EP2043861A2 - Corps multicouche comprenant une couche polymère conductrice et methode de sa fabrication - Google Patents

Corps multicouche comprenant une couche polymère conductrice et methode de sa fabrication

Info

Publication number
EP2043861A2
EP2043861A2 EP07801436A EP07801436A EP2043861A2 EP 2043861 A2 EP2043861 A2 EP 2043861A2 EP 07801436 A EP07801436 A EP 07801436A EP 07801436 A EP07801436 A EP 07801436A EP 2043861 A2 EP2043861 A2 EP 2043861A2
Authority
EP
European Patent Office
Prior art keywords
layer
transfer
electrically conductive
layers
pedot
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07801436A
Other languages
German (de)
English (en)
Inventor
Ulrich Schindler
Walter Lehnberger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Leonhard Kurz Stiftung and Co KG
Original Assignee
Leonhard Kurz Stiftung and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102006033887.1A external-priority patent/DE102006033887B4/de
Application filed by Leonhard Kurz Stiftung and Co KG filed Critical Leonhard Kurz Stiftung and Co KG
Publication of EP2043861A2 publication Critical patent/EP2043861A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
    • B32B37/203—One or more of the layers being plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges
    • B32B2519/02—RFID tags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B32B37/025—Transfer laminating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y10T156/1039—Surface deformation only of sandwich or lamina [e.g., embossed panels]
    • Y10T156/1041—Subsequent to lamination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/24413—Metal or metal compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24909—Free metal or mineral containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • Multilayer body with conductive polymer layer 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.
  • organic solar cells For the construction of organic solar cells are organic
  • Electrically conductive polymers are often present as dispersions with a low solids content. Exactly such dispersions can be applied by Duckclar 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.
  • 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.
  • 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.
  • a transfer film with a carrier layer and an electrically conductive transfer layer which has at least one electron-conducting layer in addition to the electrically conductive polymer 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.
  • 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.
  • 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.
  • the conductivity of the electrical layer is adjustable by the number of transmitted transfer layers.
  • 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.
  • 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.
  • 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.
  • the transfer layer (52) is designed as a polymer transfer layer.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the achievable resolution is essentially determined by the design of the thermal transfer print head.
  • 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.
  • 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.
  • 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.
  • a transfer film is used, which is not homogeneous itself and, for example, has different thicknesses at different locations or even a decoration.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • PEDOT / PSS in a weight ratio of 1:20 to 1: 1 is used.
  • PEDOT / PSS is used in the weight ratio of 1: 1 because it has the highest electrical conductivity.
  • 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.
  • 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.
  • a transfer film is used whose transfer layer has a layer thickness of 5 nm to 10 nm.
  • a transfer film to be used in which the areas which are dissolved out are present in domains.
  • 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.
  • the electrically conductive layer can have defects which can question its use according to the function.
  • the adjustability of the electrical parameters, for example the electrical conductivity is limited. Therefore, more than one transferred polymer layer is preferred.
  • 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.
  • the at least two superimposed polymer layers are structured differently.
  • 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.
  • the superposed electrically conductive polymer layers are formed of different materials.
  • the electrically conductive polymer layer consists of PEDOT / PSS.
  • 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.
  • the electrically conductive layer is formed as a conductor track.
  • 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.
  • At least one electron-conducting layer is arranged on or below the electrically conductive layer.
  • the electrically conductive layer prefferably arranged on a layer with a rough and / or structured and / or partially structured surface.
  • the electrically conductive layer and / or the electron-conducting layer provides personalized information.
  • the transfer layer of the transfer film has, for example, an un-filmed PEDOT / PSS layer and at least one electron-conducting layer.
  • the electron-conducting layer consists of a metallic layer.
  • 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
  • sequences such as A / B / C, C / B / A, A / C / B or A / B / A can be provided.
  • the metallic layers may consist of silver, gold, copper, titanium, aluminum, or a combination of these fvleiaiie ⁇ .
  • 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.
  • 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.
  • 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.
  • the release layer consists of PEDOT / PSS.
  • 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.
  • 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.
  • the primer 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.
  • 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.
  • the metallic layers are formed with different thickness.
  • 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.
  • 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.
  • 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.
  • the electron-conducting layer is a metallic layer, it can be applied, for example, by vapor deposition or sputtering.
  • 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.
  • 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.
  • 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.
  • the transfer film according to the invention 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.
  • FIG. 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
  • FIG. 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.
  • PEDOT / PSS poly (3,4-ethylenedioxythiophene) and polystyrene sulfonate
  • PSS negative charge carriers PEDOT positive charge carriers
  • the carrier layer 11 is Plexiglas with a thickness of 1 to 2 mm.
  • 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.
  • 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.
  • 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 k ⁇ . 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.
  • 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 k ⁇ was measured; After three minutes of heat treatment at 150 ° C, an average surface resistance of 0.7 o 3 k ⁇ was measured.
  • 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.
  • PEDOT / PSS 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.
  • 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.
  • 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 32 ⁇ to 32 3 .
  • the PEDOT / PSS sub-layer 32 ⁇ 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 .
  • 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 32 ⁇ to 32 3, for example, each of 7 sublayers, so that the sheet resistance of the three PEDOT / PSS sublayers together is about 350 ⁇ , 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 ⁇ , 250 ⁇ or 150 ⁇ .
  • 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.
  • a resistance gradient can be formed along the Klachennormaien 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.
  • FIG. 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 ⁇ m.
  • PEDOT / PSS layer 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 voroutlinedbar by series of experiments.
  • 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.
  • 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.
  • metallic layers 43a, 43b and 43c 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.
  • 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.
  • the three PEDOT / PSS layers may differ in their chemical composition and / or their thickness.
  • 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.
  • 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.
  • 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- ⁇ , 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.
  • the metallic layers can also differ in their thickness and the PEDOT / PSS layers in their chemical composition and / or their thickness.
  • 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.
  • 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.
  • fillers, additives, etc. are added to this primer layer in order to achieve desired properties.
  • 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.
  • 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).

Landscapes

  • Laminated Bodies (AREA)
  • Decoration By Transfer Pictures (AREA)

Abstract

L'invention concerne un procédé de production d'un corps multicouche (4) comprenant une couche électroconductrice (42<SUB>1</SUB>) disposée sur une couche support (41), procédé caractérisé en ce qu'on produit un film de transfert (5) qui présente une couche de transfert (52) en un polymère électroconducteur, et en ce que la couche électroconductrice est transférée du film de transfert (5) sur le corps multicouche (4). L'invention concerne en outre un film de transfert et un corps multicouche fabriqué suivant ce procédé.
EP07801436A 2006-07-21 2007-07-19 Corps multicouche comprenant une couche polymère conductrice et methode de sa fabrication Withdrawn EP2043861A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102006033887.1A DE102006033887B4 (de) 2006-07-21 2006-07-21 Verfahren zur Herstellung eines Mehrschichtkörpers mit leitfähiger Polymerschicht
DE102006053665 2006-11-13
PCT/EP2007/006422 WO2008009447A2 (fr) 2006-07-21 2007-07-19 Corps multicouche comprenant une couche polymère conductrice

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EP2043861A2 true EP2043861A2 (fr) 2009-04-08

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US20150333424A1 (en) * 2012-12-20 2015-11-19 3M Innovative Properties Company Electrical connectors and methods of making same
US20140261672A1 (en) * 2013-03-14 2014-09-18 Miami University Titanium metal as electrode for organic solar cells, flexible organic solar cell on ti foil and method of manufacture

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WO2008009447A2 (fr) 2008-01-24
US8388790B2 (en) 2013-03-05

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