Method of producing a conductive structured polymer film

• US 20030052015A1
• Filed: 08/21/2002
• Published: 03/20/2003
• Est. Priority Date: 08/24/2001
• Status: Active Grant

• Current Assignee: Zyrus BeteiligungsGmbH & Company Patente I KG
• Original Assignee: Technische Universitat Munchen
• Inventors: Johannes, Hans-Hermann, Kowalsky, Wolfgang, Becker, Eike
• Granted Patent: US 6,951,603 B2
• Time in Patent Office: Days
• US Class Current: 205/414
• CPC Class Codes: H05K 1/0393 Flexible materials H05K1/038 takes precedence; specific organic compositions are classified in H05K1/0313 and subgroups
• CPC Class Codes: H05K 2201/0329 Intrinsically conductive polymer [ICP]; Semiconductive polymer
• CPC Class Codes: H05K 2203/0117 Pattern shaped electrode used for patterning, e.g. plating or etching
• CPC Class Codes: H05K 2203/135 Electrophoretic deposition of insulating material
• CPC Class Codes: H05K 3/205 using a pattern electroplated or electroformed on a metallic carrier
• CPC Class Codes: H05K 3/207 using a prefabricated paste pattern, ink pattern or powder pattern
• CPC Class Codes: H10K 10/46 Field-effect transistors, e.g. organic thin-film transistors [OTFT] H10K10/43 takes precedence
• CPC Class Codes: H10K 19/00 Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00
• CPC Class Codes: H10K 71/125 using electrolytic deposition e.g. in-situ electropolymerisation
• CPC Class Codes: H10K 71/13 using printing techniques, e.g. ink-jet printing or screen printing
• CPC Class Codes: H10K 71/18 using non-liquid printing techniques, e.g. thermal transfer printing from a donor sheet
• CPC Class Codes: H10K 71/60 Forming conductive regions or layers, e.g. electrodes

Abstract

A two-layered anode (1′) is used for the electrochemical polymerisation. The lower layer (2) consists of a non-conductive carrier material to which a conductive electrode layer (3′) is applied, the electrode layer being removed in part-areas in order to form non-conductive areas. the non-conductive areas have a predetermined structure which corresponds to the structure of the structured polymer film (11) to be formed. the anode (1′) is held together with a platinum cathode in an electrolyte into which compounds of low molecular weight, preferably monomers of the polymer film (11) to be formed, are introduced. A current flow is produced through the electrolyte via the anode (1′) and cathode. In the course of this a conductive polymer film (11) of the predetermined structure is formed on the conductive areas which are brought into contact with the electrolyte. A non-conductive substrate layer (13) to which the structured polymer film (11) adheres is applied to the structured polymer film (11). The structured polymer film (11) with the non-conductive substrate layer (13) can be released without problems from the electrode (1′). The electrode is not damaged during this and can then be reused immediately for the deposition of a new structured polymer film. In this way conductive structured polymer films with high resolution can be produced extremely cost-effectively and in mass production.

Claims

1. A method of producing a conductive structured polymer film, comprising the steps:

a) provision of an electrode having a surface with conductive areas of a predetermined structure and with non-conductive areas,

b) bringing at least a part of the conductive areas into contact with an electrolyte, the said electrolyte containing compounds of low molecular weight,

c) generating a current flow by the electrolyte with the aid of the electrode, a conductive polymer film of the predetermined structure being formed on the conductive areas which have brought into contact with the electrolyte, and

d) then removing the structured polymer film which has been formed from the electrode.

2. The method as claimed in claim 1, wherein in step d) the structured polymer film is transferred to a substrate.

3. The method as claimed in claim 2, wherein before step d) a non-conductive substrate layer is applied to the structured polymer film, the substrate layer being selected from a group of substrate layers consisting of substrate layers on which the structured polymer film adheres, substrate layers which can be thermally glued to the structured polymer film, and substrate layers which can be photochemically glued to the structured polymer film.

4. The method as claimed in claim 3, wherein a non-conductive polymer is dissolved in a volatile solvent, thereafter the solution is applied to the structured polymer film in order to form the non-conductive substrate layer, and wherein furthermore the solvent is converted into a gaseous aggregate state and then the structured polymer film adhering to the substrate layer is removed from the electrode.

5. The method as claimed in claim 3, wherein a flexible substrate layer is used which has a thickness of 50 μ

m to 1 mm.

6. The method as claimed in claim 4, wherein a flexible substrate layer is used which has a thickness of 50 μ

m to 1 mm.

7. The method as claimed in claim 3, wherein a stabilising layer is applied to the side of the substrate layer remote from the structured polymer film and the stabilising layer is thermally glued to the substrate layer.

8. The method as claimed in claim 3, wherein a stabilising layer is applied to the side of the substrate layer remote from the structured polymer film and the stabilising layer is photochemically glued to the substrate layer.

9. The method as claimed in claim 1, wherein the conductive and non-conductive areas are structured so that at least a part of their lateral dimensions is below 50 μ

m.

10. The method as claimed in claim 1, wherein an electrode with at least two layers is used, wherein in its production a conductive electrode layer is applied to the entire surface of a lower layer made from a non-conductive carrier material, the electrode layer being removed in part-areas in order to form the non-conductive areas.

11. The method as claimed in claim 1, wherein an electrode with at least three layers is used, wherein the lowest layer is made from a carrier material on which a conductive electrode layer is applied over the entire surface, and wherein the conductive electrode layer is covered with an insulator layer in part-areas in order to form the non-conductive areas.

12. The method as claimed in claim 1, wherein at least one of the following compounds pyrrols, 3-alkylpyrrols, particularly 3-methyl-, 3-ethyl-, 3-propylpyrrols, N-alkylpyrrols, particularly N-methyl-, N-ethyl-, N-arylpyrrols, particularly N-phenyl-, N-(4-amino)phenyl-, N-(4-methoxy)phenyl-, N-naphthylpyrrols, N-heteroarylpyrrols, particularly N-(3-thienyl)-, N-(2-thienyl)-, N-(3-furanyl)-, N-(2-furanyl)-, N-(3-selenophenyl)-, N-(2-selenophenyl)-, N-(3-pyrrolyl)pyrrols, thiophenes, 3-alkylthiophenes, particularly 3-methyl-, 3-ethyl-, 3-propylthiophenes, furans, 3-alkylfurans, 3-methyl-, 3-ethyl-, 3-propylfurans, selenophenes 3-alkylselenophenes, particularly 3-methyl-, 3-ethyl-, 3-propylselenophenes, tellurophenes, anilines, biphenyls, azulenes, 2-alpha-(3-alkyl)thienyl)thiophenes, 2-(alpha-(3-alkyl)thienyl)-(3-alkyl)thiophenes, 2-(alpha-thienyl)furans, 2-(alpha-(3-alkyl)thienyl)furans), 2-alpha-(3-alkyl)thienyl)-(3-alkyl)furans, 2-(alpha-thienyl)-(3-alkyl)furans, 2-(alpha-thienyl)pyrrols, 2-(alpha-(3-alkyl)thienyl)pyrrols, 2-(alpha-(3-alkyl)thienyl)-(3-alkyl)pyrrols, 2-(alpha-thienyl)-(3-alkyl)pyrrols, 2-(alpha-furanyl)pyrrols, 2-(alpha-(3-alkyl)furanyl)pyrrols, 2-(alpha-(3-alkyl)furanyl)-(3-alkyl)pyrrols, 2-(alpha-furanyl)-(3-alkyl)pyrrols, 2-(alpha-pyrrolyl)pyrrols, 2-(alpha-(3-alkyl)pyrrolyl)pyrrols, 2-(alpha-(3-alkyl)pyrrolyl)-(3-alkyl)pyrrols, 2-(alpha-pyrrolyl)-(3-alkyl)pyrrols, 2-(alpha-selenophenyl)selenophenes, 2-(alpha-(3-alkyl)selenophenyl)selenophenes, 2-(alpha-(3-alkyl)selenophenyl)-(3-alkyl)selenophenes, 2-(alpha-thienyl)selenophenes, 2-alpha-(3-alkyl)thienyl)selenophenes, 2-(alpha-(3-alkyl)thienyl)-(3-alkyl)selenophenes, 2-(alpha-thienyl)-(3-alkyl)selenophenes, 2-(alpha-selenophenyl)furans), 2-(alpha-(3-alkyl)selenophenyl)furans, 2-(alpha-(3-alkyl)selenophenyl)-(3-alkyl)furans, 2-(alpha-selenophenyl)-(3-alkyl)furans, 2-alpha-selenophenyl)pyrrols, 2-(alpha-(3-alkyl)selenophenyl)pyrrols, 2-(alpha-(3-alkyl)selenophenyl)-(3-alkyl)pyrrols, 2-(alpha-selenophenyl)-(3-alkyl)pyrrols, thienothiophenes, thienofurans, thienoselenophenes, thienopyrrols, 2-phenylthiophenes, 2-phenylfurans, 2-phenylpyrrols, 2-phenylselenophenes, 2-phenyltellurophenes, N-vinylcarbazole, N-ethynylcarbazone, 3,4-ethylenedioxythiophenes, 2-(alpha-(3,4,ethylenedioxy)thienyl)thiophenes, 2-(alpha-(3,4-ethylenedioxy)thienyl)-3,4-ethylenedioxythiophenes, 2-(alpha-(3,4-ethylenedioxy)thienyl-(3-alkyl)thiophenes, 2-(alpha-(3,4-ethylenedioxy)thienyl)furans, 2-(alpha-(3,4-ethylenedioxy)thienyl)-(3-alkyl)furans, 2-(alpha-(3,4-ethylenedioxy(thienyl)pyrrols, 2-(alpha-(3,4-ethylenedioxy)thienyl)-(3-alkyl)pyrrols, 2-(alpha-(3,4-ethylenedioxythienyl)selenophenes or 2-alpha-(3,4-ethylenedioxythienyl)-(3-alkyl)selenophenes are used as compounds of low molecular weight, and wherein the compounds of low molecular weight have a structure or a group of structures which contains monomer units and oligomeric monomer units.

13. The method as claimed in claim 1, wherein the electrolyte contains a solvent and a salt dissolved in this solvent, the electrolyte being chosen so that the compounds of low molecular weight are soluble in it.

14. The method as claimed in claim 11, wherein at least one of the liquids propylene carbonate, acetonitrile, monovalent or polyvalent alcohols, tetrahydrofuran or water is used as the solvent.

15. The method as claimed in claim 13, wherein at least one of the substances tetraethylammonium-tetrafluoroborate, tetraethylammonium-hexafluorophosphate, tetraethylammonium-perchlorate or poly(styrenesulphonic acid) sodium salt is used as the salt.

16. The method as claimed in claim 14, wherein at least one of the substances tetraethylammonium-tetrafluoroborate, tetraethylammonium-hexafluorophosphate, tetraethylammonium-perchlorate or poly(styrenesulphonic acid) sodium salt is used as the salt.

17. The method as claimed in claim 1, wherein a structured polymer film with a thickness of 0.1 to 2 μ

m is produced.

18. The method as claimed in claim 1, wherein a rotatable electrode is used, the electrode being disposed in such a way that during the rotation the conductive areas dip into the electrolyte and then are moved out of the electrolyte.

19. The method as claimed in claim 18, wherein a circular cylindrical electrode is used.

20. The method as claimed in claim 18, wherein a structured polymer film is produced using a process or a group of processes which contains continuous and quasi-continuous processes.

21. The method as claimed in claim 1, wherein after step c) at least a part of the structured polymer film formed on the electrode is brought into contact with a solution of a metal salt and that a current flow through the solution of the metal salt is produced via the electrode, a metal film being formed on the structured polymer film brought into contact with the solution of the metal salt.

22. The method as claimed in claim 21, wherein before step d) a substrate is applied to the metal film on the side remote from the structured polymer film.

23. The method of producing a conductor structure containing source and drain electrodes at least of a field-effect transistor, wherein a conductive structured polymer film is produced by the steps:

a) provision of an electrode having a surface with conductive areas of a predetermined structure and with non-conductive areas,

b) bringing at least a part of the conductive areas into contact with an electrolyte, the said electrolyte containing compounds of low molecular weight,

c) generating a current flow by the electrolyte with the aid of the electrode, a conductive polymer film of the predetermined structure being formed on the conductive areas which have brought into contact with the electrolyte, and

d) then removing the structured polymer film which has been formed from the electrode.

24. The method as claimed in claim 26, wherein the source and drain electrodes are disposed in such a way that a channel length of 2 to 50 μ

m is produced.