DE102010033025A1 - Fabrication of alternative structure of flexible dye-sensitized solar cell and plastic solar cell involves forming optically-transparent three-dimensional cathode and bottom layer containing high-conductive carbon nanotubes on cathode - Google Patents

Abstract

Fabrication of alternative structure of flexible dye-sensitized solar cell and plastic solar cell involves forming an optically-transparent three-dimensional cathode, a bottom layer containing high-conductive carbon nanotubes and donor bonded with the cathode, a two-dimensional crystalline monolayer, pores filled with optically transparent conductive material, and an anode.

Description

The present invention relates to methods for constructing a flexible, alternative, dye-sensitized, organic solar cell:
(as registered under file number: 102009017481.8-33)
and their combination with the organic polymer cell:
(as registered under file number: 102009051068.0)
to the tandem solar cell

Furthermore, the present invention relates to the provision of substrates for the production of two-dimensionally crystalline, rod-shaped dye molecule monolayers and in two variants for the preparation of polymer donor dye acceptor molecule monolayers (SAMs).

Dye-sensitized organic solar cells offer themselves as a promising, cheap photovoltaic technology. They are due to the possibilities of cheap and versatile manufacturing processes, a current research topic.

Advantages are:
Low manufacturing costs due to cheap production technologies.
Flexibility, transparency and easy handling.
High environmental compatibility.
Adaptation to the solar spectrum through targeted dye synthesis.

The operation of the classical dye solar cell is based on the charge separation in a dye, which is located at the interface between an inorganic semiconductor and a hole conductor.

Dye-sensitized Grätzel cell organic solar cells or their variants consist of a conductive, optically transparent anode (eg ITO with a layer thickness of typically 500 nm). This is coated with a porous network of TiO2 nanocrystals.

TiO2 is a semiconductor with a band gap of about 3.2 eV, which corresponds to a wavelength of less than 400 nm to move one electron from the valence band to the conduction band. It is therefore not sensitive in the visible range and absorbs only in the near UV range. On the TiO2 - nanoparticles is a dye z. B. ruthenium-based or a metal-free dye via specific, electron-injecting groups (hydroxy, carboxy, phosphonic ...) anchored as possible monomolecular layer. It is important that the TiO2 has a very large porosity, so that the active area is several hundred times larger than the geometric area. Because only the light absorbed in the monomolecular layer of the dye determines the yield of the cell.

The essential physical trick is the monomolecular thickness of the dye. The physical properties of a small particle (Q particles, because of the quantum mechanical effect) change when the dimensions come in atomic dimensions. In such a Q-particle, the electrons can not move as freely as in a crystal, they feel the influence of the walls. The smaller a Q particle, or the thinner a layer, the greater is the splitting into discrete energy levels. The energy split in the corresponding particles is now so great that now the electrons generated by the absorption of light receive an energy that is above the conduction band level of titanium dioxide. The light-generated electrons can now pass into the conduction band of the n-type semiconductor TiO2. The generated charges migrate and are collected at the anode. From the anode, the electrons flow through the load, which converts the consumed energy (consumed) to the counter electrode (cathode). The electron loss of the dye is ultra-fast compensated by a redox electrolyte (such as iodine / potassium iodide electrolyte solution) (restoration of the ground state), which is again reduced by the electrons entering at the counter electrode. The porous TiO 2 layer is penetrated by a hole conductor material, which may be a liquid redox electrolyte or a solid or gel-like material. The injection process takes less than 25 fs, the return of the electrons from the TiO2 to the ionized dye takes milliseconds, while the liquid redox system (iodine / iodide) is regenerated after about 100 ns.

Intensive studies and optimization experiments involving changes in the nanocrystalline semiconductor, the redox electrolyte, the dye, the dye coating and the cell encapsulation did not lead to long-term stable cells with sufficient efficiency and economic relevance.

The disadvantage here is that the hole conductor of these cells consists of an iodide / triiodide solution, which has a poor long-term stability and has a complex manufacturing process result.

During the redox process occurring iodine is volatile, which is why the cell must be sealed (long-term sealing). In addition, the iodide / triiodide electrolyte can corrode the Pt electrode. The electrolytes penetrate the entire cell and can therefore be undesirable Creepage currents lead. Their conductivity can also contribute to reducing the voltage between the electrodes.

In the search for improved cell designs, a number of alternative redox mediators have been explored in addition to electrolyte systems:
Iodide / triiodide in matrix materials of solid polymers, gels, ionic liquids, a solvent-free melt of three salts, inorganic solids, organic polymers and organic-low molecular weight hole guides and others ....

Neither the desired lifetime nor sufficient efficiency was found!

When the dyes are applied to the porous TiO 2 layer or when the dyes are incorporated into all other types of dye solar cells, they do not arrange as a two-dimensionally crystalline monomolecular layer, but irregularly next to one another with different layer thicknesses and with numerous loss processes due to them.

The dyes used tend to aggregate in solution and even more on the TiO 2 surface, which depending on the particle size, more or less strongly deactivates the excited states.

Another question that still awaits the answer is the optimal dye.

With the required lifetime of the cell of 20-30 years, the dye must go through many hundreds of millions of times the oxidation-reduction process. Although transition metal complexes with ruthenium show values of 50 million cycles, they are too expensive.

A problem of a completely different kind is the structure of the anode, where the TiO2 is baked at 450-500C °.

The production of a flexible dye solar cell is thus impossible in this way.

The publication DE 60033038T2 describes such a method.

However, there is the structure in the form of a layered structure.

The task is now to provide an improved cell type by building two-dimensionally crystalline monolayers.

Alternative cell designs are said to greatly reduce or eliminate a number of innovations relating to the production of dye-sensitized solar cells using the concept described above, but also to deficiencies in other cell types and their variants, such as structure, functionality and material.

task

There are no known method that optimizes the morphology of the various types of dye solar cell in that at maximum cell surface, the dye molecules can be built on this as an ordered, self-aggregating, two-dimensional crystalline, monomolecular dye layer (SAM).

Furthermore, no method is known which provides the monolayer rod-shaped donor-acceptor dye molecules ((D-A) molecules) functionalized with an anchor group on the donor and on the head group on the acceptor with an injection group.

Also, no methods are known in which polymers and dyes in a tandem cell in cofacial or linear arrangement (along the molecular axis) electronically interact and the necessary for building a monolayer rod-shaped donor-acceptor molecules ((DA) molecules) with an anchor group on Donor, functionalized at the acceptor (head group) with an injection group

Similarly, no methods are known in which the oxidized dye molecule is not reduced by a redox mediator, but directly by a tunneling current.

The object of the present invention is therefore to provide a dye-sensitized solar cell whose morphology provides a maximally possible, active cell surface to build up a self-aggregating, ordered, two-dimensionally crystalline dye monolayer on this and the oxidized dye molecules not by a redox mediator, but directly by a tunneling current, to reduce.

According to the aspect of the invention, methods are provided for inverse construction of an alternative organic dye solar cell and two tandem cells.

The dye solar cell

The process according to the invention comprises the following construction steps and materials:

The sequential cell assembly takes place starting from the cathode.
The cathode consists of a flexible polymer film which is coated with a transparent, conductive oxide (TCO) such as SnO 2 / ITO, ZnO and other materials known to those skilled in the art as well as with Pt, Au, Cu, Ag and C in the graphene or graphite modifications ,

In order to increase the active surface of the cell many hundreds of times and at the same time provide sufficient porosity, the cathode is "extended" by a loose, three-dimensional network of optically transparent, highly conductive carbon nanotubes (CNTs).

All CNTs are connective and consistently conductive.

The CNTs are deposited on the cathode by conventional techniques such as spin coating, sputtering, printing, lamination and others.

According to one aspect of the invention, for good adhesion and optimization of electron transfer between cathode and CNT network and avoidance of phase boundary, the cathode and bottom layer of the CNT network are bridged by orbital overlap directly or with a "chemical clamp", corresponding to the coating of the cathode as required, the CNTs on their surface unchanged, decorated or less suitable, functionalized, are used.

In a preferred method of the invention, on its surface, unchanged CNTs bridge with the lowest layer of the CNT network with the top graphite or graphene-coated cathode by π-π interaction (π-stacking)

In a preferred method of the invention, on its surface, with cited thiol- or dithiocarbonate-bonding semiconductors such as ITO, ZnSe, SnO2, ZnO, or others, covalently decorated CNTs covalently bond to the bottom most layer of the CNT network with the "chemical clamp" cathode.

As chemical brackets with dithiocarboxylic acid (ester) parafunctional tetraphenylmethane tetrapods or two bridged by a short molecular wire, in para-position with dithiocarboxylic acid (ester) functionalized triphenylmethyl groups which bind three or two times on the cathode surface, depending on the positioning of the molecule ,

In a less preferred method of the invention, these are used with reservations and only as an alternative, due to the chemical properties such as hydroxy, amino, carboxylic acid and other, incompletely functionalized surface of the CNTs, but also because of their more or less modified by functionalization intrinsic properties, the bottom most layer of the CNT network covalently bridging with the cathode.

According to a further aspect of the invention, the rod-shaped (D-A) dye molecules are deposited and anchored as a two-dimensionally crystalline monolayer of solution on the CNT network (extended cathode) firmly anchored on the cathode.

Depending on the structure of the anchor group, the (D-A) molecules position themselves perpendicularly, almost vertically or tilted to the surface.

Vertical or nearly perpendicular (D-A) rod molecules with a voluminous anchor group have the necessary distance to the neighboring molecule, so that spacers do not touch each other or head groups and spacers by resting on each other. A contact, such as. B. in the Grätzel cell or other cell types by disordered positioning of the dye molecules deactivates excited states or leads to the transfer of electrons from the head group (acceptor) in the emptied donor of the neighboring molecule (electron loss mechanisms).

Nanoparticles, polymers or composites that transfer electrons almost completely to the anode after injection of electrons from the acceptors under optimal conditions, return some of the charge to the anode upon contact with the oxidized donors.

Voluminous anchor groups and solubilizing alkyl groups on the dye molecule prevent unavoidable π-stacking (aggregates) in aromatic, planar dye systems, which prevent the formation of monomolecular layers (SAMs).

In a preferred method according to the invention, the dye molecules are deposited on the non-modified CNTs as SAM from solution and anchored perpendicularly to the substrate surface, radially aligned, physically by π-π interaction (π-stacking).

Prerequisite for the vertical positioning of the (D-A) rod molecules is a symmetrical dipodal or tetrapodal anchor.

Core of the dipodal anchor molecule is triptycene. Two of the three symmetrically arranged benzene rings in the molecule are extended to pyrene or phenanthrene, while the third, remaining benzene ring as benzo (b) thiophene, benzo (b) pyrrole, Benzimidazole or 3-dialkylaminobenzo (b) thiophene on the five-membered ring in the 2-position carries the rod-shaped (DA) dye molecule.

Elongated aromatic molecules such as pyrene and phenanthrene have a preferred direction and can be arranged parallel to the tube axis with this, which maximizes the possible interaction.

Favorable for a strong interaction is also a fairly large diameter of the nanotube. The curvature of their π system is less pronounced and the distance to the aromatics increases to the outside not so strong.

Analogous to the dipodal anchor group, the core of the tetrapodal anchor group consists of a Triptycenmolekül, wherein two of the three symmetrically arranged in the molecule benzene rings on the C atom 2, 3, 6 and 7 directly or by means of a hydrocarbon bridge with an aromatic z. B. benzene, while the third, remaining benzene ring as benzo (b) thiophene, benzo (b) pyrrole, benzimidazole or 3-dialkylaminobenzo (b) thiophene on the five-membered ring in the 2-position carries the rod-shaped (D-A) dye molecule.

In a further preferred method according to the invention, the dye molecules are deposited on the decorated CNTs as SAM from solution and chemically anchored nearly perpendicular or perpendicular to the substrate surface, radially aligned.

The prerequisite for almost perpendicular positioning of the rod molecules on the decorated CNTs is a tripodal anchor group consisting of a triphenylmethyl group functionalized in the para position with dithiocarboxylic acid (ester) or a 1,3,5 triphenyladamantyl group functionalized in the para position with dithiocarboxylic acid (ester).

Prerequisite for the vertical positioning of the rod molecules on the decorated CNTs is a tetrapodal anchor group, which consists of a Triptycenmolekül core two of the three symmetrically arranged in the molecule benzene rings at the C atom 2, 3, 6 and 7 directly or by means of a hydrocarbon bridge with dithiocarboxylic acid ( ester) are functionalized, while the third, remaining benzene ring as benzo (b) thiophene, benzo (b) pyrrole, benzimidazole or 3-dialkylaminobenzo (b) thiophene at the 5-membered ring carries the rod-shaped (DA) dye molecule in a less preferred Processes according to the invention, the dye molecules are deposited on the functionalized CNTs as SAM from solution and tilted on the substrate surface, anchored monopodal.

The reason for the tilted positioning of the rod molecules as a monopodal anchor group is a functional group such as hydroxy, amine, carboxylic acid and others, which bind chemically to the functionalized CNTs by known mechanisms.

According to a further aspect of the invention, metal-free, rod-like dyes such as those in structure, stability and electronic properties (ultrafast, photo-induced electron transfer) in J. Am. Chem. Soc. 1996 118, 6767 and articles of the same subject are described, according to the requirements for the construction of self-aggregating monolayers (SAM), modified.

Along the molecular axis, the core structure of the (D-A) dye molecule at donor and acceptor is changed and expanded. The extended donor additionally receives a variable anchor group corresponding to the surface properties of the substrate, and the acceptor receives an injection group.

Carboxylic acid, phosphonic acid, sulfonic acid, hydroxyl group, acid anhydride group and other suitable groups known to those skilled in the art are used as injection groups.

To provide sufficient solubility of the molecules, they are attached to their acceptor domains and, if necessary, to the dipodal, tripodal or tetrapodal anchor group with solubilizing groups, e.g. As linear or branched alkanes, derivatized.

At the acceptor domains, additional donor substituents which increase the efficiency of the dyes can be introduced into the Bay region.

In a preferred method according to the invention in the donor-acceptor dyes photostable chromophores such as perylene, perylene derivatives, (Rylenreihe) and other various dyes are used in which the chromophoric electron acceptors a 4-aminonaphthalene-1,8-dicarboximide (A) in the 4-amine nitrogen atom is part of a piperazine ring, the second nitrogen atom of the piperazine ring being part of a para-substituted aniline donor whose para-substituent 2,6-dianvnobenzene bridges in the 1-position with the aniline donor and in the 4-position with the anchor group.

The imide group of (A) is linked via an alkylated phenyl spacer para to the imide group of a second electron acceptor (B), a naphthalene-1,4,5,8-tetracarboxylic diimide molecule.

To provide a multi-chromophore dye system that absorbs across the entire visible spectrum, the second electron acceptor (B) gradually steps along a gradient directly by NN bonding or by rigid, π-conjugated spacers on the still free imide group of (B) with perylenediimide and other rodlike representatives of the rylene series such as terrylenediimide, quaterrylenediimide ... etc, which in their Bay region additionally with donors such as phenol, Thiophenol, cyclic amines and other donors known in the art are functionalized and their derivatives, extended.

In a further preferred method according to the invention, the pore sizes and cavities remaining in the three-dimensional, nanoporous network structure after formation of the dye molecule monolayer on the CNTs, into which the head groups of the (DA) molecules functionalized with injection groups protrude, are compared with respect to their pore size and Pore structure using techniques known to those skilled in the art with optically transparent, conductive materials exhibiting good electron transfer, such as semiconductor nanoparticles (eg, TiO 2, SnO 2, ITO, ZnO, and others), conductive polymers, and composites adapted in particle size and viscosity to network structures;

Various techniques for depositing the fillers and backfills of the CNT network prefer non-contact methods to avoid damaging the delicate CNT network structures.

Printing, such as offset printing, coating techniques and other known methods can be used.

The materials introduced into the cavities together form an interpenetrating network of nanotubes, nanorods and nanowires whose top layer is crosslinked with the anode by deposition of the anode material such as SnO 2, ITO, ZnO and other common materials by means of vapor deposition or other strategies known to those skilled in the art (Extension of the anode).

According to another method of the invention, the cell may be completed by differently functionalized CNTs such as hydroxy, carboxylic acid and other suitable groups which covalently bind to the surface of the respective filled materials (anode).

Materials that are used to date for the construction of the anode are thereby wholly or partially replaceable.

As a result, the cell is an interpenetrating, cathodic and anodic, three-dimensional, disordered, optically transparent network with a greatly increased active surface, covered with a monolayer (SAM) of rod-shaped (DA) dye molecules, with their anchor and injection groups through targeted assembly of Cathodic-anodic continuous molecular chains, by orbital overlap avoid phase boundaries, thereby covalently bridging the interfaces between extended cathode and extended anode, linear, such as with a molecular wire.

The numerous monolayers allow the complete absorption of all energetically suitable photons.

In the area of the network more than a thousand (D-A) molecular layers can overlap one another.

The low charge carrier mobility of organic semiconductors thereby loses its limiting effect on the layer thickness of the cell.

The small layer thickness of the SAMs also means a small series electrical resistance and a large internal electric field.

The ordered structuring of the solar cell is necessary to reduce the respective loss mechanisms of previous dye solar cells.

Reduced to a single fundamental element of the cell, the solar cell is a molecular chain orbitally networked between cathode and anode (homo and lumo orbitals are much better aligned and thus able to overlap one another) in which the charge carriers flow as in a molecular one Wire.

Functionality:

After photoexcitation of the donor, electron transfer to the acceptors occurs. Due to quantum mechanical effects in the monolayers, the electrons generated by the absorption of light receive an energy that is above the conduction band level of the semiconductor materials filled in the remaining pores of the CNT network. The photogenerated electrons can now flow through the injection group from the acceptor system to the semiconductive fillers. From the anode, the electrons flow through the consumer to the cathode. The electron loss of the donor is ultra-fast compensated by a tunnel current from the CNTs through the anchor group.

The dye-plastic solar cell (tandem cell)

option A

Construction:

The structure of the cell is analogous to the alternative construction scheme of the dye solar cell. Instead of the (D-A) dye molecules, a donor-acceptor system (polymers as donors, dyes as acceptors) is built up.

Donor and acceptor molecules are folded over a dipodal, tripodal or tetrapodal anchored xanthene framework, U-shaped, linearly aligned, cofacially bridged.

The whole molecule has the shape of a tuning fork.

The dyes linearly connected by rigid, mostly π-conjugated spacers or directly via N-N bond (bisimides of perylene and extended perylene bisimide systems) are arranged along a gradient.

An additional donor, such as 2,6-diaminobenzene, is inserted between the polymer and the xanthene framework.

The acceptors may contain up to 5 imide or bisimide dye units. If different polymers are used simultaneously, they are also arranged along a gradient.

The length of the polymers depends on the length of the acceptors.

functionality

After photoexcitation of the polymers, the electrons are transferred through the space to the dyes (acceptors). From there via an injection group into the semiconductor molecules.

A donor (push-pull effect) additionally inserted between the xanthene and the polymer as a "check valve" allows the targeted transfer of the electrons into the acceptor (dyes), the transport of positive charge carriers to the inserted donor.

The electron loss of the inserted donor is ultra-fast compensated by a tunneling current from the CNTs through the anchor group.

Variant B

Construction:

The structure of the cell is analogous to the alternative construction scheme of the dye solar cell. Instead of the (D-A) dye molecules, a donor-acceptor system (polymers as donors, dyes as acceptors) is built up.

In contrast to variant A donors and acceptors are not next to each other, but successively linear, along the molecular axis arranged.

Between anchor group and polymer, an additional donor, such as 2,6-diaminobenzene, is inserted

If different polymers are used as monomers or oligomers and several dyes of the rylene series, these are also linked along a gradient.

functionality

After photoexcitation of the polymers, the electrons are transferred to the dyes (acceptors). From there via an injection group into the semiconductor molecules. An additional donor inserted between the anchor group and the polymer (push-pull effect) enables the targeted transfer of the electrons into the acceptor (dyes) as a "check valve", the transport of positive charge carriers to the inserted donor.

The electron loss of the inserted donor is ultra-fast compensated by a tunneling current from the CNTs through the anchor group.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 60033038 T2 [0020]

Cited non-patent literature

• J. Am. Chem. Soc. 1996 118, 6767 [0054]

Claims (10)

A process for the alternative construction of a flexible dye solar cell and its combination with the plastic solar cell, the tandem cell, the construction is carried out from the cathode, through a loose, three-dimensional network of optically transparent, highly conductive carbon nanotubes (CNTs), the bottom layer directly to the cathode binds, "expands", whereby all CNTs are connective and thus consistently conductive, then on the CNT network the (DA) molecules whose oxidized donors are reduced by a tunnel current, deposited as a two-dimensional crystalline monolayer of solution, radially aligned, whereupon the pores remaining in the three-dimensional CNT network structure are filled with optically transparent, conductive materials and crosslinked with the anode. The method of claim 1, wherein the cathode consists of an optically transparent, flexible polymer film coated with SnO 2 / ITO, ZnO, Pt, Au, Cu, Ag, C in graphene and graphite modifications. The method of claim 1, wherein the optically transparent carbon nanotubes (CNTs) are decorated with dithiocarbonate and thiol-bonding optically transparent semiconductors such as ITO, ZnSe, SnO 2, ZnO, the CNTs are functionalized with hydroxyl groups, amino groups, carboxylic acid (chloride, bromide), aromatic diazonium salts (arylation), the CNTs are neither decorated nor functionalized for cell assembly and thereby covalently bind the functionalized CNTs with the respective functional groups to the cathode, physically bond the unmodified CNTs to the carbon (graphene, graphite) coated cathode through π-π interaction (π-stacking) and the decorated CNTs are covalently anchored to the cathode with "chemical braces", as a chemical "brackets" with dithiocarboxylic acid (ester) parafunctional tetraphenylmethane tetrapods or two bridged with a short molecular wire, in para-position with dithiocarboxylic acid (ester) functionalized triphenylmethyl groups on the cathode surface, depending on the positioning of the molecule, triply or twice bind, be used. The method of claim 1, wherein in the dye solar cell and the tandem cell (variant B) rod-shaped (DA) molecules are used, the donor and acceptor domains arranged successively linear along the molecular axis and at the donor with a monopodal, dipodal, tripodal or tetrapodal anchor group, on In the tandem cell (variant A) donors and acceptors on a xanthene scaffold, aligned linearly, cofacially bridged, positioned and the xanthene skeleton is functionalized with an anchor group in the tandem cell (variant A) functionalized. Process according to claims 1 and 4, wherein in the dye cell in the donor-acceptor dye molecules photostable chromophores such as perylene, perylene derivatives (rylene series) and other various dyes are used in which the chromophoric electron acceptors are a 4-aminonaphthalene-1,8-dicarboximide ( A) in which the 4-amine nitrogen atom is part of a piperazine ring, the second nitrogen atom of the piperazine ring being part of a para-substituted aniline donor whose para-substituent is 2,6-diaminobenzene in the 1-position with the aniline donor, in the 4-position with the anchor group bridged and the imide group of (A) via a Phenylspacer para to the imide group of a second electron acceptor (B), a naphthalene-1,4,5,8-tetracarboxylic diimide, or perylenecarboxylic diimide is bound and the second electron acceptor (B) for the purpose of construction of a panchromatic absorption system stepwise along a gradient directly through NN binding or through rigid π conjugates Spacers on the still free imide group of (B) with perylene diimide and other rod-like representatives of the rylene series such as Terrylendiimid, quaterrylene diimide ... etc., which are additionally functionalized in the Bay region with donors such as phenol, thiophenol, cyclic amines and their derivatives , is extended. The method of claim 1, 4 and 5, wherein in the tandem cell (variants A and B) as donors already in solar cell-proven polymers such as poly (p-phenylenevinylene) (PPV), polythiophenes, and by fine-tuning, molecular design and synthesis produced varieties and novelties to be synthesized and in the tandem cell (variants A and B) to provide a multi-chromophore donor-acceptor molecule system which absorbs over the entire visible spectrum, along the molecular axis by a linear combination of two or more oligomers, along a gradient , z. As derivatives of PPV and regioregulärer polythiophenes whose absorption spectra are complementary to each other and absorb better over the entire solar spectrum, an energetically graded donor is constructed, further in the tandem cell (variant B) between donor polymer and anchor group, in variant (A) of Tandem cell between Xanthengerüst and polymer, in each case an additional donor such as 2,6-diaminobenzene, is inserted and as acceptors in the tandem cell (variants A and B) by rigid, usually π-conjugated spacer or directly via NN bond linearly connected dyes such as bisimides of perylene and extended perylene bisimide systems ( Rylenreihe) and their derivatives, which are arranged along a gradient can be used. A process as claimed in claims 1, 4 and 6, wherein a carboxylic acid, a carboxylic acid chloride, an amino group, a hydroxyl group or diazonium salts are used as the monopodal anchor group, the dipodal anchor group in the nucleus consists of a triptycene molecule in which two of the three symmetrically arranged in the molecule benzene rings are expanded to pyrene or phenanthrene, while the third remaining benzene ring as benzo (b) thiophene, benzo (b) pyrrole, benzimidazole or 3-dialkylaminobenzo (b) thiophene on the five-membered ring in the 2-position carries the rod-shaped (DA) molecule, the tripodal anchor group consists of a triphenylmethyl group functionalized in the para position with dithiocarboxylic acid (ester) or a triphenyl adamantyl group functionalized in the para position with dithiocarboxylic acid (ester), the tetrapodal anchor group in the core consists of a triptycene molecule, two of the three in the molecule symmetrically arranged benzene rings on carbon atom 2, 3, 6 and 7 are linked directly or by means of a hydrocarbon bridge with both dithiocarboxylic acid (ester), as well as an aromatic, while the third, remaining benzene ring as benzo (b) thiophene, benzo (B) pyrrole, benzimidazole or 3-dialkylaminobenzo (b) thiophene on the five-membered ring in the 2-position carries the rod-shaped (DA) molecule. The method of claim 4, wherein the injection group in the rod molecule binds either directly or via a spacer to the protonated nitrogen of the diimide and as an injection group, a carboxylic acid, phosphonic acid, sulfonic acid, hydroxyl group, acid anhydride group and other suitable groups. The method of claim 1, 3 and 4, wherein the (D-A) molecules on the decorated CNTs are deposited as a two-dimensional crystalline monolayer from solution and chemically anchored to the decorated CNTs perpendicular or nearly perpendicular, radially aligned, the (D-A) molecules on the functionalized CNTs are deposited as a two-dimensionally crystalline monolayer from solution and are anchored chemically to the functionalized CNTs tilted to the substrate surface, the (D-A) molecules on the unmodified CNTs as a two-dimensional crystalline monolayer are deposited from solution and anchored on the CNTs perpendicular to the substrate surface, radially aligned, physically anchored by π-π interaction (π-stacking) and after the construction of the (DA) Molecular monolayer in the three-dimensional CNT network structure remaining cavities are filled with optically transparent, conductive polymers, semiconductor nanoparticles such as SfO2, TiO2, ZnO, ITO or optically transparent composites of semiconductors and conductive polymers, while the spent in the cavities conductive materials with each other forming an interpenetrating network of nanotubes, nanorods and nanowires ("extended anode") and covalently attach the injection groups to the conductive materials filled in the network cavities. The method of claim 1 and 9, wherein after filling the cavities, the cell is completed by coating with SfO 2 / ITO, ZnO and other suitable materials (anode) or in the cell by CNTs of different strength, such as functionalized with hydroxy, carboxylic acid and other suitable groups, which bind covalently to the surface of the respectively filled materials, the anode is completely or partially replaced.