EP1815543A1 - Elément de mémoire organique, imprimable, non volatile passive et sa méthode de fabrication - Google Patents

Elément de mémoire organique, imprimable, non volatile passive et sa méthode de fabrication

Info

Publication number
EP1815543A1
EP1815543A1 EP05803400A EP05803400A EP1815543A1 EP 1815543 A1 EP1815543 A1 EP 1815543A1 EP 05803400 A EP05803400 A EP 05803400A EP 05803400 A EP05803400 A EP 05803400A EP 1815543 A1 EP1815543 A1 EP 1815543A1
Authority
EP
European Patent Office
Prior art keywords
conductive
electrode system
support
electrode
passive memory
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP05803400A
Other languages
German (de)
English (en)
Inventor
Luc c/o AGFA-GEVAERT LEENDERS
Michel c/o AGFA-GEVAERT WERTS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
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
Application filed by Agfa Gevaert NV, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Priority to EP05803400A priority Critical patent/EP1815543A1/fr
Publication of EP1815543A1 publication Critical patent/EP1815543A1/fr
Ceased legal-status Critical Current

Links

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

Definitions

  • the present invention concerns a printable passive memory element and method of making same.
  • 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
  • the memory device 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 .
  • US 6,542,397 discloses an apparatus comprising: at least one designated memory cell of a plurality of memory cells,
  • 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.
  • information is stored by
  • 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 .
  • US 6,656,763 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.
  • 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 ⁇ high' voltage pulse, thereby increasing the resistance.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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) .
  • 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.
  • 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
  • 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.
  • 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.
  • 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
  • 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
  • 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 the the
  • a A process for providing 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
  • 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.
  • passive memory means a non-volatile memory i.e. read-only memory and is to be distinguished from reversible memories.
  • support 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.
  • 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.
  • conventional printing processes 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.
  • impact printing process 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 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.
  • non-impact printing process 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.
  • conductive bridge 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) .
  • 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) .
  • pattern means a non-continuous layer which can be in any form of lines, squares, circles or any random configuration.
  • the term layer 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 ⁇ m 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 .
  • metallized support 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.
  • insulating layer 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 ⁇ A measured at a voltage of 5V.
  • conductive is related to the electric resistance of the material, the electric resistance of a layer being generally expressed in terms of surface resistance R s (unit ⁇ ; often specified as ⁇ /square) .
  • conductive as used in disclosing the present invention, means a material having a surface resistance of ⁇ 10 6
  • intrinsically conductive polymer means organic polymers which have
  • transparent means having the property of transmitting at least 70% of the incident light without diffusing it.
  • flexible 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 represents poly(styrene sulfonic acid) or poly(styrene sulfonate) .
  • PANI represents polyaniline.
  • 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
  • the second electrode system is a plurality of isolated conductive areas.
  • the passive memory element 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 is producible by a printing process.
  • Information may be stored by creating conductive bridges via a printing process.
  • 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.
  • 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.
  • 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) .
  • 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 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
  • 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.
  • 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
  • the support is a flexible or rigid plastic, glass, paper, board, carton or a composite material of any of these materials.
  • the support is a metallic support, a metallized support or a support provided with a conductive layer.
  • 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.
  • an inorganic conducting medium e.g. a metal, a semiconducting metal oxide and carbon
  • an organic conducting medium e.g. an intrinsically conductive organic polymer
  • 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.
  • 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.
  • 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) .
  • At least one of the conductive surface, the second patterned electrode systems and the at least one conductive bridge comprises poly(3,4- dioxyethylenethiophene) .
  • At least one of the conductive surface, the second patterned electrode systems and the at least one conductive bridge comprises carbon.
  • 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.
  • 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 ⁇ m to 10 mm and more preferably from 100 ⁇ m 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.
  • 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.
  • 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 may be printed on security paper.
  • the number of conductive bridges is at least two.
  • the ⁇ conductive bridges' are coloured, for example black by using a carbon black- based ink.
  • 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.
  • the memory device is overprinted with an image or homogeneously coloured or opaque layer to visually hide the location of the ⁇ conductive bridges' .
  • a coloured or opaque foil is laminated over the memory device to visually hide the location of the ⁇ conductive bridges' .
  • 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.
  • 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.
  • 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 system 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.
  • 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 a first electrode system and insulated from the
  • 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
  • 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.
  • the first or second passive memory device is exclusive of metallic silicon.
  • the conventional printing process is a non-impact printing process e.g. ink-jet printing, electrophotographic printing and electrographic printing.
  • the conventional printing process is an impact printing process e.g. offset printing, screen printing, flexographic printing and stamp printing.
  • 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.
  • the insulating pattern, the second electrode pattern and the at least one conductive bridge are performed by the same printing process .
  • the insulating pattern, the second electrode pattern and the at least one conductive bridge are performed by ink-jet printing.
  • 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
  • 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.
  • 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 yield
  • 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
  • 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.
  • 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.
  • 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.
  • high boiling point liquid also has an influence on drying time, minimum drying temperature, jetting performance, wetting properties, viscosity and surface tension.
  • volatile bases such as dimethylethanolamine, triethylamine or diisopropylethylamine might be added to neutralize the inkjet printing solution to prevent corrosion of the print head.
  • the passive memory devices 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.
  • 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.
  • 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 mm 2 .
  • 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 .
  • the resistance between the continuous first electrode and the second electrode pads was measured with a Fluke Multimeter and is given in table 2.
  • 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
  • the passive memory element of INVENTION EXAMPLE 3 was produced by screen printing lines with dimensions of 2 x 50 mm 2 spaced 1.5 mm apart using Noripet 093 Clear with a screen of mesh P79 on an ORGACON EL-1500 substrate and drying at 130 0 C 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.
  • 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.

Abstract

La présente invention concerne des mémoires passives comprenant un support présentant au moins une surface conductrice, ou couche superficielle, et sur au moins un côté du support un élément de mémoire passive (5) comprenant un premier agencement d'électrodes, un dispositif isolant et un second agencement d'électrodes. Le premier agencement d'électrode étant isolé du second agencement d'électrode. Le premier agencement d'électrode constitue une surface conductrice, ou couche conductrice d'un support; le second agencement d'électrode consiste en plusieurs zones conductrices isolées (10) et/ou plusieurs broches conductrices isolées les unes des autres. Des ponts conducteurs sont ménagés au moins entre l'une des zones conductrices, ou au moins l'une des broches conductrices, et le premier agencement d'électrodes. A l'exception du premier agencement d'électrodes qui constitue une surface conductrice (15) d'un support, les agencements et les ponts conducteurs peuvent être imprimés selon les techniques d'impression classiques. Cette invention concerne également un procédé permettant de réaliser cette mémoire passive, lequel procédé comprend les étapes qui consistent à utiliser le support, à former la couche conductrice sur le support si le support est non métallique, à réaliser un agencement de motifs isolants (20) sur la surface conductrice, ou couche conductrice, et éventuellement à ménager plusieurs zones conductrices isolées sur l'agencement de motifs isolants, puis à ménager des ponts conducteurs à des points prédéterminés entre le premier agencement d'électrodes et au moins l'une des zones conductrices isolées et/ou plusieurs broches conductrices isolées (25) les unes des autres. L'une au moins des étapes qui consistent à former une couche conductrice, à ménager un système de motifs isolants, à ménager un second agencement d'électrodes, et à ménager des ponts conducteurs, peut être mise en oeuvre selon une technique d'impression classique (30).
EP05803400A 2004-10-29 2005-10-25 Elément de mémoire organique, imprimable, non volatile passive et sa méthode de fabrication Ceased EP1815543A1 (fr)

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EP04105412 2004-10-29
EP05803400A EP1815543A1 (fr) 2004-10-29 2005-10-25 Elément de mémoire organique, imprimable, non volatile passive et sa méthode de fabrication
PCT/EP2005/055510 WO2006045783A1 (fr) 2004-10-29 2005-10-25 Element de memoire passive non volatile organique imprimable et procede de realisation correspondant

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GB2436893A (en) * 2006-03-31 2007-10-10 Seiko Epson Corp Inkjet printing of cross point passive matrix devices
US20090116275A1 (en) * 2006-04-28 2009-05-07 Leenders Luc Conventionally printable non-volatile passive memory element and method of making thereof
EP1995736A1 (fr) 2007-05-22 2008-11-26 Rijksuniversiteit Groningen Dispositif ferroélectrique et barrière dýinjection modulable
JP4898850B2 (ja) * 2009-01-22 2012-03-21 住友化学株式会社 有機エレクトロルミネッセンス素子用インクジェットインクおよび有機エレクトロルミネッセンス素子の製造方法
WO2013088240A1 (fr) * 2011-12-13 2013-06-20 Sony Corporation Dispositif de mémoire
GB2547880A (en) * 2016-01-06 2017-09-06 Merenda Ltd Veneers
CN108780842A (zh) * 2016-03-23 2018-11-09 于利奇研究中心有限公司 用于制造存储器的方法、存储器以及该存储器的应用

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TW307048B (en) * 1996-11-22 1997-06-01 United Microelectronics Corp High density read only memory structure and manufacturing method thereof
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CN101048886A (zh) 2007-10-03
KR20070073834A (ko) 2007-07-10
KR20070083852A (ko) 2007-08-24
JP2008518452A (ja) 2008-05-29
JP2008518453A (ja) 2008-05-29
CN101048885A (zh) 2007-10-03
EP1815542A1 (fr) 2007-08-08
WO2006045783A1 (fr) 2006-05-04

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