensity, organic photovoltaic cells have so far not achieved the efficiency of inorganic cells. The efficiencies are 1% (MePTCDI / ZnPc) compared to 35.8% (GaAs / GaSb). The functional principle of a photovoltaic cell is shown in FIG. 28.

In the space charge zone, which results from the contact of an n- and a p-semiconductor, electrons are excited by electromagnetic radiation from occupied to unoccupied states. The resulting pair of excitons is separated by the electric field. Another application of organic semiconductors and conductive polymers is the construction of OFET. Their mode of operation is identical to that of the inorganic field effect transistors. The currents between emitter and collector can be controlled by the voltage applied to the base. Their area of application is not limited to the amplification of currents, as is the case with inorganic transistors, but also extends to chemical sensors. The semiconducting properties of organic materials change through interactions with oxidizing or reducing substances. Electron transfer occurs, which shifts the position of the Fermi level. The currents between emitter and collector change with constant voltage at the base. This means that these substances (e.g. NH ₃ gas) can be detected. Fig. 29 shows the schematic structure of an organic field effect transistor.

A combination of an OFET with an OLED is also conceivable. The collector currents of an OFET, which will increase in the presence of a substance to be detected led an OLED. Combine the currents in the light layer Charge carrier pairs and electromagnetic radiation are emitted. Thereby gases to be detected can be converted directly into a light signal.

Furthermore, conductive polymers can be used in batteries. They are lighter than metals and therefore offer advantages. These batteries can be constructed from two differently doped polyacetylene layers, for example. One layer is doped with Li ions and the other with iodine. Filter paper impregnated with polypropylene carbonate and LiCIO ₄ can be used as the electrolyte. The structure of such a battery is shown in FIG. 30.

By introducing pigment substances into the invention according battery has the advantage that the conductivity of such Polymer battery is preserved over a long period of time. In addition, the Polymer batteries according to the invention also less sensitive to small holes in the layers used to build the battery. With another out leadership form of the batteries according to the invention are due to the ver used pigments colored. The pigment substances can be such can be chosen that the color changes, preferably in the course of the discharge operation of the battery. For the user of such a battery it is therefore - without having to use an additional battery level indicator - through the Color of the battery itself recognizable whether the battery is full or rather empty. Also can be by the combination of pigments and Polymer the increased mechanical stability of the prior art Realize batteries according to the invention.

Another application is electrochemical muscles. The invention Polymers swell when doped. This expansion can occur in actuators be used.

Fig. 31 shows a preferred embodiment of an organic field effect transistor (OFET) from 10. The OFET 10 has a metal substrate 5 . An insulator 4 is arranged on the metal substrate. The polymer layer 3 according to the invention is located on the insulator 4 . Two conductive layers are embedded in the polymer layer 3 as drain 1 and source 2 . The substrate 5 serves as the gate of the transistor 10 .

Fig. 35 shows a further embodiment of the invention. In this example, drain 1 and source 2 are made of different metals. The polymer layer 3 is also divided into two regions 3 a and 3 b, which have different polymers. A diode is thus present between 3 a and 3 b. These different areas 3 a and 3 b are produced by first polymerizing a certain polymer onto the conductors 1 and 2 , and then only on one of the areas 3 a or 3 b with another monomer - for example by changing the manufacturing bath for the polymerization - further polymerization. The change between different polymers can be repeated any number of times, so that the desired properties of the layer can be set exactly according to the requirements. In a further embodiment, different polymers are polymerized onto the conductors 1 and 2 , which can be designed, for example, in the form of the interdigital electrodes mentioned above. A measurement between the different polymers is thus possible in this embodiment. This also allows the corresponding sensor to be set to a specific sensitivity for a specific gas.

In the two aforementioned embodiments, not only those in this Registration explicitly mentioned polymers are used, but all known Polymers. These specially matched layers can, for example, in the Food detectors mentioned above are advantageous according to the invention be used.

Fig. 36 shows another example. Here, a transistor has been generated by have been used at 1 and 2 also different metals, while the areas 3 a, 3 b, and 3 c are doped differently. The regions 3 a and 3 c are p-conductive, while the region 3 b is n-conductive.

Fig. 32 shows a layer structure of an organic photoconductor Volta cell (solar cell) or an organic light emitting diode. A transparent electrically conductive, organic conductor (e.g. PeDOT) 12 or a transparent electrically conductive inorganic conductor (e.g. ITO) is located on a transparent glass substrate 11 . The polymer 13 according to the invention is located on the organic conductor 12 . An organic conductor 14 is in turn applied to the polymer. Alternatively, in the embodiment according to FIG. 32, the arrangement of further layers made of metal, organic conductors or inorganic semiconductors can be provided between layers 12 and 13 or 13 and 14 .

Fig. 33 shows a further preferred embodiment of a device 30 according to the invention. In this component 30 there is an electrical conductor 22 on a glass substrate, which can alternatively also be made of metal or plastic. An inorganic semiconductor is applied to the electrical conductor 22 . Examples include TiO ₂ or SnO ₂ . The polymer 24 according to the invention is then located on the inorganic semiconductor 23 . Fig. 33, the surface of the inorganic semiconductor 23 is rough, so that the polymer layer 24 applied to this irregular layer also has an uneven surface 24 a. Alternatively, there is a liquid, a gas mixture or an electrolyte on the surface 24 a, the latter being liquid or solid. This layer of liquid, gas mixture or electrolyte is designated by reference number 25 . This layer 25 is delimited by a further layer of an electrical conductor 26 . On the electrical conductor 26 there is again a glass substrate 27 , which can alternatively be made of plastic.

If layer 25 is a liquid or a gas mixture and layer 26 is dispensed with, component 30 forms a photooxidation cell. If the layer 25 is formed as an electrolyte, the component 30 forms a photovoltaic cell, ie a solar cell. In this embodiment, the polymer can be bonded to as well as in the inorganic semiconductor 23 .

In addition to the previously mentioned embodiments, the inventive one Polymer layer also as a semipermeable membrane for sensory applications be used.  

FIG. 34a and 34e show the schematic structure of the polymers used for the polymerization of the polymer layer according to the invention. Both pure polymers and copolymers or graft polymers can be produced from these monomers. The polymerizable group is designated by the reference number 31 . The spacer is designated by the reference numeral 32 . The reference numeral 33 denotes the organic semiconductor.

Claims (18)

1. electrical component,
with a layer which influences the electrical properties of the electrical component and contains at least one polymer, characterized in that the polymer contains at least one molecular organic semiconductor,
wherein the at least one molecular organic semiconductor has at least one polymerizable group, via which group the molecular organic semiconductor is polymerized to form the polymer. 2. Component according to claim 1,
wherein the at least one molecular organic semiconductor contains a macrocyclic ligand and / or its metal complexes, in particular substituted and / or unsubstituted phthalocyanines, substituted and / or unsubstituted porphyrins, substituted and / or unsubstituted porphyrazines, substituted and / or unsubstituted naphthalocyanines, substituted and / or contains unsubstituted biphthalocyanines, substituted and / or unsubstituted merocyanines and / or substituted and / or unsubstituted chlorines,
or a condensed aromatic, in particular substituted and / or unsubstituted perylene dyes and pigments and their derivatives, substituted and / or unsubstituted terrylenes and their derivatives, substituted and / or unsubstituted quaterrylenes and their derivatives, and / or substituted and / or unsubstituted coronenes and their Contains derivatives. 3. Component according to one of the preceding claims, wherein the at least one molecular organic semiconductor has at least one element from the amount of phthalocyanine, hemiporphyrazine, triazole hemiporphyrazine, Biphthalocyanine, naphthalocyanine, phorphyrin, perylene, perylenedicarboxylic acid hydride, perylene dicarboximide, perylene tetracarboxylic acid dianhydride, perylene tetracarboxylic acid diimide,  Perylene tetracarboxylic acid monoanhydride monoimide, coronene, Coronedicarboxylic anhydride, coronedicarboximide, coronetetracarboxylic acid redianhydride, coronetetracarboxylic acid diimide, coronetetracarboxylic acid mono anhydride monoimide, Rubicen, Rubicendicarbonsäureanhydrid, Rubicendicarbonsäurei mid, rubicentetracarboxylic acid dianhydride, rubicentetracarboxylic acid diimide, Rubicentetracarboxylic acid monoanhydride monoimide, imidazole, imidazole dicarboxylic acid reanhydride, imidazole dicarboximide, imidazole tetracarboxylic acid dianhydride, Imidazole tetracarboxylic acid diimide, and imidazole tetracarboxylic acid monoanhydride contains monoimide. 4. Component according to one of the preceding claims, the group being polymerizable by electropolymerization. 5. Component according to one of the preceding claims, the group comprising at least one element from the set consisting of aniline, pyrrole, Thiophene, ethylene, indole, paraphenylene, aminoanthracene, aminoaphthalene, Aminophenol, carbazole, benzoquinone, acrylonitrile, pyrrolidones, phenylenediamine, Tetrathiapentalen, acrylic acid and / or phenol and / or their derivatives and sub contains stituents. 6. Component according to one of the preceding claims, the group being attached to the molecular organic semiconductor via a molecular chain is bound. 7. The component according to claim 6, wherein the molecular chain at least one element from the amount of (CH ₂ ) _n , (CFH) _n , (CF ₂ ) _n , OCO (CH ₂ ) _n , OCO (CF ₂ ) _n , OCO ( CFH) _n , COO (CH ₂ ) _n , COO (CF ₂ ) _n , COO (CHF) _n , NH (CH ₂ ) _n , NH (CF ₂ ) _n , and NH (CHF) _n and / or an aryl Contains rest, where n = 0 to 20. 8. Component according to one of the preceding claims, wherein the molecular organic semiconductor with at least one other, not polymerizable group is modified. 9. The component according to claim 8, wherein the further group comprises at least one element from the group consisting of F, Cl, Br, I, CN, OH, SH, CH ₃ (CH ₂ ) _n CH ₃ , phenyl, phenoxy, ethoxy, methoxy, Contains propoxy, iso-propoxy, and tert-butyl, where n = 0 to 20. 10. The component according to one of the preceding claims, the polymer being electrically conductive. 11. The component according to one of the preceding claims, the polymer being doped. 12. Component according to one of the preceding claims, with a substrate on which the layer is arranged, the substrate, preferably in the form of interdigital electrodes, microstructured is. 13. The component according to claim 12, the substrate being electrically conductive. 14. The component according to one of claims 12 to 13, the layer being electropolymerized onto the substrate. 15. Component according to one of the preceding claims, the component being a sensor for measuring at least the presence, preferably the concentration of gases and / or liquids in a medium is, the layer for measuring the presence, preferably the Konzen tration, is sensory active.   16. The component according to one of the preceding claims, the component being an OFET, an OLED, a photovoltaic cell, a Schottky cell, an antistatic film and / or a battery. 17. A method for producing an electrical component, comprising the steps:

• - an electrical conductor is provided,
• a molecular organic semiconductor is modified with polymerizable groups,
• - The molecular organic semiconductor is electropolymerized on the electrical conductor.

18. The method according to claim 17, successively and / or simultaneously different polymerizable groups be used.