EP4008027A1 - Verfahren zum herstellen einer elektronischen vorrichtung - Google Patents
Verfahren zum herstellen einer elektronischen vorrichtungInfo
- Publication number
- EP4008027A1 EP4008027A1 EP20754616.9A EP20754616A EP4008027A1 EP 4008027 A1 EP4008027 A1 EP 4008027A1 EP 20754616 A EP20754616 A EP 20754616A EP 4008027 A1 EP4008027 A1 EP 4008027A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carrier substrate
- motif
- areas
- metallization
- regular
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
- H10K71/611—Forming conductive regions or layers, e.g. electrodes using printing deposition, e.g. ink jet printing
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1275—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by other printing techniques, e.g. letterpress printing, intaglio printing, lithographic printing, offset printing
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/162—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using laser ablation
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the invention relates to a method for manufacturing an electronic device.
- Electronic devices in particular semiconductors, solar cells or electrodes, can be obtained, for example, by means of the lift-off process known in the field of semiconductor manufacture.
- the structuring of a soluble coating in the lift-off process is usually carried out by exposing the soluble coating in areas and then structuring it in a development step.
- Methods for fine structuring of vapor-deposited material are known in the literature, see, for example, the publication KDM Rao, C. Hunger, R. Gupta, GU Kulkarni, M.
- Thelakkat “A cracked polymer templated metal network as a transparent conducting electrode for ITO-free organic solar cells ", Phys. Chem. Chem. Phys., 2014, volume 16, pages 15107-15110, and the text S.
- a coating is first applied to a film which forms numerous cracks on drying. These cracks form a dense, coherent network. During the subsequent vapor deposition of a material, the material is deposited both on (ie above) the coating and in the cracks. When the coating is removed, for example by washing with suitable solvents, the material vapor deposited above the coating is also removed. All that remains is the vapor-deposited material present in the crack lines.
- Alternatives to the production of transparent electrodes are named in the article "Towards low-cost transparent conducting electrodes" by Kulkarni et al. In Current opinion in Chemical Engineering, May 2015, 8: 60-68.
- WO 2016/192858 A1 a further developed method for producing an electronic device is described, which is based on the idea of using the technologies known in the field of security element production for value documents for fine structuring of metallizations for the provision of electronic devices.
- the technologies include the use of a (photo) resist, the use of an etching medium and the use of washing color.
- a crack-forming coating is applied to a carrier substrate, the crack-forming coating is dried, the coating forming numerous cracks in the form of a close-meshed, coherent network during drying, and application a metallization on the carrier substrate, so that metallic material is deposited on the carrier substrate within the cracks of the coating provided with cracks.
- the crack formation in the crack-forming coating applied before metallizing takes place statistically or randomly, so that depending on the material nature of the crack-forming coating, the drying parameters and the layer thickness of the Crack-forming coating metallic network structures with random metal lines and with random network geometry can be obtained.
- a targeted metal line guidance is not possible with the manufacturing method described in WO 2016/192858 A1.
- the present invention is based on the object of improving the manufacturing method known in the prior art.
- a second motif-forming areas (6) outside the first, a first motif-forming areas (5) metal (8) is deposited on the carrier substrate (3) in the form of a regular, metallic, coherent network, the washing ink droplets ( 4) having first regions (5) forming a first motif form regular islands within the regular, metallic, coherent network;
- a first motif-forming areas (5) metal (7) is deposited above the washing ink droplets (4); D) the removal of the washing ink droplets (4) in the first areas (5) together with the metal (7) present thereon, so that the carrier substrate (3) obtained is such that it:
- step B namely the orderly, printing application of aqueous washing ink droplets (4) to the carrier substrate (3) in first areas (5) forming a first motif, by means of a cell grid having printing cylinder or a printing plate having a cell grid, the geometry of the metallization produced in the process in the form of a regular, coherent network being determined by a suitable choice of the parameters cell arrangement, surface cell geometry, cell depth and web width.
- aqueous washing ink droplets (4) in step B) are based on an aqueous washing ink containing a binder, the binding agent preferably being a polymer and the polymer particularly preferably from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, in particular with a low molecular weight and with a medium degree of hydrolysis, polyvinylpyrrolidone, polyethylene glycol and casein.
- the binding agent preferably being a polymer and the polymer particularly preferably from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, in particular with a low molecular weight and with a medium degree of hydrolysis, polyvinylpyrrolidone, polyethylene glycol and casein.
- the present invention is based on the idea of using the technology known in the field of security element production for documents of value of the use of a washing ink for the fine structuring of metallizations for the provision of electronic devices.
- Security elements with characters that are visually recognizable in transmitted light and possibly also in incident light are known.
- the characters can have any shape, such as numbers, letters, patterns, geometric or figurative representations, etc., and are generally referred to as "negative writing" regardless of their shape.
- the security elements are produced, for example, by using a transparent substrate with a coating, generally a metallic coating (or metallization), which is then removed again at certain points. If the security element is held up to the light, the areas with metallic or other coating appear dark. The areas from which the coating was removed appear on the other hand bright or at least significantly lighter than the coated areas, depending on the transparency of the substrate: the more transparent, ie the more translucent, a substrate is, the more the contrast between coated and coating-free areas is more pronounced. In the case of very transparent substrates, the negative writing is clearly recognizable not only in transmitted light but also in reflected light.
- metallic coatings are essentially created over the entire surface.
- the provision of recesses within the metallic coating can be done by inserting a screen or a shielding plate during the vapor deposition process. This measure only leads to coarsely structured metallizations. However, visually appealing security elements require fine structuring. Finely structured metallizations can be done, for example, by a so-called washing process.
- WO 99/13157 A1 describes a washing process in which a carrier film is printed with a printing ink with a high pigment content in the form of characters, coated with a thin cover layer (for example made of aluminum) and the printing ink and the cover layer above it are then washed out with it a liquid is removed to produce coating-free areas in the form of the characters.
- WO 92/11142 A1 (corresponds to EP 0516790 A1) or its German priority application DE 4041025 A1 discloses printing inks which can be activated by the action of heat, for example waxy emulsions. When heated, these emulsions soften and thereby reduce the adhesion to the carrier film, so that both the softened printing ink and the overlying layers can be removed in these poorly adhering areas, supported by mechanical treatment such as ultrasound, brushing or rubbing.
- activatable printing inks inks with foaming additives as are customary in the production of foams, disclosed. These blowing agents split off gas under the action of heat and create foam structures. This increases the volume of the printing ink, as a result of which the adhesion to the carrier film is reduced and the layers overlying the printing ink are curved outwards, so that they offer a good point of attack for mechanical removal.
- WO 97/23357 A1 refers to EP 0516790 A1 and moreover discloses activatable printing inks which are activated, i.e. washed out, by treatment with a suitable solvent.
- the present invention is based on the knowledge that in experiments with solvents containing
- washing paint compositions with increasing water content of the washing paint the wetting of the carrier substrate to be wetted became worse.
- a suitable choice of the water content can produce such a solubility state in which the washing ink can be applied to the carrier substrate by printing in the form of a quasi-standing grid that does not extend further due to the surface energy conditions.
- the webs of the printing cylinder or printing plate used separate the washing ink droplets printed on the carrier substrate in a geometric correspondence to the cells of the printing cylinder or printing plate. This is followed by the step of metallizing. After the washing-out step, in which the washing ink droplets are removed together with the metal present on them, the webs of the printing cylinder or printing plate correspond to the metallic lines of the metallic network.
- washing step use is made of the solubility of the binder contained in the washing dye, in particular a polymer, in the washing medium.
- the metal deposited on the washing ink areas is removed in the washing process together with the binder and other particles that may be contained in the washing ink. What remains is the carrier substrate, on which the vapor-deposited metallic mesh remains largely undamaged in the areas not previously coated with washing paint.
- the metallic network obtainable according to the method according to the invention does not have a statistical or random network structure, but a defined metallic network structure with a defined metal line width and a defined metal line structure. In this way, metallic network structures with freely selectable transparency and freely selectable electrical conductivity can be created.
- the printing cylinder or printing plate used can have a plurality of areas with different cell arrangements and / or cell geometry, metallic network structures with areas of different network properties, in particular different transparency and / or different electrical conductivity, can be produced without any problems.
- the binder contained in the washing dye one of the substances that are used in the state cited above with reference to the washing process is basically suitable. Polymers which have been found to be particularly advantageous for the process according to the invention have good solubility both in water and in organic solvents, typically alcohols and / or esters.
- binders examples include hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, in particular with a low molecular weight and with a medium degree of hydrolysis, polyvinylpyrrolidone, polyethylene glycol and casein.
- the metallic line widths that can be achieved at the end of the production process are preferably in the range from 1 ⁇ m to 50 ⁇ m, the lines generally being so fine that they can only be recognized as lines when a magnifying glass is used.
- the human eye does not dissolve the individual lines in the surface, but a difference can be seen in incident light (or reflection) as well as in transmitted light (or transmission) compared to the untreated or bare carrier substrate.
- the reflectivity or the light transmission can be adjusted in a suitable manner.
- the metallized network structure according to the invention is extremely advantageous with regard to the significantly higher chemical resistance.
- conventional semitransparent metallization is very thin and therefore susceptible to corrosion, especially in the case of Al and Cu.
- the fiction like ate metallization in the form of a regular, close-meshed, cohesive network shows electrical conductivity and optical transmission that is comparable to a full-surface GGO layer.
- the fine metallic lines can be used in combination with customary embossing lacquers, customary primer compositions and customary heat-sealing lacquers and act as a reflector.
- aqueous washing ink droplets are applied in order to a carrier substrate, such as a glass substrate, a film or a multilayer structure, by printing technology in first areas that form a first motif.
- the term "ordered” hereby denotes a regular spacing of the individual washing ink droplets.
- the printing technology application can preferably take place by means of a (engraving) gravure printing plate which has individual cells at regular intervals.
- individual cell groups can be present, e.g. Groups, the cell groups being regularly spaced from one another.
- a printing cylinder can also be used.
- a metallization is then applied, so that in second areas forming a second motif outside of the first areas forming a first motif, metal on the carrier substrate is deposited in the form of a regular, metallic, coherent network, the washing ink droplets having first areas forming a first motif within the regular, metallic, coherent network forming regular islands en.
- metal is above the Wash color droplets deposited.
- the washing ink droplets are then removed in the first areas together with the metal present thereon, so that the carrier substrate obtained is such that it has no metallization in the first areas that form a first motif and one in the second areas that form a second motif has transparent, conductive metallization in the form of a regular, coherent network.
- the carrier substrate which is provided with a metallic network structure
- An overcoating with a metal that has a different color than the metal of the metallic network structure could also take place. In this case, the viewer would see a mixed color.
- additional primer layers and / or heat seal lacquer layers can be used.
- Other optical effects, e.g. fluorescence are easily possible by applying additional effect layers, as the reflector used, i.e. the metallic network structure, is only partially present.
- the method for removing the washing color is advantageously carried out by dissolving it with a suitable solvent.
- a suitable solvent for example, water, aqueous solutions, mixtures of solvents and water, possibly with surfactants, possibly with defoamers and other additives, are used.
- the detachment or dissolution can also be supported by spray nozzles or mechanically by brushes, rollers or felts.
- the choice of solvent is expediently made in accordance with the coating.
- the following solvents can be used in addition to water: methyl acetate, ethyl acetate, propyl acetate, Butyl acetate, methoxypropy I acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methylene chloride, chloroform, toluene, xylene, methanol, ethanol, 2-propanol. Furthermore, acetals or mixtures of the abovementioned solvents can be used.
- the metallization of the electronic device according to the invention can be based on a single metal. Suitable metals are e.g. aluminum, silver, copper, nickel, iron, chromium, cobalt, gold, titanium, tin, zinc or an alloy of one or more of the elements mentioned above (e.g. an iron-silicon alloy).
- the metallization can be based on a multilayer metallization, which can be obtained, for example, by successive vapor deposition.
- An advantageous multilayer metallization is, for example, a Cr layer followed by an Al layer. The adhesion of the Al layer to the layer structure is improved by the Cr layer.
- the electrical conductivity of the metallization according to the invention can be improved in the form of a regular, close-meshed, coherent network by an additional coating with an electrically conductive polymer.
- An electrically conductive polymer based on thiophene such as poly-3,4-ethylenedioxythiophene (PEDOT or PEDT), for example, is suitable as the electrically conductive polymer.
- PEDOT or PEDT poly-3,4-ethylenedioxythiophene
- inorganic, transparent and conductive layers for example metal oxides such as titanium dioxide, indium tin oxide or fluorotin oxide, can be applied. These additional layers can also serve to make the electrical To modify properties of the metallization according to the invention, such as the work function, in a controlled manner.
- the transparent, conductive metallization obtained in the manufacturing process according to the invention in the form of a regular, close-meshed, coherent network, can be subsequently removed in certain areas by means of laser radiation (so-called laser demetallization).
- laser demetallization the transparent, conductive metallization can be structured, i.e. voids or demetallized areas can be provided.
- Figure 1 shows a first fiction, contemporary electronic device in
- FIG. 2 shows the first electronic device according to the invention, magnified 100 times
- FIG. 3 shows a second electronic device according to the invention, magnified 25 times
- FIG. 4 shows the second electronic device according to the invention, magnified 100 times; and FIGS. 5-8 show the manufacture of an electronic device according to the invention.
- FIG. 1 shows a top view of a first electronic device 1 according to the invention, magnified 25 times.
- the electronic device was obtained by using a cellular gravure plate.
- the washing ink used for the printing application of aqueous washing ink droplets was based on the binder polyvinylpyrrolidone.
- a metallization in the example an Ag layer
- the step of washing out with an aqueous washing solution took place.
- the carrier substrate in the example a polyethylene terephthalate (PET) film, a transparent, conductive metallization remained in the form of a regular, coherent network.
- PET polyethylene terephthalate
- FIG. 2 shows the photo of the first electronic device 1 according to the invention in 100 'magnification in a top view.
- FIG. 3 shows the recording of a second electronic device 2 according to the invention in 25 'magnification in a top view.
- the electronic device 2 was obtained essentially in accordance with the same production method as the electronic device 1 described above, although in the case of the second electronic device 2 according to the invention, it is aqueous for the printing application Wash ink droplets a different gravure printing plate with a larger web width was used.
- FIG. 4 shows the photo of the second electronic device 2 according to the invention in 100 'magnification in a top view.
- FIGS. 5 to 8 each illustrate, in cross-sectional view, the production of an electronic device 9 according to the invention.
- a carrier substrate 3 in the example a polyethylene terephthalate (PET) film, is provided.
- PET polyethylene terephthalate
- first areas 5 forming a first motif.
- Second areas 6 forming a second motif are intended for the later formation of a transparent, conductive metallization in the form of a regular , coherent network.
- a metallization 7, 8 is applied to the carrier substrate 3, so that in second areas 6 forming a second motif outside the first areas 5 forming a first motif, metal 8 on the carrier substrate 3 in the form of a regular, metallic, coherent network is deposited, wherein the washing ink droplets 4 having first, a first motif-forming areas 5 within the regular, metallic, coherent network form regular islands.
- metal 7 is deposited above the washing ink droplets 4. Subsequently, the washing ink droplets 4 are removed in the first areas 5 together with the metal 7 present thereon.
- FIG. 8 shows the product 9 of the invention
- the carrier substrate 3 obtained is such that it has no metallization in the first regions 5 forming a first motif and has a transparent, conductive metallization in the form of a regular, coherent network in the second regions 6 forming a second motif.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electrodes Of Semiconductors (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Printing Methods (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102019005455.5A DE102019005455A1 (de) | 2019-08-02 | 2019-08-02 | Verfahren zum Herstellen einer elektronischen Vorrichtung |
| PCT/EP2020/025347 WO2021023394A1 (de) | 2019-08-02 | 2020-07-27 | Verfahren zum herstellen einer elektronischen vorrichtung |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4008027A1 true EP4008027A1 (de) | 2022-06-08 |
Family
ID=72050794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20754616.9A Pending EP4008027A1 (de) | 2019-08-02 | 2020-07-27 | Verfahren zum herstellen einer elektronischen vorrichtung |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP4008027A1 (de) |
| CN (1) | CN114009155B (de) |
| DE (1) | DE102019005455A1 (de) |
| WO (1) | WO2021023394A1 (de) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4041025C2 (de) | 1990-12-20 | 2003-04-17 | Gao Ges Automation Org | Magnetischer, metallischer Sicherheitsfaden mit Negativschrift |
| DE19548528A1 (de) | 1995-12-22 | 1997-06-26 | Giesecke & Devrient Gmbh | Sicherheitsdokument mit einem Sicherheitselement und Verfahren zu dessen Herstellung |
| DE19739193B4 (de) | 1997-09-08 | 2006-08-03 | Giesecke & Devrient Gmbh | Verfahren zur Herstellung von Sicherheitsfolien für Wertpapiere |
| JP5760003B2 (ja) * | 2010-10-29 | 2015-08-05 | リンテック株式会社 | 透明導電性フィルム、電子デバイス及び電子デバイスの製造方法 |
| CN105745357A (zh) * | 2013-11-08 | 2016-07-06 | 默克专利有限公司 | 包含银纳米材料的透明导电基体的结构化方法 |
| FR3032724B1 (fr) * | 2015-02-12 | 2019-12-13 | Jet Metal Technologies | Procede et dispositif de realisation de motifs metalliques sur un substrat a des fins decoratives et/ou fonctionnelles fabrication d'objets integrant cette realisation et ensemble de consommables utilises |
| DE102015007238B4 (de) | 2015-06-05 | 2017-06-22 | Giesecke & Devrient Gmbh | Verfahren zum Herstellen einer optoelektronischen Vorrichtung |
| CN109972128A (zh) * | 2019-03-29 | 2019-07-05 | 南昌大学 | 喷墨打印结合无电镀工艺制备超薄金属网格柔性透明电极的方法 |
-
2019
- 2019-08-02 DE DE102019005455.5A patent/DE102019005455A1/de not_active Withdrawn
-
2020
- 2020-07-27 EP EP20754616.9A patent/EP4008027A1/de active Pending
- 2020-07-27 WO PCT/EP2020/025347 patent/WO2021023394A1/de not_active Ceased
- 2020-07-27 CN CN202080047174.7A patent/CN114009155B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| DE102019005455A1 (de) | 2021-02-04 |
| CN114009155A (zh) | 2022-02-01 |
| WO2021023394A1 (de) | 2021-02-11 |
| CN114009155B (zh) | 2025-02-11 |
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