WO2006045783A1 - Printable organic non-volatile passive memory element and method of making thereof - Google Patents

Printable organic non-volatile passive memory element and method of making thereof Download PDF

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Publication number
WO2006045783A1
WO2006045783A1 PCT/EP2005/055510 EP2005055510W WO2006045783A1 WO 2006045783 A1 WO2006045783 A1 WO 2006045783A1 EP 2005055510 W EP2005055510 W EP 2005055510W WO 2006045783 A1 WO2006045783 A1 WO 2006045783A1
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WO
WIPO (PCT)
Prior art keywords
conductive
electrode system
support
electrode
passive memory
Prior art date
Application number
PCT/EP2005/055510
Other languages
French (fr)
Inventor
Luc Leenders
Michel Wetrs
Original Assignee
Agfa-Gevaert
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.)
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Publication date
Application filed by Agfa-Gevaert filed Critical Agfa-Gevaert
Priority to JP2007538401A priority Critical patent/JP2008518453A/en
Priority to EP05803400A priority patent/EP1815543A1/en
Publication of WO2006045783A1 publication Critical patent/WO2006045783A1/en

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Classifications

    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
    • G11C13/02—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using elements whose operation depends upon chemical change
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
    • G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
    • G11C13/0009—RRAM elements whose operation depends upon chemical change
    • G11C13/0014—RRAM elements whose operation depends upon chemical change comprising cells based on organic memory material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
    • G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
    • G11C13/0009—RRAM elements whose operation depends upon chemical change
    • G11C13/0014—RRAM elements whose operation depends upon chemical change comprising cells based on organic memory material
    • G11C13/0016—RRAM elements whose operation depends upon chemical change comprising cells based on organic memory material comprising polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B99/00—Subject matter not provided for in other groups of this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K19/00—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
    • H10K19/202—Integrated devices comprising a common active layer
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C2213/00—Indexing scheme relating to G11C13/00 for features not covered by this group
    • G11C2213/70—Resistive array aspects
    • G11C2213/77—Array wherein the memory element being directly connected to the bit lines and word lines without any access device being used

Abstract

Passive memory devices comprising a support having at least one conductive surface or surface layer and having on at least one side of the support a passive memory element, the passive memory element comprising a first electrode system, an insulating system and a second electrode system, wherein the first electrode system is insulated from the second electrode system, wherein the first electrode system is a conductive surface, or a conductive layer of a support, the second electrode system is a plurality of isolated conductive areas and/or a plurality of conducting pins isolated from one another; and conductive bridges are present between at least one of the isolated conductive area, or at least one of the conducting pins, and the first electrode system; wherein with the exception of the first electrode system being a conductive surface of a support, the systems and the conductive bridges are printable using conventional printing processes; and a process for providing the passive memory device comprising the steps of: providing the support, realizing the conductive layer on the support if the support is non-metallic, realizing an insulating pattern system on the conductive surface or conductive layer, optionally providing a plurality of isolated conducting areas on the insulating pattern system, and providing conductive bridges at predesignated points between the first electrode system and at least one of the isolated conductive areas and/or a plurality of conducting pins isolated from one another, wherein at least one of the steps of optionally providing a conductive layer, providing an insulating pattern system, optionally providing a second electrode layer system and providing conductive bridges is realized with a conventional printing process.

Description

PRINTABLE NON-VOLATILE PASSIVE MEMORY ELEMENT AND METHOD OF MAKING THEREOF
FIELD OF THE INVENTION 5
The present invention concerns a printable passive memory element and method of making same.
BACKGROUND OF THE INVENTION
10
There is currently an increasing demand for disposable, inexpensive, flexible, passive memory device-containing tags and labels in which information is stored, for example as anti- counterfeiting tags in packaging. Production of such non-volatile
75 memory elements, including writing of the information, should be easy and inexpensive and preferably should be capable of being incorporated in the tag, label and package printing process or in the packaging process itself and should consist of uncomplicated and inexpensive materials and involve a minimum of processing
20 steps. For use in packages, it is important that the memory device is relatively robust and fairly insensitive to mechanical shock, temperature changes and other environmental influences .
Conventional silicon-based semiconductor memories have the disadvantage of requiring expensive and complex processing, the
25 high process temperatures and the non-flexibility making them unsuitable for use on packaging substrates. Moreover, silicon- based semiconductor memories pose considerable environmental issues upon disposal. US 6,542,397 discloses an apparatus comprising: at least one designated memory cell of a plurality of memory cells,
30 each designated memory cell having a resistance-altering constituent disposed therein, but only exemplifies silicon-based read-only resistor memories. US 6,649,499 discloses a method of making a memory comprising: diffusing of a resistance-altering constituent into a plurality of memory cells, the plurality of
35 memory cells comprising polycrystalline silicon and the resistance- altering constituent comprising at least one Group IA element; and moving at least a portion of an implanted dose of the resistance- altering constituent from the conductive layer of at least one memory cell. In these resistor memories, information is stored by
40 alteration of the resistance at pre-selected crossing points.
Crosstalk between adjacent word lines are reduced if the resistance in each memory cell is significantly higher than the resistance of the bit lines and word lines. However, this does not prevent the existence of alternative current paths.
US 6,107,666 discloses a high density ROM device, comprising: a substrate; and at least one memory array, including: a first insulating layer located over a surface of the substrate, plural bit lines located over the first insulating layer and extending in a first direction, said bit lines being spaced from one another at essentially equal intervals; a second insulating layer formed over the plural bit lines, at least one via formed in the second insulating layer and exposing a portion of the bit lines, and plural word lines located over the second insulating layer and extending in a second direction that crosses the first direction to form an angle, said word lines being spaced from one another at essentially equal intervals; and wherein some of the word lines are connected to the bit lines using the via and some of the word lines are isolated from the bit lines using the second insulating layer.
US 6,107,666 discloses a read only memory device which is not based on silicon, but in which metal bit lines and word lines are present. Electrical interconnects are made by the application of a metal in pre-selected vias present between the bit lines and word lines .
However, the production processes for the resistor memory cells disclosed in US 6,107,666, US 6,542,397 and US 6,649,499 all rely on evaporation and etching methods to apply the metal or silicon structures, requiring high temperatures in the range of 3000C to 4000C, which results in melting or severe degradation of polymer-based or paper-based substrates, hence making it unsuitable for packaging. Therefore such metal or silicon structures neither lend themselves to incorporation into tag, label and package printing process or into the packaging process nor do they lend themselves to environmentally friendly disposal.
Information can be stored electrically in a WORM memory by using the anti-fuse principle. US 6,656,763, for example, discloses a method of making an organic memory cell comprising: providing a first electrode; forming a passive layer comprising a conductivity facilitating compound over the first electrode; forming an organic semiconductor layer over the passive layer using a spin-on technique, the spin-on technique comprising applying a mixture of i) at least one of a conjugated organic polymer, a conjugated organometallic compound, a conjugated organometallic polymer, a buckyball, and a carbon nanotube and ii) at least one solvent selected from the group consisting of glycol ether esters, glycol ethers, furans, and alkyl alcohols containing from about 4 to about 7 carbon atoms; and providing a second electrode over the organic semiconductor layer.
Furthermore, US 2004/0149, 552Al discloses an electronic switch comprising: a first conductor; a second conductor; and a conductive organic polymer layer in contact with, and lying between, the first conductor and the second conductor, the conductive organic polymer layer in one of a first state in which the organic polymer layer conducts current between the first conductor and the second conductor with relatively high conductivity, and a second state, in which the organic polymer layer conducts current between the first conductor and the second conductor with relatively lower conductivity. The resistance of a semiconductor layer present between word lines and bit lines can be electrically altered by applying a Λhigh' voltage pulse, thereby increasing the resistance. To prevent alternative current paths it is necessary to include additional layers between the word lines and bit lines in each memory cell to form diodes, hereby making the manufacturing process more complicated.
The printing of memories has been proposed in the art for several different types of devices. US 2003/0230, 746Al discloses a memory device comprising: a first semiconducting polymer film having a first side and a second side, wherein said first semiconducting polymer film includes an organic dopant; a first plurality of electrical conductors substantially parallel to each other coupled to said first side of said first semiconducting polymer layer; and a second plurality of electrical conductors substantially parallel to each other, coupled to said second side of said first semiconducting polymer layer and substantially mutually orthogonal to said first plurality of electrical conductors, wherein an electrical charge is localized on said organic dopant. The structures of the doped semiconducting film, layered between two conducting line patterns are simple. However, these memories are volatile, and the information is lost if no power is applied. US 2001/039124A1 discloses a method for manufacturing a memory device which stores a state in accordance with the presence or the absence of a covering insulating film on a surface of an electrode at a memory cell position, the method comprising: selectively ejecting the insulating material using an inkjet head to the surface of the electrode at a predetermined memory cell position so as to cover the surface of the electrode at the predetermined memory cell position with the insulating material. WO 02/0029706A1 discloses an electronic bar code comprising: a bar code circuit that stores a code that is electronically readable, wherein the code is defined by a polymer printing process; and an interface coupled to the bar code circuit to allow a bar code reader to access the code stored in the bar code circuit. However, the printed electronic circuit does not consist of a passive matrix but a number of electronic components of which the presence or absence of the component or its connection determines the stored information. US 5,464,989 discloses a mask ROM having a plurality of memory cells, comprising: a semiconductor substrate having a main surface; a plurality of parallel first signal lines extending in a column direction on said main surface of said semiconductor substrate, a plurality of parallel second signal lines extending in a row direction on said main surface of said semiconductor substrate, crossing said plurality of first signal lines at a plurality of crossovers each forming a respective memory cell of said plurality of memory cells; an insulation film formed between said plurality of first signal lines and said plurality of second signal lines; and selecting means for selecting one of said plurality of first signal lines and one of said plurality of second signal lines and causing electric field between the selected first signal line and the selected second signal line by applying potential difference between the selected first signal line and the selected second signal line, said insulation film having, at each of said plurality of crossovers for storing data, one of i) a first thickness necessary for keeping an insulating state between the selected first signal line and the selected second signal line even if an electric field is received between the first signal line selected by the selecting means and the second signal line selected by the selecting means, ii) a second thickness for causing a first tunnel current to flow between the selected first signal line and the selected second signal line when the electric field is received between the first signal line and the second signal line selected by the selecting means, and iii) a third thickness for causing a second tunnel current to flow between the selected first signal line and the selected second signal line when the electric field is received between the first signal line and the second signal line selected by the selecting means. The production of a passive matrix ROM is thereby disclosed in US 5,464,989 based on conductive electrodes, separated by an isolating oxide film in which a tunnel phenomenon is generated with storage of multiple bit levels in one memory cell. Variations in the oxide layer thickness leads to different tunnel currents through the layer, which encode for multiple levels in the information in each cell.
WO 02/079316A discloses an aqueous composition containing a polymer or copolymer of a 3, 4-dialkoxythiophene in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion and a non-Newtonian binder; a method for preparing a conductive layer comprising: applying the above-described aqueous composition to an optionally subbed support, a dielectric layer, a phosphor layer or an optionally transparent conductive coating; and drying the thereby applied aqueous composition; antistatic and electroconductive coatings prepared according to the above- described method for preparing a conductive layer; a printing ink or paste comprising the above-described aqueous composition; and a printing process comprising: providing the above-described printing ink; printing the printing ink on an optionally subbed support, a dielectric layer, a phosphor layer or an optionally transparent conductive coating. However, WO 02/079316A only discloses the application of such inks for applying antistatic or electroconductive layers to an optionally subbed support, a dielectric layer, a phosphor layer or an optionally transparent conductive layer, which may be a step in the production of electroluminescent devices which can be used in lamps, displays, back-lights e.g. LCD, automobile dashboard and keyswitch backlighting, emergency lighting, cellular phones, personal digital assistants, home electronics, indicator lamps and other applications in which light emission is required.
WO 03/000765A discloses a non-dye containing flexographic ink containing a polymer or copolymer of a 3, 4-dialkoxythiophene in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion and a latex binder in a solvent or aqueous medium, characterized in that the polymer or copolymer of a 3,4- dialkoxythiophene is present in a concentration of at least 0.1% by weight in the ink and that the ink is capable of producing a colorimetrically additive transparent print; a method of preparing the flexographic ink; and a flexographic printing process therewith. However, WO 03/000765A only indicates the application of such inks for applying antistatic and electroconductive patterns to an optionally subbed support, a dielectric layer, a phosphor layer and a transparent conductive layer, which may be a step in the production of electrical circuitry for single and limited use items such as toys, in capacitive antennae as part of radiofrequency tags, in electroluminescent devices which can be used in lamps, displays, back-lights e.g. LCD, automobile dashboard and keyswitch back-lighting, emergency lighting, cellular phones, personal digital assistants, home electronics, indicator lamps and other applications in which light emission is required.
There is therefore a need for an easy and inexpensive means of storing information which can be easily incorporated in a tag, label or package printing process or the packaging process itself. Moreover, such easy and inexpensive means of storing information must be capable of lending itself to environmentally friendly disposal.
PRIOR ART:
Heretofore, the following prior art documents are known to the applicant:
US 5,464,989 published on November 7, 1995
US 6,107,666 published on August 22, 2000
US 6,542,397 published on April 1, 2003 US 6,649,499 published on November 18, 2003
US 6,656,763 published on December 2, 2003
US 2001/039124A1 published on November 8, 2001
US 2003/0230746A1 published on December 18, 2003
US 2004/0149552A1 published on August 5, 2004 WO 02/029706A1 published on April 11, 2002
WO 02/079316A1 published on October 10, 2002
WO 03/000765A1 published on January 3, 2003
Shawn Smith and Stephen R. Forrest: "A low switching voltage organic-on-inorganic heterojunction memory element utilizing a conductive polymer fuse on a doped silicon substrate" in Applied
Physics Letters, volume 84(24), pages 5019-5021 (2004) publication date June 14, 2004.
ASPECTS OF THE INVENTION:
It is therefore an aspect of the present invention to provide inexpensive non-volatile memory elements.
It is therefore a further aspect of the present invention to realize an easy and inexpensive means of storing information which can be easily incorporated in a tag, label or package printing process or the packaging process itself. It is a further aspect of the present invention to realize an easy and inexpensive means of storing information which is capable of lending itself to environmentally friendly disposal.
It is a still further aspect of the present invention to realize an electronic device which is characterized in that pads of an electrical conducting or semiconducting material are provided on a conductive surface and that an isolating material is provided between the first and second electrode, such that the two electrode planes are on top of one another without direct physical and electrical contact, and that an electrical conducting or semiconducting material is provided at pre-selected positions, contacting both the first and second electrode to make an electrical interconnect (conductive bridge) .
Further aspects and advantages of the invention will become apparent from the description hereinafter.
SUMMARY OF THE INVENTION
It has been surprisingly found that an element comprising a first electrode system, a second patterned electrode system, an insulating system between the first electrode system and the second patterned electrode system and at least one conductive bridge between the first electrode system and the second patterned electrode system, wherein the first electrode system is a conductive surface, or a conductive layer and wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first and the second electrode systems, is printable by conventional printing processes.
Aspects of the present invention are realized by a passive memory element comprising a first electrode system and a second electrode system, wherein the first electrode system is insulated from the second electrode system by a patterned insulating system, wherein the first electrode system is a conductive surface, or a conductive layer; wherein the second electrode system is a plurality of isolated conductive areas and/or a plurality of conducting pins isolated from one another; wherein conductive bridges are present between at least one of the isolated conductive areas of the second electrode system and the first electrode system or at least one conductive blob is provided from at least one predesignated point on the side of the insulating system not contiguous with the first electrode system to the conductive surface or the conductive layer which makes a conductive bridge, for read-out purposes only, between the first and the second electrode systems upon one of the plurality of conductive pins of the second electrode system coming into contact with the part of the conductive blob on the patterned insulating system; wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first and the second electrode systems; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, the systems, the at least one conductive bridge and the at least one conductive blob are printable using conventional printing processes.
Aspects of the present invention are also realized by a first passive memory device comprising at least one passive memory element and a support having at least one conductive surface or surface layer on the at least one side provided with the passive memory element, the passive memory element comprising a first electrode system and a second electrode system, wherein the first electrode system is insulated from the second electrode system by a patterned insulating system, wherein the first electrode system is a conductive surface, or a conductive layer; wherein the second electrode system is a plurality of isolated conductive areas optionally together with a plurality of conductive pins isolated from one another; wherein conductive bridges are present between at least one of the isolated conductive areas of the second electrode system and the first electrode system; wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first and the second patterned electrode systems; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, the systems and the conductive bridges are printable using conventional printing processes.
Aspects of the present invention are also realized by a precursor for a second passive memory device comprising a support and on at least one side of the support: a conductive surface of the support or a conductive layer on the support, a patterned insulating system on the conductive surface or the conductive layer and at least one conductive blob linking the conductive surface or the conductive layer to at least one position on the patterned insulating system, wherein the optional conductive layer, the patterned insulating system and the at least one conductive blob are printable using conventional printing techniques.
Aspects of the present invention are also realized by a second passive memory device comprising at least one passive memory element and a support having at least one conductive surface or surface layer on the at least one side provided with the passive memory element, the passive memory element comprising the conductive surface of the support or the surface layer on the support as a first electrode system, an insulating system, at least one conductive blob is provided from at least one predesignated point on the side of the insulating system not contiguous with the first electrode system to the first electrode system which makes a conductive bridge, for read-out purposes only, between the first and the second electrode systems upon one of the plurality of conductive pins of the second electrode system coming into contact with the part of the conductive blob on the patterned insulating system, wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first electrode system and second electrode system; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, the systems and the at least one conductive blob are printable using conventional printing processes .
Aspects of the present invention are also realized by a process for providing a first passive memory device comprising at least one passive memory element and a support having at least one conductive surface or conductive layer on the at least one side provided with the passive memory element, the passive memory element comprising a first electrode system and a second electrode system, wherein the first electrode system is insulated from the second electrode system, wherein the first electrode system is a conductive surface, or a conductive layer; wherein the second electrode system is a plurality of isolated conductive areas optionally together with a plurality of conductive pins isolated from one another; wherein conductive bridges are present between at least one of the isolated conductive areas of the second electrode system and the first electrode system; wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first and the second patterned electrode systems; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, the systems and the conductive bridges are printable using conventional printing processes, comprising the steps of: providing the support, realizing the conductive layer on the support if the support is non-metallic; realizing a patterned insulating system on the conductive surface or conductive layer, providing a plurality of isolated conducting areas on the patterned insulating system, and providing conductive bridges at predesignated points between at least one of the isolated conductive areas and the conductive surface or the conductive layer, wherein at least one of the steps of optionally providing a conductive layer, providing an patterned insulating system, providing a plurality of isolated conducting areas and providing conductive bridges is realized with a conventional printing process.
Aspects of the present invention are also realized by a process for providing a precursor for a second passive memory device, the precursor comprising a support and on at least one side of the support: a conductive surface of the support or a conductive layer on the support, a patterned insulating system on the conductive surface or the conductive layer and at least one conductive blob linking the conductive surface or the conductive layer to at least one position on the patterned insulating system, wherein the optional conductive layer, the patterned insulating system and the at least one conductive blob are printable using conventional printing techniques, comprising the steps of: providing the support, realizing the conductive layer on the support if the support is non-metallic, realizing the patterned insulating system and providing conductive blobs at predesignated points from the side of the insulating system not contiguous with the first electrode system to the conductive surface or the conductive layer, wherein at least one of the steps of optionally providing a conductive layer, providing the insulating system, and providing the the conductive blobs is realized with a conventional printing process.
Aspects of the present invention are also realized by a A process for providing a second passive memory device, the passive memory device comprising at least one passive memory element and a support having at least one conductive surface or surface layer on the at least one side provided with the passive memory element, the passive memory element comprising the conductive surface of the support or the surface layer on the support as a first electrode system, an insulating system, at least one conductive blob is provided from at least one predesignated point on the side of the insulating system not contiguous with the first electrode system to the first electrode system which makes a conductive bridge, for read-out purposes only, between the first and the second electrode systems upon one of the plurality of conductive pins of the second electrode system coming into contact with the part of the conductive blob on the patterned insulating system, wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first electrode system and second electrode system; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, the systems and the at least one conductive blob are printable using conventional printing processes, comprising the steps of: providing the support, realizing the conductive layer on the support if the support is non-metallic, realizing the patterned insulating system, providing at least one conductive blob from at least one predesignated point on the side of the insulating system not contiguous with the first electrode system to the conductive surface or the conductive layer and realizing a plurality of pins as the second electrode system for read-out purposes only, wherein at least one of the steps of optionally providing a conductive layer, providing the insulating system, providing the conductive blobs and providing the second electrode system is realized with a conventional printing process.
Preferred embodiments of the present invention are disclosed in the detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS:
Fig. 1 shows a top view of two memory devices with a continuous first electrode according to an embodiment of the present invention.
Fig. 2 illustrates a simple device in which the second electrode pattern is not printed.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
The term passive memory, as used in disclosing the present invention, means a non-volatile memory i.e. read-only memory and is to be distinguished from reversible memories.
The term "support", as used in disclosing the present invention, means a "self-supporting material" so as to distinguish it from a "layer" which may be coated on a support, but which is itself not self-supporting. It also includes any treatment necessary for, or layer applied to aid, either adhesion to a conductive surface layer or to an insulating system. The term printable, as used in disclosing the present invention, means capable of being printed by conventional impact and/or non-impact printing processes and excludes processes such as evaporation, etching, diffusion processes used in the production of conventional electronics e.g. silicon-based electronics.
The term conventional printing processes, as used in disclosing the present invention, includes but is not restricted to ink-jet printing, intaglio printing, screen printing, flexographic printing, offset printing, stamp printing, gravure printing and thermal and laser-induced processes.
The term impact printing process, as used in disclosing the present invention, means a printing process in which contact is made between the medium in which the print is produced and the printing system e.g. printers that work by striking an ink ribbon such as daisy-wheel, dot-matrix and line printers, and direct thermal printers in which the thermographic material is printed by direct contact with heating elements in a thermal head and printers in which a master is covered with an ink layer on areas corresponding to a desired image or shape, after which the ink is transferred to the medium, such as offset, gravure or flexographic printing.
The term non-impact printing process, as used in disclosing the present invention, means a printing process in which no contact is made between the medium in which the print is produced and the printing system e.g. electrographic printers, electrophotographic printers, laser printers, ink jet printers in which prints are produced without needing to strike the print medium. The term conductive bridge, as used in disclosing the present invention, means a conductive blob having any shape providing an electrical contact between the first and second electrode systems, which can be permanent or for read-out purposes only. An example of a permanent conductive bridge is one between an isolated conductive area (second electrode system) and a conductive surface or a conductive layer (first electrode system) . An example of a conductive bridge for read-out purposes only is one which is formed upon contact between the end of a conductive blob, forming a bridge between a conductive surface or a conductive layer (first electrode system) and a position on the side of the insulating system not contiguous with the first electrode system, on the insulating system with a predesignated pin (second electrode system) .
The term pattern, as used in disclosing the present invention, means a non-continuous layer which can be in any form of lines, squares, circles or any random configuration.
The term layer, as used in disclosing the present invention, means a coating covering the whole area of the entity referred to e.g. a support. The term conducting pin, as used in disclosing the present invention, means a conducting object capable of making contact to a conducting surface and can have any shape, and any profile, for example a square, rectangular, circular or ellipsoidal profile with for example dimensions in the range of 10 μm to 10mm, provided that no contact is made with neighbouring pins and contact with the conducting surface or conductive layer is realized. The conducting pins may therefore be conductive pads .
The term metallized support, as used in disclosing the present invention, means a support at least one surface of which is covered with metal by any process known to one skilled in the art e.g. printing, lamination, attachment of metal foil, sputtering and evaporation.
The term insulating layer, as used in disclosing the present invention, is a layer having high electrical resistance used for separating conducting layers, which prevents an undesired flow of current between conducting layers contiguous with either side of the insulating layer and specifically is a layer providing a leak current between two electrodes of < 5 μA measured at a voltage of 5V.
The term conductive is related to the electric resistance of the material, the electric resistance of a layer being generally expressed in terms of surface resistance Rs (unit Ω; often specified as Ω/square) . Alternatively, the conductivity may be expressed in terms of the specific (volume) resistivity Rv = Rs • d, wherein d is the thickness of the layer, and Rv or p is in units of ohm-cm. The term conductive, as used in disclosing the present invention, means a material having a surface resistance of < 106
4 ohm/square, preferably < 10 ohm/square or having a specific resistivity of < 102 ohm-cm, preferably < 1 ohm-cm.
The term intrinsically conductive polymer, as used in disclosing the present invention, means organic polymers which have
(poly) -conjugated π-electron systems (e.g. double bonds, aromatic or heteroaromatic rings or triple bonds) and whose conductive properties are not influenced by environmental factors such as relative humidity.
The term transparent, as used in disclosing the present invention, means having the property of transmitting at least 70% of the incident light without diffusing it. The term flexible, as used in disclosing the present invention, means capable of following the curvature of a curved object such as a drum e.g. without being damaged. PEDOT, as used in disclosing the present invention, represents poly(3, 4-ethylenedioxythiophene) .
PSS, as used in disclosing the present invention, represents poly(styrene sulfonic acid) or poly(styrene sulfonate) . PANI, as used in disclosing the present invention, represents polyaniline.
Passive memory element
Aspects of the present invention are realized by a passive memory element comprising a first electrode system and a second electrode system, wherein the first electrode system is insulated from the second electrode system by a patterned insulating system, wherein the first electrode system is a conductive surface, or a conductive layer; wherein the second electrode system is a plurality of isolated conductive areas and/or a plurality of conducting pins isolated from one another; wherein conductive bridges are present between at least one of the isolated conductive areas of the second electrode system and the first electrode system or at least one conductive blob is provided from at least one predesignated point on the side of the insulating system not contiguous with the first electrode system to the conductive surface or the conductive layer which makes a conductive bridge, for read-out purposes only, between the first and the second electrode systems upon one of the plurality of conductive pins of the second electrode system coming into contact with the part of the conductive blob on the patterned insulating system; wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first and the second electrode systems; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, the systems, the at least one conductive bridge and the at least one conductive blob are printable using conventional printing processes . According to a first embodiment of the passive memory element, according to the present invention, the second electrode system is a plurality of conducting pins, which are part of a read-out device.
According to a second embodiment of the passive memory element, according to the present invention, the second electrode system is a plurality of isolated conductive areas.
The passive memory element, according to the present invention, can be produced in an inexpensive way by reel-to-reel printing. The printing process consists of at least one step, a) optionally printing a conductive layer being the first electrode system on a non-metallic support, b) printing of a pattern of an insulating material on a conductive substrate, c) optionally printing of the conductive pads of a second electrode on the insulating material thereby realizing the second electrode pattern, such that the two electrode planes are on top of one another without direct physical and electrical contact. Information is then stored either by the separate printing of a conducting material at pre-selected positions to form conductive bridges or the information is stored together with the printing of the second electrode pattern step in the printing of the passive memory element.
Such an off-line step of storing the information by applying conductive bridges on pre-selected positions between the conductive surface of the substrate and the second electrode pattern can be carried out by, for example, ink-jet printing, at the same or at a different location, at the same time or at a later time. This enables the personalization of each passive memory element with different information.
The passive memory element, according to the present invention, is producible by a printing process. Information may be stored by creating conductive bridges via a printing process.
In another embodiment, information is stored in the memory device by a combination of two or more printing steps, for example one part of the information is printed together with the second electrode and a second part is printed in a separate printing step in which additional ^conductive bridges' are printed. The first part of information might contain fixed information such as the name of a manufacturer, while the second part is variable, such as the production date or batch number.
According to a third embodiment of the passive memory element, according to the present invention, the passive memory element comprises a first electrode system, an insulating system and a second electrode system, wherein the first electrode system is insulated from the second electrode system, wherein the first electrode system is a conductive surface or a conductive layer of a support, wherein the second electrode system is a plurality of isolated conductive areas, or a plurality of conducting pins isolated from one another, wherein at least one conductive bridge is present between at least one conducting pin and the first electrode system, wherein with the exception of the first electrode system being a conductive surface, the systems and the conductive bridges are printable using conventional printing processes.
Passive memory element - operation
The present invention provides a passive memory device comprising at least one simple passive memory element, that is producible by printing processes, in which information is stored by providing electrical interconnects (conductive bridges) between a conductive surface or conductive layer (first electrode) and the second electrode system at pre-selected positions. Information is stored by the presence or absence of a conductive bridge. The conductive surface or conductive layer and second electrode system are electrically insulated from one another by an insulating system (material) . By means of printing of a conducting system at a pre¬ selected position, a conductive bridge is formed between the conductive surface or conductive layer (first electrode system) and the second electrode system. Read-out of the data is accomplished by measuring the resistance between the conductive surface or conductive layer (first electrode system) and the second electrode system for all possible positions. The resistivity can be read-out electrically in contact or capacitively and corresponds to logical values in a binary code.
The structure of the passive memory element in the passive memory device, according to the present invention, preferably comprises a two-dimensional array of electrically conductive pads on a conductive surface and comprising an insulating material between the first and second electrodes, such that the two electrode planes are on top of one another without direct physical and electrical contact, and comprising an electrical conducting or semiconducting material, provided at pre-selected positions of the first and second electrode, contacting both the first and second electrode to make a conductive bridge.
Another aspect of the present invention relates to the retrieval of the covert information in the memory device by subsequent measurement of the resistance between the conductive surface and each conductive pad, wherein a low resistance, corresponding to an electrical conductive bridge, denotes one binary state and a high resistance, corresponding to a conductive pad without an electrical conductive bridge, denotes a second binary state. Passive memory device - configuration
Aspects of the present invention are realized by a first passive memory device comprising at least one passive memory element and a support having at least one conductive surface or surface layer on the at least one side provided with the passive memory element, the passive memory element comprising a first electrode system and a second electrode system, wherein the first electrode system is insulated from the second electrode system by a patterned insulating system, wherein the first electrode system is a conductive surface, or a conductive layer; wherein the second electrode system is a plurality of isolated conductive areas optionally together with a plurality of conductive pins isolated from one another; wherein conductive bridges are present between at least one of the isolated conductive areas of the second electrode system and the first electrode system; wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first and the second patterned electrode systems; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, the systems and the conductive bridges are printable using conventional printing processes.
Aspects of the present invention are realized by second passive memory device comprising at least one passive memory element and a support having at least one conductive surface or surface layer on the at least one side provided with the passive memory element, the passive memory element comprising the conductive surface of the support or the surface layer on the support as a first electrode system, an insulating system, at least one conductive blob is provided from at least one predesignated point on the side of the insulating system not contiguous with the first electrode system to the first electrode system which makes a conductive bridge, for read-out purposes only, between the first and the second electrode systems upon one of the plurality of conductive pins of the second electrode system coming into contact with the part of the conductive blob on the patterned insulating system, wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first electrode system and second electrode system; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, the systems and the at least one conductive blob are printable using conventional printing processes . According to a first embodiment of the passive memory devices, according to the present invention, the first or second passive memory device is exclusive of metallic silicon.
According to a second embodiment of the passive memory devices, according to the present invention, the support is a flexible or rigid plastic, glass, paper, board, carton or a composite material of any of these materials.
According to a third embodiment of the passive memory devices, according to the present invention, the support is a metallic support, a metallized support or a support provided with a conductive layer.
According to a fourth embodiment of the passive memory devices, according to the present invention, at least one of the conductive surface, the second patterned electrode systems and the at least one conductive bridge comprises an inorganic conducting medium, e.g. a metal, a semiconducting metal oxide and carbon, or an organic conducting medium, e.g. an intrinsically conductive organic polymer.
According to a fifth embodiment of the passive memory devices, according to the present invention, at least one of the conductive surface, the second patterned electrode systems and the at least one conductive bridge comprises an organic conducting medium, which is an intrinsically conductive organic polymer.
According to a sixth embodiment of the passive memory devices, according to the present invention, at least one of the conductive surface, the second patterned electrode systems and the at least one conductive bridge comprises a polythiophene, a polyaniline or a polypyrrole.
According to a seventh embodiment of the passive memory devices, according to the present invention, at least one of the conductive surface, the second patterned electrode systems and the at least one conductive bridge comprises a poly(3,4- dioxyalkylenethiophene) .
According to an eighth embodiment of the passive memory devices, according to the present invention, at least one of the conductive surface, the second patterned electrode systems and the at least one conductive bridge comprises poly(3,4- dioxyethylenethiophene) .
According to a ninth embodiment of the passive memory devices, according to the present invention, at least one of the conductive surface, the second patterned electrode systems and the at least one conductive bridge comprises carbon. According to a tenth embodiment of the passive memory devices, according to the present invention, at least one of the conductive surface, the second patterned electrode systems and the at least one conductive bridge comprises a metal e.g. silver or gold. According to an eleventh embodiment of the passive memory devices, according to the present invention, at least one of the conductive surface, the second patterned electrode systems and the at least one conductive bridge comprises a semiconducting metal oxide or doped metal oxide e.g. vanadium pentoxide, indium tin oxide or a metal antimonate.
The conductivity of the electrodes and conductive bridges needs to be sufficient to have a current flowing through a conductive bridge that is significantly higher than the current measured without a conductive bridge. The resistance is preferably in the range of 1 Ohm to 100 kOhm per square and more preferably lower than 20,000 Ohm per square. The width and length of the isolated conductive areas can be in the range from 5 μm to 10 mm and more preferably from 100 μm to 0.5 mm.
The position of the ^conductive bridges' in the memory device may be different for each device, thus storing personalized/individual information, such as name, address, date of birth, etc or a products' manufacturing date/time and pricing.
According to a twelfth embodiment of the passive memory devices, according to the present invention, the passive memory device is transparent, thereby becoming almost invisible to the unaided eye. This can be realized by using for example PEDOTrPSS as the conductive material for the electrodes and ^conductive bridges', and by using a transparent isolating material, for example a UV-curable ink. According to a thirteenth embodiment of the passive memory device, according to the present invention, the passive memory device may be combined with one or more security features e.g. security inks based on magnetic, infrared-absorbing, thermochromic, photochromic, coin-reactive, optically variable, fluorescent or phosphorescent compounds and the like, chemical or biological taggants based on isotopes, DNA, antibodies or specific detectable ingredients and the like can be included in one of the layers of the memory device. The memory device may be overcoated or overprinted with a hologram, tamper proof security film, a barcode or the like. The memory device, according to the present invention, may be printed on security paper. According to a fourteenth embodiment of the passive memory devices, according to the present invention, the number of conductive bridges is at least two.
According to a fifteenth embodiment of the first passive memory device, according to the present invention, the ^conductive bridges' are coloured, for example black by using a carbon black- based ink.
According to a sixteenth embodiment of the first passive memory device, according to the present invention, to visually hide the location of the ^conductive bridges', non-conducting black bridges may be printed on the remaining positions without conductive bridges . The conducting and non-conducting bridges may have any colour, for example by adding dyes or pigments.
According to a seventeenth embodiment of the first passive memory device, according to the present invention, the memory device is overprinted with an image or homogeneously coloured or opaque layer to visually hide the location of the ^conductive bridges' .
According to an eighteenth embodiment of the first passive memory device, according to the present invention, a coloured or opaque foil is laminated over the memory device to visually hide the location of the ^conductive bridges' .
According to a nineteenth embodiment of the first passive memory device, the first passive memory device comprises a support having at least one conductive surface or surface layer and on at least one side of the support a passive memory element, the passive memory element comprising a conductive surface or the surface layer of the support, a plurality of isolated conductive areas and a patterned insulating system between the conductive surface or surface layer of the support and the plurality of isolated conducting areas, there being a conductive bridge between at least one predesignated isolated conductive area of the plurality of isolated conductive areas and the conductive surface or surface layer of the support, wherein the passive memory element is producible using conventional printing processes and is exclusive of silicon metal and in the absence of the at least one conductive bridge there is no direct electrical contact between the first and the second patterned electrode systems.
According to a fifteenth embodiment of the second passive memory device, the second passive memory device comprises a support having at least one conductive surface or surface layer and on at least one side of the support a passive memory element, according to claim 1, the passive memory element comprising the conductive surface or the surface layer of the support, a plurality of conducting pins isolated from another making contact with the patterned insulating system thereby being a second electrode system, there being a conductive bridge between at least one predesignated conductive pin and the conductive surface or surface layer of the support, wherein the passive memory element excluding the conducting pins is producible using conventional printing processes and is exclusive of silicon metal and in the absence of the at least one conductive bridge there is no direct electrical contact between the first electrode system and the at least one of the plurality of conducting pins.
In one embodiment, the first electrode is continuous, the second electrode can be one-dimensional (one row of conducting lines, Fig. Ia) or two-dimensional (patches/dots of a conducting or semiconducting material in an array configuration) . The first electrode may be an integral part of a package, such as a metallic blister package. The second electrode is physically and electrically isolated from the first electrode. Conductive bridges are made at pre-selected positions between the first and second electrode. This might be in a separate printing step, or combined with the printing of the second electrode. (Fig. Ib) .
Fig. 2 shows a more simple embodiment, in which the second electrode is not printed, but conductive bridges and conducting patches are only printed at pre-selected positions. Electrical readout will differentiate between an area where no conducting material is present (only insulating material on first electrode system) and an area where an isolated conducting area and conductive bridge is present.
Insulating Systems
The term insulating system, as used in disclosing the present invention, means a permanently insulating system i.e. a system whose properties are unchangeable under normal ambient conditions, whose resistance is unalterable by applying high voltage electrical pulses and excludes semiconducting layers whose conductivity can be influenced by doping, such as disclosed in US 6,656,763, and conductive organic polymer layers whose conductivity state can change upon the application of a relatively large voltage differential between a first and a second electrode contiguous each continuous with one of the sides of the insulating system, such as disclosed in US 2004/0149552A1. Suitable insulation materials are inorganic and organic materials e.g. polymeric materials such as homopolymers and copolymers selected, for example, from the group consisting of acrylates, olefins, methacrylates, acrylamides, methacrylamides, acrylonitrile, vinyl chloride, vinyl alcohol, vinylidene chloride, vinyl fluoride, vinylidene fluoride, other fluorinated ethylene compounds, vinyl alcohol, vinyl acetals, vinyl acetate, styrene and butadiene; inorganic fillers, such as silica, alumina, alumina hydrates, and inorganic fibres, such as glass fibres. The insulating system can also be a UV-curable ink or varnish.
Process for producing the memory passive device
Aspects of the present invention are realized by a process for providing a first passive memory device comprising at least one passive memory element and a support having at least one conductive surface or conductive layer on the at least one side provided with the passive memory element, the passive memory element comprising a first electrode system and a second electrode system, wherein the first electrode system is insulated from the second electrode system, wherein the first electrode system is a conductive surface, or a conductive layer; wherein the second electrode system is a plurality of isolated conductive areas optionally together with a plurality of conductive pins isolated from one another; wherein conductive bridges are present between at least one of the isolated conductive areas of the second electrode system and the first electrode system; wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first and the second patterned electrode systems; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, the systems and the conductive bridges are printable using conventional printing processes, comprising the steps of: providing the support, realizing the conductive layer on the support if the support is non-metallic; realizing a patterned insulating system on the conductive surface or conductive layer, providing a plurality of isolated conducting areas on the patterned insulating system, and providing conductive bridges at predesignated points between at least one of the isolated conductive areas and the conductive surface or the conductive layer, wherein at least one of the steps of optionally providing a conductive layer, providing an patterned insulating system, providing a plurality of isolated conducting areas and providing conductive bridges is realized with a conventional printing process.
Aspects of the present invention are realized by a process for providing a second passive memory device, the passive memory device comprising at least one passive memory element and a support having at least one conductive surface or surface layer on the at least one side provided with the passive memory element, the passive memory element comprising the conductive surface of the support or the surface layer on the support as a first electrode system, an insulating system, at least one conductive blob is provided from at least one predesignated point on the side of the insulating system not contiguous with the first electrode system to the first electrode system which makes a conductive bridge, for read-out purposes only, between the first and the second electrode systems upon one of the plurality of conductive pins of the second electrode system coming into contact with the part of the conductive blob on the patterned insulating system, wherein in the absence of the at least one conductive bridge there is no direct electrical contact between the first electrode system and second electrode system; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, the systems and the at least one conductive blob are printable using conventional printing processes, comprising the steps of: providing the support, realizing the conductive layer on the support if the support is non-metallic, realizing the patterned insulating system, providing at least one conductive blob from at least one predesignated point on the side of the insulating system not contiguous with the first electrode system to the conductive surface or the conductive layer and realizing a plurality of pins as the second electrode system for read-out purposes only, wherein at least one of the steps of optionally providing a conductive layer, providing the insulating system, providing the conductive blobs and providing the second electrode system is realized with a conventional printing process. All the layers in the memory device, isolated conductive areas, insulating pattern system and ^conductive bridges', can be applied by conventional printing processes including but not restricted to ink-jet printing, intaglio printing, screen printing, flexographic printing, offset printing, stamp printing, gravure printing and thermal and laser-induced processes. Either one printing process can be used for all the layers in the memory device, or a combination of two or more printing processes can be used. According to a first embodiment of the processes, according to the present invention, the first or second passive memory device is exclusive of metallic silicon.
According to a second embodiment of the processes, according to the present invention, the conventional printing process is a non-impact printing process e.g. ink-jet printing, electrophotographic printing and electrographic printing.
According to a third embodiment of the processes, according to the present invention, the conventional printing process is an impact printing process e.g. offset printing, screen printing, flexographic printing and stamp printing.
According to a fourth embodiment of the processes, according to the present invention, the conventional printing process is selected from the group consisting of ink-jet printing, intaglio printing, screen printing, flexographic printing, offset printing, stamp printing, gravure printing, electrophotographic printing, electrographic printing and thermal and laser-induced processes.
Printing according to the processes, according to the present invention, can be carried out directly on a package, on a label, a ticket, an ID-card, a bank card, a legal document and banknotes. The memory device may act as an identification system, a security feature, an anti-counterfeiting feature, etc.
According to a fifth embodiment of the process for providing a first passive memory device, according to the present invention, the insulating pattern, the second electrode pattern and the at least one conductive bridge are performed by the same printing process .
According to a sixth embodiment of the process for providing a first passive memory device, according to the present invention, the insulating pattern, the second electrode pattern and the at least one conductive bridge are performed by ink-jet printing.
According to a sixth embodiment of the process for providing a second passive memory device, according to the present invention, the process for providing a second passive memory device comprising a support having at least one conductive surface or surface layer and on at least one side of the support a passive memory element, the passive memory element comprising a conductive surface or the surface layer of the support, a plurality of isolated conductive areas and a patterned insulating system between the conductive surface of the metallic support and the plurality of isolated conducting areas, there being a conductive bridge between at least one predesignated isolated conductive areas of the plurality of isolated conductive areas and the conductive surface or surface layer of the support, and wherein each of a plurality of conducting pins makes contact with one of the plurality of isolated conducting areas, wherein the passive memory element is producible using conventional printing processes and is exclusive of silicon metal and in the absence of the at least one conductive bridge there is no direct electrical contact between the first and the second patterned electrode systems, comprises the steps of: realizing the insulating pattern system on the conductive surface layer, providing a plurality of isolated conducting areas on the insulating pattern system, and providing conductive bridges at predesignated points between at least one of the isolated conductive areas and the conductive surface layer, and bringing each of the isolated conductive areas into electrical contact with one of the conductive pins, wherein at least one of the steps of providing an insulating pattern system, providing a plurality of isolated conducting areas and providing conductive bridges is realized with a conventional printing process.
Conductive screen printing inks
WO-A 02/079316 discloses an aqueous composition containing a polymer or copolymer of a 3, 4-dialkoxythiophene in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion and a non-Newtonian binder; a method for preparing a conductive layer comprising: applying the above-described aqueous composition to an optionally subbed support, a dielectric layer, a phosphor layer or an optionally transparent conductive coating; and drying the thereby applied aqueous composition; antistatic and electroconductive coatings prepared according to the above- described method for preparing a conductive layer; a printing ink or paste comprising the above-described aqueous composition; and a printing process comprising: providing the above-described printing ink; printing the printing ink on an optionally subbed support, a dielectric layer, a phosphor layer or an optionally transparent conductive coating. The screen printing ink formulations disclosed in WO-A 02/079316 are specifically incorporated herein by reference.
WO-A 03/048228 discloses a method for preparing a composition containing between 0.08 and 3.0% by weight of polymer or copolymer of a 3, 4-dialkoxythiophene in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion and at least one non-aqueous solvent from a dispersion of the polymer or copolymer of (3, 4-dialkoxythiophene) and the polyanion in water which is prepared in the substantial absence of oxygen, comprising in the following order the steps of: i) mixing at least one of the non¬ aqueous solvents with the aqueous dispersion of the polymer or copolymer of (3, 4-dialkoxythiophene) and the polyanion; and ii) evaporating water from the mixture prepared in step i) until the content of water therein is reduced by at least 65% by weight; a printing ink, printing paste or coating composition, capable of yielding layers with enhanced conductivity at a given transparency, prepared according to the above-described method; a coating process with the coating composition thereby producing a layer with enhanced conductivity at a given transparency; and a printing process with the printing ink or paste thereby producing a layer with enhanced conductivity at a given transparency. The screen printing ink formulations disclosed in WO-A 03/048228 are specifically incorporated herein by reference.
WO-A 03/048229 discloses a method for preparing a composition containing between 0.08 and 3.0% by weight of a polymer or copolymer of a 3, 4-dialkoxythiophene in which the two alkoxy groups may be the same or different or together represent a oxy-alkylene- oxy bridge optionally substituted with substituents selected from the group consisting of alkyl, alkoxy, alkyoxyalkyl, carboxy, alkylsulphonato, alkyloxyalkylsulphonato and carboxy ester groups, a polyanion and at least one polyhydroxy non-aqueous solvent from a dispersion of the polymer or copolymer of (3, 4-dialkoxythiophene) and the polyanion in water comprising in the following order the steps of: i) mixing at least one of the non-aqueous solvents with the aqueous dispersion of the polymer or copolymer of (3,4- dialkoxythiophene) and the polyanion; and ii) evaporating water from the mixture prepared in step i) until the content of water therein is reduced by at least 65% by weight; a printing ink, printing paste or coating composition, capable of yielding layers with an enhanced transparency at a given surface resistance, prepared according to the above-described method; a coating process with the coating composition thereby producing a layer with enhanced transparency at a given surface resistance; and a printing process with the printing ink or paste thereby producing a layer with enhanced transparency at a given surface resistance. The screen printing ink formulations disclosed in WO-A 03/048229 are specifically incorporated herein by reference.
Conductive flexographic printing inks WO-A 03/000765 discloses a non-dye containing flexographic ink containing a polymer or copolymer of a 3, 4-dialkoxythiophene in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion and a latex binder in a solvent or aqueous medium, characterized in that the polymer or copolymer of a 3,4- dialkoxythiophene is present in a concentration of at least 0.1% by weight in the ink and that the ink is capable of producing a colorimetrically additive transparent print; a method of preparing the flexographic ink; and a flexographic printing process therewith. The flexographic printing ink formulations disclosed in WO-A 03/000765 are specifically incorporated herein by reference.
Conductive ink-jet inks
Formulations containing a polymer or copolymer of a 3,4- dialkoxythiophene in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy- alkylene-oxy bridge, a polyanion and a high boiling point liquid in a solvent or aqueous medium can be prepared, which are suitable for ink- jet printing. Critical properties, such as the viscosity, which at the jetting temperature is preferably in the range of 3 to 15 mPa.s for a Universal Print Head (from AGFA-GEVAERT) , can be adjusted by changing the concentration of conductive polymer and the amount and type of high boiling point liquid. A 1.2% by weight dispersion of PEDOTrPSS has a viscosity of approximately 30 mPa.s at room temperature and a 0.6% by weight dispersion has a viscosity at room temperature of approximately 10 mPa.s.
The surface tension is preferably in the range of 28 to 36 mN/m under jetting conditions for a Universal Print Head, and can be adjusted by adding appropriate anionic, cationic or non-ionic surfactants or solvents, e.g. alcohols. Surfactants can also influence the jetting performance, wetting properties of the ink on a substrate and the UV-stability of printed layers. The addition of, for example, 5 to 20% by weight of high boiling point liquids improves the conductivity of the printed layer after drying; useful high boiling point liquids include ethylene glycol, diethylene glycol, propylene glycol, glycerol, N-methylpyrrolidon and 2-pyrrolidon. The choice of high boiling point liquid also has an influence on drying time, minimum drying temperature, jetting performance, wetting properties, viscosity and surface tension. Optionally, volatile bases, such as dimethylethanolamine, triethylamine or diisopropylethylamine might be added to neutralize the inkjet printing solution to prevent corrosion of the print head.
Industrial application
The passive memory devices, according to the present invention, can be used in security and anti-counterfeiting applications e.g. in tickets, labels, tags, an ID-card, a bank card, a legal document, banknotes and packaging and can also be integrated into packaging.
The invention is illustrated hereinafter by way of comparative examples and invention examples . The percentages and ratios given in these examples are by weight unless otherwise indicated.
Commercial coatings used in the elements of the INVENTION EXAMPLES:
• AGORIX MAGENTA INK, a UV-hardenable ink-jet ink from AGFA-DOTRIX N.V. ;
• ED4000, a carbon black ink from ELECTRA POLYMERS;
• NORIPET® 093 Clear, an insulating screen printing ink from Prδll
Ingredients used in non-commercial coatings used in the elements of the INVENTION EXAMPLES:
• TANACOTE® FG3, an aqueous carboxylated polypropylene emulsion from SYBRON CHEMICALS;
• PANIPOL® W, a 6% by weight aqueous dispersion of polyaniline from PANIPOL LTD. ;
• DYNOL® 604, an acetylenic glycol-based surfactant from AIR PRODUCTS.
INVENTION EXAMPLE 1
FULLY INKJET PRINTED ELEMENT WITH CONDUCTIVE PADS
The passive memory element of INVENTION EXAMPLE 1 was produced by inkjet printing two layers of AGORIX Magenta INK on top of one another on four different conductive surfaces, using the Universal Printhead (from AGFA-GEVAERT) and then UV-cured, thereby forming an insulating line pattern consisting of 8 lines spaced 3 mm apart with dimensions of 55 x 2.5 mm2. The four conductive surfaces used, were:
1) a 13 μm thick aluminium foil;
2) a Thermostar P970 aluminium offset printing plate (backside) ;
3) a subbed PET-substrate with a continuous layer of flexographic PEDOTrPSS ink:
Figure imgf000030_0001
applied via flexo printing and dried at 80 0C for 3 minutes; and 4) a subbed PET-substrate with a continuous silver layer, applied via a diffusion transfer reversal process with a non-exposed silver halide donor sheet (Copyproof Negative Film NPC from Agfa-Gevaert) .
The second electrode system was produced by inkjet printing conductive pads of 1 x 4 mm with a PEDOTrPSS inkjet ink having the composition given in table 1, on top of the insulating pattern. Finally ^conductive bridges' were applied by inkjet printing lines of 1 x 3 mm using the Universal Printhead with the PEDOTrPSS ink-jet ink at pre-selected positions to form the conductive bridges .
Table Ir
Figure imgf000030_0002
Figure imgf000031_0001
The resistance between the continuous first electrode and the second electrode pads was measured with a Fluke Multimeter and is given in table 2.
Table 2:
Figure imgf000031_0002
INVENTION EXAMPLE 2
10
INKJET PRINTED ELEMENT WITHOUT CONDUCTIVE PADS
The passive memory element of INVENTION EXAMPLE 2 was produced as described in INVENTION EXAMPLE 1, with the exception that no
75 second electrode pads were printed. In addition to ink-jet printing the conductive bridges with the PEDOTrPSS ink-jet ink, conductive bridges were also applied manually, using PANIPOL W and ED4000. The resistance is measured either between the continuous first electrode and a conductive bridge, or between
20 the continuous first electrode and an area on the insulating pattern without conductive bridge, the results are given in Table 3.
Table 3:
25
Figure imgf000031_0003
Figure imgf000032_0001
INVENTION EXAMPLE 3
FULLY TRANSPARENT DEVICE VIA COMBINATION OF SCREEN AND INKJET PRINTING
The passive memory element of INVENTION EXAMPLE 3 was produced by screen printing lines with dimensions of 2 x 50 mm2 spaced 1.5 mm apart using Noripet 093 Clear with a screen of mesh P79 on an ORGACON EL-1500 substrate and drying at 1300C for 3 minutes.
Conductive bridges with or without second electrode pads were prepared by inkjet printing PEDOTrPSS, as described in INVENTION EXAMPLES 1 and 2. Electrical measurements were performed as described in INVENTION EXAMPLES 1 and 2 and results are given in Table 4.
Table 4:
Figure imgf000032_0002
The present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention. In view of the foregoing description it will be evident to a person skilled in the art that various modifications may be made within the scope of the invention.

Claims

1. A passive memory element comprising a first electrode system and a second electrode system, wherein said first electrode system is insulated from said second electrode system by a patterned insulating system, wherein said first electrode system is a conductive surface, or a conductive layer; wherein said second electrode system is a plurality of isolated conductive areas and/or a plurality of conducting pins isolated from one another; wherein conductive bridges are present between at least one of said isolated conductive areas of said second electrode system and said first electrode system or at least one conductive blob is provided from at least one predesignated point on the side of the insulating system not contiguous with said first electrode system to said conductive surface or said conductive layer which makes a conductive bridge, for read-out purposes only, between said first and said second electrode systems upon one of said plurality of conductive pins of the second electrode system coming into contact with the part of the conductive blob on said patterned insulating system; wherein in the absence of said at least one conductive bridge there is no direct electrical contact between said first and said second electrode systems; and wherein, with the exception of said first electrode system being the conductive surface of a metallic support, said systems, said at least one conductive bridge and said at least one conductive blob are printable using conventional printing processes.
2. Passive memory element according to claim 1, wherein said second electrode system is a plurality of conducting pins, which are part of a read-out device.
3. Passive memory element according to claim 1, wherein said second electrode system is a plurality of isolated conductive areas .
4. A first passive memory device comprising at least one passive memory element and a support having at least one conductive surface or surface layer on the at least one side provided with said passive memory element, said passive memory element comprising a first electrode system and a second electrode system, wherein the first electrode system is insulated from the second electrode system by a patterned insulating system, wherein the first electrode system is a conductive surface, or a conductive layer; wherein said second electrode system is a plurality of isolated conductive areas optionally together
5 with a plurality of conductive pins isolated from one another; wherein conductive bridges are present between at least one of said isolated conductive areas of said second electrode system and said first electrode system; wherein in the absence of said at least one conductive bridge there is no direct io electrical contact between said first and said second patterned electrode systems; and wherein, with the exception of said first electrode system being the conductive surface of a metallic support, said systems and said conductive bridges are printable using conventional printing processes.
75
5. First passive memory device according to claim 4, wherein said first passive memory device is exclusive of metallic silicon.
20 6. First device according to claim 4 or 5, wherein said first passive memory device is transparent.
7. First device according to any one of claims 4 to 6, wherein said conductive bridges are coloured.
25
8. First device according to any one of claims 4 to 7, said passive memory device is overprinted with an image or a homogeneously coloured or opaque layer to visually hide the location of said conductive bridges.
30
9. First device according to any one of claims 4 to 8, a coloured or opaque foil is laminated over said passive memory device to visually hide the location of said conductive bridges.
35 10. First device according to any one of claims 4 to 9, wherein at least one of said first and second patterned electrode systems comprises an inorganic conducting medium or an organic conducting medium.
40 11. First device according to claim 10, wherein said organic conducting medium is an intrinsically conductive organic polymer.
12. First device according to claim 11, wherein said intrinsically conductive organic polymer is a polythiophene, a polyaniline or a polypyrrole.
13. First device according to claim 11 or 12, wherein said polythiophene is a poly(3, 4-dioxyalkylenethiophene) .
14. First device according to any one of claims 11 to 13, wherein said polythiophene is poly(3, 4-dioxyethylenethiophene) .
15. A precursor for a second passive memory device comprising a support and on at least one side of said support: a conductive surface of said support or a conductive layer on said support, a patterned insulating system on said conductive surface or said conductive layer and at least one conductive blob linking said conductive surface or said conductive layer to at least one position on said patterned insulating system, wherein said optional conductive layer, said patterned insulating system and said at least one conductive blob are printable using conventional printing techniques .
16. A second passive memory device comprising at least one passive memory element and a support having at least one conductive surface or surface layer on the at least one side provided with said passive memory element, said passive memory element comprising said conductive surface of said support or said surface layer on said support as a first electrode system, an insulating system, at least one conductive blob is provided from at least one predesignated point on the side of the insulating system not contiguous with said first electrode system to said first electrode system which makes a conductive bridge, for read-out purposes only, between said first and said second electrode systems upon one of said plurality of conductive pins of the second electrode system coming into contact with the part of the conductive blob on said patterned insulating system, wherein in the absence of said at least one conductive bridge there is no direct electrical contact between the first electrode system and second electrode system; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, said systems and said at least one conductive blob are printable using conventional printing processes.
17. A process for providing a first passive memory device comprising at least one passive memory element and a support having at least one conductive surface or conductive layer on the at least one side provided with said passive memory 5 element, said passive memory element comprising a first electrode system and a second electrode system, wherein the first electrode system is insulated from the second electrode system, wherein the first electrode system is a conductive surface, or a conductive layer; wherein the second electrode
10 system is a plurality of isolated conductive areas optionally together with a plurality of conductive pins isolated from one another; wherein conductive bridges are present between at least one of said isolated conductive areas of said second electrode system and said first electrode system; wherein in
75 the absence of said at least one conductive bridge there is no direct electrical contact between said first and said second patterned electrode systems; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, said systems and said conductive bridges
20 are printable using conventional printing processes, comprising the steps of: providing said support, realizing said conductive layer on the support if the support is non- metallic; realizing a patterned insulating system on said conductive surface or conductive layer, providing a plurality
25 of isolated conducting areas on said patterned insulating system, and providing conductive bridges at predesignated points between at least one of said isolated conductive areas and said conductive surface or the conductive layer, wherein at least one of the steps of optionally providing a conductive
30 layer, providing an patterned insulating system, providing a plurality of isolated conducting areas and providing conductive bridges is realized with a conventional printing process .
35 18. Process according to claim 17, wherein said conventional printing process is a non-impact printing process.
19. Process according to claim 17, wherein said conventional printing process is an impact printing process.
40
20. Process according to claim 17, wherein said conventional printing process is selected from the group consisting of ink- jet printing, intaglio printing, screen printing, flexographic printing, offset printing, stamp printing, gravure printing, electrophotographic printing, electrographic printing and thermal and laser-induced processes.
21. A process for providing a precursor for a second passive memory device, said precursor comprising a support and on at least one side of said support: a conductive surface of said support or a conductive layer on said support, a patterned insulating system on said conductive surface or said conductive layer and at least one conductive blob linking said conductive surface or said conductive layer to at least one position on said patterned insulating system, wherein said optional conductive layer, said patterned insulating system and said at least one conductive blob are printable using conventional printing techniques, comprising the steps of: providing said support, realizing said conductive layer on said support if said support is non-metallic, realizing said patterned insulating system and providing conductive blobs at predesignated points from the side of the insulating system not contiguous with said first electrode system to said conductive surface or said conductive layer, wherein at least one of said steps of optionally providing a conductive layer, providing said insulating system, and providing said said conductive blobs is realized with a conventional printing process.
22. A process for providing a second passive memory device, said passive memory device comprising at least one passive memory element and a support having at least one conductive surface or surface layer on the at least one side provided with said passive memory element, said passive memory element comprising said conductive surface of said support or said surface layer on said support as a first electrode system, an insulating system, at least one conductive blob is provided from at least one predesignated point on the side of the insulating system not contiguous with said first electrode system to said first electrode system which makes a conductive bridge, for read-out purposes only, between said first and said second electrode systems upon one of said plurality of conductive pins of the second electrode system coming into contact with the part of the conductive blob on said patterned insulating system, wherein in the absence of said at least one conductive bridge there is no direct electrical contact between the first electrode system and second electrode system; and wherein, with the exception of the first electrode system being the conductive surface of a metallic support, said systems and said at least one conductive blob are printable using conventional printing processes, comprising the steps of: providing said support, realizing said conductive layer on said support if said support is non-metallic, realizing said patterned insulating system, providing at least one conductive blob from at least one predesignated point on the side of the insulating system not contiguous with said first electrode system to said conductive surface or said conductive layer and realizing a plurality of pins as said second electrode system for read-out purposes only, wherein at least one of said steps of optionally providing a conductive layer, providing the insulating system, providing the conductive blobs and providing said second electrode system is realized with a conventional printing process.
23. Process for providing a second memory device according to claim 22, wherein said process further comprises the step of providing an insulating pattern system on said conductive surface or conductive layer, wherein said step of providing said insulating pattern system is realized with a conventional printing process.
PCT/EP2005/055510 2004-10-29 2005-10-25 Printable organic non-volatile passive memory element and method of making thereof WO2006045783A1 (en)

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KR20070073834A (en) 2007-07-10
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EP1815543A1 (en) 2007-08-08
WO2006045764A1 (en) 2006-05-04

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