EP1927141A2

EP1927141A2 - Fluorescent solar conversion cells based on fluorescent terylene dyes

Info

Publication number: EP1927141A2
Application number: EP06793240A
Authority: EP
Inventors: Markus Hammermann; Martin KÖNEMANN; Alfred Rennig; Axel Grimm; Arno BÖHM; Peter Erk
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-09-12
Filing date: 2006-09-05
Publication date: 2008-06-04
Also published as: CN101263608A; WO2007031446A3; US20120138125A1; JP2009512122A; WO2007031446A2; CN101263608B; US20080245411A1; AU2006290820A1; DE102005043572A1

Abstract

The invention relates to fluorescent solar conversion cells based on one or more panels consisting of a polymer that is doped with a fluorescent dye and/or glass panels that are coated with a doped polymer and photovoltaic cells that are mounted on the edges of the panels. Said photovoltaic cells, contain one or more fluorescent dyes based on terylene carboxylic acid derivatives or a combination of said fluorescent dyes and additional fluorescent dyes.

Description

Fluorescence conversion solar cells based on terrylene fluorescent dyes

description

The present invention relates to fluorescence conversion solar cells based on one or more plates of polymer doped with at least one fluorescent dye and / or glass plates coated with the doped polymer and photovoltaic cells attached to the edges of the plates containing one or more fluorescent dyes based on terrylenecarboxylic acid derivatives or a combination thereof - Contain fluorescent dyes with other fluorescent dyes.

In principle, photovoltaic cells can only partially convert radiated sunlight into electrical energy; a large part of the energy is lost in the form of heat. Thus, e.g. Silicon solar cell absorbs all photons that have an energy above the band edge of 1.1 eV of crystalline silicon, i. a wavelength of <1300 nm. The excess energy of the absorbed photons is converted into heat and leads to a heating of the photovoltaic cell. As a result, their efficiency is lowered.

For this reason, fluorescence conversion cells were already described in the 1970s, which represent a combination of photovoltaic cells with fluorescent light collection systems (solar collectors) and enable better use of the energy of sunlight. The solar collectors convert the absorbed sunlight into longer-wave, but still energetically above the silicon band edge lying light and thus reduce the heating of the photovoltaic cell. By using a plurality of fluorescent substances which absorb or emit at different wavelengths (so-called cascades), the irradiated sunlight can be converted particularly effectively into light for the photovoltaic cell of suitable energy.

In addition, the area to be occupied by photovoltaic cells is reduced by the use of fluorescent solar collectors. Thus, the light in the fluorescence-containing or coated with this plate is passed by total reflection to the non-mirrored edge and concentrated there, and only this edge must be covered with photovoltaic cells. As a result, the costs of the overall structure can be significantly reduced.

The structure and mode of action of these fluorescence conversion solar cells is from Appl. Phys. 14, 123-139 (1977) and US-A-4 1 10 123, respectively.

In Nature 274, 144-145 (1978) and US-A-4,367,367, fluorescence conversion solar cells based on several doped with fluorescent metal ions such as Uθ2 ²⁺ , Eu ³⁺ , Cr ³⁺ , Yb ³⁺ and Nd ³⁺ and with Fluorescent dyes (Violanthrone, Rhodamine 6G) described in PMMA matrix coated glass plates. The use of alkoxylated violanthrones and isoviolanthrones as fluorescent dyes for solar collectors is also known from EP-A-073 007.

EP-A-041 274 describes the use of vat dyes, i.a. also of perylene tetracarboxylic diimides, in fluorescence conversion solar cells.

Due to their photostability, perylene-based fluorescent dyes are of particular interest for use in fluorescence conversion solar cells.

In Ed. Chem. Tech. Lab. 28, 716-718 (1980), N, N'-bis (2,5-di-tert-butylphenyl) perylenetetracarboxylic acid diimide is used for this purpose. From DE-A-32 35 526 and 35 45 004 the use of substituted in Perylengerüst, u.a. Tetraphenoxy-substituted and tetrahalogenated, Perylentetracarbonsäurediimiden known for the areal concentration of light. WO-A-97/08756 describes solar collectors based on polycarbonate plates which contain perylene-based fluorescent dyes (N, N'-bis (2,6-diisopropylphenyl) perylenetetracarboxylic diimide and perylene-3,9- or 3,10-dicarboxylic acid diisobutyl ester) in combination with sterically hindered amines as stabilizers. Finally, in ECN report ECN-RX-05-009: 20th European Photovoltaic Solar Energy Conference and Exhibition (Barcelona, Spain, 6-10 June 2005), a fluorescence conversion solar cell with N, N'-bis (7-tridecyl) perylenetetracarboxylic diimide is obtained and a red coumarin dye.

The systems described so far have not yet been used commercially. One reason is that the proposed fluorescent dyes do not have sufficient light stability and / or make only too narrow a wavelength range of the sunlight accessible by fluorescence conversion for the photovoltaic cell.

The object of the invention was therefore to remedy these deficiencies and to provide fluorescence conversion solar cells which can be advantageously used to convert sunlight into electrical energy.

Accordingly, fluorescence conversion solar cells were found based on one or more plates of at least one fluorescent dye-doped polymer and / or with the doped polymer coated glass plates and attached to the edges of the plates photovoltaic cells containing one or more fluorescent dyes based on Terrylencarbonsäurederivaten or a combination of these fluorescent dyes contain further fluorescent dyes.

The fluorescence conversion solar cells according to the invention preferably contain at least one NIR-emitting fluorescent dye based on terrylenecarboxylic acid derivatives in combination with at least one at a shorter wavelength absorbing and emitting fluorescent dye. Particularly preferably, the emission maximum of the shorter-wavelength absorbing dye and the absorption maximum of the next-following dye are largely the same (dye cascade).

If the fluorescent dye based on terrylene is a multiple chromophore, ie a dye which combines the building blocks of different chromophores in one molecule, the bathochromic shift of the emitted light in the dye molecule takes place, a physical mixture of different dyes can be at least partially omitted.

The fluorescence conversion solar cell according to the invention can be constructed from a polymer plate doped with the fluorescent dye (s) or a glass plate coated with the doped polymer or from a plurality of such plates or combinations of the polymer and glass plates.

If a combination of different fluorescent dyes is used, then the terrylene-based fluorescent dye is preferably used in a separative polymer plate or polymer coating.

In Fig. 1, the schematic structure of a plate-stack type fluorescence conversion solar cell is shown.

Fig. 2 shows a polymer plate based fluorescence conversion solar cell.

The fluorescence conversion solar cell exemplified in FIG. 1 is composed of three polymer plates (F1 to F3) doped with different fluorescent dyes. The uppermost plate (F1) is preferably doped with the shortest wavelength absorbing fluorescent dye at a high concentration, the middle plate (F2) contains a medium wavelength absorbing fluorescent dye, and the lowermost plate (F3) is finally with the NIR emitting fluorescent dye doped.

One or more edges of the polymer plate stack are each covered with one or more photovoltaic cells (PVZ), the uncovered edges are mirrored (S).

The photovoltaic cell PVZ can be constructed from conventional materials, for example crystalline, polycrystalline, amorphous or thin film SiIi cium, CIS (CuInSe ₂ ), CdTe, GaAs, InP or GaInAsP.

The polymer plates may be optically coupled or interconnected via gas-filled (eg, air-filled) spaces. In order to guide the light emitted outside the total reflection angle (about 20%) into the plate, optionally a selectively reflecting bandpass filter layer (BPF) may be applied to the illumination side (L).

If desired, a UV-absorbing layer and / or a scratch-resistant coating can be applied to the upper side of the uppermost polymer plate (F1) for protection.

The transmitted light is scattered back into the fluorescence conversion solar cell via a diffuse (white) reflector (Diff) or a mirror.

The fluorescence conversion solar cell shown in Fig. 2 is based on a polymer plate doped with a mixture of fluorescent dyes (FM).

The cell shown by way of example has a photovoltaic cell (PVZ) on both edges.

The other structure is the same as the disk stack type fluorescence conversion solar cell.

The fluorescence conversion solar cells according to the invention preferably contain at least one fluorescent dye from the group of terrylenetetracarboxylic diimides, terrylenetetracarboxylic monoanhydride monoimides, terrylenetetracarboxylic dianhydrides, terrylenedicarboximides, terrylenedicarboxylic anhydrides, condensation products of terrylene tetra- and dicarboxylic acid anhydrides with aromatic diamines and multiple chromophore having terrylene units.

The term "carboxylic acid anhydride" is intended to include in each case also the acid present in free form or as a salt.

The fluorescent dyes based on a terrylene building block as the sole chromophore (referred to below briefly as "terrylene dyes Ia") preferably have the general formula Ia

in which the variables have the following meaning:

_B a1 with each other to form a six-membered ring connected to a radical of formula (a), (b) or (c)

(a) (b) (C)

both hydrogen or a radical -COOM or one of the two radicals is a radical R or bromine and the other radical is hydrogen;

_B a2 independently of B ^a1 with each other to form a six-membered ring connected to a radical of formula (a), (b) or (c) or both a radical -COOM;

R aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is represented by one or more groupings -O-, -S-, -NR ¹ -, -N = CR ¹ - , -CO-, -SO- and / or -SO2- can be fused, wherein the entire ring system is mono- or polysubstituted by the radicals (i), (ii), (iii), (iv) and / or (v) may be substituted:

(i) C 1 -C 30 -alkyl whose carbon chain is substituted by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ - , -CO-, -SO- and / or -SO ₂ - may be interrupted and may be mono- or polysubstituted by: C ₁ -C ₂ -alkoxy, C ₁ -C ₆ -alkylthio, -C≡CR ¹ , - CR ¹ = CR ¹ ₂ , hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ³ R ² , Aryl and / or saturated or unsaturated C ₄ -C 6 -cycloalkyl, whose carbon skeleton is represented by one or more groupings -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ - , -CO-, -SO- and / or -SO ₂ - may be interrupted, wherein the aryl and cycloalkyl radicals in each case be mono- or polysubstituted by Ci-Cis-alkyl and / or the above, as substituents for alkyl radicals can; (ii) Ca-Cs-cycloalkyl, whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO - and / or -SO ₂ - may be interrupted and to the further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, the entire ring system may be monosubstituted or polysubstituted by: Cis-alkyl, Ci-Ci ₂ -alkoxy, Ci-Cβ-alkylthio, -C≡CR ¹ , -CR ¹ = CR ¹ ₂ , hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² and / or -SO ₃ R ² ; (iii) aryl or hetaryl, to which in each case further saturated or unsaturated 5- to

7-membered rings whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, be anneliert, wherein the entire ring system may be mono- or polysubstituted by: Ci-Cis-alkyl, Ci-Ci ₂ -alkoxy, Ci-Cβ-alkylthio, -C≡CR ¹ , -CR ¹ = CR ¹ ₂ , hydroxy, mercapto, halogen, cyano, nitro,

-NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , aryl and / or hetaryl, each one or more times by Ci -Cis-alkyl, Ci-Ci ₂ -alkoxy, hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² and / or -SO ₃ R ² may be substituted; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ¹ -, -CO-, -SO- or -SO ₂ - means; (v) Ci-C ₂ alkoxy, C -C alkylthio -Al _6, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² or -SO ₃ R ² , wherein the radicals R may be the same or different for n>1; R ^{1 is} hydrogen or C ¹ -C 6 -alkyl, where R ^{1 may be the} same or different if they occur more than once; R ² , R ^{3 are} independently hydrogen; Ci-Cis-alkyl, whose carbon chain by one or more groups

-O-, -S-, -CO-, -SO- and / or -SO ₂ - may be interrupted and the one or more times by Ci-Ci ₂ -alkoxy, Ci-Cβ-alkylthio, hydroxy, mercapto, halogen , Cyano, nitro and / or -COOR ¹ may be substituted; Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -CO- and / or -SO ₂ - be annelated can, wherein the entire ring system may be mono- or polysubstituted by Ci-Ci ₂ alkyl and / or the above, as substituents for alkyl radicals may be substituted; Hal bromine or cyano;

R 'C ₄ -C ₃ O-AlkVl, whose carbon chain through one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - be interrupted and which may be mono- or polysubstituted by the radicals (ii), (iii), (iv) and / or (v) mentioned as substituents for the radicals R; Ca-Cs-cycloalkyl to which further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is replaced by one or more -O-,

-S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, wherein the entire ring system mono- or polysubstituted by the radicals (i), (ii), (iii), (iv) and / or (v) mentioned as substituents for the radicals R; Aryl or hetaryl, to which in each case further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, wherein the entire ring system may be mono- or polysubstituted by the radicals mentioned as substituents for the radicals R (i) , (ii), (iii), (iv), (v) and / or aryl and / or hetarylazo, which are each mono- or polysubstituted by C 1 -C 10 -alkyl, C 1 -C 6 -alkoxy and / or cyano can;

E 1, 2-phenylene, 1, 8 or 2,3-naphthylene or 2,3- or 3,4-pyridylene, each represented by Ci-Ci ₂ alkyl, Ci-Cδ-alkoxy, hydroxy, nitro and / or halogen may be substituted;

M is hydrogen, alkali metal cation, [NH ₄ J ⁺ or [NR ² ₄ ] ⁺ ; n is 2 to 6 or also 0, if (1) the radicals B ^a1 and B ^{a2 are} each a radical of the formula (a) or (2) the radicals B ^{a1 are} a radical of the formula (a) and the radicals B ^{a2 are} both Is hydrogen or one of the two radicals B ^{a2 is} bromine and the other radical B ^{a2 is} hydrogen; z is 0 to 6, where n + z <6 and z can only be different from 0 if the radicals B ^a1 and B ^a2 each represent a radical of the formula (a).

The terrylene dyes Ia and their preparation are described in WO-A-03/104 232 and 02/66438, the unpublished WO-A-2006/058674 and the older German patent applications 10 2005 021 362.6, 10 2005 032 583.1 and 10 2005 037 1 15.9 described.

The terrylene dyes Ia can be unsubstituted in the case of Terrylentetracarbonsäurediimide and Terrylendicarbonsäureimide in Terrylengerüst (bay positions). Otherwise, they are substituted by 1 to 6 substituents, preferably in 1, 6,9,14-position by 4 substituents R or in the case of Terrylentetracarbonsäurediimide also by HaI.

The brominated terrylene dyes Ia also serve as starting material for the terrylene dyes Ia substituted by the radicals R. Bromsoms can therefore also be due to incomplete replacement in the terrylene dyes Ia.

Particularly preferred terrylene dyes Ia are substituted in the terrylene skeleton by the aryloxy, arylthio, hetaryloxy or hetarylthio radicals R, in particular phenoxy, thiophenoxy, pyridyloxy, pyrimidyloxy, pyridylthio or pyrimidylthio radicals R 1.

Very particular preference is given to terrylene dyes Ia which are substituted by 4 radicals R.

Preferred radicals R are phenoxy and thiophenoxy radicals, which may each be monosubstituted or polysubstituted by identical or different radicals (i), (ii), (iii), (iv) and / or (v):

(i) C 1 -C 30 -alkyl whose carbon chain is interrupted by one or more -O-, -S-, -NR ¹ -, -C≡C-, -CR ¹ = CR ¹ - and / or -CO- groups may be mono- or polysubstituted by: Ci-Ci2-alkoxy, hydroxy, halogen, cyano and / or aryl, which may be mono- or polysubstituted by Ci-Cis-alkyl and / or Ci-Cδ-alkoxy can; (Ii) Ca-Cs-cycloalkyl whose carbon skeleton may be interrupted by one or more moieties -O-, -S-, -NR ¹ -, -CR ¹ = CR ¹ - and / or -CO- and the one or can be substituted several times by Ci-Cis-Alkyl, Ci-Ci2-Alkoxy and / or Ci-Cβ-Alkylthio; (iii) Aryl or hetaryl, to which in each case further 5- to 7-membered saturated or unsaturated rings whose carbon skeleton is replaced by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ - , -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, the entire ring system may be monosubstituted or polysubstituted by: alkyl, Ci-C ₂ alkoxy, -C = CR ¹ -, -CR ¹ = CR ¹ -, hydroxy, halogen, cyano, -NR ² R ^3, -NR ² COR ^3, -CONR ² R ^3, -SO ₂ NR ² R ³ , -COOR ² and / or -SO ₃ R ² ; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals which are mentioned as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ¹ -, -CO-, -SO- or -SO ₂ -;

(v) Ci-C ₂ alkoxy, C -C alkylthio -Al _6, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² or -SO ₃ R ² .

The (thio) phenoxy radicals R can be unsubstituted or simply substituted in ortho, meta or preferably para position. They can also be substituted two-, three-, four- or five-fold, whereby all conceivable substitution patterns are possible.

Particularly preferred radicals R are ortho, ortho'-disubstituted (thio) phenoxy radicals of the formula

The radicals R "in the two ortho positions may be the same or different, but they are preferably the same.

The (thio) phenoxy radicals R can also be substituted in one, two or all three other ring positions by identical or different radicals R '"which are different from hydrogen.

Preferably, the (thio) phenoxy radicals R are substituted only in the ortho and ortho position or additionally in the para position.

In particular, the variables in the above formula have the following meaning:

Y is -O- or -S-, preferably -O-; R "same or different radicals:

(i) C 1 -C 18 -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -NR ¹ - and / or -CO- and which is mono- or polysubstituted by C ¹ -C 12 -alkoxy , Hydroxy and / or halogen may be substituted, wherein at most one of the alkyl radicals R "in 1-position may have a tertiary carbon atom;

(ii) C 1 -C 8 -cycloalkyl which may be mono- or polysubstituted by C 1 -C 6 -alkyl and / or C 1 -C 12 -alkoxy, where at most one of the radicals R "in the 1-position may have a tertiary carbon atom; iii) aryl or hetaryl which is in each case mono- or polysubstituted by C 1 -C 6 -alkyl,

Ci-Ci2-alkoxy, hydroxy and / or halogen can be substituted; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals as substituents for the aryl radicals (iii), where U is a grouping -O-, -S- or -NR ¹ - means; (v) Ci-Ci2-alkoxy, hydroxy, halogen or cyano;

R '"are identical or different radicals: hydrogen, one of the radicals (i), (ii), (iii), (iv) and (v) mentioned for R", where the alkyl radicals (i) and the cycloalkyl radicals (ii) are present in the 1-position can have a tertiary carbon atom;

R ^{1 is} hydrogen or C ¹ -C ₆ -alkyl. Preferred radicals R "are alkyl, cycloalkyl and phenyl radicals, especially alkyl radicals having a secondary or primary carbon atom in the 1-position, and methyl and cycloalkyl radicals having a secondary carbon atom in the 1-position, the alkyl and cycloalkyl radicals having a secondary carbon atom in 1-position are particularly noteworthy.

Specific examples of particularly preferred (thio) phenoxy radicals are:

2,6-dimethylphenoxy, 2,6-diethylphenoxy, 2,6-diisopropylphenoxy, 2,6-di (2-butyl) phenoxy, 2,6-di (n-butyl) phenoxy, 2,6-di (2 -hexyl) phenoxy, 2,6-di (n-hexyl) phenoxy, 2,6-di (2-dodecyl) phenoxy, 2,6-di (n-dodecyl) phenoxy, 2,6-dicyclohexylphenoxy, 2,6 Diphenylphenoxy, 2,6-di-methyl-4- (n-butyl) phenoxy, 2,6-diethyl-4- (n-butyl) phenoxy, 2,6-diisopropyl-4- (n-butyl) phenoxy, 2,6-di (2-butyl) -4- (n -butyl) phenoxy, 2,4,6-tri (n-butyl) phenoxy, 2,6-di (2-hexyl) -4- (n-) butyl) phenoxy, 2,6-di (n-hexyl) -4- (n -butyl) phenoxy, 2,6-di (2-dodecyl) -4- (n -butyl) phenoxy, 2,6-di ( n-dodecyl) -4- (n -butyl) phenoxy, 2,6-dicyclohexyl-4- (n -butyl) phenoxy, 2,6-diphenyl-4- (n -butyl) phenoxy, 2,6-dimethyl 4- (n-nonyl) phenoxy, 2,6-diethyl-4- (n-nonyl) phenoxy, 2,6-diisopropyl-4- (n-nonyl) phenoxy, 2,6-di (2-butyl) - 4- (n-nonyl) phenoxy, 2,6-di (2-butyl) -4- (n-nonyl) phenoxy, 2,6-di (2-hexyl) -4- (n-nonyl) phenoxy, 2 , 6-di (n-hexyl) -4- (n-nonyl) phenoxy, 2,6-di (2-dodecyl) -4- (n-nonyl) phenoxy, 2,6-di (n-dodecyl) -4- (n-nonyl) phenoxy, 2,6-dicyclohexyl-4- (n-nonyl ) phenoxy, 2,6-diphenyl-4- (n-nonyl) phenoxy, 2,6-dimethyl-4- (n-octadecyl) phenoxy, 2,6-diethyl-4- (n-octadecyl) phenoxy, 2, 6-Diisopropyl-4- (n-octadecyl) phenoxy, 2,6-di (2-butyl) -4- (n-octadecyl) phenoxy, 2,6-di (2-butyl) -4- (n-octadecyl ) phenoxy, 2,6-di (2-hexyl) -4- (n-octadecyl) phenoxy, 2,6-di (n-hexyl) -4- (n-octadecyl) phenoxy, 2,6-di (2-dodecyl) -4- (n-octadecyl) phenoxy, 2,6-di (n-dodecyl) -4- (n-octadecyl) phenoxy, 2,6-dicyclohexyl-4- (n-octa) decyl) phenoxy, 2,6-dimethyl-4- (tert -butyl) phenoxy, 2,6-diethyl-4- (tert -butyl) phenoxy, 2,6-diisopropyl-4- (tert -butyl) phenoxy, 2,6-di (2-butyl) -4- (tert -butyl) phenoxy, 2,6-di (n-butyl) -4- (tert -butyl) phenoxy, 2,6-di (2-hexyl) -4- (tert -butyl) phenoxy, 2,6-di (n-hexyl) -4- (tert -butyl) phenoxy, 2,6-di (2-dodecyl) -4- (tert-butyl) phenoxy, 2,6-di (n-dodecyl) -4- (tert-butyl) phenoxy, 2,6-dicyclohexyl-4- (tert-butyl) phenoxy, 2,6-diphenyl 4- (tert-butyl) phenoxy, 2,6-dimethyl-4- (tert-octyl) phenoxy, 2,6-diethyl-4- (tert-octyl) phenoxy, 2,6-diisopropyl-4 - (tert-octyl) phenoxy , 2,6-di (2-butyl) -4- (tert-octyl) phenoxy, 2,6-di (n-butyl) -4- (tert-octyl) phenoxy, 2,6-di ( 2-hexyl) -4- (t-octyl) phenoxy, 2,6-di (n-hexyl) -4- (t-octyl) phenoxy, 2,6-di (2-dodecyl) -4- ( tert.-octyl) phenoxy, 2,6-di (n-dodecyl) -4- (tert.octyl) phenoxy, 2,6-dicyclohexyl-4- (tert.octyl) phenoxy and 2,6-diphenyl- 4- (tert -octyl) phenoxy;

2,6-dimethylthiophenoxy, 2,6-diethylthiophenoxy, 2,6-diisopropylthiophenoxy, 2,6-di (2-butyl) thiophenoxy, 2,6-di (n-butyl) thiophenoxy, 2,6-di (2-) hexyl) thiophenoxy, 2,6-di (n-hexyl) thiophenoxy, 2,6-di (2-dodecyl) thiophenoxy, 2,6-di (n-dodecyl) thiophenoxy, 2,6-dicyclohexylthiophenoxy, 2,6- Diphenylthiophenoxy, 2,6-dimethyl-4- (n-butyl) thio phenoxy, 2,6-diethyl-4- (n-butyl) thiophenoxy, 2,6-diisopropyl-4- (n-butyl) thiophenoxy, 2,6-di (2-butyl) -4- (n -butyl) thiophenoxy, 2,4,6-tri (n-butyl) thiophenoxy, 2,6-di (2-hexyl) -4- (n-butyl) thiophenoxy, 2,6-di (n-hexyl) -4- (n-butyl) thiophenoxy, 2,6-di (2-dodecyl) -4- (n-butyl) thiophenoxy, 2,6-di (n-dodecyl) -4- (n-butyl) thiophenoxy, 2.6 Dicyclohexyl-4- (n-butyl) thiophenoxy, 2,6-diphenyl-4- (n-butyl) thiophenoxy, 2,6-di-methyl-4- (n-nonyl) thiophenoxy, 2,6- Diethyl 4- (n-nonyl) thiophenoxy, 2,6-diisopropyl-4- (n-nonyl) thiophenoxy, 2,6-di (2-butyl) -4- (n-nonyl) thiophenoxy, 2,6- Di (2-butyl) -4- (n-nonyl) thiophenoxy, 2,6-di (2-hexyl) -4- (n-nonyl) thiophenoxy, 2,6-di (n-hexyl) -4- ( n-nonyl) thiophenoxy, 2,6-di (2-dodecyl) -4- (n-nonyl) thiophenoxy, 2,6-di (n-dodecyl) -4- (n-nonyl) thiophenoxy, 2,6- Di-cyclohexyl-4- (n-nonyl) thiophenoxy, 2,6-diphenyl-4- (n-nonyl) thiophenoxy, 2,6-dimethyl-4- (n-octadecyl) thiophenoxy, 2,6-diethyl-4 - (n-octadecyl) thiophenoxy, 2,6-diisopropyl-4- (n-octadecyl) thiophenoxy, 2,6-di (2-butyl) -4- (n-octadec l) thiophenoxy, 2,6-di (2-butyl) -4- (n-octadecyl) thiophenoxy, 2,6-di (2-hexyl) -4- (n-octadecyl) thiophenoxy, 2,6-di ( n-hexyl) - 4- (n-octadecyl) thiophenoxy, 2,6-di (2-dodecyl) -4- (n-octadecyl) thiophenoxy, 2,6-di (n-dodecyl) -4- (n-) octadecyl) thiophenoxy, 2,6-dicyclohexyl-4- (n-octadecyl) thiophenoxy, 2,6-dimethyl-4- (tert-butyl) thiophenoxy, 2,6-diethyl-4- (tert-butyl ) thiophenoxy, 2,6-diisopropyl-4- (tert -butyl) thiophenoxy, 2,6-di (2-butyl) -4- (tert -butyl) thiophenoxy, 2,6-di- (n -butyl ) -4- (tert -butyl) thiophenoxy, 2,6-di (2-hexyl) -4- (tert -butyl) thiophenoxy, 2,6-di (n-hexyl) -4- (tert. butyl) thiophenoxy, 2,6-di (2-dodecyl) -4- (tert -butyl) thiophenoxy, 2,6-di (n-dodecyl) -4- (tert -butyl) thiophenoxy, 2,6- Dicyclohexyl-4- (tert-butyl) thiophenoxy, 2,6-

Diphenyl 4- (tert -butyl) thiophenoxy, 2,6-dimethyl-4- (tert -octyl) thiophenoxy, 2,6-diethyl-4- (tert-octyl) thiophenoxy, 2,6-diisopropyl 4- (tert -octyl) thiophenoxy, 2,6-di (2-butyl) -4- (tert -octyl) thiophenoxy, 2,6-di- (n-butyl) -4- (tert -octyl ) thiophenoxy, 2,6-di (2-hexyl) -4- (t-octyl) thiophenoxy, 2,6-di (n-hexyl) -4- (t-octyl) thiophenoxy, 2,6-di (2-dodecyl) -4- (t-octyl) thiophenoxy, 2,6-di (n-dodecyl) -4- (t-octyl) thiophenoxy, 2,6-dicyclohexyl-4- (tert-octyl ) thiophenoxy and 2,6-diphenyl-4- (t-octyl) thiophenoxy.

The terrylene dyes Ia preferably contain at least one imide function, i.e., the terrylenetetracarboxylic diimides, terrylenetetracarboxylic monoanhydride monoimides, terrylenedicarboximides, and the simple imidate condensation products of terrylenetetracarboxylic dianhydrides with aromatic diamines are preferred.

Particularly preferably, the terrylene dyes Ia contain exclusively imide functions. Thus, the terrylenetetracarboxylic diimides and terrylenedicarboximides are particularly preferred, with the terrylenetetracarboximides being most preferred.

The substituent R 'on the imide nitrogen atom has the following meaning in particular:

C 4 -C 30 -alkyl whose carbon chain may be interrupted by one or more groups -O- and / or -CO- and which may be monosubstituted or polysubstituted may be substituted by: C 1 -C 6 -alkoxy, cyano and / or aryl which may be mono- or polysubstituted by C 1 -C 18 -alkyl and / or C 1 -C 6 -alkoxy;

Cs-Cs-cycloalkyl which may be mono- or polysubstituted by C 1 -C 12 -alkyl; Phenyl, naphthyl, pyridyl or pyrimidyl which may each be monosubstituted or polysubstituted by: C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, halogen, cyano, nitro, -CONR ² R ³ ,

-SOaNR ² R ³ and / or phenyl and / or Naphthylazo, which may each be mono- or polysubstituted by Ci-Cio-alkyl, Ci-Cδ-alkoxy and / or cyano may be substituted.

Particularly preferably, R 'has the following meaning:

C 4 -C 30 -alkyl whose carbon chain may be interrupted by one or more groups -O- and / or -CO- and which may be monosubstituted or polysubstituted by: C 1 -C 6 -alkoxy, cyano and / or aryl, which is a - or may be substituted several times by C 1 -C 18 -alkyl and / or C 1 -C 6 -alkoxy; Cs-Cs-cycloalkyl which may be mono- or polysubstituted by C 1 -C 6 -alkyl; Phenyl, naphthyl, pyridyl or pyrimidyl, which is mono- or each may be substituted several times by: Ci-Cis-alkyl, Ci-C ₆ alkoxy, halogen, cyano, nitro, -CONR ² R ^3, -Sθ2NR ² R ³ and or phenyl and / or naphthylazo, which may each be mono- or polysubstituted by Ci-Cio-alkyl, Ci-Cδ-alkoxy and / or cyano.

R ² and R ^{3 are} independently of one another:

Hydrogen;

C 1 -C 6 -alkyl which may be mono- or polysubstituted by C 1 -C 6 -alkoxy, hydroxyl, halogen and / or cyano;

Aryl or hetaryl, which may each be mono- or polysubstituted by Ci-Cβ-alkyl and / or the above, as substituents for alkyl radicals may be substituted.

The radicals R 'preferably have 4 to 24 C atoms in order to ensure sufficient solubility and fluorescence.

Very particularly preferred radicals R 'are ortho.ortho'-dialkyl-substituted aryl radicals, especially those which are also part of the radical R, and linear alkyl chains which are bonded to the imide nitrogen atom via a middle carbon atom. Selected examples of these radicals R 'are 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-diisopropyl-4-butylphenyl, 5-undecyl, 7-tridecyl and 9-pentadecyl.

As examples of preferred terrylene dyes Ia may be mentioned:

N, N'-bis (2,6-diisopropylphenyl) terrylene-3,4: 1 1, 12-tetracarboxylic diimide, N, N'-bis (tridecyl) -trylene-3,4: 1 1, 12-tetracarboxylic diimide, N, N'-bis (2,6-diisopropylphenyl) -1,6,9,14-tetra (4-tert-octylphenoxy) -trylene-3,4: 1,1-12-tetracarboxylic diimide, N ₁ N ' Bis (2,6-diisopropylphenyl) -1,6,9,14-tetra (2,6-diisopropylphenoxy) terrylene-3,4: 1 1, 12-tetracarboxylic diimide, N- (2,6-diisopropylphenyl) terrylene-3 , 4-dicarboxylic acid imide, N- (7-tridecyl) -trylene-3,4-dicarboxylic acid imide, N- (2,6-diisopropylphenyl) -1, 6,9,14-tetra (4-tert-octylphenoxy) -trylene-3 , 4-dicarboxylic acid imide and N- (2,6-diisopropylphenyl) -1,6,9,14-tetra (2,6-diisopropylphenoxy) -trylene-3,4-dicarboxylic acid imide.

The fluorescence conversion solar cells according to the invention can also contain multiple chromophores with terrylene building blocks as the fluorescent dye.

The terrestrial chromophore preferably forms the central building block to which the further chromophores, preferably perylene and / or naphthalene chromophores, are bound. However, the chromophores can also be arranged in reverse order.

The type of linkage determines the shape of the multiple chromophore molecule. Thus, e.g. in the linking of a central N, N'-bis (2,6-diisopropylphenoxy) terrylenetetracarboxylic acid diimide molecule with 4 or 8 N- (2,6-diisopropylphenyl) perylenedicarboximide units or with 4 N- (2,6-diisopropylphenyl) perylenedicarboximide units and 8 N- (2,6-diisopropylphenyl) naphthalenedicarboxylic imide units over (pentaphenyl) phenyl units are dendritic polychromophores (Angew. Chem. 1 14, 1980-1984 (2002)).

According to the invention, however, preference is given to multiple chromophores of the general formula Ib (referred to below as "terrylene dyes Ib")

in which the variables have the following meaning:

B ^b1 together with formation of a six-membered ring to form a radical of the formula (a) or (d)

or a radical hydrogen and the other radical is a radical X;

B ^b2 connected together to form a six-membered ring to form a radical of the formula (a), when the radicals B ^b1 together form a radical of the formula (a); with each other to form a six-membered ring connected to a radical of the formula (a), when a radical B ^{b1 is} hydrogen and the other radical is a radical X, where x = 0 and n ≠ 0; with one another to form a six-membered ring to form a radical of the formula (d) if the radicals B ^b1 together are a radical of the formula (a) or (d) or one radical B ^{b1 is} hydrogen and the other radical is an X or R radical, where: x = 0 and n ≠ 0;

R aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is represented by one or more groupings -O-, -S-, -NR ¹ -, -N = CR ¹ - , -CO-, -SO- and / or

Wherein the entire ring system may be monosubstituted or polysubstituted by the radicals (i), (ii), (iii), (iv) and / or (v): (i) C 1 -C 30 -alkyl whose carbon chain is substituted by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted and may be mono- or polysubstituted by: Ci-Ci2-alkoxy, Ci -C ₆ -alkylthio, -C≡CR ¹ , -CR ¹ = CR ¹ ₂ , hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ³ R ² , Aryl and / or saturated or unsaturated C ₄ -C 6 -cycloalkyl, the carbon skeleton of which is represented by one or more groups -O-, -S-, -NR ¹ -,

-N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, wherein the aryl and cycloalkyl radicals each one or more times by Ci-Cis-alkyl and / or the abovementioned radicals which are mentioned as substituents for alkyl may be substituted; (ii) C ³ -C 8 -cycloalkyl whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO - and / or -SO ₂ - may be interrupted and to the further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted surfaces, which may be fused, where the entire ring system may be mono- or polysubstituted by: C ¹ -C 18 -alkyl, C ¹ -C 12 -alkoxy, C ¹ -C 6 -alkylthio, -C≡CR ¹ , -CR ¹ CRCR ¹ ₂ , hydroxyl, mercapto, halogen, cyano, nitro, NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² and / or -SO ₃ R ² ; (iii) aryl or hetaryl, to which further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is replaced by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, where the entire ring system may be mono- or polysubstituted by: Ci-Cis-alkyl, Ci-Ci ₂ -alkoxy, C ¹ -C 6 -alkylthio, -C≡CR ¹ , -CR ¹ = CR ¹ ₂ , hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , aryl and / or hetaryl which are in each case mono- or polysubstituted by C ₁ -C 6 -alkyl, C ₁ -C ₂ -alkoxy, hydroxyl, mercapto, Halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² and / or -SO ₃ R ² may be substituted; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ¹ -, -CO-, -SO- or -SO ₂ - means; (v) Ci-C ₂ alkoxy, C -C alkylthio -Al _6, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² or -SO ₃ R ² , wherein the radicals R may be the same or different for n>1;

R ^{1 is} hydrogen or C ¹ -C 6 -alkyl, where R ^{1 may be the} same or different if they occur more than once;

R ² , R ^{3 are} independently hydrogen;

C 1 -C 6 -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -CO-, -SO- and / or -SO ₂ - and which is mono- or polysubstituted by Ci-Ci ₂ - Alkoxy, C 1 -C 6 -alkylthio, hydroxy, mercapto, halogen, cyano, nitro and / or -COOR ¹ may be substituted; Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -CO- and / or -SO ₂ - be annelated can, wherein the entire ring system may be mono- or polysubstituted by Ci-Ci ₂ alkyl and / or the above, as substituents for alkyl radicals may be substituted;

X is a perylenedicarboximide radical of the formula

R 'C4-C3o-Alkyl, whose carbon chain is represented by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ -, - CO-, -SO- and / or -SO ₂ - may be interrupted and substituted one or more times by the substituents mentioned for the radicals R radicals (ii), (iii), (iv) and / or (v) can be;

Ca-Cs-cycloalkyl to which further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is replaced by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, the entire ring system being mono- or polysubstituted by the radicals (i) mentioned as substituents for the radicals R , (ii), (iii),

(iv) and / or (v) may be substituted;

Aryl or hetaryl, to which in each case further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, wherein the entire ring system may be mono- or polysubstituted by the radicals mentioned as substituents for the radicals R (US Pat. i), (ii), (iii), (iv), (v) and / or aryl and / or hetarylazo, in each case mono- or polysubstituted by C 1 -C 10 -alkyl, C 1 -C 6 -alkoxy and / or cyano may be substituted; Y is -O- or -S-;

Z is a bridge member having at least one aromatic or heteroaromatic radical, the groups Y being bonded to the aromatic or heteroaromatic radical; x 2 to 6, when the radicals B ^b1 and B ^b2 each represent a radical of the formula (a); 0 for all other meanings of the radicals B ^b1 and B ^b2 ; n 0 to 8, where x + n <8 and n ≠ 0 when x = 0; n1 0 to 2.

The terrylene dyes Ib and their preparation are described in the earlier German patent application 10 2005 037 1 15.9.

In the case of the terrylene dyes Ib, the perylene chromophores are bonded directly to the ring skeleton of the terrylene chromophore via the grouping -Y-Z-Y- and / or via the grouping -Z-Y- to the imide nitrogen atoms of the terrestrial chromophore.

The connecting bridge member Z in this case has at least one aromatic or heteroaromatic radical to which Y or the imide nitrogen atom is bonded.

Preferably Z is an arylene or hetarylene radical of the formulas

in which the rings P may be identical or different, may contain heteroatoms as ring atoms and / or fused 5- to 7-membered rings, the carbon of which is provided by one or more groupings -O-, -S-, -NR ¹ - , -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO 2- may be interrupted, wherein the entire ring system one or more times by the above as substituents for the radicals R mentioned radicals (i), (ii), (iii) and / or (v) may be substituted.

G means:

a chemical bond; a grouping -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ -, -CO-, -SO- or -SO ₂ - or Ci -Ci2-alkylene or C ₄ -Cz-CyClOaI alkylene, the carbon chain may be interrupted in each case one or more times by these groups and each one or more times by the above mentioned as substituents for the radicals R radicals (i), (ii ), (iii) and / or (v) may be substituted;

Arylene or hetarylene, which may also be monosubstituted or polysubstituted by the radicals (i), (ii), (iii) and / or (v), where hydroxy and mercapto are excluded as radicals (v).

Particularly preferred bridge members Z are arylene radicals of the formulas

in which the phenylene or naphthylene rings may be monosubstituted or polysubstituted by C 1 -C 6 -alkyl and G is a chemical bond, methylene or isopropylene.

Examples of particularly preferred bridge members Z are in detail:

1, 4, 1, 3 and 1, 2-phenylene, 1, 4- [2,5-di (tert-butyl)] phenylene, 1, 4- (2,5-dihexyl) phenylene, 1, 4- [2,5-di (tert-octyl)] phenylene, 1,4- (2,5-didodecyl) phenylene, 1,4- [2,5-di (2-dodecyl)] phenylene, 1, 4 and 1, 8-naphthylene, 4,4'-, 3,3'- and 2,2'-biphenylene, 4,4'-di (2,2 ', 6,6'-tetramethyl ) phenylene, 4,4'-di (2,2 ', 6,6'-tetraethyl) phenylene, 4,4'-di (2,2', 6,6'-tetraisopropyl) phenylene, 4,4 'Di (2,2', 6,6'-tetrahexyl) phenylene, 4,4'-di [2,2 ', 6,6'-tetra (2-hexyl)] phenylene 4,4'-di [2,2 ', 6,6'-tetra (tert-octyl)] phenylene, 4,4'-di (2,2', 6,6'-tetradodecyl) phenylene and 4,4'-di [2,2 ', 6,6'-tetra (2-dodecyl)] phenylene and

where R "" is hydrogen, methyl, ethyl or phenyl.

Very particularly preferred bridge members Z are 1, 4-phenylene and 4,4'-di (2,2 ', 6,6'-tetramethyl) phenylene.

The terrylene dyes Ib, like the terrylene dyes Ia, may additionally be substituted by (Het) aryloxy and (Het) arylthio radicals R.

R and the other variables occurring in formula Ib have the same meaning as in formula Ia. The same preferences apply.

The advantage of the fluorescence conversion solar cells containing terrylene-based fluorescent dyes according to the invention lies in the fact that the irradiated sunlight can be converted into long-wave NIR radiation and radiation which is particularly well adapted to silicon photovoltaic cells. For example, the terrylene dyes Ia absorb at about 480 to 770 nm and emit at about 650 to 850 nm. In the case of the terrylene dyes Ib, the absorption range at the short-wave end is extended to about 400 nm and clearly in the range from 400 to 600 nm compared to the terrylene dye - Ia strengthened.

A particularly efficient conversion of sunlight can be achieved when the terrylene dyes are combined in combination with shorter wavelength absorbing and emitting fluorescent dyes, especially in the form of a dye cascade.

Fluorescent dyes from the group of the perylenecarboxylic acid derivatives, naphthalenecarboxylic acid derivatives and (iso) violanthrone derivatives are particularly suitable for these dye combinations, wherein the combination with perylene-based fluorescent dyes is preferred.

Examples of fluorescent dyes based on perylenecarboxylic acid derivatives (referred to hereinafter as "perylene dyes") include perylenetetracarboximides, perylenetetracarboxylic monoanhydride monoimides, perylenetetracarboxylic dianhydrides, perylenedicarboximides, perylene-3,4-dicarboxylic anhydrides, perylenedicarboxylic esters, perylenedicarboxamides and multichromophores having perylene units and containing no terrylene building blocks. suitable, wherein the Perylenedicarboxylic acid esters are preferred, the perylenedicarboximides particularly preferred and the perylenetetracarboximides are very particularly preferred.

The perylenedicarboximides are derived from perylene-3,4-dicarboxylic acid and the perylenedicarboxylic acid esters and amides from the isomeric perylene-3,9- and 3,10-dicarboxylic acids.

In the case of the perylenecarboximides, the radicals R 'are particularly suitable as substituents on the imide nitrogen atom, as in the terrylene dyes. The same preferences apply.

The perylene dyes may be unsubstituted as the terrylene dyes Ia. Preferably, however, they are substituted by 1 to 5 (in the case of perylenetetracarboximides, especially 2 or 4) (Het) aryloxy or (het) arylthio radicals R.

Furthermore, the perylene dyes may also be substituted by cyano groups. This substitution is of particular importance for perylenedicarboximides and perylenedicarboxylic acid esters.

Examples of particularly suitable perylene dyes are:

N, N'-bis (2,6-diisopropylphenyl) perylene-3,4: 9,10-tetracarboxylic acid diimide, N, N'-bis (2,6-dimethylphenyl) perylene-3,4: 9,10-tetracarboxylic acid diimide, N, N'-bis (7-tridecyl) perylene-3,4: 9, 10-tetracarboxylic diimide, N, N'-bis (2,6-diisopropylphenyl) -1, 6,7,12-tetra (4-tert octylphenoxy) perylene-3,4: 9,10-tetracarboxylic diimide, N, N'-bis (2,6-diisopropylphenyl) -1,6,7,12-tetraphenoxyperylene-3,4: 9,10-tetracarboxylic diimide, N, N'-bis (2,6-diisopropylphenyl) -1,6- and -1, 7-bis (4-tert-octylphenoxy) perylene-3,4,9,10-tetracarboxylic diimide, N , N'-bis (2,6-diisopropylphenyl) -1, 6- and -1, 7-bis (2,6-diisopropylphenoxy) perylene-3,4: 9,10-tetracarboxylic diimide, N- (2,6 -Diisopropylphenyl) perylene-3,4-dicarboxylic acid imide, N- (2,6-diisopropylphenyl) -9-phenoxyperylene-3,4-dicarboximide, N- (2,6-diisopropylphenyl) -9- (2,6- diisopropylphenoxy) perylene-3,4-dicarboximide, N- (2,6-diisopropylphenyl) -9-cyano-3,4-dicarboxylic acid imide, N- (7-tridecyl) -9-phenoxy-3,4-dicarboxylic acid imide, perylene-3 Diisobutyl, 9- and 3,10-dicarboxylates, 4,10-dicyano-perylene-3,9- and 4,9-dicyano-perylene-3,10-dicarboxylic acid diisobutyl esters and perylene-3,9- and 3,10- dicarboxylic acid (2,6-diisopropylphenyl) amide.

The perylene-based multiple chromophores are preferably constructed analogously to the multichromophoric terrylene dyes Ib from a central perylene chromophore and naphthalimide chromophores bound thereto. The naphthalene imidchromophores can be attached via the grouping -YZY- directly to the ring skeleton of the phraryl chromophore (2 to 4 naphthalimides) and / or via the grouping -ZY- to the imide nitrogen atoms of a central perylenetetracarboximide, to the amide stick atoms of a central perylenedicarboxamide or to the hydroxyl oxygen atoms of a central perylene-3,9 / 3,10-dicarboxylic acid (esterification).

The perylene chromophore can also be substituted by (Het) aryloxy or (Het) arylthio radicals R. In the case of ester-based multiple chromophores, substitution by halogen or cyano in the 4,10 / 4,9 positions is also possible.

The perylene dyes are generally known or in the older German Patentanimidations 10 2005 032 583.1 (substitution with ortho.ortho'-disubstituted

(Thio) phenoxy radicals R) and 10 2005 037 1 15.9 (multiple chromophores) described.

They usually absorb in the wavelength range from 360 to 630 nm and emit at about 470 to 750 nm. In the multichromophoric perylene dyes, the absorption extends into the range of about 300 nm.

Sunlight in the range of 360 to 770 nm can therefore be absorbed by the combination of terrylene and perylene dyes and converted into NIR radiation.

Not only the perylene dyes themselves are suitable for this combination, but also fluorescent dyes with related structures, in particular those based on violanthrones and isoviolanthrones, as described in EP-A-073 007.

Particularly suitable examples are alkoxylated violanthrones and isoviolanthrones, such as 6,15-didodecyloxyisoviolanthrenone- (9,18) called.

Finally, it is also possible to use fluorescent dyes based on naphthalenecarboxylic acid derivatives in combination with the terrylene dyes and, if desired, perylene dyes and / or (iso) violanthrones.

The naphthalene-based fluorescent dyes absorb in the UV range at wavelengths of about 300 to 420 nm and emit at about 380 to 520 nm. They not only cause the conversion of UV light into longer-wave light, but above all provide effective UV protection for the fluorescence Kon- version solar cells according to the invention.

The imides, ie the naphthalene-1, 8: 4,5-tetracarboxylic diimides and in particular the naphthalene-1, 8-dicarboxylic acid imides (referred to below as "naphthalimides" for short) are also preferred for the naphthalenecarboxylic acid derivatives.

The naphthalimides, in particular the naphthalene-1, 8: 4,5-tetracarboxylic diimides, may also be unsubstituted in the naphthalene skeleton. Preferably wear especially the Naphthalenedicarbonsäureimide but 1 or preferably 2 alkoxy, aryloxy or cyano groups as substituents.

The alkoxy groups have in particular 1 to 24 C atoms. Preferred aryloxy groups are phenoxy radicals which may be unsubstituted or substituted.

Examples of particularly suitable naphthalimides are:

N- (2-ethylhexyl) -4,5-dimethoxynaphthalene-1,8-dicarboximide, N- (2,6-diisopropylphenyl) -4,5-dimethoxynaphthalene-1,8-dicarboximide, N- (7-tridecyl ) -4,5-dimethoxynaphthalene-1,8-dicarboximide, N- (2,6-diisopropylphenyl) -4,5-diphenoxynaphthalene-1, 8-dicarboximide and N, N'-bis (2,6-diisopropylphenyl ) -1, 8: 4,5-naphthalene tetracarboxylic diimide.

The concentration of the fluorescent dyes is preferably adjusted such that the extinction over the layer thickness of the polymer plate doped with the respective fluorescent dye is close to 1 over the widest possible spectral range, and is thus dependent on the dimensions of the polymer plates, which are about 5 to 100 cm, preferably 5 can be up to 30 cm, in length and width and about 1 to 20 mm, preferably 1 to 10 mm in thickness.

Accordingly, the dye concentration in the respective polymer plate is usually 10 to 20,000 ppm, preferably 50 to 1,000 ppm, and more preferably 100 to 500 ppm.

In the case of polymer-coated glass plates, the concentration of the fluorescent dye in the polymer coating is typically about 10,000 ppm, and the thickness of the polymer coating is usually about 100 to 300 μm.

The polymer plates doped with the fluorescent dyes or the polymer coating containing the fluorescent dyes applied to the glass plates preferably consist of colorless transparent thermoplastic polymers.

Examples of preferred thermoplastic polymers are acrylic resins, styrene polymers, polycarbonates, polyamides, polyesters, thermoplastic polyurethanes, Polyethersulfone ne, polysulfones, vinyl polymers or mixtures thereof, wherein the acrylic resins and the polycarbonates are particularly suitable.

Suitable acrylic resins include the polyalkyl and / or aryl esters of (meth) acrylic acid, poly (meth) acrylamides and poly (meth) acrylonitrile. Preferred acrylic resins are polyalkyl methacrylates, such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), also in impact-modified form, with PMMA and impact-modified PMMA (HI (High Impact) PMMA) are particularly preferred. Preferably, the PMMA contains a proportion of usually not more than 20 wt .-% of (meth) acrylate comonomers such as n-butyl (meth) acrylate or methyl acrylate. HI-PMMA is impact-resistant with suitable additives. Suitable impact modifiers are, for example, EPDM rubbers, polybutyl acrylates, polybutadiene, polysiloxanes or methacrylate / butadiene / styrene (MBS) and methacrylate / acrylonitrile / butadiene / styrene copolymers. Suitable impact-modified PMMA are described, for example, by M. Stickler, T.Rhein in Ullmann's encyclopedia of industrial chemistry Vol. A21, pages 473-486, VCH Publishers Weinheim, 1992, and H. Domininghaus, Die Kunststoffe und ihre Eigenschaften, VDI-Verlag Dusseldorf , 1992. Suitable polymethyl those skilled in the rest of known and available, for example under the trademarks Altuglas ^® (Arkema) and Plexiglas ^® (Rohm).

As styrene polymers are all (co) polymers in question, which are composed completely or in part of vinyl aromatic compounds. Suitable vinylaromatic compounds are, for example, styrene and styrene derivatives, such as mono- or polyalkyl- and / or halogen-substituted styrene, and corresponding naphthyl compounds. Preference is given to using styrene copolymers. Examples of these include graft copolymers of acrylonitrile and styrene on butadiene rubbers, also known as ABS-poly merisate known (for example Terluran ^® (BASF)), graft copolymers of styrene and acrylonitrile on polyalkyl, also called ASA polymers known (eg Luran ^® S ( BASF)), or styrene-acrylonitrile copolymers, also called SAN copolymers (eg Luran ^® (BASF)).

Suitable polycarbonates are known per se. Polycarbonates within the meaning of the invention also include copolycarbonates. The (co) polycarbonates preferably have a molecular weight (weight average M _w , determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range from 10,000 to 200,000 g / mol. Preferably M _{w is} in the range of 15,000 to 100,000 g / mol. This corresponds to relative solution viscosities in the range of 1, 1 to 1, 5, preferably from 1 15 to 1, 33, in each case measured in 0.5 wt .-% solution in dichloromethane at 25 ^° C.

Polycarbonates are e.g. according to the process of DE-C-1 300 266 by interfacial polycondensation or according to the process of DE-A-14 95 730 by reaction of diphenyl carbonate with bisphenols obtainable. Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, commonly referred to as bisphenol A.

Instead of bisphenol A, it is also possible to use other aromatic dihydroxy compounds, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4 'Dihydroxydiphenylsulfite, 4,4'-dihydroxydiphenylmethane, 1,1-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkanes, preferably dihydroxydiphenyl cyclohexanes or dihydroxycyclopentanes, in particular 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and also mixtures of the abovementioned dihydroxy compounds.

Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the abovementioned aromatic dihydroxy compounds.

It is also possible to use copolycarbonates according to US Pat. No. 3,737,409. Of particular interest are copolycarbonates based on bisphenol A and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and / or 1, 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexyl, which are characterized by high heat resistance.

Are commercially available, for example, the polycarbonates Makrolon ^® (Bayer) and Lexan ^® (GE Plastics).

Suitable polyamides (PA) may be polycondensation products of diamines and dicarboxylic acids, for example adipic acid and hexamethylenediamine, or of amino acids, for example aminoundecanoic acid, or be prepared by ring-opening polymerization of lactams, for example caprolactam or laurolactam. Examples are Ultramid ^® (BASF), Zytel ^® and Minion ^® (Du Pont), Sniamid ^®, Technyl ^® and Amodel ^® (Nyltech) Durethan ^® (Bayer), Akulon ^® and Stanyl ^® (DSM), Grilon ^®, Grilamid ^® and Grivory ^® (EMS), Orgamid ^® and Rilsan ^® (Atochem) and Nivionplast ^® (Enichem) called.

Polyamides, mixtures of polyamides and polyethylene ionomers such as ethene / methacrylic acid copolymers containing, for example, sodium, zinc and / or lithium counter ions (such as Surlyn ^® (DuPont)) are used.

Suitable polyesters are the higher to high molecular weight esterification products of dibasic acids, in particular terephthalic acid, with dihydric alcohols, especially ethylene glycol. Among the polyalkylene is polyethylene terephthalate (pet; Arnite® ^® (Akzo), Grilpet ^® (EMS-Chemie), Valox ^® (GEP)) is particularly suitable.

Thermoplastic polyurethanes (TPU) are finally the reaction products of diisocyanates and long-chain diols. Compared with those of polyisocyanates (containing at least three isocyanate groups) and polyhydric alcohols (containing at least three hydroxyl groups), in particular polyether and polyester polyols, polyurethane foams thermoplastic polyurethanes have little or no crosslinking and therefore have a linear structure. Thermoplastic polyurethanes are well known to the person skilled in the art and can be found, for example, in the Kunststoff-Handbuch, Volume 7, Polyurethane, ed. G. Oertel, 2nd ed., Carl Hanser Verlag. Munich, 1983, in particular on pages 428-473 described. As a commercially available product is here called eg Elastolan ^® (Elastogran).

The polymer classes of polyethersulfones and polysulfones those skilled likewise known and commercially available under the trade name Ultrason ^® E and Ultrason ^® S (BASF).

Finally, polyvinyl chloride (PVC) may be mentioned as a suitable vinyl polymer, for example.

If desired, the polymer material may additionally contain stabilizing additives.

Particularly suitable additives are light stabilizers (UV-A and / or UV-B absorbers) and antioxidants.

Preferably, these additives are colorless or have only a slight intrinsic color (no or only slight absorption in the visible range). High migration fastness and temperature resistance are further preferred properties of these additives.

Examples of suitable light stabilizers include the known classes of sterically hindered amines, benzophenones and benzotriazoles.

The light stabilizers based on sterically hindered amines (HALS) contain as essential building block a 2,6-dialkyl-substituted, in particular a 2,6-dimethyl-substituted, piperidine which is linked in the 4-position via the various bridge members with further piperidine units. The additives from this group act simultaneously as antioxidants. Examples of particularly suitable commercial products are Tinuvin ^® 123, 571, 770, 765 and 622 (Ciba).

The benzophenone based light stabilizers are 2-hydroxy- and 2,2'-dihydroxybenzophenone which may be substituted by further hydroxy or alkoxy groups. A particularly suitable example is the commercial product Uvinul ^® 3008 (BASF).

The light stabilizers based on benzotriazole carry on the central nitrogen atom, a 2-Hydroxylphenylrest which may be substituted in 5- and optionally also in the 3-position by preferably tertiary alkyl groups. Examples of particularly suitable commercial products include Tinuvin ^® P, 571, 350 and 234 (Ciba), and Cyasorb ^® UV 541 1 (Cytec). Examples of suitable antioxidants include the known classes of sterically hindered phenols and phosphites and phosphonites.

The antioxidants based on sterically hindered phenols contain, as an essential building block, a phenol substituted by at least one tert-butyl group in the ortho position, in particular by tert-butyl groups in both ortho positions, to the OH group. Most known products contain several of these building blocks, which are interconnected by different bridge members. Particularly suitable commercial products of this class are, for example, Irganox ^® 1076, 1010 and 245 (Ciba).

The antioxidants based on phosphites and phosphonites are usually the esters of the corresponding phosphoric acids with alkyl-substituted, in particular tert-butyl, substituted phenols. Particularly suitable commercial products Irgaphos® ^® 168 and P-EPQ (Ciba) may be mentioned.

When such additives are used in the fluorescent conversion solar cells of the present invention, their amount of use is usually 500 to 5,000 ppm, preferably 1,000 to 3,000 ppm, based on the polymer matrix.

The polymer plates containing the fluorescent dyes can be prepared in a known manner. For example, PMMA sheets can be obtained by the casting process or by extrusion. Extrusion is also the preferred method for the production of polycarbonate sheets.

Glass plates coated with the fluorescent dye-containing polymer can likewise be produced by known methods. In this case, a polymer solution, e.g. applied to the glass plate with a squeegee and then dried.

example

First, two PMMA plates doped with different fluorescent dyes were prepared by the casting method.

For this purpose, in each case 1 kg of a PMMA prepolymer in the form of a 10% strength by weight solution in MMA at 10 ° C. with 8 g of azobisisobutyronitrile, (1) 300 ppm of N, N'-bis (2,6-diisobutyl). propylphenyl) -1,6,7,12-tetraphenoxyperylene-3,4: 9,10-tetracarboxylic diimide and 300 ppm of N- (2,6-diisopropylphenyl) -9-cyanoperylene-3,4: 9,10-dicarboxylic acid imide or (2) 120 ppm of N, N'-bis (2,6-diisopropylphenyl) -1,6,9,14-tetra (2,6-diisopropylphenoxy) - terrylene-3,4: 1 1, 12-tetracarboxylic added. The mixture was stirred at 10 ° C until all ingredients were dissolved (about 3 hours). The resulting solution was placed between two plane-parallel silicate glass plates (50 cm x 40 cm) and a 0.2 cm thick spacer sealing the cavity between the silicate plates. injected. The mold was placed in a 70 ° C water bath for 2 h and then stored for a further 0.5 h at 1 10 ° C to complete the polymerization. After complete cooling, a 5 cm × 10 cm plate was sawn from the obtained plate, the edges of which were polished.

Subsequently, the sawn PMMA plates were connected to silicon photovoltaic cells and converted into fluorescence conversion solar cells.

Initially, only the optoelectric cell efficiency η of the PMMA plate (1) was determined. For this purpose, two silicon cells measuring 47 mm × 1 mm were glued to an end of the PMMA plate (1) with an epoxy resin. The efficiency η was then determined using an IEPC scanner from Aescusoft under irradiation with AM 1, 5 light (1000 W) at 25 ° C. Extrapolated to the occupation of all slab edges with silicon cells, this resulted in an η value of 2.1%. From an outdoor measurement of short-circuit current and clamping voltage in the blue sky, an efficiency η of 2.7% was determined with the known filling factor of the silicon cells.

The PMMA plate (1) was then placed over the terrylene dye-containing PMMA plate (2) similarly provided with two silicon cells by making a 0.1 mm-thick air gap. The plate stack was irradiated as described above with the PMMA plate (1) facing the light source. The plate stack showed an over the PMMA plate (1) increased by 0.3% efficiency.

Claims

claims

1. Fluorescence conversion solar cells based on one or more plates of polymer doped with at least one fluorescent dye and / or with the doped polymer coated glass plates and attached to the edges of the plates photovoltaic cells containing one or more fluorescent dyes based on Terrylencarbonsäurederivaten or a combination of these fluorescent dyes with others Contain fluorescent dyes.

Fluorescence conversion solar cells according to claim 1, which contain at least one fluorescent dye from the group of terrylenetetracarboximides, terrylenetetracarboxylic monoanhydride monoimides, terrylenetetracarboxylic dianhydrides, terrylenedicarboximides, terrylenedicarboxylic anhydrides, condensation products of terrylenetetra- and dicarboxylic anhydrides with aromatic diamines and terrylene building blocks having multiple chromophores.

Fluorescence conversion solar cells according to claim 1 or 2, which contain at least one NIR-emitting fluorescent dye based on Terrylencarbonsäurederivaten in combination with at least one at shorter wavelength absorbing and emitting fluorescent dye.

4. fluorescence conversion solar cells according to claims 1 to 3, the at least one fluorescent dye of general formula Ia

in which the variables have the following meaning:

B ^a1 with each other to form a six-membered ring connected to a radical of formula (a), (b) or (c)

(a) (b) (C)

both hydrogen or a radical -COOM or one of the two radicals is a radical R or bromine and the other radical hydrogen;

B ^a2 independently of B ^a1 with each other to form a six-membered ring connected to a radical of formula (a), (b) or (c) or both a radical -COOM; R aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings whose carbon is substituted by one or more groupings -O-, -S-, -NR ¹ -, - N = CR ¹ -, -CO-, -SO- and / or -SO ² - may be interrupted, wherein the entire ring system one or more times by the radicals (i), (ii), (iii), (iv) and / or (v) may be substituted: (i) C 1 -C 30 -alkyl whose carbon chain is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ² - may be interrupted and may be mono- or polysubstituted by: Ci-Ci ₂ -alkoxy, Ci - C ₆ -Al kylthio, -C≡CR ¹ , -CR ¹ = CR ¹ 2, hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , aryl and / or saturated or unsaturated C 4 -C 7 -cycloalkyl, whose carbon skeleton is represented by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ² - may be interrupted, wherein the aryl and cycloalkyl radicals each one or more times by Ci-Cis-alkyl and / or the abovementioned radicals which may be mentioned as substituents for alkyl may be substituted;

(ii) Ca-Cs-cycloalkyl, whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO - and / or -SO2- can be interrupted and to the other saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ² - may be interrupted, wherein the entire ring system may be mono- or polysubstituted by: Ci-Cis alkyl, Ci-C, -C ₆ alkylthio -AI, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydro- xy ₂ -alkoxy, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ³ , -CONR ² R ³ ,

-SO ₂ NR ² R ³ , -COOR ² and / or -SO ₃ R ² ; (iii) Aryl or hetaryl, to which in each case further saturated or unsaturated 5- to 7-membered rings, whose carbon skeleton is represented by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, - CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ² - may be interrupted, may be annelated, wherein the entire ring system may be mono- or polysubstituted by: Ci-Cis-alkyl,

Ci-Ci2 alkoxy, _Ci-C6 alkylthio-Al, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ^3, -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO3R ² , aryl and / or hetaryl, each one or more times by Ci-Cis-alkyl, Ci-Ci2-alkoxy, hydroxy, mercapto , Halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² and / or

-SO 3 R ² may be substituted;

(iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals which are mentioned as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ¹ -, -CO-, -SO- or -SO ₂ -;

(v) Ci-C ₂ alkoxy, CrC ₆ -AI alkylthio, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² or -SO ₃ R ² , wherein the radicals R may be the same or different for n>1; R ^{1 is} hydrogen or C ¹ -C 6 -alkyl, where R ^{1 may be the} same or different if they occur more than once; R ² , R ^{3 are} independently hydrogen;

Ci-Cis-alkyl, the carbon chain by one or more groups -O-, -S-, -CO-, -SO- and / or -SO ₂ - may be interrupted and the one or more times by Ci-Ci ₂ Alkoxy, C ₁ -C ₆ -alkylthio, hydroxy,

Mercapto, halogen, cyano, nitro and / or -COOR ¹ may be substituted; Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -CO- and / or -SO ₂ - may be interrupted, be annelated can, wherein the entire ring system may be mono- or polysubstituted by Ci-Ci ₂ alkyl and / or the above, as substituents for alkyl radicals may be substituted; Hal bromine or cyano; R 'C4-C3o-Alkyl, whose carbon chain is replaced by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ , -CO-, -SO- and / or

-SO ₂ - may be interrupted and may be mono- or polysubstituted by the substituents mentioned for the radicals R radicals (ii), (iii), (iv) and / or (v); Ca-Cs-cycloalkyl to which further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is replaced by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or Wherein the entire ring system may be mono- or polysubstituted by the radicals (i), (ii), (iii), (iv) and / or (v) mentioned as substituents for the radicals R.sup.2- may be substituted; Aryl or hetaryl, to which in each case further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO2- may be interrupted, can be fused where the entire ring system may be mono- or polysubstituted by the substituents mentioned as substituents for the radicals R radicals (i), (ii), (iii), (iv), (v) and / or aryl and / or hetarylazo, which may each be mono- or polysubstituted by C 1 -C 10 -alkyl, C 1 -C 6 -alkoxy and / or cyano ; 1, 2-phenylene, 1, 8 or 2,3-naphthylene or 2,3- or 3,4-pyridylene, each represented by Ci-Ci2-alkyl, Ci-Cδ-alkoxy, hydroxy, nitro and / or halogen may be substituted;

M is hydrogen, alkali metal cation, [NH ₄ J ⁺ or [NR ² ₄ ] ⁺ ; n is 2 to 6 or also 0, if (1) the radicals B ^a1 and B ^{a2 are} each a radical of the formula (a) or (2) the radicals B ^{a1 are} a radical of the formula (a) and the radicals B ^{a2 are} both Is hydrogen or one of the two radicals B ^{a2 is} bromine and the other radical B ^{a2 is} hydrogen; 0 to 6, where n + z <6 and z may be different from 0 only if the radicals B ^a1 and B ^a2 each represent a radical of the formula (a),

contain.

Fluorescence conversion solar cells according to claims 1 to 3, comprising at least one fluorescent dye of general formula Ib

in which the variables have the following meaning:

or a radical hydrogen and the other radical is a radical X;

R aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CO-, -SO- and / or -SO2- may be interrupted, can be fused where the entire ring system may be mono- or polysubstituted by the radicals (i), (ii), (iii), (iv ) and / or (v) may be substituted: (i) C ¹ -C 30 -alkyl whose carbon chain is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C ≡C-, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ² - may be interrupted and may be mono- or polysubstituted by: Ci-Ci ₂ -alkoxy, Ci -C ₆ -Al kylthio, -C≡CR ¹ , -CR ¹ = CR ¹ 2, hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , aryl and / or saturated or unsaturated C 4 -C 7 -cycloalkyl, whose carbon skeleton is represented by one or more groups -O-, -S-, -NR ¹ -, - N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ² - may be interrupted, wherein the aryl and cycloalkyl radicals in each case one or more times by Ci-cis-alkyl and / or the above radicals which may be mentioned as substituents for alkyl may be substituted;

(ii) C ³ -C 8 -cycloalkyl whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO - and / or -SO2- may be interrupted and to the further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO 2 - can be interrupted, be anneliert, wherein the entire ring system may be mono- or polysubstituted by: Ci-Cis-alkyl, Ci-Ci ₂ -Akoxy, Ci -C ₆ -Al kylthio, -C 1CR ¹ , -CR ¹ = CR ¹ ₂ , hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² and / or -SO ₃ R ² ;

(iii) Aryl or hetaryl, to which in each case further saturated or unsaturated 5- to 7-membered rings, whose carbon skeleton is represented by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, - CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ² - may be interrupted, may be annelated, wherein the entire ring system may be mono- or polysubstituted by: Ci-Cis-alkyl,

Ci-Ci ₂ -alkoxy, CrC ₆ -AI alkylthio, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ^3, - CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO3R ² , aryl and / or hetaryl, each one or more times by Ci-Cis-alkyl, Ci-Ci ₂ -alkoxy, hydroxy, mercapto , Halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² and / or

-SO 3 R ² may be substituted;

(v) Ci-C ₂ alkoxy, CrC ₆ -AI alkylthio, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² or -SO ₃ R ² , wherein the radicals R may be the same or different for n>1; R ^{1 is} hydrogen or C ¹ -C 18 -alkyl, where the radicals R ^{1 may be} identical or different if they occur more than once; R ² , R ^{3 are} independently hydrogen;

C 1 -C 8 -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -CO-, -SO- and / or -SO ₂ - and which is mono- or polysubstituted by CrCl ₂ -alkoxy, CrC _6- alkylthio, hydroxy,

Mercapto, halogen, cyano, nitro and / or -COOR ¹ may be substituted; Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -CO- and / or -SO ₂ - may be interrupted, be annelated can, wherein the entire ring system may be mono- or polysubstituted by CrCi ₂ alkyl and / or the above, as substituents for alkyl radicals may be substituted; X is a perylenedicarboximide radical of the formula

R 'is C4-C30-alkyl whose carbon chain is substituted by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO2- may be interrupted and the one or more times by the radicals mentioned as substituents for the radicals R radicals (ii), (iii), (iv) and / or (v) substituted can be;

C ³ -C 8 -cycloalkyl to which further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is replaced by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ² - can be interrupted, the entire ring system one or more times by the substituents mentioned for the radicals R radicals (i), (ii ), (iii), (iv) and / or (v) may be substituted; Aryl or hetaryl, to which in each case further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO2- may be interrupted, can be fused where the entire ring system may be mono- or polysubstituted by the substituents mentioned as substituents for the radicals R radicals (i), (ii), (iii), (iv), (v) and / or aryl and / or hetarylazo, which may each be mono- or polysubstituted by C 1 -C 10 -alkyl, C 1 -C 6 -alkoxy and / or cyano ;

Y is -O- or -S-;

Z is a bridge member having at least one aromatic or heteroaromatic radical, the groups Y being bonded to the aromatic or heteroaromatic radical; x 2 to 6, when the radicals B ^b1 and B ^b2 each represent a radical of the formula (a); 0 for all other meanings of the radicals B ^b1 and B ^b2 ; n 0 to 8, where x + n <8 and n ≠ 0 when x = 0; n1 0 to 2,

contain.

Fluorescence conversion solar cells according to claims 1 to 5, which contain at least one fluorescent dye from the group of terrylene tetracarboxylic diimides and terrylenedicarboximides.

7. fluorescence conversion solar cells according to claims 1 to 6, which contain at least one fluorescent dye based on Terrylencarbonsäurederivaten in combination with at least one fluorescent dye from the group of Perylencarbonsäurederivate, naphthalenecarboxylic acid derivatives, isoviolanthrone derivatives and Violanthronderivate.

8. fluorescence conversion solar cells according to claims 1 to 7, comprising at least one fluorescent dye based on Terrylencarbonsäurederivaten in combination with at least one fluorescent dye from the group of

Perylenetetracarboximides, perylenetetracarboxylic monoanhydride monoimides, perylenetetracarboxylic dianhydrides, perylenedicarboximides, perylenedicarboxylic anhydrides, perylenedicarboxylic acid esters, perylenedicarboxylic acid amides, multichromophores having perylene units and containing no terrylene units, naphthalene tetracarboxylic diimides, naphthalenedicarboxylic acid imides, isoviolanthrones and violanthrones.

9. fluorescence conversion solar cells according to claims 1 to 8, wherein the polymer additionally contains at least one stabilizing additive from the group of light stabilizers and antioxidants.

10. fluorescence conversion solar cells according to claims 1 to 9, which contain a polymer from the group of polyacrylates and polycarbonates.

1 1. fluorescence conversion solar cells according to claims 1 to 10, which have a white diffuser on the underside of the bottom plate.

12. fluorescence conversion solar cells according to claims 1 to 1 1, which have on the upper side of the uppermost plate a band-pass filter.

13. Fluorescence conversion solar cells according to claims 1 to 12, which are based on at least two plates which are doped and / or coated with fluorescent dyes which absorb and emit at different wavelengths of the electromagnetic spectrum.