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WO1998054767A1 - Systeme stratifie conducteur et son utilisation dans des systemes electroluminescents - Google Patents

Systeme stratifie conducteur et son utilisation dans des systemes electroluminescents Download PDF

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Publication number
WO1998054767A1
WO1998054767A1 PCT/DE1998/001467 DE9801467W WO9854767A1 WO 1998054767 A1 WO1998054767 A1 WO 1998054767A1 DE 9801467 W DE9801467 W DE 9801467W WO 9854767 A1 WO9854767 A1 WO 9854767A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
transparent
electroluminescent
arrangement according
electroluminescent arrangement
Prior art date
Application number
PCT/DE1998/001467
Other languages
German (de)
English (en)
Inventor
Martin HÜPPAUFF
Ralf Sybrichs
Andreas Gehrig
Original Assignee
Robert Bosch Gmbh
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 DE19757874A external-priority patent/DE19757874A1/de
Application filed by Robert Bosch Gmbh filed Critical Robert Bosch Gmbh
Publication of WO1998054767A1 publication Critical patent/WO1998054767A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/816—Multilayers, e.g. transparent multilayers
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof

Definitions

  • the present invention relates to an electrically conductive, transparent layer system, consisting of at least one electrically conductive organic layer and an electrically conductive inorganic layer according to the preamble of the main claim.
  • Electroluminescent arrangements are characterized in that they emit light when an electrical voltage is applied under current flow. Such arrangements have long been known under the name “light emitting diodes”. Electroluminescence is the direct conversion of electrical energy into light. This phenomenon is caused by different mechanisms depending on the material used.
  • inorganic semiconductors For example, ZnS or GaS compounds doped with foreign atoms are used
  • the origin of electroluminescence in inorganic semiconductor materials lies in the excitation caused by electron injection of luminescent centers (e.g. doping atoms such as Mn or Tb) in the inorganic guest lattices.
  • ITO Indium tin oxide
  • doped tin oxide is generally used as the material for the anode of an electroluminescent arrangement. These materials have the advantage that they are transparent or semi-transparent and thus optically transparent to the light emitted. With these metal oxides, surface resistances of up to a few ohm squares are achieved, the transparency being greater than 70% transmission. Typical sheet resistances of commercially available ITO are in the range of 20-50 ohm square. The disadvantage of these conductive oxide layers is the relatively high manufacturing price, since the layers are used in vacuum processes, e.g. by reactive sputtering.
  • EP 0 686 662 A2 it is known from EP 0 686 662 A2 that, instead of transparent metal oxides, electrically conductive, transparent or semitransparent polymers, for example polythiophenes, can be used. Thin layers of these polymers are produced from a solution using simple, known methods, such as, for example, spin coating, knife coating, casting or printing. Furthermore, it is known from WO 96/08 047 to use polyaniline (PAN) and poly-3, 4-ethylene-dioxythiophene (PEDOT) as the transparent electrode. Other similar systems are described in EP 302 304 AI based on polypyrroles and in EP 440 957 AI based on polythiophenes.
  • PAN polyaniline
  • PEDOT 4-ethylene-dioxythiophene
  • the conductive layer system consists of a combination of at least two layers, one layer containing an organic or organometallic electrically conductive polymer which is transparent or semi-transparent in the visible region of the electromagnetic spectrum, and a second layer at least one electrically conductive inorganic compound or a metal or a corresponding one contains doped semimetal.
  • organic system and the inorganic system can be solved from solutions using methods such as
  • an electrically conductive, transparent or semitransparent polymer is used for the first layer.
  • polymers from the compound classes of polythiophenes, polypyrroles, polyanilines, polyacetylenes or their optionally substituted derivatives are preferred.
  • Materials from the group Cu, Ag, Au, Pt, Pd, Fe, Cr, Sn, Al and their alloys or conductive carbon are advantageously used for the second layer, so that this layer has a high electrical conductivity.
  • the inorganic layer is preferably applied in the form of a broken lattice structure which forms conductor tracks. This increases the average conductivity of the inorganic layer and of the entire layer system without the transparency of the layer system suffering significantly.
  • this conductive layer system is used as an anode instead of ITO in an electroluminescent arrangement, generally consisting of a transparent substrate, a first electrode, the anode, consisting of the conductive layer system according to the invention, an electroluminescent element and a second electrode, the cathode , used.
  • an electroluminescent arrangement generally consisting of a transparent substrate, a first electrode, the anode, consisting of the conductive layer system according to the invention, an electroluminescent element and a second electrode, the cathode , used.
  • the first layer is advantageously arranged adjacent to the electroluminescent element and the second layer is located above the first layer on the transparent substrate.
  • the width of the individual lattice elements of the lattice structure forming the interconnects is 5-500 ⁇ m, so that the emitting regions of the inorganic system cannot be resolved by the human eye. This appears to the viewer
  • a diffuser is arranged over the transparent substrate. This is made possible by that of the light emitting
  • the entire system represented or illustrated luminous areas, such as symbols of a clock face, display elements or displays are so small that they lie between the conductive inorganic areas.
  • the interconnect spacing can also be selected such that complex miniaturization of the same is not necessary.
  • the width of the individual lattice elements of the lattice structure forming conductor tracks is more than 300 ⁇ m, so that these dimensions can be resolved by the human eye.
  • FIG. 1 shows an electroluminescent arrangement according to the invention
  • FIG. 2 shows a further embodiment of the electroluminescent arrangement
  • FIG. 3 shows yet another embodiment.
  • a polymeric layer system for example based on polythiophene derivatives, as described in EP 0 686 662 A2, is applied with a doctor blade to a substrate, for example a glass plate.
  • the wet layer thickness of the polymer layer is approximately 50-100 ⁇ m.
  • the layer is annealed in an oven at about 200 ° Celsius.
  • the sheet resistance achieved is between 100 and 300 ohm square.
  • conductor tracks made of conductive silver are printed on using a screen printing process.
  • An inorganic electroluminescent element for example based on ZnS doped with Mn or Tb, is printed on the electrode thus prepared, for example using the screen printing method.
  • a counter electrode for example made of aluminum or MgAl, is then applied.
  • the conductor tracks according to the invention consist of structured organic conductive layers, the conductivity of which along the conductor tracks is reinforced by inorganic, also structured, very thin conductor tracks.
  • the light transmits through the transparent or semi-transparent organic areas.
  • the organic layer is in structures with typical
  • the conductivity in the range of this application is typically between 200 and 10,000 ohms / square. 500 to 3000 are particularly preferred
  • the layer thicknesses are in the range of 0.1 to 1 ⁇ m for the organic layer.
  • the inorganic layer preferably has layer thicknesses in the range from 0.01 to 100 ⁇ m.
  • Glycidyloxypropyltrimethoxysilane 400 mg of a 5% aqueous solution of a surfactant and 500 mg of a 1% aqueous solution of an ammonium polyacrylate.
  • the resulting solution was spun onto a PET film at 800 rpm and then annealed in an oven at 140 ° C. for 5 hours.
  • the absorption of the layers in the visible spectral range is less than 10%.
  • the surface resistance is approximately 1.5 kOhm / square.
  • Printed conductors made of conductive silver with dimensions of approx. 2 mm are printed on the transparent film coated in this way, which surround the light-emitting field and serve for contacting.
  • the light-emitting field has dimensions of 40 x 80 square millimeters.
  • the system (100 volts, 400 Hertz) the system emits blue light.
  • the intensity is about 50 Cd / m2.
  • the light emission is homogeneously distributed over the light-emitting field.
  • ITO indium tin oxide
  • FIG. 1 shows the basic structure of the electroluminescent arrangement 10 according to the invention using a layer system 13, 14 according to the invention as an electrode.
  • the electroluminescent arrangement 10 consists of an electrode, the cathode 11, for example of MgAl or other materials used in electroluminescent arrangements.
  • the electroluminescent element 12 arranged adjacent to it consists, for example, of ZnS doped with Mn or Tb. All other known inorganic electroluminescent materials can of course also be used, for example correspondingly doped GaAs or InS connections.
  • the adjacent layer 13 consists of an inorganic layer which is designed as a grid structure forming conductor tracks. It consists of conductive silver or another electrically conductive compound, for example Cu, Ag, Au, Cr, their alloys or conductive carbon.
  • the structures or the conductor tracks of the electrically conductive inorganic layer 13 are very fine.
  • the structure size, i.e. the width of the conductor tracks is designated by X in FIG. 1. It is in the range of 5-500 ⁇ m.
  • a dial 16 consisting of transparent and non-transparent areas is attached adjacent to the transparent substrate 15 in such a way that the non-transparent areas of the dial
  • Orders of magnitude of the conductor tracks in layer 13 correspond.
  • the exemplary embodiment is not limited to dials, but rather all display elements or displays, the light symbols of which are of the order of magnitude transparent areas between the conductor tracks of layer 13 can be realized with this arrangement.
  • Lattice structures or conductor tracks in layer 13 have a width X of more than 300 ⁇ m. They can thus be resolved by the human eye, which no longer sees a homogeneous total emitting area. Therefore, in addition to the transparent substrate 15 is adjacent
  • Diffuser 17 attached, which homogenizes the distribution of the emitted light. With this structure, large-area display elements and displays can therefore also be implemented.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un système stratifié conducteur à base de matériaux électroconducteurs organiques et inorganiques, qui est transparent ou semi-transparent. Ce système stratifié comprend au moins deux couches. La première couche contient un polymère organique ou organométallique électroconducteur, transparent ou semi-transparent dans la zone visible du spectre électromagnétique et la seconde couche contient au moins un composé inorganique électroconducteur ou un métal ou un métalloïde dopé de manière appropriée. Ce système stratifié constitue une électrode hybride à plusieurs couches, s'utilisant comme cathode dans des systèmes électroluminescents.
PCT/DE1998/001467 1997-05-31 1998-05-29 Systeme stratifie conducteur et son utilisation dans des systemes electroluminescents WO1998054767A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19722946.8 1997-05-31
DE19722946 1997-05-31
DE19757874.8 1997-12-24
DE19757874A DE19757874A1 (de) 1997-05-31 1997-12-24 Leitfähiges Schichtsystem und dessen Verwendung in elektrolumineszierenden Anordnungen

Publications (1)

Publication Number Publication Date
WO1998054767A1 true WO1998054767A1 (fr) 1998-12-03

Family

ID=26037051

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1998/001467 WO1998054767A1 (fr) 1997-05-31 1998-05-29 Systeme stratifie conducteur et son utilisation dans des systemes electroluminescents

Country Status (1)

Country Link
WO (1) WO1998054767A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7026079B2 (en) 2002-08-22 2006-04-11 Agfa Gevaert Process for preparing a substantially transparent conductive layer configuration
US7118836B2 (en) 2002-08-22 2006-10-10 Agfa Gevaert Process for preparing a substantially transparent conductive layer configuration
WO2009086161A1 (fr) * 2007-12-20 2009-07-09 Cima Nanotech Israel Ltd. Revêtement conducteur transparent ayant un matériau de charge
US20150072159A1 (en) * 2012-04-09 2015-03-12 Konica Minolta, Inc. Conductive film and organic electroluminescent element
EP3561829A1 (fr) * 2004-11-22 2019-10-30 Fujikura, Ltd. Contre-électrode poreuse pour une cellule solaire sensible à un colorant

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0510541A1 (fr) * 1991-04-19 1992-10-28 Mitsubishi Chemical Corporation Dispositif électroluminescent organique
WO1995024056A1 (fr) * 1994-03-03 1995-09-08 Uniax Corporation Electrodes composites bi-couches destinees a des diodes
DE19627071A1 (de) * 1996-07-05 1998-01-08 Bayer Ag Elektrolumineszierende Anordnungen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0510541A1 (fr) * 1991-04-19 1992-10-28 Mitsubishi Chemical Corporation Dispositif électroluminescent organique
WO1995024056A1 (fr) * 1994-03-03 1995-09-08 Uniax Corporation Electrodes composites bi-couches destinees a des diodes
DE19627071A1 (de) * 1996-07-05 1998-01-08 Bayer Ag Elektrolumineszierende Anordnungen

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7026079B2 (en) 2002-08-22 2006-04-11 Agfa Gevaert Process for preparing a substantially transparent conductive layer configuration
US7118836B2 (en) 2002-08-22 2006-10-10 Agfa Gevaert Process for preparing a substantially transparent conductive layer configuration
EP3561829A1 (fr) * 2004-11-22 2019-10-30 Fujikura, Ltd. Contre-électrode poreuse pour une cellule solaire sensible à un colorant
WO2009086161A1 (fr) * 2007-12-20 2009-07-09 Cima Nanotech Israel Ltd. Revêtement conducteur transparent ayant un matériau de charge
US8795462B2 (en) 2007-12-20 2014-08-05 Cima Nanotech Israel Ltd. Transparent conductive coating with filler material
US20150072159A1 (en) * 2012-04-09 2015-03-12 Konica Minolta, Inc. Conductive film and organic electroluminescent element
JPWO2013153971A1 (ja) * 2012-04-09 2015-12-17 コニカミノルタ株式会社 導電膜及び有機エレクトロルミネッセンス素子

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