DE102018214496A1 - Short-circuit proof electrode system for electronic components - Google Patents

Abstract

The present invention relates to a method for producing an electronic component, wherein (i) an electrically conductive substrate coating is applied to a substrate, (ii) a photoactive or light-emitting coating is applied to the substrate coating and (iii) an electrically conductive material on the photoactive or light-emitting coating is applied by a liquid deposition medium; wherein the outermost layer of the substrate coating from step (i) is soluble in the deposition medium from step (iii) or is chemically modifiable by this deposition medium.

Description

The present invention relates to electronic components with improved short-circuit strength and a method for their production.

Organic electronic components such as organic light-emitting diodes (OLEDs) and organic solar cells contain, as active layers, organic semiconductor layers which are photoactive (solar cell) or light-emitting (light-emitting diode) and are present between two layer-like electrodes. In order to achieve the most efficient possible extraction of the photogenerated charge carriers at the corresponding contacts, charge-selective transport layers are often applied between the photoactive layer and the two electrodes in solar cells. An electron transport layer has a high electron affinity and high electron mobility, while a hole transport layer has a high hole mobility and a high ionization potential.

Because of the low charge carrier mobilities, it is necessary for the organic semiconductor layers to have very small layer thicknesses, for example in the range of 100-300 nm. This makes electronic components with very thin organic semiconductor layers very susceptible to defects due to wetting problems, dust and scratching. These defects in the semiconductor layers quickly lead to short circuits between the electrodes, as a result of which the function of the electronic components is severely impaired. The result is a low technical yield and inexpensive production is prevented.

The problem of short circuits due to defects in the thin layers is also known for other thin-film components such as inorganic thin-film solar cells or perovskite solar cells.

The problem of the short circuits caused by defects in the thin semiconductor layers is clearly evident in the attempt to scale up the production of such electronic components using roll-to-roll coating processes. Appropriate attempts often fail due to completely short-circuited components. Previous approaches have been based on the use of very high layer thicknesses (which is reflected in a significantly reduced efficiency of the components and increased costs), very complex process conditions (vacuum or clean room), very high demands on the surface quality of the deflection rollers (until they are avoided) or complex Cleaning procedures. This leads to an increase in production costs.

US 2010/062550 A1 describes the subsequent isolation of defective areas using a laser, which means a high level of process engineering and thus high costs.

A. Oostra et al., Organic Electronics, 15, 2014, 1166-1172 describe a process for the production of an organic light-emitting diode, in which electrically conductive layers of indium tin oxide (ITO, acts as the first electrode) and PEDOT: PSS (functions as the HIL, “hole injection layer”) are first deposited on a transparent substrate. The active, ie light-emitting polymer layer is then applied to the hole injection layer. Due to their small layer thickness, defects may be present in the active layer, which expose the underlying PEDOT: PSS layer. Before a metal acting as a second electrode is deposited, the active layer is first brought into contact with an aqueous NaClO solution. In the defective areas of the active layer, the NaClO solution comes into contact with the underlying PEDOT: PSS layer and causes an oxidation of the PEDOT, which leads to a significant reduction in the electrical conductivity of the polymer in these contact areas. Then aluminum, which acts as a second electrode, is applied by means of a physical vapor deposition.

P. Apilo et al., Prog. Photovolt.: Res. Appl., 2015, 23, pp. 918-928 describe the use of intermediate layers with low conductivity, so that defects with a small area have a sufficiently high resistance and therefore only a small part of the total current can flow through this short circuit.

DE 103 26 546 A1 describes a solar cell with a photoactive layer and two electrodes, an intermediate layer with asymmetrical conductivity being arranged between the photoactive layer and the electrodes. This approach is very dependent on the contact formation of the two layers, since so-called recombination layers for tandem solar cells can also be produced in the same way, provided surface conditions are present at the interface or the conductivities are very high, for example by doping. According to the current state of knowledge, the required characteristic of the asymmetrical conductivities is not sufficient to reliably guarantee the desired high parallel resistance.

TR Andersen et al., Solar Energy Materials & Solar Cells, 149, 2016, pp. 103-109 describe an organic solar cell manufactured using a roll-to-roll process. A silver / PEDOT: PSS electrode is placed on a plastic substrate and a photoactive layer on this electrode upset. Subsequently, aluminum-doped zinc oxide (AZO) is applied to the photoactive layer using a liquid deposition medium, and finally a layer of aluminum is applied by sputtering. No measures are taken in the manufacturing process in order to avoid short circuits that could result from defects in the photoactive layer.

An object of the present invention is the production of an electronic component, in particular an optoelectronic component such as e.g. a solar cell or an organic light-emitting diode, using a process that can be carried out efficiently (e.g. also as a roll-to-roll process) and reduces the risk of short-circuits in the finished electronic component.

1. (i) Aufbringen einer oder mehrerer elektrisch leitfähiger Schichten auf einem Substrat unter Erhalt einer elektrisch leitfähigen Substratbeschichtung, wobei die zuletzt aufgebrachte elektrisch leitfähige Schicht die Außenschicht der Substratbeschichtung darstellt;
2. (ii) Aufbringen einer aktiven Beschichtung, die photoaktiv oder lichtemittierend ist, auf der Außenschicht der Substratbeschichtung;
3. (iii) Aufbringen eines elektrisch leitfähigen Materials auf der aktiven Beschichtung durch ein flüssiges Abscheidungsmedium;

wobei zumindest die Außenschicht der Substratbeschichtung (d.h. die in Schritt (i) zuletzt aufgebrachte und in Kontakt mit der aktiven Beschichtung stehende Schicht) in dem Abscheidungsmedium löslich ist oder durch das Abscheidungsmedium chemisch modifizierbar ist.The object is achieved by a method for producing an electronic component, comprising the following steps:

1. (i) applying one or more electrically conductive layers on a substrate to obtain an electrically conductive substrate coating, the last applied electrically conductive layer representing the outer layer of the substrate coating;
2. (ii) applying an active coating, which is photoactive or light emitting, to the outer layer of the substrate coating;
3. (iii) applying an electrically conductive material to the active coating through a liquid deposition medium;

wherein at least the outer layer of the substrate coating (ie the last layer applied in step (i) and in contact with the active coating) is soluble in the deposition medium or can be chemically modified by the deposition medium.

The electrically conductive layers of the substrate coating usually function as the first electrode and optionally as charge carrier-selective layers (electron and hole transport layers) of the electronic component. In step (iii), an electrically conductive material is applied to the active (i.e. photoactive or light emitting) coating via a liquid deposition medium. This electrically conductive material forms, for example, the second electrode or a further charge carrier-selective layer.

If there is a defect in the active coating of the electronic component, the liquid deposition medium can come into contact with the outer layer of the substrate coating. The liquid deposition medium used in step (iii) and the outer layer of the substrate coating applied in step (i) are matched to one another in such a way that the deposition medium dissolves or chemically modifies the deposition medium when there is appropriate contact. This in turn enables the electrical conductivity of the substrate coating in the defect areas of the active coating to be modified in a targeted manner. In the context of the present invention, the liquid deposition medium used in step (iii) therefore has a dual function. On the one hand, it effects the application of a further functional layer (e.g. the second electrode or another charge carrier-selective layer), on the other hand it can cause a targeted modification of the electrical conductivity of the substrate coating in the areas in which the active coating has defects.

• - ist zumindest eine der elektrisch leitfähigen Schichten der Substratbeschichtung eine Schicht aus einem selbstpassivierenden Metall, einem selbstpassivierenden Halbleiter oder einem elektrisch leitfähigen Metalloxid,
• - ist die Außenschicht der Substratbeschichtung in dem flüssigen Abscheidungsmedium löslich und
• - liegt die Außenschicht der Substratbeschichtung direkt auf der Schicht aus dem selbstpassivierenden Metall, selbstpassivierenden Halbleiter oder elektrisch leitfähigen Metalloxid vor oder weist die Substratbeschichtung eine oder mehrere elektrisch leitfähige Zwischenschichten zwischen der Schicht aus dem selbstpassivierenden Metall, selbstpassivierenden Halbleiter oder elektrisch leitfähigen Metalloxid und der Außenschicht auf und jede der Zwischenschichten ist in dem flüssigen Abscheidungsmedium löslich.

In a preferred embodiment

• at least one of the electrically conductive layers of the substrate coating is a layer made of a self-passivating metal, a self-passivating semiconductor or an electrically conductive metal oxide,
• - The outer layer of the substrate coating is soluble in the liquid deposition medium and
• - Is the outer layer of the substrate coating directly on the layer of self-passivating metal, self-passivating semiconductor or electrically conductive metal oxide or does the substrate coating have one or more electrically conductive intermediate layers between the layer of self-passivating metal, self-passivating semiconductor or electrically conductive metal oxide and the outer layer and each of the intermediate layers is soluble in the liquid deposition medium.

As is known to the person skilled in the art, self-passivating metals or semiconductors are those metals or semiconductors which can spontaneously form a passivating, very thin oxide layer in air at room temperature (25 ° C.).

Suitable self-passivating metals are in particular aluminum, titanium, nickel, chromium, zinc, lead or zirconium or an alloy of one of these metals. Aluminum or an aluminum alloy is particularly preferred as the self-passivating metal.

A suitable self-passivating semiconductor is, for example, silicon.

A suitable electrically conductive metal oxide is in particular a titanium oxide or a chromium oxide. A titanium oxide is particularly preferred.

If the liquid deposition medium used in step (iii) comes in via defective areas of the active coating in contact with the substrate coating, this substrate coating is thus dissolved in these contact areas until the self-passivating metal or semiconductor layer or the layer made of the electrically conductive metal oxide (in particular a titanium oxide) is exposed.

After being exposed, the self-passivating metal or semiconductor layer spontaneously forms a thin, electrically insulating oxide film, which prevents short circuits in the finished electronic component. Even after its exposure, the metal (for example Al or an Al alloy) or the semiconductor (for example Si) is due to the spontaneously formed surface oxide layer compared to the electrically conductive material (for example an electrically conductive polymer such as PEDOT) applied in step (iii): PSS) electrically isolated, which prevents short circuits.

Due to the formation of the superficial oxide film, the self-passivating metal or semiconductor layer is also protected from being dissolved by the liquid deposition medium used in step (iii). The layer of self-passivating metal or semiconductor is therefore not or only partially detached by the liquid deposition medium used in step (iii) (until the protective surface oxide film has formed).

If the layer of the electrically conductive metal oxide (in particular a titanium oxide) is exposed, this metal oxide comes into contact with the electrically conductive material applied in step (iii), for example an electrically conductive polymer such as PEDOT: PSS. Since both materials, i.e. the metal oxide (in particular a titanium oxide) and the polymer (e.g. PEDOT: PSS) as such are electrically conductive, it would be expected that short circuits would form in these contact areas. However, it has surprisingly been found that the electrical component nevertheless has a high short-circuit strength.

The layer of self-passivating metal is applied, for example, by physical vapor deposition (e.g. sputtering, thermal evaporation, electron beam evaporation), chemical vapor deposition (CVD), electrochemical or galvanic deposition or in the form of a film (which can be rolled or not rolled) . The layer made of the self-passivating metal is particularly preferably applied by physical vapor deposition.

The layer made of the self-passivating semiconductor, in particular silicon, is applied, for example, by physical vapor deposition (e.g. sputtering, thermal evaporation) or chemical vapor deposition (preferably plasma-assisted vapor deposition).

The layer made of the electrically conductive metal oxide, in particular a titanium oxide, is applied, for example, via chemical vapor deposition, physical vapor deposition (e.g. sputtering) or deposition via a liquid phase (e.g. via a rotary coating, an immersion process, a spraying process, a wet chemical deposition) .

The layer made of the self-passivating metal, the self-passivating semiconductor or the electrically conductive metal oxide can be applied directly to the substrate. Alternatively, it is also possible to first create one or more electrically conductive layers (e.g. one or more adhesion promoter layers made of a metal oxide (e.g. a doped zinc oxide such as AZO) or a metal (e.g. Cr, Ni), one or more layers made of a non-self-passivating metal ( such as Cu or Ag), an electrically conductive polymer or a transparent, electrically conductive oxide (e.g. an indium tin oxide) on the substrate and only then apply the layer of self-passivating metal, the self-passivating semiconductor or the electrically conductive metal oxide Electrically conductive metal oxide (preferably a titanium oxide) is preferably present on a layer of silver or a TCO.

Suitable substrates for the application of electrically conductive layers in electronic components are known to the person skilled in the art. Typically, the substrate is electrically non-conductive (i.e. an electrical insulator). The substrate can optionally be optically transparent. For example, the substrate is a plastic, glass or ceramic substrate.

Suitable layer thicknesses for the electrically conductive layers in an electronic component such as e.g. a solar cell or a light-emitting diode are known to the person skilled in the art. The layer made of the self-passivating metal, the self-passivating semiconductor or the electrically conductive metal oxide has, for example, a thickness in the range from 0.1 nm to 400 nm. If the layer is to be transparent or semi-transparent, a layer thickness in the range of 0.1-20 nm, more preferably 1-20 nm, more preferably 5-10 nm is preferably selected.

The outer layer of the substrate coating which is soluble in the liquid deposition medium is, for example, a layer of a metal oxide which is optionally doped, or a metal sulfide or a layer which contains an electrically conductive polymer, or a dipole layer.

The metal oxide that is soluble in the liquid deposition medium is, for example, a transparent, electrically conductive metal oxide (“transparent conductive oxides”, “TCOs”). Such oxides, known as TCO, are known to the person skilled in the art. The metal oxide which is soluble in the deposition medium is preferably a zinc oxide which is optionally doped, for example with aluminum, indium or gallium or a combination of at least two of these doping elements.

The metal sulfide soluble in the liquid deposition medium is, for example, a zinc sulfide.

If the outer layer soluble in the liquid deposition medium contains an electrically conductive polymer, this is, for example, a polythiophene (e.g. poly-3,4-ethylenedioxythiophene (PEDOT), optionally in combination with another component such as a polystyrene sulfonate (PEDOT: PSS)); a polytriarylamine (PTAA); a polyethyleneimine (PEI); an ethoxylated polyethyleneimine (PEIE) or a polyfluorene (e.g. poly [(9,9-bis (3 '- (N, N-dimethylamino) propyl) -2,7-fluorenes) -alt-2,7- (9.9 -dioctylfluorenes)]).

The outer layer of the substrate coating, which is soluble in the liquid deposition medium, is applied, for example, by chemical vapor deposition (for example ALD; atomic layer deposition process), physical vapor deposition (for example sputtering) or deposition via a liquid phase (for example via a rotary coating). a dipping process, a spray process, a wet chemical deposition).

As already mentioned above, the outer layer soluble in the liquid deposition medium can be present directly on the layer made of the self-passivating metal (preferably Al or an Al alloy), the self-passivating semiconductor (preferably Si) or the electrically conductive metal oxide (preferably a titanium oxide) alternatively, one or more electrically conductive intermediate layers can be present between the layer of the self-passivating metal, the self-passivating semiconductor or the electrically conductive metal oxide and the outer layer, each of the intermediate layers also being soluble in the liquid deposition medium. With regard to suitable materials for the formation of such an intermediate layer, reference can be made to the above-mentioned materials of the outer layer (e.g. an intermediate layer made of an optionally doped metal oxide or a metal sulfide or an intermediate layer which contains an electrically conductive polymer).

With regard to suitable deposition methods for the formation of such an intermediate layer, reference can also be made to the abovementioned deposition methods for the outer layer (in particular chemical or physical vapor deposition or deposition via a liquid phase).

The layer thickness of the outer layer and, if present, an intermediate layer is in each case, for example, 0.1-100 nm, more preferably 0.1-50 nm, even more preferably 0.1-20 nm.

The layer of self-passivating metal or semiconductor and the intermediate layer or outer layer present thereon are preferably applied in such a way that the formation of a surface oxide film on the self-passivating metal or semiconductor does not take place or only to a very small extent.

For example, the layer made of the self-passivating metal or self-passivating semiconductor and the intermediate layer or outer layer present thereon are applied under vacuum or an inert or reducing atmosphere.

If necessary, the layer of self-passivating metal or semiconductor can be subjected to a depassivation before the application of the next layer (i.e. an intermediate layer or the outer layer) in order to remove any surface oxide layer that may have formed. The depassivation treatment can e.g. by treatment with an alkaline medium, by plasma treatment or ion implantation.

In a preferred embodiment, the layer of self-passivating metal or self-passivating semiconductor and the outer layer thereon or, if present, intermediate layer are applied by physical vapor deposition under vacuum (in particular sputtering), the application of these layers preferably in the same deposition device without breaking the vacuum he follows.

As already mentioned above, the electrically conductive layers that form the substrate coating act, for example, as a first electrode and optionally as hole or electron transport layers of the electronic component.

After in step (i) the substrate coating, which contains at least one layer of a self-passivating metal, self-passivating semiconductor or electrically conductive metal oxide and an outer layer which is soluble in the liquid deposition medium and optionally one or more intermediate layers which are likewise soluble in the liquid deposition medium, was applied, the active ones are applied in step (ii) Coating on the substrate coating. The active coating is photoactive (e.g. solar cell) or light-emitting (e.g. organic light emitting diode).

Depending on the type of electronic component to be produced, the person skilled in the art knows which materials can be used for the photoactive or light-emitting coating. The electronic component is, for example, an organic solar cell, an inorganic thin-film solar cell, a perovskite solar cell or an organic light-emitting diode (OLED).

The photoactive coating of an organic solar cell can contain, for example, an organic, in particular a polymeric acceptor component and / or an organic, in particular polymeric donor component. An overview of suitable materials for the photoactive coating of an organic solar cell is provided, for example, by A. Facchetti, Materials Today, 16, April 2013, pp. 123-132.

The photoactive coating of an inorganic thin-film solar cell contains, for example, cadmium telluride, copper indium gallium diselenide or amorphous or polycrystalline silicon.

The active coating is applied using methods known to those skilled in the art, e.g. a printing process (such as flexographic printing, pad printing, gravure printing, inkjet printing, aerosol printing), a casting such as slot die casting or curtain casting, a spray coating, a rotary coating, a dip coating, a physical vapor deposition or a chemical vapor deposition (e.g. a plasma-assisted chemical vapor deposition).

In step (iii), an electrically conductive material is applied to the active coating by a liquid deposition medium.

The electrically conductive material applied in step (iii) functions in the electronic component, for example, as a second electrode or as a hole or electron transport layer. The electrically conductive material is preferably a polymer, a transparent, electrically conductive oxide (TCO) such as e.g. an indium tin oxide (ITO), a carbon-based material (e.g. carbon black, graphite, graphene or carbon nanotubes) or silver. In a particularly preferred embodiment, the electrically conductive material applied in step (iii) is an electrically conductive polymer.

Electrically conductive polymers which can act as an electrode or as a charge carrier-selective transport layer are known to the person skilled in the art. For example, the electrically conductive polymer is a polythiophene (e.g. poly-3,4-ethylenedioxythiophene (PEDOT), optionally in combination with another component such as e.g. a polystyrene sulfonate (PEDOT: PSS)); a polytriarylamine (PTAA); a polyethyleneimine (PEI); an ethoxylated polyethyleneimine (PEIE) or a polyfluorene (e.g. poly [(9,9-bis (3 '- (N, N-dimethylamino) propyl) -2,7-fluorenes) -alt-2,7- (9.9 -dioctylfluorenes)]).

The electrically conductive material or a precursor of this electrically conductive material is preferably dissolved or dispersed in the liquid deposition medium.

The liquid deposition medium is, for example, an aqueous deposition medium or a deposition medium that contains one or more organic solvents (for example an alcohol). The person skilled in the art can choose a suitable liquid in which the outer layer of the substrate coating is soluble, on the basis of his general specialist knowledge. The liquid deposition medium can optionally contain a surfactant.

If there is a defect in the active coating of the electronic component, the liquid coating medium can come into contact with the outer layer of the substrate coating. The deposition medium used in step (iii) and the outer layer applied in step (i) and the optional intermediate layer of the substrate coating are matched to one another such that, when there is appropriate contact, the deposition medium dissolves the outer layer and, if present, the intermediate layer.

Preferably, the liquid (e.g. aqueous) deposition medium has an acidic pH (e.g. in the range 0-4, more preferably 0.5-3) or a basic pH. The acidic or basic pH of the liquid deposition medium can promote the dissolution of the outer layer (for example a metal oxide such as doped or undoped zinc oxide) and, if present, the intermediate layers.

After step (iii), further deposition steps can optionally be carried out, in which further electrically conductive layers are applied.

• - ist zumindest eine der elektrisch leitfähigen Schichten der Substratbeschichtung eine Schicht aus einem nicht selbstpassivierenden Metall,
• - ist die Außenschicht der Substratbeschichtung in dem flüssigen Abscheidungsmedium löslich,
• - liegt die Außenschicht der Substratbeschichtung direkt auf der Schicht aus dem nicht selbstpassivierenden Metall vor oder weist die Substratbeschichtung eine oder mehrere elektrisch leitfähige Zwischenschichten zwischen der Schicht aus dem nicht selbstpassivierenden Metall und der Außenschicht auf und jede der Zwischenschichten ist in dem flüssigen Abscheidungsmedium löslich, und
• - ist das nicht selbstpassivierende Metall durch das flüssige Abscheidungsmedium oxidierbar.

According to another preferred embodiment

• at least one of the electrically conductive layers of the substrate coating is a layer made of a non-self-passivating metal,
• the outer layer of the substrate coating is soluble in the liquid deposition medium,
• - the outer layer of the substrate coating is directly on the layer of the non-self-passivating metal or the substrate coating has one or more electrically conductive intermediate layers between the layer of the non-self-passivating metal and the outer layer and each of the intermediate layers is soluble in the liquid deposition medium, and
• - The non-self-passivating metal can be oxidized by the liquid deposition medium.

The non-self-passivating metal is, for example, copper, silver, gold or iron or an alloy of one of these metals.

With regard to suitable methods for applying the layer of the non-self-passivating metal, reference can be made to the methods described above for applying the self-passivating metal layer, in particular physical vapor deposition (e.g. sputtering, thermal evaporation, electron beam evaporation), chemical vapor deposition (CVD), one electrochemical or galvanic deposition or application in the form of a film.

With regard to a suitable outer layer and, if present, suitable intermediate layers, reference can also be made to the above statements, i.e. a layer of a metal oxide that is optionally doped, or a metal sulfide or a layer that contains an electrically conductive polymer, or a dipole layer.

The layer of the non-self-passivating metal can be applied directly to the substrate. Alternatively, it is also possible to first create one or more electrically conductive layers (e.g. one or more adhesion promoter layers made of a metal oxide (e.g. a doped zinc oxide such as AZO) or a metal (e.g. Cr, Ni), one or more layers made of a non-self-passivating metal ( for example Cu or Ag), an electrically conductive polymer or a transparent, electrically conductive oxide (for example an indium tin oxide)) on the substrate and only then apply the layer of the non-self-passivating metal. Suitable substrates for the application of electrically conductive layers in electronic components are known to the person skilled in the art. Typically, the substrate is electrically non-conductive (i.e. an electrical insulator). The substrate can optionally be optically transparent. For example, the substrate is a plastic, glass or ceramic substrate.

Regarding step (ii), i.e. Application of the active coating can also be made to the above statements.

In step (iii), in this preferred embodiment, a liquid deposition medium is used which, with appropriate contact (ie in defective areas of the active coating), can not only dissolve the outer layer and, if present, the intermediate layers, but also the layer made of the non-self-passivating one Can at least superficially oxidize metal in the exposed areas.

The liquid, preferably aqueous, deposition medium preferably has a pH value that is set such that the layer of the non-self-passivating metal forms an oxide film on its surface when it comes into contact with the liquid deposition medium (that is, if there are defects in the active coating). Suitable pH values can be determined using Pourbaix diagrams (also referred to as potential pH diagrams). In Pourbaix diagrams, reduction potentials of half reactions, each for different oxidation levels of an element, are shown graphically depending on the pH value. The person skilled in the art can thus determine the pH conditions under which an oxide film forms on the surface of a metal.

In addition, the liquid deposition medium can contain at least one oxidizing agent, which can convert the non-self-passivating metal into an oxidized compound. The oxidizing agent is e.g. an oxidizing acid (e.g. nitric acid or sulfuric acid) or lye. The oxidized compound of the non-self-passivating metal is in particular a compound with one or more elements from group 14 (for example C or Si), group 15 (for example N or P), group 16 (O or S) and / or group 17 (for example F , Cl, Br or I) of the Periodic Table of the Elements (IUPAC 2016).

With regard to suitable electrically conductive materials that can be applied in step (iii) with the liquid aqueous deposition medium, reference can be made to the above statements, i.e. the electrically conductive material is preferably a polymer, a transparent, electrically conductive oxide (TCO) such as e.g. an indium tin oxide (ITO), a carbon-based material (e.g. carbon black, graphite, graphene or carbon nanotubes) or silver. The electrically conductive material applied in step (iii) functions in the electronic component, for example, as a second electrode or as a hole or electron transport layer. The electrically conductive material or a precursor of this electrically conductive material is preferably dissolved or dispersed in the liquid deposition medium.

According to a further preferred embodiment, all layers are Substrate coating (ie the outer layer and, if present, all further layers between the outer layer and the substrate) is soluble in the liquid deposition medium.

In this preferred embodiment, in the areas in which the active coating has defects, the underlying substrate coating can be removed down to the substrate. As mentioned above, the substrate is usually formed by an electrically non-conductive material (e.g. a plastic, glass or ceramic substrate). Since only small-area defects are usually present in the active coating, the functionality of the electronic component is not significantly restricted by the removal of the substrate coating lying below these defects.

With regard to suitable layers of the substrate coating and a suitable liquid deposition medium, which are coordinated with one another in such a way that these layers dissolve upon appropriate contact (that is, when there are defects in the active coating) with the deposition medium, reference can be made to the above statements.

In the preferred embodiments described above, the outer layer and, if present, the at least one intermediate layer of the substrate coating applied in step (i) and the liquid deposition medium used in step (iii) were coordinated with one another in such a way that, with appropriate contact, the outer layer and the optional intermediate layers be dissolved in the liquid deposition medium. Alternatively, it is also possible within the scope of the present invention that the liquid coating medium does not dissolve the outer layer with appropriate contact (i.e. in the case of defects in the active coating), but rather chemically modifies it.

The chemical modification increases the electrical contact resistance in the areas where the active coating is defective, so that a short circuit is prevented.

The chemical modification of the outer layer upon contact with the deposition medium can be, for example, an oxidation or a change in the chemical composition.

For example, the outer layer is a layer made of a metal and the pH of the liquid, preferably aqueous, coating medium is set such that an oxide film is formed on the surface of the metal layer when there is appropriate contact. As already mentioned above, suitable pH values can be determined using Pourbaix diagrams.

The metal that can be oxidized by contact with the liquid coating medium is e.g. Copper, silver, gold or iron or an alloy of one of these metals.

In addition, the liquid coating medium can contain an oxidizing agent, so that when the coating medium comes into contact with the outer layer of the substrate coating, the outer layer is at least superficially oxidized in the contact area. The oxidizing agent is e.g. an oxidizing acid (e.g. nitric acid or sulfuric acid) or lye.

Furthermore, it is possible within the scope of the present invention that the outer layer of the substrate coating contains a semiconductor, the degree of doping of which changes on contact with the liquid coating medium at least in this contact area.

For example, the liquid coating medium contains a dopant that can diffuse into the outer layer of the substrate coating. Alternatively, it is also possible for the outer layer to contain a doped semiconductor and for the dopants of the doped semiconductor to diffuse into the coating medium at least in this contact region when in contact with the liquid coating medium (that is to say “released” by the coating medium from the outer layer formed by the doped semiconductor. become).

The present invention further relates to an electronic component which can be obtained by one of the methods described above.

1. (a) ein Substrat,
2. (b) eine auf dem Substrat vorliegende elektrisch leitfähige Substratbeschichtung, die mindestens zwei Schichten S1 und S2 aufweist, wobei
   • - die Schicht S2 die Außenschicht der Substratbeschichtung ist,
   • - die Schicht S2 direkt auf der Schicht S1 vorliegt oder die Schicht S2 auf einer Zwischenschicht S3 vorliegt und die Zwischenschicht S3 auf der Schicht S1 vorliegt,
   • - die Schicht S1 eine Schicht aus einem selbstpassivierenden Metall oder einem selbstpassivierenden Halbleiter ist,
   • - die Schicht S2 und, sofern vorhanden, die Schicht S3 eine Schicht aus einem Zinkoxid, das optional dotiert ist, oder einem Zinksulfid oder eine Schicht, die ein elektrisch leitfähiges Polymer enthält, ist,
3. (c) eine auf der Schicht S2 vorliegende aktive Beschichtung, die photoaktiv oder lichtemittierend ist,
4. (d) eine auf der aktiven Beschichtung vorliegende elektrisch leitfähige Schicht S4, wobei die Schicht S4 eine Schicht ist, die ein elektrisch leitfähiges Polymer, ein transparentes, elektrisch leitfähiges Oxid (z.B. ein Indiumzinnoxid), ein Kohlenstoff-basiertes Material (z.B. Ruß, Graphit, Graphen oder Kohlenstoffnanoröhren) oder metallisches Silber enthält.

In a preferred embodiment, the electronic component of the present invention contains

1. (a) a substrate,
2. (b) an electrically conductive substrate coating which is present on the substrate and has at least two layers S1 and S2, wherein
   • layer S2 is the outer layer of the substrate coating,
   • the layer S2 is present directly on the layer S1 or the layer S2 is present on an intermediate layer S3 and the intermediate layer S3 is present on the layer S1,
   • the layer S1 is a layer made of a self-passivating metal or a self-passivating semiconductor,
   • - layer S2 and, if present, layer S3 is a layer of a zinc oxide which is optionally doped, or a zinc sulfide or a layer which contains an electrically conductive polymer,
3. (c) an active coating which is present on layer S2 and is photoactive or light-emitting,
4. (d) an electrically conductive layer S4 present on the active coating, the layer S4 being a layer which is an electrically conductive polymer, a transparent, electrically conductive oxide (for example an indium tin oxide), a carbon-based material (for example carbon black, graphite) , Graphene or carbon nanotubes) or metallic silver.

Layer S1 is preferably a layer made of aluminum or an aluminum alloy.

With regard to suitable electrically conductive polymers for the outer layer S2 and / or the optional intermediate layer S3, reference can be made to the above statements.

If the zinc oxide is doped, aluminum, indium or gallium or a combination of at least two of these doping elements can be used, for example.

If present, the intermediate layer S3 is preferably a layer made of a doped zinc oxide, in particular a zinc oxide, which is doped with aluminum, indium or gallium or a combination of at least two of these doping elements. As already mentioned above, the material for the outer layer S2 of the substrate coating is selected from an electrically conductive polymer, a zinc oxide, which is optionally doped, and a zinc sulfide.

With regard to suitable electrically conductive polymers for layer S4, reference can also be made to the above statements.

With regard to a suitable substrate, reference can be made to the above statements.

With regard to suitable photoactive or light-emitting coatings for electronic components such as solar cells or light-emitting diodes, reference can be made to the above statements.

The layer S1 can be present directly on the substrate. Alternatively, it may be preferred for one or more electrically conductive adhesion promoter layers to be present between the layer S1 and the substrate. Suitable adhesion promoter layers are known to the person skilled in the art. The adhesive layer is, for example, a layer made of a metal (e.g. Cr or Ni or an alloy of one of these metals).

1. (a) ein Substrat,
2. (b) eine auf dem Substrat vorliegende elektrisch leitfähige Substratbeschichtung, die mindestens zwei Schichten S1 und S2 aufweist, wobei
   • - die Schicht S2 die Außenschicht der Substratbeschichtung ist,
   • - die Schicht S2 direkt auf der Schicht S1 vorliegt oder die Schicht S2 auf einer Zwischenschicht S3 vorliegt und die Zwischenschicht S3 auf der Schicht S1 vorliegt,
   • - die Schicht S1 eine Schicht aus einem Titanoxid ist,
   • - die Schicht S2 und, sofern vorhanden, die Schicht S3 eine Schicht aus einem Zinkoxid, das optional dotiert ist, oder einem Zinksulfid oder eine Schicht, die ein elektrisch leitfähiges Polymer enthält, ist,
3. (c) eine auf der Schicht S2 vorliegende aktive Beschichtung, die photoaktiv oder lichtemittierend ist,
4. (d) eine auf der aktiven Beschichtung vorliegende elektrisch leitfähige Schicht S4, wobei die Schicht S4 eine Schicht ist, die ein elektrisch leitfähiges Polymer enthält.

In another preferred embodiment, the electronic component of the present invention includes

1. (a) a substrate,
2. (b) an electrically conductive substrate coating which is present on the substrate and has at least two layers S1 and S2, wherein
   • layer S2 is the outer layer of the substrate coating,
   • the layer S2 is present directly on the layer S1 or the layer S2 is present on an intermediate layer S3 and the intermediate layer S3 is present on the layer S1,
   • the layer S1 is a layer made of a titanium oxide,
   • the layer S2 and, if present, the layer S3 is a layer of a zinc oxide which is optionally doped, or a zinc sulfide or a layer which contains an electrically conductive polymer,
3. (c) an active coating which is present on layer S2 and is photoactive or light-emitting,
4. (d) an electrically conductive layer S4 present on the active coating, the layer S4 being a layer containing an electrically conductive polymer.

If the zinc oxide is doped, aluminum, indium or gallium or a combination of at least two of these doping elements can be used, for example.

If present, the intermediate layer S3 is preferably a layer made of a doped zinc oxide, in particular a zinc oxide, which is doped with aluminum, indium or gallium or a combination of at least two of these doping elements. As already mentioned above, the material for the outer layer S2 is selected from an electrically conductive polymer, a zinc oxide, which is optionally doped, and a zinc sulfide.

With regard to suitable electrically conductive polymers for layer S4, reference can be made to the above statements. In a preferred embodiment, layer S4 contains a polythiophene (e.g. poly-3,4-ethylenedioxythiophene (PEDOT), optionally in combination with another component such as a polystyrene sulfonate (PEDOT: PSS)).

With regard to a suitable substrate, reference can be made to the above statements.

With regard to suitable photoactive or light-emitting coatings for electronic components such as solar cells or light-emitting diodes, reference can be made to the above statements.

The layer S1 can be present directly on the substrate. Alternatively, it may be preferred for one or more electrically conductive layers to be present between the layer S1 and the substrate. For example, the layer S1 is on a layer of a metal (preferably silver) and between this metal layer and the substrate there are one or more electrically conductive adhesive layers (e.g. one or more layers of a transparent, electrically conductive metal oxide).

1. (a) ein Substrat,
2. (b) eine auf dem Substrat vorliegende elektrisch leitfähige Substratbeschichtung, die mindestens zwei Schichten S1 und S2 aufweist, wobei
   • - die Schicht S2 die Außenschicht der Substratbeschichtung ist,
   • - die Schicht S2 direkt auf der Schicht S1 vorliegt oder die Schicht S2 auf einer Zwischenschicht S3 vorliegt und die Zwischenschicht S3 auf der Schicht S1 vorliegt,
   • - die Schicht S1 eine Schicht aus einem selbstpassivierenden Metall oder einem selbstpassivierenden Halbleiter ist,
   • - die Schicht S2 eine Schicht aus einem elektrisch leitfähigen Material LM2 und, sofern vorhanden, die Schicht S3 eine Schicht aus einem elektrisch leitfähigen Material LM3 ist,
3. (c) eine auf der Schicht S2 vorliegende aktive Beschichtung, die photoaktiv oder lichtemittierend ist,
4. (d) eine auf der aktiven Beschichtung vorliegende elektrisch leitfähige Schicht S4 aus einem elektrisch leitfähigen Material LM4,

wobei
die aktive Beschichtung und die äußerste Schicht S2 sowie, wenn vorhanden, die Zwischenschicht S3 der Substratbeschichtung jeweils mindestens einen Bereich aufweisen, der das elektrisch leitfähige Material LM4 enthält,
die Schicht S1 aus dem selbstpassivierenden Metall oder selbstpassivierenden Halbleiter auf der der aktiven Beschichtung zugewandten Seite mindestens einen oxidierten Bereich aufweist, in dem die Schicht S1 oberflächlich oxidiert ist,
der oxidierte Bereich der Schicht S1 aus dem selbstpassivierenden Metall oder selbstpassivierenden Halbleiter an den das elektrisch leitfähige Material LM4 enthaltenden Bereich der äußersten Schicht S2 oder, sofern vorhanden, der Zwischenschicht S3 grenzt.Furthermore, the present invention relates to an electronic component containing

1. (a) a substrate,
2. (b) an electrically conductive substrate coating which is present on the substrate and has at least two layers S1 and S2, wherein
   • layer S2 is the outer layer of the substrate coating,
   • the layer S2 is present directly on the layer S1 or the layer S2 is present on an intermediate layer S3 and the intermediate layer S3 is present on the layer S1,
   • the layer S1 is a layer made of a self-passivating metal or a self-passivating semiconductor,
   • the layer S2 is a layer of an electrically conductive material LM2 and, if present, the layer S3 is a layer of an electrically conductive material LM3,
3. (c) one on the layer S2 present active coating that is photoactive or light-emitting,
4. (d) an electrically conductive layer S4 of an electrically conductive material LM4 present on the active coating,

in which
the active coating and the outermost layer S2 and, if present, the intermediate layer S3 of the substrate coating each have at least one region which contains the electrically conductive material LM4,
the layer S1 made of the self-passivating metal or self-passivating semiconductor has at least one oxidized area on the side facing the active coating, in which the layer S1 is oxidized on the surface,
the oxidized area of the layer S1 made of the self-passivating metal or self-passivating semiconductor borders on the area of the outermost layer S2 containing the electrically conductive material LM4 or, if present, the intermediate layer S3.

As already mentioned above, suitable substrates for the application of electrically conductive layers in electronic components are known to the person skilled in the art. Typically, the substrate is electrically non-conductive (i.e. an electrical insulator). The substrate can optionally be optically transparent. For example, the substrate is a plastic, glass or ceramic substrate.

Suitable self-passivating metals are in particular aluminum, titanium, nickel, chromium, zinc, lead or zirconium or an alloy of one of these metals. Aluminum or an aluminum alloy is particularly preferred as the self-passivating metal.

A suitable self-passivating semiconductor is, for example, silicon.

The layer S1 made of the self-passivating metal or semiconductor can be present directly on the substrate. Alternatively, it is also possible to first coat one or more electrically conductive layers (e.g. at least one layer made of a non-self-passivating metal such as Cu or Ag, an electrically conductive polymer or a transparent, electrically conductive oxide (TCO) such as an indium tin oxide (ITO)) to be applied to the substrate and only then to apply the layer S1 made of the self-passivating metal or semiconductor.

The self-passivating metal or semiconductor layer S1 has, for example, a thickness in the range from 0.1 nm to 400 nm. If the self-passivating metal or semiconductor layer S1 is to be transparent or semitransparent, a layer thickness in the range of 0.1-20 nm, more preferably 1-20 nm, more preferably 5-10 nm is preferably selected.

The electrically conductive material LM2 of the outermost layer S2 (hereinafter also referred to as the outer layer) of the electrically conductive substrate coating is, for example, a metal oxide, which is optionally doped, or an electrically conductive polymer.

The metal oxide of the outer layer S2 is, for example, a transparent, electrically conductive metal oxide ("transparent conductive oxides", "TCOs"). Such oxides, known as TCO, are known to the person skilled in the art. This is preferred Metal oxide is a zinc oxide that is optionally doped, for example with aluminum, indium or gallium or a combination of at least two of these doping elements.

If the electrically conductive material LM2 of the outer layer S2 of the substrate coating is an electrically conductive polymer, this is, for example, a polythiophene (for example poly-3,4-ethylenedioxythiophene (PEDOT), optionally in combination with another component such as a polystyrene sulfonate (PEDOT: PSS)); a polytriarylamine (PTAA); a polyethyleneimine (PEI); an ethoxylated polyethyleneimine (PEIE) or a polyfluorene (e.g. poly [(9,9-bis (3 '- (N, N-dimethylamino) propyl) -2,7-fluorenes) -alt-2,7- (9.9 -dioctylfluorenes)]).

The outer layer S2 of the substrate coating can be present directly on the self-passivating metal or semiconductor layer S1. Alternatively, an intermediate layer S3 made of an electrically conductive material LM3 can be present between the layer S1 made of the self-passivating metal or semiconductor and the outer layer S2. With regard to suitable materials for the formation of such an intermediate layer S3, reference can be made to the above-mentioned materials of the outer layer S2 (e.g. an intermediate layer made of an optionally doped metal oxide such as AZO or a metal sulfide or an intermediate layer which contains an electrically conductive polymer).

If present, the intermediate layer S3 is preferably a layer made of a zinc oxide which is doped with aluminum, gallium or indium or a combination of at least two of these doping elements.

The layer thickness of the outer layer S2 and, if present, an intermediate layer S3 is in each case, for example, 0.1-100 nm, more preferably 0.1-50 nm, even more preferably 0.1-20 nm.

Depending on the type of electronic component to be produced, the person skilled in the art knows which materials can be used for the photoactive or light-emitting coating. The electronic component is, for example, an organic solar cell, an inorganic thin-film solar cell, a perovskite solar cell or an organic light-emitting diode (OLED).

The photoactive coating of an organic solar cell can contain, for example, an organic, in particular a polymeric acceptor component and / or an organic, in particular polymeric donor component. An overview of suitable materials for the photoactive coating of an organic solar cell is provided, for example, by A. Facchetti, Materials Today, 16, April 2013, pp. 123-132.

The photoactive coating of an inorganic thin-film solar cell contains, for example, cadmium telluride, copper indium gallium diselenide or amorphous or polycrystalline silicon.

The electrically conductive material LM4, which forms the layer S4 present on the photoactive or light-emitting coating, functions in the electronic component, for example, as a second electrode or as a hole or electron transport layer. The electrically conductive material LM4 is preferably a polymer, a transparent, electrically conductive oxide (TCO) such as e.g. an indium tin oxide (ITO), a carbon-based material (e.g. carbon black, graphite, graphene or carbon nanotubes) or silver.

Electrically conductive polymers which can act as an electrode or as a charge carrier-selective transport layer are known to the person skilled in the art. For example, the electrically conductive polymer is a polythiophene (e.g. poly-3,4-ethylenedioxythiophene (PEDOT), optionally in combination with another component such as e.g. a polystyrene sulfonate (PEDOT: PSS)); a polytriarylamine (PTAA); a polyethyleneimine (PEI); an ethoxylated polyethyleneimine (PEIE) or a polyfluorene (e.g. poly [(9,9-bis (3 '- (N, N-dimethylamino) propyl) -2,7-fluorenes) -alt-2,7- (9.9 -dioctylfluorenes)]).

The electronic component is, for example, an organic solar cell, an inorganic thin-film solar cell, a perovskite solar cell or an organic light-emitting diode (OLED).

Due to the manufacturing process, the active (i.e. photoactive or light-emitting) coating of the electronic component can have one or more defective areas. The active coating is interrupted in the defective area, i.e. there is no photoactive or light-emitting material in the defective area. When the layer S4 formed from the electrically conductive material LM4 is applied, this material LM4 can partially or completely fill the defective areas. At least one area that contains the electrically conductive material LM4 is formed in the active coating.

As described above, in the event of a defective area of the active coating, the outer layer S2 and, if present, the intermediate layer S3 of the substrate coating in this defective area are detached during the production process and the underlying self-passivating metal (or the self-passivating semiconductor) of the layer S1 is exposed . This causes one superficial oxidation of the self-passivating layer S1 in the exposed area. Since the outer layer S2 and, if present, the intermediate layer S3 of the substrate coating below the defective area of the active coating have been removed, the electrically conductive material LM4 is now present in each of these areas.

In adjacent layers, the areas described above (i.e. the LM2-containing areas of the active coating, the outer coating and the optional intermediate layer and the oxidized area of the self-passivating layer) adjoin one another.

The oxidized area of the self-passivating metal or semiconductor layer S1 borders on the area of the outer layer S2 containing the electrically conductive material LM4 or, if present, the intermediate layer S3 of the substrate coating, i.e. these areas have a common interface.

In addition, the regions of the active coating and the outer layer S2, which contain the electrically conductive material LM4, adjoin one another.

The respective area of the areas of the active coating containing the electrically conductive material LM4, the outer layer S2 and the optional intermediate layer S3 as well as the oxidized area of the self-passivating layer S1 depends on the area of the defect which has arisen in the active coating during manufacture . The LM4-containing areas of the active coating, the outer layer and the optional intermediate layer and the oxidized area of the self-passivating layer can each have, for example, an area (in a plane parallel to the substrate surface) of less than 10 mm ² or less than 1 mm ² or less than Have 100 µm ² .

The invention is described in more detail with reference to the following examples.

Examples

example 1

In Example 1, an organic solar cell was manufactured as follows:

Glass was used as the substrate. A layer of aluminum (i.e. a layer of a self-passivating metal) was first deposited on this substrate and then a layer of an aluminum-doped zinc oxide (AZO) was subsequently deposited on the Al layer. Both layers were applied by sputtering in the same sputtering device without breaking the vacuum.

The aluminum layer and the AZO layer represent the substrate coating, the AZO layer being the outer layer of the substrate coating.

P3HT: PCBM was applied as a photoactive coating on the AZO layer. The photoactive coating was applied by spin coating.

PEDOT: PSS was then applied to the photoactive coating as an electrically conductive material. It was applied by means of an aqueous dispersion which contained PEDOT: PSS, that is to say an aqueous coating medium. The pH of the aqueous coating medium was 1.5. At this pH, AZO is soluble in an aqueous medium.

Comparative Example 1

Comparative example 1 differs from example 1 only in that a layer of silver was applied instead of the self-passivating aluminum layer. The substrate coating of Comparative Example 1 thus contains an Ag layer and an AZO layer functioning as an outer layer. The photoactive layer present on the AZO layer and the PEDOT: PSS layer present on the photoactive layer were applied under the conditions described in Example 1. Silver is neither a self-passivating metal nor can an Ag layer be oxidized by an aqueous medium with a pH of 1.5 (i.e. the pH of the aqueous PEDOT: PSS-containing deposition medium).

If the substrate coating has a layer of a self-passivating metal and an electrically conductive layer applied to it, which is soluble in the liquid deposition medium used in step (iii), short circuits are largely avoided.

This effect is from the 1 and 2 seen.

1 shows the current density as a function of voltage for the Al / AZO / PEDOT: PSS system, while 2 shows the current density as a function of voltage for the Ag / AZO / PEDOT: PSS system.

Out 2 it can be seen that when the first and second electrodes come into full contact, a short circuit occurs which is so strong that a solar cell of the same size can no longer deliver electrical power to a consumer if these surfaces are electrically connected to one another. Out 1 it can be seen that with the The method according to the invention and the layer sequence according to the invention obtained therewith can achieve an acceptable efficiency even if the short-circuited and the intact solar cell area are of the same size.

The research that led to this result was funded by the European Union.

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included 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.

Patent literature cited

• US 2010062550 A1 [0006]
• DE 10326546 A1 [0009]

Non-patent literature cited

• A. Oostra et al., Organic Electronics, 15, 2014, 1166-1172 [0007]
• P. Apilo et al., Prog. Photovolt.: Res. Appl., 2015, 23, pp. 918-928 [0008]
• T.R. Andersen et al., Solar Energy Materials & Solar Cells, 149, 2016, pp. 103-109 [0010]

Claims (15)

Method for producing an electronic component, comprising the following steps: (i) applying one or more electrically conductive layers on a substrate to obtain an electrically conductive substrate coating, the last applied electrically conductive layer representing the outer layer of the substrate coating; (ii) applying an active coating, which is photoactive or light emitting, to the outer layer of the substrate coating; (iii) applying an electrically conductive material to the active coating through a liquid deposition medium; wherein at least the outer layer of the substrate coating is soluble in the deposition medium or can be chemically modified by the deposition medium. Procedure according to Claim 1 , wherein at least one of the electrically conductive layers of the substrate coating is a layer of a self-passivating metal, a self-passivating semiconductor or an electrically conductive oxide, the outer layer of the substrate coating is soluble in the liquid deposition medium and the outer layer of the substrate coating is directly on the layer of the self-passivating metal , self-passivating semiconductor or electrically conductive oxide or the substrate coating has one or more electrically conductive intermediate layers between the layer of self-passivating metal, self-passivating semiconductor or electrically conductive oxide and the outer layer and each of the intermediate layers is soluble in the liquid deposition medium. Procedure according to Claim 2 , wherein the self-passivating metal is aluminum, titanium, nickel, chromium, zinc, lead or zircon or an alloy of one of these metals; the self-passivating semiconductor is silicon; and / or the electrically conductive metal oxide is a titanium oxide. The method of any one of the preceding claims, wherein the outer layer soluble in the liquid deposition medium and, if present, intermediate layer of the substrate coating is a layer of a metal oxide, optionally doped, or a metal sulfide, or a layer containing an electrically conductive polymer . Procedure according to Claim 4 , wherein the metal oxide is a zinc oxide which is optionally doped with aluminum, indium or gallium or a combination of at least two of these doping elements, or the metal sulfide is a zinc sulfide; or the electrically conductive polymer is a polythiophene, a polytriarylamine, a polyethyleneimine, an ethoxylated polyethyleneimine or a polyfluorene Procedure according to one of the Claims 2 - 5 , wherein the layer of self-passivating metal or self-passivating semiconductor and the intermediate layer or outer layer of the substrate coating applied thereon are applied by physical vapor deposition under vacuum, in particular sputtering, and the application of both layers takes place in the same deposition device without breaking the vacuum. Method according to one of the preceding claims, wherein the electrically conductive material applied in step (iii) is a polymer; a transparent, electrically conductive oxide; is a carbon-based material or silver; and / or wherein the liquid deposition medium has an acidic or basic pH. Procedure according to Claim 1 , wherein at least one of the electrically conductive layers of the substrate coating is a layer of a non-self-passivating metal, the outer layer of the substrate coating is soluble in the liquid deposition medium, the outer layer of the substrate coating is present directly on the layer of the non-self-passivating metal, or the substrate coating is one or more has electrically conductive intermediate layers between the layer of the non-self-passivating metal and the outer layer and each of the intermediate layers is soluble in the liquid deposition medium, and the non-self-passivating metal can be oxidized by the liquid deposition medium. Procedure according to Claim 8 , the non-self-passivating metal being copper, silver, gold or iron or an alloy of one of these metals. Procedure according to Claim 8 or 9 , wherein the liquid deposition medium has a pH value which is set such that the layer of the non-self-passivating metal forms an oxide film on its surface upon contact with the liquid deposition medium; and / or wherein the deposition medium contains at least one oxidizing agent. Procedure according to Claim 1 , wherein the outer layer of the substrate coating is a layer of a metal and the pH of the coating medium is adjusted so that the outer layer of the metal forms an oxide film on its surface upon contact with the liquid deposition medium. Procedure according to one of the Claims 1 - 11 , wherein the electronic component is a solar cell, in particular an organic solar cell, an inorganic thin-film solar cell or a perovskite solar cell, or an organic light-emitting diode. Electronic component containing (a) a substrate, (b) an electrically conductive substrate coating which is present on the substrate and has at least two layers S1 and S2, wherein layer S2 is the outer layer of the substrate coating, the layer S2 is present directly on the layer S1 or the layer S2 is present on an intermediate layer S3 and the intermediate layer S3 is present on the layer S1, the layer S1 is a layer made of a self-passivating metal or a self-passivating semiconductor, the layer S2 and, if present, the layer S3 is a layer of a zinc oxide which is optionally doped, or a zinc sulfide or a layer which contains an electrically conductive polymer, (c) an active coating which is present on layer S2 and is photoactive or light-emitting, (d) an electrically conductive layer S4 present on the active coating, the layer S4 being a layer which is an electrically conductive polymer, a transparent, electrically conductive oxide (for example an indium tin oxide), a carbon-based material (for example carbon black, graphite) , Graphene or carbon nanotubes) or metallic silver. Electronic component containing (a) a substrate, (b) an electrically conductive substrate coating which is present on the substrate and has at least two layers S1 and S2, wherein layer S2 is the outer layer of the substrate coating, the layer S2 is present directly on the layer S1 or the layer S2 is present on an intermediate layer S3 and the intermediate layer S3 is present on the layer S1, the layer S1 is a layer made of a titanium oxide, the layer S2 and, if present, the layer S3 is a layer of a zinc oxide which is optionally doped, or a zinc sulfide or a layer which contains an electrically conductive polymer, (c) an active coating which is present on layer S2 and is photoactive or light-emitting, (d) an electrically conductive layer S4 present on the active coating, the layer S4 being a layer containing an electrically conductive polymer. Electronic component containing (a) a substrate, (b) an electrically conductive substrate coating which is present on the substrate and has at least two layers S1 and S2, wherein layer S2 is the outer layer of the substrate coating, the layer S2 is present directly on the layer S1 or the layer S2 is present on an intermediate layer S3 and the intermediate layer S3 is present on the layer S1, the layer S1 is a layer made of a self-passivating metal or a self-passivating semiconductor, the layer S2 is a layer of an electrically conductive material LM2 and, if present, the layer S3 is a layer of an electrically conductive material LM3, (c) an active coating which is present on layer S2 and is photoactive or light-emitting, (d) an electrically conductive layer S4 of an electrically conductive material LM4 present on the active coating, in which the active coating and the outer layer S2 and, if present, the intermediate layer S3 of the substrate coating each have at least one region which contains the electrically conductive material LM4, the layer S1 made of the self-passivating metal or self-passivating semiconductor has at least one oxidized area on the side facing the active coating, in which the layer S1 is oxidized on the surface, the oxidized area of the layer S1 made of the self-passivating metal or self-passivating semiconductor borders on the area of the outermost layer S2 containing the electrically conductive material LM4 or, if present, the intermediate layer S3.

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