DE102009021881B4 - Organic semiconducting component - Google Patents

Abstract

The present invention relates to an organic semiconducting component which is constructed from a plurality of layers in a pin structure, at least one of the layers comprising at least one compound of the general formula A, B or C:

Description

The present invention relates to an organic semiconductive device constructed of multiple layers. One or more layers may comprise compounds which may act as light absorber, charge transport material and / or dopant.

In recent years, organic compounds having intense absorption in the red and infrared spectral regions have acquired special interest because of their utility in many fields of science and technology. Thus, such compounds can be used as active media in laser-driven recording media, such as CD or DVD, or in solar cells for converting thermal radiation into electrical energy and thermal insulation materials to prevent heating inside closed spaces, such as in vehicles or shop-window areas. In addition, such long-wave absorbing compounds must additionally have the property of being as largely as possible without appreciable absorption in the shorter-wave visible spectral range, as well as being thermally very stable, in order to be able to be applied for the particular application, for example by vacuum evaporation processes.

So far, numerous types of compounds have already become known which, in addition to intensive light absorption in the red and infrared spectral range, also have various other characteristic features which determine their respective intended use. Most often, however, the spectrum of desired property characteristics can not be met by a particular type of compound alone. Thus, for example, polymethine dyes, which usually have a sufficient length of the polymethine chain contained in them sufficiently intense light absorption in the red and infrared spectral range, a very low thermal stability, which, due to their mostly ionic nature, an undeterred evaporability in the way. The same applies to the oxidation products of aromatic or heteroaromatic di- and polyamines, such as the type of 4,4 ', 4' ', 4' '' - tetrakis- (diarylamino) -N, N-tetraphenyl-benzidine and their arylene Homologs, which have very long-wave light absorption in their oxidized state, but because of their ionic nature as well unverdampfbar and unsuitable for many applications. In contrast, nickel dithiolene complexes, which also have very long-wave absorptions in the infrared spectral range, usually well vaporized by a sufficient thermal stability, but their light absorption in the long-wavelength spectral range is often quite low, so that they with these compounds high absorption cross sections in the IR To achieve spectral range can be used in high concentrations or layer thicknesses, but then usually cause disturbing absorptions in the visible spectral region appear.

The only known material for organic solar cells with an absorption above 700 nm are compounds from the series of phthalocyanines. Although these compounds are characterized by an intensive long-wave absorption and high stability, but these compounds can not or only with difficulty be optimized with regard to other properties such as the energetic position of the frontier orbitals due to their low solubility.

It is therefore an object of the present invention to provide organic semiconducting components which contain organic compounds with intensive absorption in the red and infrared spectral range, which overcome the disadvantages of the prior art and in particular are evaporated without decomposition for the production of the component, ie a good thermal stability show and absorb light in the long wave range.

wobei M ein Metall-Ion ist, dessen Ladung vorzugsweise so bemessen ist, dass elektroneutrale Komplexe des Typs B bzw. C resultieren; jedes R unabhängig ausgewählt ist aus unsubstituiertem oder substituiertem C₁-C₂₀-Alkyl, C₁-C₂₀-Heteroalkyl, C₆-C₂₀-Aryl, C₆-C₂₀-Heteroaryl, gesättigtem oder ungesättigtem Carbo- oder Heterocyclus; L¹ und L², die gleich oder verschieden sein können, Atom- oder Molekülgruppierungen darstellen, die die Valenzschale von M absättigen; und –X_i-ein Molekülfragment darstellt, das mit der angrenzenden C-C-Doppelbindung des Pyrrolrings ein aromatisches oder heteroaromatisches Strukturelement ausbildet.This object is achieved by an organic semiconductive component which is made up of a plurality of layers in the pin structure, wherein at least one of the layers comprises at least one compound of the general formula A, B or C:

where M is a metal ion, the charge of which is preferably such as to result in B or C type electroneutral complexes; each R is independently selected from unsubstituted or substituted C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ heteroalkyl, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ heteroaryl, saturated or unsaturated carbocyclic or heterocycle; L ¹ and L ² , which may be the same or different, represent atomic or molecular moieties that saturate the valence shell of M; and -X _{i represents} a molecular fragment which forms an aromatic or heteroaromatic structural element with the adjacent CC double bond of the pyrrole ring.

It is particularly preferred that the device is an organic solar cell or a photodetector. Light-emitting diodes should not fall under the organic semiconducting devices claimed according to the invention, but generally organic-inorganic hybrid devices.

It is preferably proposed that the metal ion M is selected from ions of the elements of the 9th to 13th group of the Periodic Table of the Elements, preferably Cu, Zn, Ni, B or Al.

wobei R¹-R⁷ unabhängig ausgewählt sind aus Wasserstoff, Halogen, unsubstituiertem oder substituiertem C₁-C₂₀-Alkyl, C₁-C₂₀-Heteroalkyl, C₆-C₂₀-Aryl, C₆-C₂₀-Heteroaryl, gesättigtem oder ungesättigtem Carbo- oder Heterocyclus, oder wobei zwei benachbarte Reste R¹-R⁶ Bestandteil eines weiteren carbocyclischen oder heterocyclischen Rings sind; und wobei Q für eine zweibindige, die Elemente C, N, O oder S enthaltende Atomgruppierung steht.An advantageous embodiment is characterized in that each X _l is independently selected

wherein R ¹ -R ^{7 are} independently selected from hydrogen, halogen, unsubstituted or substituted C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ heteroalkyl, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ heteroaryl, saturated or unsaturated carbo or heterocycle, or wherein two adjacent radicals R ¹ -R ^{6 are} part of a further carbocyclic or heterocyclic ring; and Q is a divalent atomic grouping containing elements C, N, O or S.

Q can be, for example, -CH ₂ -, -NH-, -O- or -S-.

It is further preferred that L ¹ and L ^{2 are} independently selected from halogen, alkyl, aryl, alkyloxy, aryloxy, acyl, aroyl, alkenyl or alkynyl, or L ¹ and / or L ² may each be attached to an R, respectively.

If L ¹ and / or L ^{2 are} attached to radicals R, a further ring can thereby be formed via the linkage MLR. This can be done, for example, in the form of MOR of an ether bridge or MSR of a thioether bridge.

It is also preferably provided that the at least one layer comprising the compound of the formula A, B or C is a light absorber layer or charge carrier transport layer.

Finally, it is preferred that the device is photoactive.

The radicals R ¹ -R ⁷ and R may preferably be selected from alkyl, alkoxy, dialkylamine, alkylsulfanyl, alkylsulfenyl, alkylsulfonyl, phenyl, naphthyl, anthryl, fluorenyl, aryloxy, arylsulfanyl, arylsulfenyl, arylsulfonyl, arylalkylamine, diarylamine, pyrrolidine, tetrahydrofuran, Tetrahydrothiophene, piperidine, tetrahydropyran, tetrahydrothiopyran, pyrrole, furan, thiophene, pyridine, pyrylium ion, thiopyrylium ion, quinoline, purine, oxazole, Thiazole, benzothiazole, pyrazine, imidazole, pteridine, acridine, pyrimidine and indole. It is also conceivable that adjacent radicals are constituents of another carbocyclic or heterocyclic ring.

The compounds of the formula type AC can be prepared in various ways, preferably from the compounds of general formula type 2, 4 or 8 (see below) known per se, in which the symbols X and R have the abovementioned meaning, by adding them to the Ammonium salt of a preferably organic acid, such as formic acid or acetic acid, in a high-boiling dipolar solvent (sols), such as a prim. or sec. alkanol having a boiling point above 150 ° C, an aliphatic carboxylic acid amide, such as formamide, DMF or dimethylacetamide, or else in a polyhydric alkanol of the 1,2-, 1,3-diols or 1,2,3- Triols, resulting in mostly smooth reaction, as described by VF Donyagina, S. Shimizu, N. Kobayashi and EA Lukyanets in Tetrahedron Lett. 2008, 49, 6152 by way of example, first the compounds recognizable by their deep color form the general formula type A, which is then, if necessary, after their isolation by heating with a compound of the general formula ML ¹ L ² L ³ , in which L ¹ and L ^{2 have} the same meaning as stated above and L ^{3 is} a ligand identical or different from L ¹ and L ² , which, like L ¹ and L ² with the atom M, can form a stable coordination sphere in a polar solvent, such as a lower or higher alkanol, an aliphatic carboxylic acid amide such as formamide, DMF or dimethylacetamide, a carboxylic acid anhydride such as acetic or propionic anhydride, methylene chloride or 1,2-dichloroethane, to the target compounds of the formula B or C.

With respect to the aforementioned compounds of the formula type 2, 4 or 8, the compounds of type 2 can be obtained by reacting compounds of the formula type 1 as described by H. Bredereck and HW Vollmann in Chem. Ber. 1972, 105, 2271, with an organometallic compound of the general formula type R-MZ _n , in which the radical R has the same meaning as in formula A, n is either 0 or 1 and M is a metal ion of preferably is the 1st or 2nd group of the Periodic Table, wherein in the latter case n = 1 and thus this metal ion still with a suitable, the valency of M saturating radical Z, such as preferably a halogen atom, may be reacted containing the compounds of the formula type 4 in that compounds of the formula type 3 as described by MAT Rogers in J. Chem. Soc. 1943, 590, with a nitrosating reagent NO-Y, as with z. Example, sodium nitrite in mineral acid solution or with Salpetrigsäurealkylestern in alcoholic / mineral acid solution, are reacted, and the compounds of the formula type 8 in that either compounds of the formula type 5 with isopropylmagnesium chloride, such as A. Krasovskiy and P. Knochel in Angew, Chem. Int. Ed. 2004, 43, 3333, are first converted into compounds of formula type 6 and then these, as described for example by RJ Kloetzing, A. Krasovsky, and P. Knochel in Chem. Eur. J., 2007, 215, by reaction with a compound of the general formula type 7 or compounds of the general formula type 9 with metal cyanides, as described, for example, by K. Kobayashi et al. in Bull. Chem. Soc. Japan 2006, 79, 1126 described.

Surprisingly, it has been found that the organic semiconducting devices according to the invention do not have the disadvantages found in the prior art, in particular by the use of the compounds of the type AC in an excellent spectral range are active and show high thermal stability.

The compounds A, B and C have semiconductive properties which were previously unknown in the prior art. This means that a layer which is made exclusively of material of the compounds A, B and / or C, already without semiconducting properties without additives or further chemical changes. According to the organic semiconducting components according to the invention, the compounds A, B and / or C are used there as semiconducting layers and not as dopants. A doping is understood to mean that a few individual molecules (dopant) are incorporated into a layer (matrix) in order to absorb or release charges there and to change the semiconducting properties of the layer (matrix).

According to the invention, the component of different material layers, which fulfill different functions, constructed by the materials are vapor-deposited successively on the previous layer. In this context, a closed layer means that the previous layer is completely covered. As a result, charge carriers must be transported in this layer (or through this layer). Consequently, these layers must have semiconducting capabilities and enable high mobility of charge carriers. Both properties need not satisfy a dopant.

The combination of the absorption properties and the electrical properties of the compounds A, B and C surprisingly result in an organic semiconducting, preferably photoactive, component which has hitherto been unknown in the prior art and extremely satisfactory overall properties, such as excellent activity in the desired one Spectral range and high thermal stability, shows.

According to the invention, preference is given to organic semiconducting components in which the layers which comprise at least one compound of the general formula A, B or C are closed layers or layers with interpenetrating networks. As already stated above, a closed layer means that the previous layer is completely covered by it. A layer with an interpenetrating network is to be understood as meaning a layer in which components of the layer penetrate one another. This can be achieved, for example, by co-evaporation of two materials, which then arrange themselves in a mixed layer. An interpenetrating network in this case has closed percolation paths (paths for charge carriers) which are achieved in a mixed layer if the material contained in a lesser amount is contained at least in a mixing ratio of> 20 percent by mass. This is in contrast to a doping of a matrix material in which the dopant is present at only about four percent by mass, so that there arise isolated units or clusters of the dopant in the matrix layer. Interpenetrating networks with closed percolation paths allow the utilization of the good charge carrier mobilities. It is therefore particularly preferred to provide organic semiconducting components according to the invention in which at least one compound of the general formula A, B or C is present in a closed layer or closed percolation paths within a mixed layer.

The usually thermally stable to mostly well above 300 ° C stable and therefore under high vacuum below this temperature undetached volatile compounds of the formula type AC can be used in different ways in a device, so preferably because of their long-wavelength light absorption in the red or near infrared spectral region as a light absorber in organic solar cells or due to their high redox stability as charge generation or charge transport material in organic solar cells and organic field effect transistors. For this purpose, the compounds mentioned are applied to a suitable substrate, which is constructed as described below by being evaporated in a vacuum chamber at pressures of 10 ^-7 Torr from a container so that no substance decomposition occurs and produces a vapor deposited with a defined thickness if necessary, in association with other layers, each of which has a specific electronic function.

A particular advantage of the compounds A-C as photoactive layers in organic solar cells is that they show an increased spectral sensitivity in the long-wave spectral range due to the long-wavelength absorption of the light absorber used. Thus, the portion of the light energy converted into electrical energy can be extended to a range above 600 nm, but preferably to above 700 nm and particularly preferably above 800 nm.

As an important parameter in photovoltaic devices is the open circuit voltage, which can reach high values by the use of the above compounds. It results from the relative location of the energy levels of the donor and acceptor materials, the energy levels of which can be varied as necessary by appropriate electron withdrawing or electron donating groups such that the electron transfer energy loss is reduced and the open circuit voltage is increased. In addition to the previous advantages in the use of the abovementioned compounds in solar cells, such components have a particularly high fill factor, which in the specific case of compound B1 (see below) is 64.89%. This is given by the quotient of the maximum power and the product of no-load and short-circuit current and thus describes the "squareness" of the current-voltage characteristic as a measure of the quality of a solar cell.

Of particular advantage in increasing the efficiency of organic components is the so-called pin structure. Here, the intrinsic, active layers are introduced between doped layers of organic semiconductors, which preferably have a large bandgap and are therefore transparent. The p-doped layer follows the donor material and has HOMO energy matched to the HOMO energy of the donor. The n-doped layer follows the acceptor material and has LUMO energy matched to the LUMO energy of the acceptor material. These layers have a very good conductivity due to their doping and lead to several improvements. The adaptation of the energies leads to the n-doped layers preferably transporting excited electrons and p-doped layers preferably transporting excited holes. They are therefore also referred to as electron or hole transport layers (ETL or HTL). This results in a pin structure to support the, especially in photoactive devices such. As solar cells necessary, separation of the charge carriers. The high conductivity of the layers leads to a reduction of the charge carrier injection barrier, which would otherwise be a loss mechanism. When transparent materials are used as the ETL or HTL, these layers can be used to shift the active absorbing layers to the location of the optical maximum of the incident light to thereby reduce the amount of light absorbed in the active layer and hence the efficiency of the light Increase building element. (Maennig et al., Appl. Phys. A79, 1-14 (2004)) Further advantages and features of the device according to the invention will become apparent from the following detailed description of preferred embodiments with reference to the accompanying drawings, in which:

1 shows an absorption spectrum of the compound Al in dichloromethane;

2 shows a cyclic voltammogram of the compound Al in dichloromethane with ferrocene as internal standard and tetrabutylammonium hexafluorophosphate (1 mmol) as conducting salt at a scanning speed of 100 mV / s at 25 ° C;

3 shows an absorption spectrum of compound A2 in dichloromethane;

4 shows a cyclic voltammogram of compound A2 in dichloromethane with ferrocene as internal standard and tetrabutylammonium hexafluorophosphate (1 mmol) as the conducting salt at a scan rate of 100 mV / s at 25 ° C;

5 shows an absorption spectrum of compound B1 in dichloromethane;

6 shows a cyclic voltammogram of compound B1 in dichloromethane with ferrocene as internal standard and tetrabutylammonium hexafluorophosphate (1 mmole) as the conducting salt at a scan rate of 100 mV / s at 25 ° C;

7 shows an absorption spectrum of Compound B2 in dichloromethane;

8th shows a cyclic voltammogram of compound B2 in dichloromethane with ferrocene as internal standard and tetrabutylammonium hexafluorophosphate (1 mmole) as the conducting salt at a scan rate of 100 mV / s at 25 ° C;

9 Layer structures of different embodiments of the semiconducting device according to the invention shows;
First, some synthesis examples are given for the preparation of the compounds of the type AC.

synthesis Examples

1. Preparation of Diisoindolylazamethines of General Structure A

1.a Synthesis of (3-phenyl-2H-isoindol-1-yl) - (3-phenyl-isoindol-1-ylidene) -amine (Al)

To a suspension of phthalonitrile (12.8 g, 0.1 mol) in toluene (100 mL) is added, with stirring at room temperature, one of bromobenzene (15.7 g, 0.1 mol) and magnesium turnings (2.7 g, 0 , 11 moles) of phenylmagnesium bromide solution prepared by known methods, and then the resulting mixture is stirred for 2 hours or overnight.

The resulting reaction mixture is treated with chlorotrimethylsilane (10.8 g, 0.1 mol) and the precipitate formed is filtered off with suction and washed with diethyl ether. The resulting solid is then heated in formamide (500 mL) for about 10 minutes until a deep dark blue color appears and a copper colored precipitate forms. It is allowed to cool and sucks off the precipitate, which is then washed with water and methanol. The virtually reagent-pure compound can be further purified by column chromatography on silica gel by elution with chloroform.
Yield: 12 g (30 mmol, 30%), red-violet needles.
M.p. 260.7 ° C
¹ H-NMR (500 MHz, CDCl _3): 7:32 (t, 2H, J = 7.9 Hz) 7:41 (t, 2H, J = 7.7 Hz), 7:47 (t, 2H, J = 7:37 Hz), 7:57 (t , 4H, J = 7.47 Hz), 7.96 (d, 2H, J = 8.0 Hz), 8.03 (d, 4H, J = 7.12 Hz), 8.13 (d, 2H, J = 7.89 Hz).
¹³ C-NMR (125 MHz, _CDCl3): 121.31, 122.14, 126.33, 127.57, 127.74, 129.22, 129.42, 129.92, 133.18, 135.38, 143.86, 148.58.
MS (ESI): Calculated [M + 1]: 398.47. Found: 398.2.
Calculated for C ₂₈ H ₁₉ N ₃ : C 84.61, H 4.82, N 10.47. Found: C 82.6, H 5.1, N 9.9.

The absorption spectrum of the compound Al in dichloromethane and the cyclic voltammogram of compound Al in dichloromethane with ferrocene as internal standard and tetrabutylammonium hexafluorophosphate (1 mmol) as conducting salt at a scanning speed of 100 mV / s at 25 ° C 1 respectively. 2 shown.

1b. Synthesis of [3- (4-methoxyphenyl) -2H-isoindol-1-yl] - [3- (4-methoxyphenyl) -isoindol-1-ylidene] amine (A2)

To a suspension of phthalonitrile (12.8 g, 0.1 mol) in toluene (100 mL) is added, while stirring at room temperature, one of p-bromobenzene (18.7 g, 0.1 mol) and magnesium turnings (2.7 g , 0.1 mol) produced para-methoxyphenyl-magnesium bromide solution is added dropwise and the resulting mixture then stirred for 2 hours or overnight.

The resulting reaction mixture is treated with chlorotrimethylsilane (10.8 g, 0.1 mol) and the resulting precipitate is washed with diethyl ether after filtration with suction. The resulting solid is then heated in formamide (500 mL) for about 10 minutes until a deep dark blue solution forms, from which a copper-colored precipitate separates. After cooling the solution, the resulting precipitate is filtered off with suction and washed with water and methanol. If necessary, the practically reagent-pure product can be further purified by column chromatography on silica gel by elution with chloroform.
Yield: 9.5 g (19 mmol, 19%), red-violet needles.
Mp 154 ° C
¹ H-NMR (500 MHz, CDCl _3): 3.91 (s, 6H), 7:08 (d, 2H, J = 8.85 Hz), 7.2 (t, 2H, J = 7:01 Hz), 7:37 (t, 2H, J = 7.03 Hz), 7.91 (d, 2H, J = 8.08 Hz), 7.97 (d, 4H, J = 8.83 Hz), 8.10 (d, 2H, J = 7.91 Hz).
¹³ C-NMR (125 MHz, _CDCl3): 55.50, 114.73, 121.19, 122.07, 125.4, 126.04, 127.42, 129.21, 129.66, 135.30, 143.42, 147.64, 160.68.
MS (ESI): Calculated [M + 1]: 458.5. Found: 458.2.
Calculated for C ₃₀ H ₂₃ N ₃ O _2: C, 78.75, H 5.07 N 09.18. Found: C 78.43, H 4.99, N 8.02.

The absorption spectrum of the compound A2 in dichloromethane and the cyclic voltammogram of compound A2 in dichloromethane with ferrocene as internal standard and tetrabutylammonium hexafluorophosphate (1 mmol) as conducting salt at a scan speed of 100 mV / s at 25 ° C are in 3 respectively. 4 shown.

2. Preparation of Diisoindolylazamethine Complexes of General Structure B

2a. Synthesis of 11,11-difluoro-10,12-diphenyl-11H-5,10a-diiaza-11a-azonium-11-boranato-indeno [2,1-b] fluorene (B1)

To a solution of compound Al (3.97 g, 10 mmol) in dichloroethane (80 mL) are added at room temperature first with diisopropylethylamine (6.45 g, 50 mmol) followed by boron trifluoride diethyl etherate (7.05 g, 50 mmol). dripped. The solution thus obtained is heated and refluxed for about 10 minutes until the initially blue solution has turned green and no starting material could be detected by thin-layer chromatography. Allow to cool and mixed with water (100 mL). The organic phase is washed three times with water (50 ml each) and the solvent removed in vacuo. The remaining residue is dissolved in chloroform for purification and filtered through silica gel (chloroform).
Yield: 3.9 g (8.8 mmol, 88%), red-violet needles.
M.p. 273 ° C
¹ H-NMR (500 MHz, CDCl ₃ ): 7.30 (t, 2H, J = 6.98 Hz), 7.51 (m, 8H), 7.62 (d, 2H, J = 8.15 Hz), 7.87 (d, 4H, J = 7.86 Hz), 8.11 (d, 2H, J = 8.00 Hz).
¹³ C-NMR (125 MHz, _CDCl3): 121.19, 124.15, 127.03, 128.44, 130.16, 130.19, 130.31, 130.47, 131.14, 133.63, 139.34, 153.20.
¹⁹ F-NMR (2282. MHz, CDCl _3): -129.51 (q, 2F, J = 31.0 Hz)
MS (ESI): Calculated [M + 1]: 446.1. Found: 446.2.
Calculated for C ₂₈ H ₁₈ BF ₂ N 3: C, 75.53, H 4:07, N 9:44. Found: C 75.33, H 3.94, N 9.27.

The absorption spectrum of the compound B1 in dichloromethane and the cyclic voltammogram of compound B1 in dichloromethane with ferrocene as internal standard and tetrabutylammonium hexafluorophosphate (1 mmol) as conducting salt at a scanning speed of 100 mV / s at 25 ° C are in 5 respectively. 6 shown.

2 B. Synthesis of 11,11-difluoro-10,12-bis (-p-methoxyphenyl) -11H-5,11a-diaza-10a-azonium-11-boranato-indeno [2,1-b] fluorene (B2)

To a solution of compound A2 (5.05 g, 10 mmol) in dichloroethane (80 mL) at room temperature, first diisopropylethylamine (6.45 g, 50 mmol) and then boron trifluoride diethyl etherate (7.05 g, 50 mmol). The resulting solution is heated and refluxed for about 10 minutes until the initially blue solution has turned green and no starting material can be detected by thin-layer chromatography. Allow to cool and mixed with water (100 mL). The organic phase is washed three times with water (50 mL each) and the solvent is removed in vacuo. The residue is dissolved in chloroform for purification and filtered through silica gel.
Yield: 4.1 g (8.1 mmol, 81%), copper colored needles.
Mp .: 256 ° C.
¹ H-NMR (500 MHz, CDCl _3): 3.88 (s, 6H), 7:03 (d, 4HM, J = 8.92), 7.29 (t, 2H, J = 7:01 Hz), 7:48 (t, 2H, J = 7.15), 7.65 (d, 2H, J = 8.11 Hz), 7.89 (d, 4H, J = 8.84 Hz), 8.09 (d, 2H, J = 8.00 Hz).
¹³ C-NMR (125 MHz, _CDCl3): 55.36, 114.10, 121.14, 122.95, 124.14, 126.81, 130.11, 131.06, 132.04, 133.51, 139.09, 152.41, 161.32.
¹⁹ F-NMR (228.2 MHz, CDCl _3): -129.70 (q, 2F, J = 31.0 Hz)
MS (ESI): Calculated [M + 1]: 506.3. Found: 506.2.
Calculated for C ₂₈ H ₁₈ BF ₂ N _3: C, 71.31, H 4:39, N 8:32. Found: C 71.14, H 4.58, N 8.22.

The absorption spectrum of the compound B2 in dichloromethane and the cyclic voltammogram of the compound B2 in dichloromethane with ferrocene as internal standard and tetrabutylammonium hexafluorophosphate (1 mmol) as conducting salt at a scanning speed of 100 mV / s at 25 ° C are shown in 7 respectively. 8th shown.

3. Preparation of Diisoindolylazamethine Complexes of General Structure C

3a. Synthesis of bis [3- (4-methoxyphenyl) -2H-isoindol-1-yl] [3- (4-methoxyphenyl) -isoindol-1-ylidene] amine-zinc complex (C1)

To a solution of Compound Al (5.05 g, 10 mmol) in dichloroethane (80 mL) is added a solution of diisopropylethylamine (6.45 g, 50 mmol) and ZnCl ₂ (7.0 g, 50 mmol) and then heated under reflux for about 10 min until the initially blue solution has turned green and thin-layer chromatography indicates that no starting material can be detected. Allow to cool and mixed with water (100 mL). The organic phase is washed three times with water (50 mL each) and the solvent is removed in vacuo. The residue is dissolved in chloroform for purification and filtered through silica gel.
Yield: 4.6 g (8.1 mmol, 88%), copper colored needles.
Zers. pts. > 320 ° C

Exemplary embodiments

By using the described compounds of the general formula type A, B and C, a workable solar cell can be constructed. The photoactive component, in which the above-mentioned compounds are used, is characterized in particular by a high thermal stability and by a good photostability, whereby a particularly long life of the device is achieved. The photoactive layers can be used in solar cells with MiM, Mip, Min, pin or pii structure. (M = metal, p or n = p- or n-doped, organic or inorganic semiconductor, i = intrically conductive combination of organic layers, see, for example, J. Drechsel et al., Org. Electron., 5 (4 ), 175 (2004) or Maennig et al., Appl. Phys. A79, 1-14 (2004)).

The photoactive layers can also be used in tandem solar cells (v. Peumans et al., J. Appl. Phys. 93 (7), 3693-3723 (2003)) or in tandem / multiple solar cells of two or more stacked MiM, Mip, Min, pin, pii diodes (see J. Drechsel et al., Thin Solid Films, 451452, 515-517 (2004)). In this case, a multiple solar cell composed of at least two electrodes and a stack of any number, but at least two, layers, of which at least one layer comprises compounds of the type AC. It can also be provided to provide a further layer, which may consist of organic and / or inorganic materials and serves as a so-called conversion contact for the recombination of electrons and holes.

A photoactive device according to the invention may further comprise conversion contacts made of thin metal layers, inorganic materials (for example so-called nanocrystals which consist of clusters of metal or inorganic material having a size of less than 100 nm) or organic materials (for example doped or undoped molecules or polymers ) contain.

Also, a photoactive device according to the invention may contain anti-diffusion layers of metals or transition metals, for example titanium, palladium or chromium.

According to the invention, it is likewise possible to provide materials for the component which serve for the encapsulation, for example SiN or SiO ₂ . Also transparent outer layers of organic materials are conceivable, namely N, N, N ', N'-tetrakis (4-methoxyphenyl) benzidine or tris (8-hydroxy-quinolinato) aluminum, or inorganic materials such as TiO ₂ or SiO ₂ .

The organic device according to the invention or parts thereof can also be produced in reverse order ("inverted"), for example by exchanging hole transport layer and electron transport layer or exchange of top contact and ground contact.

The organic device may further comprise contacts of thin metal layers composed of one metal or a combination of several metals. An advantageous embodiment of the invention contains in such electrical contacts elements selected from aluminum, silver, gold, ytterbium, chromium, nickel, magnesium and iron.

It is also conceivable that the component comprises contacts made of organic material, which may be a conductive polymer or a combination of a plurality of organic materials. An advantageous embodiment of the invention contains poly (ethylenedioxythiophene): poly (styrenesulfonate) [PEDOT: PSS].

It can also be provided that the organic component according to the invention is produced on a substrate, for example on glass, wood, aluminum foil, a metal surface, such as steel, copper, etc., textile materials or plastic film.

On such a substrate may preferably be present a base contact made of metal, a conductive polymer or a transparent conductive oxide or a combination thereof.

The production of such a device according to the invention is known to a person skilled in the art. The device or at least parts thereof can be made by thermal evaporation or other thermal processes, by spin coating, dip coating, drop casting, doctor blading, chemical vapor phase deposition , CVPD, or organic vapor phase deposition, OVPD), electrodeposition or other chemical, electrochemical or wet chemical processes, screen printing, offset printing, inkjet printing or other pressure based processes, magnetron sputtering or other sputtering based processes, molecular beam epitaxy or comparable processes, roll-to-roll processes or comparable processes, film lamination or similar processes, self-assembled monolayer processes or similar processes ,

Based on the in 9 The following exemplary components have been produced.

Example 1 (pin structure - single layers): a sample on glass ( 1 ), with transparent cover contact ITO ( 2 ), a comparatively very thin layer of gold ( 3 ), a doped PV-TPD layer ( 4 ), a comparatively thin undoped layer of PV-TPD ( 5 ), a photoactive layer of compounds of the formula type AC ( 6 ), a photoactive layer of Buckminster fullerene C ₆₀ ( 7 ), an n-doped layer C ₆₀ ( 8th ) and a cover contact made of aluminum ( 9 ).

Example 2 (pin structure - mixed layer): a sample on glass ( 1 ), with transparent cover contact ITO ( 2 ), a comparatively very thin layer of gold ( 3 ), a doped PV-TPD layer ( 4 ), a comparatively thin undoped layer of PV-TPD ( 5 ), a photoactive mixed layer of C ₆₀ and compounds of the formula type AC ( 6 ), an n-doped layer C ₆₀ ( 7 ) and a cover contact made of aluminum ( 8th ).

Example 3 (pin structure - combination of mixed and single layer): a sample on glass ( 1 ), with transparent cover contact ITO ( 2 ), a comparatively very thin layer of gold ( 3 ), a doped PV-TPD layer ( 4 ), a comparatively thin undoped layer of PV-TPD ( 5 ), a photoactive layer of compounds of the formula type AC ( 6 ), a photoactive mixed layer of C ₆₀ and compounds of the formula type AC ( 7 ), a photoactive layer of Buckminster fullerene C ₆₀ ( 8th ), an n-doped layer C ₆₀ ( 9 ) and a cover contact made of aluminum ( 10 ).

Example 4 (tandem cell): a sample on glass ( 1 ), with transparent cover contact ITO ( 2 ), a comparatively very thin layer of gold ( 3 ), a doped PV-TPD layer ( 4 ), a comparatively thin undoped layer of PV-TPD ( 5 ), a photoactive layer of compounds of the formula type AC ( 6 ), a photoactive mixed layer of C ₆₀ and compounds of the formula type AC ( 7 ), a photoactive layer of Buckminster fullerene C ₆₀ ( 8th ), an n-doped layer C ₆₀ ( 9 ), a comparatively thin, comparatively heavily n-doped layer C ₆₀ ( 10 ), a comparatively thin, comparatively heavily p-doped PV-TPD ( 11 ), a layer of p-doped PV-TPD ( 12 ), a comparatively thin undoped layer of PV-TPD ( 13 ), a photoactive layer of compounds of the formula type AC ( 14 ), a photoactive mixed layer of C ₆₀ and compounds of the formula type AC ( 15 ), a photoactive layer of Buckminster fullerene C ₆₀ ( 16 ), an n-doped layer C ₆₀ ( 17 ) and a cover contact made of aluminum ( 18 ).

Such a construction thus enables the presence of active layers which absorb photons and which are applied together in a mixed layer (Example 2, (FIG. 5 )).

Common hole transport materials ( 9 Example 1, item 4) which can be combined with compounds of the formula type AC are 4,4 ', 4 "-tris (1-naphthyl-phenylamino) -triphenylamines (TNATA), N, N'-di (naphthalene-1 -yl) -N, N'-diphenylbenzidine (alpha-NPD), 4,4'-bis (N, N-diphenylamino) quaterphenyl (4P-TPD), N, N'-diphenyl-N, N '-bis (4' - (N, N-bis (naphth-1-yl) amino) biphenyl-4-yl) benzidine (di-NPB), N, N, N ', N'-tetrakis ( 4-methoxyphenyl) benzidines (MeO-TPD). An advantageous embodiment contains in the hole transport layer materials serving as dopants (acceptors). Example is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ).

Examples of Electron Transport Materials (ETL) ( 9 Example 1, item 7), which can be combined with compounds of the formula type AC, are 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) or buckminsterfullerene (C ₆₀ ). An advantageous embodiment contains materials which serve as dopants (donors) in the ETL. Example is (N, N, N ', N'-tetramethylacridine-3,6-diamine) (AOB).

The features disclosed in the present description, the claims and the drawing may be essential both individually and in any combination for the realization of the invention in its various embodiments.

Claims (7)

An organic semiconductive device made up of a plurality of layers in a pin structure, wherein at least one of the layers comprises at least one compound of the general formula A, B or C:

where M is a metal ion whose charge is preferably such as to result in type B or C electroneutral complexes; each R is independently selected from unsubstituted or substituted C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ heteroalkyl, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ heteroaryl, saturated or unsaturated carbocyclic or heterocycle; L ¹ and L ² , which may be the same or different, represent atomic or molecular moieties that saturate the valence shell of M; and -X _l - represents a molecular fragment which forms an aromatic or heteroaromatic structural element with the adjacent CC double bond of the pyrrole ring. Organic semiconductive component according to claim 1, characterized in that the component is an organic solar cell or a photodetector. Organic semiconductive device according to claim 1 or 2, characterized in that M stands for a metal ion which is selected from ions of the elements of the 9th to 13th group of the Periodic Table of the Elements, preferably Co, Ni, Cu, Zn, Hg , B or Al. Organic semiconducting component according to one of the preceding claims, characterized in that each X _i is independently selected

wherein R ¹ -R ^{7 are} independently selected from hydrogen, halogen, unsubstituted or substituted C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ heteroalkyl, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ heteroaryl, saturated or unsaturated carbo or heterocycle, or wherein two adjacent radicals R ¹ -R ^{6 are} components of another carbocyclic or heterocyclic ring; and Q is a divalent atomic grouping containing elements C, N, O or S. Organic semiconductive device according to one of the preceding claims, characterized in that L ¹ and L ^{2 are} independently selected from halogen, alkyl, aryl, alkyloxy, aryloxy, acyl, aroyl, alkenyl or alkynyl or wherein L ¹ and / or L ² each an R is or are bound. Organic semiconducting component according to one of the preceding claims, characterized in that the at least one layer comprising the compound of the formula A, B or C is a light absorber layer or charge carrier transport layer. Organic semiconducting component according to one of the preceding claims, characterized in that it is photoactive.

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