EP2043861A2

EP2043861A2 - Multilayered body comprising an electroconductive polymer layer and method for the production thereof

Info

Publication number: EP2043861A2
Application number: EP07801436A
Authority: EP
Inventors: Ulrich Schindler; Walter Lehnberger
Original assignee: Leonhard Kurz Stiftung and Co KG
Current assignee: Leonhard Kurz Stiftung and Co KG
Priority date: 2006-07-21
Filing date: 2007-07-19
Publication date: 2009-04-08
Also published as: US20100078065A1; WO2008009447A2; WO2008009447A3; US8388790B2

Abstract

The invention relates to a method for producing a multilayered body (4) comprising an electroconductive layer (421) arranged on a carrier layer (41). According to said method, a transfer film (5) comprising a transfer layer (52) consisting of an electroconductive polymer is provided. The electroconductive layer is transferred from the transfer film (5) to the multilayered body (4). The invention also relates to a transfer film and a multilayered body produced using said method.

Description

Multilayer body with conductive polymer layer

The invention relates to a multilayer body with an electrically conductive polymer layer, to a production method for this, and to a transfer film for producing the multilayer body.

Increasingly, conventional products and processes in the semiconductor industry have been replaced by products and processes using organic layers. Although organic semiconductors and conductors often do not meet all technical requirements, significant advances are emerging, for example in organic solar cells or polymer solar cells.

For the construction of organic solar cells are organic

Conductor tracks and electrode layers required whose electrical properties must be adjustable. It is known to electrochemically adjust the electrical conductivity of organic layers. However, this limits mass production according to the roll-to-roll process, which shifts to constant production conditions.

Electrically conductive polymers are often present as dispersions with a low solids content. Exactly such dispersions can be applied by Duckverfahren not or structured only with quality losses, because they usually have a water-like consistency.

The invention is based on the object to provide a multilayer body having electrically conductive organic layers, which are adjustable in their electrical properties without the use of chemical methods and a Specify a method suitable for mass production for the formation of structured electrically conductive organic layers.

The object of the invention is achieved by a method for producing a multilayer body having an electrically conductive layer arranged on a carrier layer, wherein it is provided that a transfer film is provided with a transfer layer having an electrically conductive polymer, and that the electrically conductive layer is transferred by transferring the transfer layer is formed by the transfer film on the multi-layer body. The object is further achieved with a transfer film, preferably an embossing film, with a carrier layer and an electrically conductive transfer layer, it being provided that the transfer layer has N electron-conducting layers and N + 1 electrically conductive polymer layers, wherein alternately an electrically conductive polymer layer and an electron-conducting Layer is arranged and N> 1. The object is further achieved with a multilayer body having a structured electrically conductive layer, it being provided that the electrically conductive layer comprises at least two electrically conductive polymer layers arranged one above the other.

With the method according to the invention, it is proposed to use a transfer film whose transfer layer is formed from an electrically conductive polymer.

Numerous quality problems are avoided in that the electrical properties of the electrically conductive layer are fundamentally adjusted during the preparation of the polymer dispersion and / or the production of the transfer film. In the transfer of the transfer layer to the multilayer body, in particular, the geometric properties of the electrically conductive layer are determined, i. its contour and its thickness. The contour of the electrically conductive layer can be formed by the transfer layer according to the invention with a high contour sharpness.

Further advantages result from the fact that a transfer film with a carrier layer and an electrically conductive transfer layer is provided, which has at least one electron-conducting layer in addition to the electrically conductive polymer layer. By this electron-conducting layer, the electrical conductivity of the transfer layer of the transfer film can be significantly increased, without having to sacrifice the advantages of easy transfer and the layered structure of conductive structures. For example, antennas for RFID transponders can be embossed, with the antennas being able to have good electrical efficiency because of the good conductivity of the transfer layer of the transfer film.

It is furthermore advantageous that the efficiency of the photovoltaic effect occurring in the organic semiconductor layer of an organic solar cell can be increased with the aid of the electron-conducting layers, for example by reducing the work function. If, for example, the electron-conducting layer is a thin semitransparent layer, then it can be further protected against oxidation in the composite, although the advantages such as transparency and optical conductivity are present.

The multilayer body according to the invention has an electrically conductive layer with precisely adjustable thickness, wherein the thickness tolerance is determined essentially by the thickness of the transfer layer. Thus, for example, the conductivity of the electrical layer is adjustable by the number of transmitted transfer layers. When n transfer layers are transferred, the electrically conductive layer formed in this way has the n-times conductivity of the transfer layer transferred in each manufacturing step. The resistance or area resistance can be calculated according to the equations of the parallel connection of resistors.

The transfer of the transfer layer from the transfer film to the multi-layer body may advantageously be provided in a roll-to-roll process. The multi-layer body may be a film body from which, after completion of the manufacturing process, sections are separated which are placed on the market.

Further advantageous features are designated in the subclaims. It can be provided that a non-filmed transfer layer is provided. A non-filmed transfer layer does not form a coherent film. The non-fused transfer layer has a powdery consistency when detached with the thumb sample from the carrier layer of the transfer film. This suggests the formation of predetermined breaking points in the transfer layer, which are caused by the fact that the transfer layer is applied from a dispersion and then the dispersant is expelled rapidly at a temperature of 30 to 40 ⁰ C. As a result, no coherent polymer film is formed and the adhesion to the carrier film is so small that the transfer layer is easily peeled off during transfer. A filmed transfer layer is not at all or only incompletely separable from the carrier film of the transfer film when releasing onto the multilayer body and / or can not be separated in an undefined manner.

It can further be provided that the transfer layer (52) is designed as a polymer transfer layer.

It may further be provided that a transfer layer is provided in which the electrically conductive polymer is concentrated in domains and the transfer layer is preferably separable along the domain boundaries. Electrically conductive polymers may be formed as mixtures of substances and have structures in which the electrically conductive polymer forms domains embedded in a matrix of a second polymer. The electrically conductive polymer may also be present in low concentration in the matrix. Conventional layers of the electrically conductive polymer form a tightly contiguous film which has no preferred breaking boundaries. By contrast, the transfer layer according to the invention can be an electrically conductive polymer layer in which the domain boundaries serve as predetermined breaking points, so that the transfer layer can be transferred in a structured manner. The domains may, for example, in plan view, have a cigar-shaped profile with the dimensions 500 nm X 1000 nm. However, they may also be circular domains, wherein the thickness of the domains may be determined essentially by the thickness of the transfer layer. The domains can So be formed a flat shape.

It can be provided that the electrically conductive layer is formed from one or more superimposed transmission beams by structured embossing of the transfer film onto the multi-layer body. In this case, the hot stamping may be preferred. About the surface geometry of the die can be determined in a simple manner, the surface geometry of the electrically conductive layer. Very high resolutions and very high register accuracy can be achieved here. The limits of the resolution are determined essentially by the size of the domains of the transfer layer of the transfer film.

In a further advantageous embodiment, it is provided that the electrically conductive layer is formed from one or more superposed transfer layers by thermal transfer printing on the multi-layer body. It can be provided that the transfer film a

Wax release layer between transfer layer and carrier film has. As far as the achievable resolution is concerned, it can be assumed that the achievable resolution is essentially determined by the design of the thermal transfer print head.

It may further be provided that transmission layers which have a different electrical conductivity are used to form gradients of the resistance along the surface normals of the electrically conductive layer.

It can be provided that the transfer layer is solidified upon transfer from the transfer film to the multi-layer body by the action of temperature and / or pressure and / or chemical reaction and connected to the arranged under the transfer layer of the multilayer body. It can also be provided that additives are added to the polymers which improve, for example, adhesion or intercoat adhesion.

But it can also be provided that the transfer layer after transfer from the transfer film to the multi-layer body by Temperature action and / or pressure and / or chemical reaction is filmed and connected to the arranged under the transfer layer of the multilayer body. It can also be provided that the transfer layer is applied to non-conductive other layers, which crosslink in a subsequent process and cause intercoat adhesion.

In a further advantageous embodiment it can be provided that a transfer film is used, which is not homogeneous itself and, for example, has different thicknesses at different locations or even a decoration.

It can further be provided that a transfer film is used in which the conductive layer is embedded in other layers or surrounded by other layers, which in turn may have different properties.

It can further be provided that the transfer layer is both during transfer and after transfer from the transfer film to the multilayer body by temperature and / or pressure and / or chemical reaction filmed and connected to the arranged under the transfer layer of the multilayer body. It may, for example, be provided to then subject the finished conductive layer to a heat treatment in order to improve the homogeneity and adhesive strength, wherein the heat treatment may be provided in a protective gas atmosphere or in a vacuum.

Further advantages in this connection are, for example, applications on rough and pre-structured layers, which can not be coated by a normal coating process. It is therefore possible to provide a multilayer body in which the electrically conductive layer is arranged on a layer with a rough and / or structured and / or partially structured surface.

The parameters to be set can preferably be determined by experiments by varying the values of a parameter starting from starting values and the values of the remaining parameters are kept constant. In general, it is sufficient to vary four parameters: temperature, contact pressure, time duration and the substrate on which is embossed, for example

Roughness and chemical composition.

The electrically conductive layer according to the invention may also have a sandwich-like structure after its completion, which can be seen in the sectional image or on the vertical outside edges structured similarly to a book edge, if no homogeneous filming in the direction perpendicular to the layers has taken place.

It can be provided that the transfer layer of the transfer film is formed from PEDOT / PSS. PEDOT / PSS is a short name for a mixture of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonate, i. a polymer mixture of two ionomers. Both components of PEDOT / PSS contribute different charge carriers to form the electrical conductivity: PEDOT positive charge carriers, PSS negative charge carriers. A PEDOT / PSS layer has domains with a predominant proportion of PEDOT, which are integrated in a PSS matrix or in a PEDOT / PSS matrix with a low PEDOT content.

PEDOT / PSS is preferably prepared as an aqueous dispersion of polymer particles. It is preferably provided to apply the transfer layer from an aqueous PEDOT / PSS dispersion in a proportion of about 1.2% by weight.

It can be provided that PEDOT / PSS in a weight ratio of 1:20 to 1: 1 is used. Preferably, PEDOT / PSS is used in the weight ratio of 1: 1 because it has the highest electrical conductivity.

It can further be provided that a transfer film is used whose transfer layer has a layer thickness> 500 nm. It can also be provided that a transfer film is used whose transfer layer has a layer thickness of 50 nm to 500 nm.

It can preferably be provided that a transfer film is used whose transfer layer has a layer thickness of 5 nm to 50 nm. An electrically conductive layer of 50 nm thickness can therefore be constructed, for example, from 10 to 1 transfer layer.

Further preferably, it can be provided that a transfer film is used whose transfer layer has a layer thickness of 5 nm to 10 nm.

In a further advantageous embodiment, provision can be made for a transfer film to be used in which the areas which are dissolved out are present in domains.

It can be provided that the electrically conductive layer of the multilayer body according to the invention consists of at least two electrically conductive polymer layers arranged one above the other. In the case of only one transferred polymer layer, the electrically conductive layer can have defects which can question its use according to the function. Furthermore, with only one polymer layer, the adjustability of the electrical parameters, for example the electrical conductivity, is limited. Therefore, more than one transferred polymer layer is preferred.

It can be provided that the at least two polymer layers arranged one above the other are structured identically. The electrically conductive layer of such a multilayer body is thus characterized in that it is constructed in each area from the same number of superimposed polymer layers.

Alternatively it can be provided that the at least two superimposed polymer layers are structured differently. In this way, for example, areas with different electrical conductivity can be formed, ie areas of the electrically conductive layer can For example, assume the function of a resistance. It can be provided, for example, that the voltage drop occurring at this resistor is evaluated and serves as input to an electronic circuit, for example a control circuit or an alarm transmitter.

It can further be provided that the superposed electrically conductive polymer layers are formed of different materials.

Advantageously, it can be provided that the electrically conductive polymer layer consists of PEDOT / PSS.

It can further be provided that the electrically conductive polymer layer of PEDOT / PSS is formed in a weight ratio of 1:20 to 1: 1.

The electrically conductive layer may be formed as a separation layer between a semiconductor layer and an electrode layer.

It can also be provided that the electrically conductive layer is formed as a conductor track.

In a further advantageous embodiment it is provided that the electrically conductive layer has electron-conducting particles. Such a modified layer may have increased electrical conductivity. The electron-conducting particles can also act as electrical shielding. However, they can also serve as scattering centers in the case of superimposed light extraction. The particles can be different in shape, material, size and concentration.

It can also be provided that at least one electron-conducting layer is arranged on or below the electrically conductive layer.

It is possible that the electron-conducting particles and / or the electron-conducting layer of silver, gold, copper, titanium, aluminum or a combination of consist of these metals.

It is further possible for the electrically conductive layer to be arranged on a layer with a rough and / or structured and / or partially structured surface.

It can further be provided that the electrically conductive layer and / or the electron-conducting layer provides personalized information.

Further advantageous embodiments are directed to the transfer film. As already explained above, the transfer layer of the transfer film has, for example, an un-filmed PEDOT / PSS layer and at least one electron-conducting layer.

Advantageously, it can be provided that the electron-conducting layer consists of a metallic layer.

It may further be provided that the electron-conducting layer consists of a sequence of two or more metallic layers, wherein in each case two adjoining metallic layers consist of different material. For example, if three designated A, B and C metallic

Layers are provided, then sequences such as A / B / C, C / B / A, A / C / B or A / B / A can be provided.

This will u.a. the advantage is achieved that the chemical stability to adjacent layers, but also to the environment can be improved. Furthermore, the adhesion to other layers is improved.

It is possible for the two electron-conducting layers adjacent to an electrically conductive polymer layer to have the same sequence of the metallic layers.

But it is also possible that the two of an electrically conductive polymer layer adjacent electron-conducting layers a different sequence of have metallic layers.

The metallic layers may consist of silver, gold, copper, titanium, aluminum, or a combination of these fvleiaiieπ. The metallic layers can be applied, for example, by sputtering or vapor deposition, with layer thicknesses in the range from 10 nm to 50 nm being preferred.

Advantageously, it can be provided that the electrically conductive polymer layer consists of PEDOT / PSS. The PEDOT / PSS layer is advantageously a non-filmed PEDOT / PSS layer, as described above. The PEDOT / PSS layer is first filmed by transfer by means of heat and / or pressure and then securely adheres to the substrate to which it was applied by the embossing process.

The transfer layer of the transfer film advantageously has a release layer which enables the transfer layer to be detached from the carrier layer, the release layer consisting of an electrically conductive polymer. Such a release layer can make a contribution to the power line after the embossing of the transfer layer and the filming. It thus fulfills a dual function in that it is easily removable from the carrier layer as an un-filmed polymer layer and forms a firmly adhering electrically conductive layer as a film-coated polymer layer.

It can be provided that the release layer consists of PEDOT / PSS.

It can further be provided that the transfer layer on the side facing away from the carrier layer has an adhesive layer for fixing the transfer layer on a target substrate and that the adhesive layer consists of an electrically conductive polymer. Again, the different behavior of an unfilmed and a filmed polymer layer is used. This may be a polymer layer formed from the same material as the release layer, which acts as an adhesive as a result of the filming during embossing. The adhesive layer may consist of PEDOT / PSS. Furthermore, it is also possible to add additives to the PEDOT / PSS to improve the adhesion or to modify the PEDOT / PSS accordingly.

It can further be provided that the transfer layer on the

Carrier layer facing away from a primer layer and that the primer layer consists of an electrically conductive polymer. The primer layer may be provided for bonding and may be formed of the same material as the peel layer and the adhesive layer described above.

The primer layer may consist of PEDOT / PSS. Furthermore, it is also possible to add additives to the PEDOT / PSS to improve the adhesion or to modify the PEDOT / PSS accordingly.

In a further advantageous embodiment, it is provided that the transfer layer has an intermediate layer formed between two electron-conducting layers and formed from an electrically conductive polymer. The intermediate layer may be provided to impart adhesion between the two electron-conducting layers.

The intermediate layer may be formed of PEDOT / PSS. It is thus possible to provide a transfer foil having alternatingly superimposed electrically conductive polymer layers-preferably consisting of un-filmed PEDOT / PSS layers-and electron-conducting layers-preferably formed as a layer composite of more than one metallic layer-which can be adapted to a wide range of application conditions.

It may further be provided that the metallic layers are formed with different thickness.

It is also possible that the electrically conductive polymer layers are formed with different thicknesses and / or a different chemical Have composition.

The production of the transfer film according to the invention can be carried out essentially in three successive steps, which can be carried out in a roll-to-roll process.

In the first step, the lowermost PEDOT / PSS layer can be applied to the carrier layer, wherein it should be ensured that the PEDOT / PSS layer thus applied is not filmed after drying. This ensures that the PEDOT / PSS layer easily separates from the carrier layer after embossing. The bottom PEDOT / PSS layer can therefore be used as a release layer, so that a special release layer can be omitted. The lowest PEDOT-PSS layer can be applied, for example, by gravure printing, screen printing or coating.

In the second step, one or more electron-conducting layers can be applied to the PEDOT / PSS layer, the layer thickness of which may advantageously be... Nm to... Nm. If the electron-conducting layer is a metallic layer, it can be applied, for example, by vapor deposition or sputtering. If a conductive paste is provided as the electron-conducting layer, it can be applied by the method mentioned above for applying the PEDOT / PSS layer. As stated above, preferred metals are silver, gold, copper, titanium and aluminum. Combinations of metals are also possible due to the layered structure of the electron-conducting layer, it being possible for the combinations to be metallic alloys.

As a third step, the application of one or more primer layers or one or more PEDOT / PSS layers is provided. If only one primer layer or PEDOT / PSS layer has been described above, then it is to be understood that these layers, like the electron-conducting layers, can be formed from a plurality of partial layers. The thickness of the PEDOT / PSS layers can be adjusted for example by repeated layer application. It can be provided that steps 1 and 2 are repeated one or more times before the production step 3 is carried out. In the case of production step 1, it should be noted that the PEDOT / PSS layer is applied to the respective upper layer of the stamping foil during repetition steps.

It is possible to use the transfer film according to the invention to build up a polymer solar cell comprising an electrically conductive layer formed from a transfer layer of the transfer film having an electrically conductive polymer. It is advantageous that the electrical layer can be "tailored" and in this way, in cooperation with, for example, the active layer of the solar cell, the efficiency of the solar cell can be increased.

In the following the invention will be clarified by way of example with reference to several embodiments with the aid of the accompanying drawings.

Show it

1 shows a schematic cross section of a first embodiment of the multilayer body according to the invention;

Fig. 2 is a diagram of the dependence of the sheet resistance of the

Embossing number for the multi-layer body in Fig. 1;

3 is a schematic plan view of a second embodiment of the multilayer body according to the invention;

Fig. 4 is a schematic sectional view taken along the section line IV-IV in Fig.

3;

5a, 5b manufacturing stages of a third embodiment of the multilayer body according to the invention; Fig. 6a to 11b embodiments of the embossing film according to the invention.

1 shows a multilayer body 1 which was produced by multiple embossing, consisting of an electrically insulating carrier layer 11 and a PEDOT / PSS layer 12. PEDOT / PSS (poly (3,4-ethylenedioxythiophene) and polystyrene sulfonate) are to a polymer mixture of two ionomers. Both components contribute different charge carriers: PSS negative charge carriers, PEDOT positive charge carriers.

The carrier layer 11 is Plexiglas with a thickness of 1 to 2 mm. In the exemplary embodiment illustrated in FIG. 1, the multilayer body is a test pattern for detecting the electrical properties of the PEDOT / PSS layer 12. The material and / or the thickness of the carrier layer 11 can be adapted to the intended use, for example to the Use of the multilayer body 1 as a polymer solar cell. The carrier layer 11 may be an organic semiconductor layer of said polymer solar cell, which is constructed on further layers and a substrate in which the PEDOT / PSS layer is applied as a layer between the semiconductor layer and an electrode layer. In Fig. 1, such further layers are not shown.

The PEDOT / PSS layer 12 is composed of PEDOT / PSS partial layers ^ 2 ^ to 12 ₂₂ , which are successively applied by embossing a PEDOT / PSS embossing film. Here, embossing different PEDOT / PSS types is conceivable. In this context, it was found that applications on rough and pre-structured layers are possible, which can not be coated by a normal coating process or coated very inadequate.

The PEDOT / PSS embossing film is in the embodiments described in Fig. 1 and the other figures by doctoring and drying a PEDOT / PSS dispersion formed on a carrier film. The dried PEDOTVPSS layer forms a transfer layer of the PEDOT / PSS embossing foil.

The carrier film was embossed onto the carrier layer 11, wherein the temperature of the embossing wheel was set to 190 to 200 ⁰ C. Some of the test multilayer body 1 was baked after embossing for about 10 minutes at about 130 to 150 ⁰ C. This step is used for further homogenization and filming as well as for expelling residual solvents.

In a first example, Baytron FCCP from HCStarck was used. Baytron FCCP has a solids content of 1.25% and was applied with a doctor R 30/3 (application weight 10 g / m ² at a solids content of 38.54%). The consistency of this dispersion is very low. The samples were then dried in the air stream of a hot air blower at about 35 to 40 ⁰ C. The drying time was about 2 minutes. The generated by said method

PEDOT / PSS layer was easily removed from the carrier film with a thumb sample, with the PEDOT / PSS layer crumbling powdery. This material property is caused by being a non-filmed PEDOT / PSS layer, i. the PEDOT / PSS layer applied by the method described above does not form a coherent film.

The samples initially had a mean sheet resistance of 4.078 kΩ. According to a further three-minute heat treatment at 150 ⁰ C, the samples exhibited a mean sheet resistance of 3,856 kOhm. The samples were filmed after the said temperature treatment and could no longer be replaced with the thumb sample.

In contrast, the PEDOT / PSS layer dried in a drying oven at 130 ^° C. to 150 ^° C. for about 5 minutes adhered more firmly to the carrier film and formed a firmly coherent film which was difficult to remove with the rubbing test (thumb sample). Similarly, the PEDOT / PSS layer dried at 35 to 40 ^° C. with the above-mentioned processes after prolonged storage (10 to 14 days) can form a more firmly adhering film and is therefore no longer suitable as a transfer layer of the PEDOT / PSS embossing film. It is because of that intended to process the PEDOT / PSS embossing foil promptly after production or to wind up the PEDOT / PSS embossing foil so that the carrier foil is at the same time a protective foil for the PEDOT / PSS transfer layer and prevents or prevents the subsequent application of the PED / PSS transfer layer at least very delayed. The long-term stability also depends on the PEDOT / PSS used.

In a second example, Orgacon S500 Pedot from AGFA was applied in the manner described above. Orgacon PEDOT has a solids content of 1.29% and was applied with a R 30/3 doctor blade. After drying, a mean sheet resistance of 0.658 kΩ was measured; After three minutes of heat treatment at 150 ° C, an average surface resistance of 0.7 o 3 kΩ was measured.

In a third example, two different layers of PEDOT were applied to each other, namely Orgacon S500 with a solids content of 1.29% and Baytron FCCP with a solids content of 1.25%. The layers were also coated with the R 30/3 doctor blade, the doctor blade having an application weight of 10 g / m ² , after the solids content, which was 38.54%. The samples were then dried in the air stream of a hot air blower at about 35 to 40 ⁰ C. The drying time was about 2 minutes. Initially, the samples had a mean sheet resistance of 0.565 kΩ and after a further three-minute heat treatment at 150 ^° C. they had a mean sheet resistance of 0.613 kΩ. The samples were filmed after the said temperature treatment and could no longer be replaced with the thumb sample.

As the latter second example has shown, the total surface resistance calculated from the individual values of the surface resistance agrees very well with the measured total resistance. It was assumed that the stacked PEDOT / PSS layers can be modeled as a parallel connection of resistors.

1 / R _g es = 1 / Rβaytron FCCP + 1 / Rθrgacon = 1 / 4.078 kΩ + 1 / 0.658 kΩ = 1 / 0.5665 kΩ

Rges = 0.5665 kΩ The measured total resistance was, as stated above, 0.565 kΩ.

It can also be provided to apply the PEDOT / PSS by means of spin coating or else via a nozzle coating onto the carrier film and then to dry in the manner described above.

FIG. 2 shows, with reference to FIG. 1, a diagram showing the dependence of the sheet resistance of the PEDOT / PSS layer 12 as a function of the number of PEDOT / PSS partial layers 12 _! to 12 ₂ 2 shows. As can be seen in FIG. 2, the result is a nonlinear profile of the surface resistance, wherein in the exemplary embodiment illustrated in FIG. 2 the sheet resistance has dropped to 9% of the initial value after 8 preamplifiers and to about 4% of the initial value after a further 14 preambles. The sheet resistance was determined in each case according to the so-called four-point method as in the three examples mentioned above. This is a measurement method used inter alia in geophysics, in which the specific resistance of a body or a layer without sampling is determined by measurements on the surface.

Table 1 In Table 1, the measured surface resistances, depending on the embossing number, correspond to the calculated reciprocals of the surface resistance (conductance). The Leitweil i & i, in good approximation of the number of prague proportionally. It is thus possible to produce PEDOT / PSS layers with defined conductance by repeated embossing.

FIG. 3 now shows a multilayer body 3 which has on a rectangular carrier layer 31 a PEDOT / PSS layer 32, formed from three PEDOT / PSS partial layers 32τ to 32 ₃ . The PEDOT / PSS sub-layer 32τ is formed as a horizontally arranged strip-shaped region and is arranged directly on the carrier layer 31. The PEDOT / PSS sub-layer 32 ₂ is arranged above the PEDOT / PSS sub-layer 32i and has three separate regions, wherein the left and the middle region are formed as vertically extending strip-shaped regions, which terminate with the horizontal edges of the carrier layer 31 and the right portion only the right edge portion of the PEDOT / PSS sub-layer 32-, covered. The PEDOT / PSS sublayer 31 ₃ is the uppermost PEDOT / PSS sublayer and has two separate regions. The left portion of the PEDOT / PSS sublayer 31 ₃ covers the left portion of the PEDOT / PSS sublayer 32 ₂ and the right portion of the PEDOT / PSS sublayer 31 ₃ covers the right portion of the PEDOT / PSS sublayer 32 ₂ .

In the exemplary embodiment illustrated in FIG. 3, the PEDOT / PSS layer 32 is formed for the sake of clarity only from three PEDOT / PSS partial layers. However, it may be provided to construct each of the three PEDOT / PSS sublayers 32τ to 32 _3, for example, each of 7 sublayers, so that the sheet resistance of the three PEDOT / PSS sublayers together is about 350 Ω, assuming the embossing foil described in FIG , In the aforementioned embodiment of the three PEDOT / PSS partial layers, partial regions are formed in which 7, 14 or 21 partial layers are arranged one above the other, which have surface resistivities of 350 Ω, 250 Ω or 150 Ω.

Fig. 4 shows the multilayer body along the section line IV in Fig. 3. It is therefore not only possible, the sheet resistance of the PEDOT / PSS layer by the number of to set successively applied, superposed PEDOT / PSS sub-layers, but also to locally change the sheet resistance of the PEDOT / PSS layer. In addition, a resistance gradient can be formed along the Fächennormaien the PEDüT / PSS layer. In this way, for example, working resistances connected to one another and / or to other components can be produced, wherein the areas of the low-surface resistance PEDOT / PSS layer can form strip conductors which connect the aforementioned components to one another in an electronic circuit.

FIGS. 5a and 5b now show production steps of a multilayer body 4.

FIG. 5a shows a multilayer body 4a, which forms the first manufacturing stage of the multilayer body 4. The multilayer body 4a is formed from a carrier layer 41 and a first PEDOT / PSS sub-layer A2y, which covers the carrier layer 41 over the entire area.

The multilayer body 4a is in contact with a stamping foil 5 formed of a carrier layer 51 and a transfer layer 52 of PEDOT / PSS. From the stamping foil 5, a section 52p of the transfer layer 52 is now transferred to the multilayer body 4a by means of a stamping tool 53.

5b now shows a multilayer body 4b on whose first PEDOT / PSS sub-layer 42i a second PEDOT / PSS sub-layer 42 _{2 is} applied, the second PEDOT / PSS sub-layer 42 ₂ from the section 52p of the transfer layer 52 of the embossing film 5 is formed (Fig. 5a).

FIG. 5b further shows the embossing foil 52r drawn from the multi-layer body 4b, which now has a residual transfer layer 52r, which no longer has the detached portion 52p.

The production steps illustrated in FIGS. 5a and 5b can be repeated until the PEDOT / PSS layer is formed in the desired layer thickness and / or structure. It can be provided to use successively different embossing tools 53 to one or more sub-layers of PEDOT / PSS layer to structure differently, as described above in Fig. 3 and 4. However, it can also be provided to transfer the PEDOT / PSS layer by means of a thermal transfer printer and to build it up in layers, it being possible to subsequently film the PEDOT / PSb layer by means of a thermal pressing tool. In addition, it can be provided that the stamping substrate is rough, structured or partially textured.

FIGS. 6 a to 11 b now show exemplary embodiments of the embossing foil according to the invention in a schematic sectional illustration.

The stamping foils are each formed from a carrier layer 41 and further layers arranged on the carrier layer 41, wherein the further layers form a transfer layer, which can be transferred to a substrate by an embossing process under the effect of temperature and / or pressure. The carrier layer is, for example, a PET carrier with a layer thickness of 19 to 23 μm.

On the carrier layer 41 a PEDOT / PSS layer is arranged, which forms a release layer 42a. This basic layer structure is provided in all embodiments shown in FIGS. 6a to 11b. The PEDOT / PSS layer has a thickness of about 300 nm in the illustrated embodiment.

Fig. 6a shows a stamping foil whose transfer layer is formed of three layers. Disposed on the release layer 42a is a metallic layer 43a covered by a second PEDOT / PSS layer formed as an adhesive layer 42k. The metallic layer may preferably be made of silver, gold, copper, titanium or aluminum.

The release layer 42a and the adhesive layer 42k can differ in their chemical composition and / or in their thickness, which are selected such that both PEDOT / PSS layers optimally fulfill the intended functions. The optimization is preferably vornehmbar by series of experiments. The stamping foil shown in FIG. 6a has N = 1 metallic layers and N + 1 = 2 PEDOT / PSS layers, wherein the number of metal types X = 1.

The Fiy. FIG. 6b shows a stamping foil, which in principle is designed like the stamping foil shown in FIG. 6a, but where a plurality of metallic layers arranged one above the other are provided. In the embodiment shown in Fig. 6b are three metallic layers 43a, 43b and 43c, each consisting of a different material. It can be provided that at least two of different thickness are formed by the three metallic layers.

The embossing foil shown in Fig. 6b has N = 1 electron-conducting layers consisting of X = 3 metallic layers 43a, 43b and 43c and N + 1 = 2 PEDOT / PSS layers, wherein the number of metal species is Z = 3 ,

FIG. 7a now shows a stamping foil which has a further PEDOT / PSS layer. The further PEDOT / PSS layer forms an intermediate layer 42z, which is arranged between two metallic layers 4Sa ₁ and 43a ₂ . The intermediate layer 42z is provided, for example, to improve the adhesion between the individual metallic layers.

As also provided in the exemplary embodiments in FIGS. 6a and 6b, the three PEDOT / PSS layers may differ in their chemical composition and / or their thickness.

The embossing foil shown in FIG. 7a has N = 2 electron-conducting layers consisting of X = 1 metallic layers 43a and N + 1 = 3 PEDOT / PSS layers, wherein the number of metal types Z = X = 1. FIG. 7b now shows an embossing foil which, in principle, is designed like the embossing foil described in FIG. 7a, but in which the metallic layers are formed from a plurality of metallic layers 43a-1, 43a ₂ to 43c- ₁ , 43c ₂ . The metallic layers each have the same layer sequence, ie the layer sequence abc.

The embossing foil shown in FIG. 7b has N = 2 electron-conducting layers which consist of X = 3 metallic layers 43a-1, 43a ₂ to 43ci, 43c ₂ and N + 1 = 3 PEDOT / PSS layers, wherein the number of the metal types Z = X = 3.

The embodiment shown in Fig. 8a shows an embossing film, the transfer layer 52 is formed in principle as the transfer layer 52 in Fig. 7a, but the intermediate layer 42z is now arranged between metallic layers 43a and 43c of different material.

The embossing foil shown in Fig. 8a has N = 2 electron-conducting layers consisting of X = 1 metallic layers 43a and 43c and N + 1 = 3 PEDOT / PSS layers.

The exemplary embodiment in FIG. 8b shows an embossing foil whose transfer layer 52 is designed in principle like the transfer layer 52 in FIG. 7b, but the metallic layers arranged above and below the intermediate layer 42z now have a different layer sequence and / or other materials. The metallic layer below the intermediate layer 42z is formed from the superimposed layers 43a-ι, 43bi and 43a ₂ , thus has the layer sequence aba. The metallic layer arranged above the intermediate layer is formed from the layers 43a3, 43c and 43b2 arranged one above the other, thus has the layer sequence acb. As also noted for the above-mentioned embodiments of the stamping foil, the metallic layers can also differ in their thickness and the PEDOT / PSS layers in their chemical composition and / or their thickness. The embossing foil shown in FIG. 8b has N = 2 electron-conducting layers consisting of Xi = 3 metallic layers and X ₂ = 3 metallic layers, and N + 1 = 3 PEDOT / PSS layers, wherein the number of metal types Z ₁ = 3 and Z ₂ = 2. Generally good for the embodiment shown in Fig. Ba: Number of metal types: Z ₁ + Z ₂ + Z ₃ + ... + Z _N where Z ₁ <X ₁ , Z ₂ <X ₂ , Z ₃ <X _3,. .., Z _N <XN-

FIGS. 9a and 9b now show exemplary embodiments in which only one PEDOT / PSS layer is provided, namely the release layer 42a. The peel layer 42a allows the easy peeling of the

Transfer layer of the carrier layer. This is, as shown above, a non-filmed PEDOT / PSS layer, which is easily removable from the example of PET existing carrier layer.

Fig. 9a shows an embodiment which differs from the embodiment shown above in Fig. 6a in that instead of the adhesive layer 42k of PEDOT / PSS an adhesive layer 44 is provided, which is not formed of PEDOT / PSS. This layer may also be formed as a primer layer. As also provided for the other layers, the adhesive layer 44 may also be formed of several layers. The material of the adhesive layer 44 may be, for example, a hot melt adhesive. The primer layer may for example consist of an acrylate mixture. Furthermore, it can be provided that fillers, additives, etc. are added to this primer layer in order to achieve desired properties.

The embossing foil shown in FIG. 9a has N = 1 metallic layers and N = 1 PEDOT / PSS layers, wherein the number of metal types X = 1.

FIG. 9b now shows in an analogous manner an exemplary embodiment that differs from the exemplary embodiment shown in FIG. 6b in that, instead of the adhesive layer 42k formed from PEDOT / PSS, the adhesive layer 44 not formed from PEDOT / PSS is provided. The embossing foil shown in FIG. 9b has N = 1 electron-conducting layers consisting of X = 3 metallic layers 43a, 43b and 43c and N = 1 PEDOT / PSS layers, wherein the number of metal types Z = 3.

Further embodiments in which the trained from PEDOT / PSS

Adhesive layer 42k is replaced by the adhesive layer 44 not formed of PEDOT / PSS, in FIGS. 10a (otherwise as in FIG. 7a), FIG. 10b (otherwise as in FIG. 7b), FIG. 11a (otherwise in FIG 8a) and 11b (otherwise the same as Fig. 11b).

It can be provided that for forming a multi-layer body successively different embossing foils are molded one above the other, so that from the embossing foils shown in FIGS. 6a to 11b multilayer bodies can be produced by selecting the stamping foils and / or the combination of embossing foils for a intended function are optimally designed.

Claims

claims

A method for producing a multilayer body having an electrically conductive layer disposed on a carrier layer, characterized in that a transfer film (5) having a transfer layer (52) comprising an electrically conductive polymer is provided, and in that the electrically conductive layer is transferred by transferring the transfer layer (52) is formed by the transfer film (5) on the multi-layer body (4).

2. The method according to claim 1, characterized in that a non-filmed transfer layer (52) is provided.

3. The method according to claim 1 or 2, characterized in that the transfer layer (52) is formed as a polymer transfer layer.

4. The method according to any one of the preceding claims, characterized in that a transfer layer (52) is provided, in which the electrically conductive polymer is concentrated in domains.

5. The method according to any one of the preceding claims, characterized in that the electrically conductive layer (42) consists of one or more superimposed arranged transfer layers (52) by structured embossing of the transfer film (5) is formed on the multi-layer body (4).

6. The method according to claim 5, characterized in that for forming gradients of the resistance along the surface normals of the electrically conductive layer (42) transfer layers (52) are used, which have a different electrical conductivity.

7. The method according to any one of the preceding claims, characterized in that the transfer layer (52) when transferred from the transfer film (5) on the multi-layer body (4) filmed by the action of temperature and / or pressure and / or chemical reaction and with the under

Transfer layer (52) arranged layer of the multilayer body (4) is connected.

8. The method according to any one of the preceding claims, characterized in that a transfer film (5) is used, in which the conductive layer is embedded in other layers or surrounded by other layers, which in turn may have different properties.

9. The method according to any one of claims 1 to 6, characterized in that the transfer layer (52) filmed after transfer from the transfer film (5) on the multi-layer body (4) by the action of temperature and / or pressure and / or chemical reaction and with the under the transfer layer (52) arranged layer of the multilayer body (4) is connected.

10. The method according to any one of the preceding claims, characterized the transfer layer (52) of the transfer film (5) is formed from PEDOT / PSS.

11. The method according to claim 10, characterized in that PEDOT / PSS in a weight ratio of 1: 20 to 1: 1 is used.

12. The method according to any one of the preceding claims, characterized in that a transfer film (5) is used, in which the areas which are dissolved out, are present in domains.

13. The method according to any one of the preceding claims, characterized in that a transfer film (5) is provided, the transfer layer (52) comprises one or more layers (42) consisting of an electrically conductive polymer and one or more electron-conducting layers (43).

14. The method according to claim 13, characterized in that the one or more electron-conducting layers consist of an electron-conducting material, in particular of a metal or a metal alloy.

15. The method according to claim 13 or 14, characterized in that for forming the electron-conducting layer (43) has a layer of silver,

Gold, copper, titanium, aluminum or a combination of these metals

Sputtering and / or vapor deposition (52) is applied.

16. The method according to claim 13 or 14, characterized in that for forming the electron-conducting layer (43) an electrically conductive paste by gravure printing and / or screen printing and / or coating on the Transfer layer is applied.

17. Transfer film, in particular embossing film, with a carrier layer (41) and an electropneumatic transfer layer [52], characterized in that the transfer layer (52) has N electron-conducting layers (43) and N + 1 polymer layers (42), wherein alternately one electrically conductive polymer layer (42) and an electron-conducting layer is arranged and N> 1.

18. Transfer film according to claim 17, characterized in that the electron-conducting layer (43) consists of a metallic layer.

19. A transfer film according to claim 17, characterized in that the electron-conducting layer (43) consists of a sequence of two or more metallic layers (43a to 43c), wherein each two adjacent metallic layers (43a to 43c) consist of different material.

20. Transfer film according to claim 19, characterized in that the two of an electrically conductive polymer layer adjacent electron-conducting layers (43) the same sequence of metallic

Layers (43a to 43c) have.

21. The transfer film as claimed in claim 19, characterized in that the two electron-conducting layers (43) adjacent to an electrically conductive polymer layer have a different sequence of the metallic layers (43a to 43c).

22. Transfer film according to one of claims 18 to 21, characterized in that the metallic layers consist of silver, gold, copper, titanium, aluminum or a combination of these metals.

23. Transfer film according to claim 17, characterized in that the electrically conductive polymer layer (42) consists of PEDOT / PSS.

24. A transfer film according to any one of claims 17 to 23, characterized in that the transfer layer (52) comprises a release layer (42a) which allows the transfer layer to detach from the support layer (41) and the release layer (42a) is made of an electrically conductive material Polymer exists.

25. Transfer film according to claim 24, characterized in that the release layer (42a) consists of PEDOT / PSS.

26. Transfer film according to claim 17, characterized in that the transfer layer (52) has an adhesive layer (42k) on the side facing away from the carrier layer (41) for fixing the transfer layer (52) on a target substrate and in that the adhesive layer ( 42k) consists of an electrically conductive polymer.

27. Transfer film according to claim 26, characterized in that the adhesive layer (42k) consists of PEDOT / PSS.

28. Transfer film according to one of claims 17 to 27, characterized in that the transfer layer (52) on the carrier layer (41) facing away from a primer layer and that the primer layer of an electrically conductive polymer.

29. Transfer film according to claim 28, characterized in that the primer layer consists of PEDOT / PSS.

30. Transfer foil according to one of claims 17 to 28, characterized in that the transfer layer (52) has an electrically conductive polymer which is arranged between two electron-conducting layers (43)

Intermediate layer (42z) has.

31. Transfer film according to claim 30, characterized in that the intermediate layer (42z) consists of PEDOT / PSS.

32. Transfer film according to one of claims 18 to 31, characterized in that the metallic layers (43a to 43c) are formed with different thickness.

33. Transfer film according to one of claims 17 to 32, characterized in that the electrically conductive polymer layers are formed with different thickness and / or have a different chemical composition.

34. Multi-layer body with a structured electrically conductive layer, characterized in that the electrically conductive layer (12, 32) at least two superimposed electrically conductive polymer layers (12i to 12 ₂₂ , 32i to 32 ₃ ).

35. Multi-layer body according to claim 34, characterized in that the superposed electrically conductive polymer layers (12i to 12 ₂₂ , 32i to 32 ₃ ) are formed of different materials.

36. Multilayer body according to one of claims 34 or 35, characterized in that the electrically conductive layer (12, 32) is formed as a separating layer between a semiconductor layer and an electrode layer.

37. Multilayer body according to one of claims 34 to 36, characterized in that the electrically conductive layer (12, 32) is formed as a conductor track.

38. Multilayer body according to one of claims 34 to 37, characterized in that the electrically conductive layer (12, 32) has electron-conducting particles.

39. Multilayer body according to one of claims 34 to 38, characterized in that on or below the electrically conductive layer (12, 32) at least one electron-conducting layer (43) is arranged.

40. Multilayer body according to claim 38 or 39, characterized in that the electron-conducting particles and / or the electron-conducting layer (43) consists of silver, gold, copper, titanium, aluminum, a combination of these metals or of nanoparticles.

41. Multilayer body according to one of claims 34 to 40, characterized in that the electrically conductive polymer layer consists of PEDOT / PSS.

42. Multi-layer body according to claim 41, characterized in that the electrically conductive polymer layer of PEDOT / PSS in a weight ratio of 1: 20 to 1: 1 is formed.

43. Multilayer body according to one of claims 34 to 42, characterized in that the electrically conductive layer (12, 32) is arranged on a layer having a rough and / or structured and / or partially textured surface.

44. Multilayer body according to one of claims 34 to 43, characterized in that the electrically conductive layer (12, 32) and / or the electron-conducting layer (43) provides personalized information.

45. A polymer solar cell comprising an electrically conductive layer formed from a transfer layer comprising an electrically conductive polymer transfer layer.

46. Use of a transfer film according to one of claims 17 to 33 for the production of antennas.

47. Use of a transfer film according to one of claims 17 to 33, as

Precursor of a galvanization process, for example for antennas.