EP1883856A2 - Electrodes of electrochemical/electrically-driven devices - Google Patents

Electrodes of electrochemical/electrically-driven devices

Info

Publication number
EP1883856A2
EP1883856A2 EP06794447A EP06794447A EP1883856A2 EP 1883856 A2 EP1883856 A2 EP 1883856A2 EP 06794447 A EP06794447 A EP 06794447A EP 06794447 A EP06794447 A EP 06794447A EP 1883856 A2 EP1883856 A2 EP 1883856A2
Authority
EP
European Patent Office
Prior art keywords
layer
electrochemical
electrode
layers
barrier layer
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.)
Withdrawn
Application number
EP06794447A
Other languages
German (de)
French (fr)
Inventor
Emmanuel Valentin
Samuel Dubrenat
Xavier Fanton
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.)
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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 Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Publication of EP1883856A2 publication Critical patent/EP1883856A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
    • B32B17/10467—Variable transmission
    • B32B17/10495—Variable transmission optoelectronic, i.e. optical valve
    • B32B17/10513—Electrochromic layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making

Definitions

  • the present invention relates to an electrochemical device, and / or electrically controllable type glazing and optical properties and / or variable energy, or a photovoltaic device, or a light emitting device.
  • glazing may be the control of solar input through glazing mounted outdoors in buildings or vehicles of the car, train or plane type.
  • the goal is to be able to limit excessive heating inside the interiors / premises, but only in case of strong sunshine.
  • it may be the generation of light through the glazing to control the level of brightness or color generated.
  • electrochromic systems To modulate the light transmission and / or the thermal transmission of the glazings, there are also so-called electrochromic systems. These, in known manner, generally comprise two layers of electrochromic material separated by an electrolyte layer and framed by two electroconductive layers. Each of the layers of electrochromic material can reversibly insert cations and electrons, the modification of their degree of oxidation following these insertions / phasesinsertions leading to a change in its optical and / or thermal properties. We can notably modulate their absorption and / or their reflection in the wavelengths of the visible and / or infra-red. It is customary to arrange the electrochromic systems in three categories:
  • the electrolyte in the form of a polymer or a gel; for example a proton-conductive polymer such as those described in patents EP-253 713 or EP-670 346, or a conductive polymer of lithium ions such as those described in patents EP-382 623, EP-518 754 and 532,408; the other layers of the system are generally of a mineral nature,
  • optical valves There are also systems called “optical valves". They are films comprising a generally crosslinked polymer matrix in which are dispersed micro-droplets containing particles which are capable of being placed in a preferred direction under the action of a magnetic or electric field. It is thus known from WO.93 / 09460 an optical valve comprising a polyorganosilane matrix and polyiodide particles that intercept much less light when the film is turned on.
  • liquid crystal systems a mode of operation similar to the previous ones. They are based on the use of a film placed between two conducting layers and based on a polymer in which liquid crystal droplets, in particular nematic with positive dielectric anisotropy, are arranged.
  • the liquid crystals when the film is energized, are oriented along a preferred axis, which allows vision. When the crystals are not aligned, the film becomes diffused and prevents vision. Examples of such films are described in particular in European patents EP-0 238 164, and US-4,435,047, US-4,806,922, US-4,732,456. This type of film, once laminated and incorporated between two glass substrates, is marketed by Saint-Gobain Vitrage under the trade name "Priva-Lite".
  • NCAP Nematic Curvilinearly Aligned Phases
  • PDLC Polymer Dispersed Liquid Crystal
  • electroluminescent systems comprise a material or a stack of electroluminescent, organic or inorganic materials powered by electricity. electrodes. All these systems combined have in common the need to be equipped with current leads supplying electrodes generally in the form of two electroconductive layers on either side of the layer or the various active layers (s) of the system.
  • electroconductive layers (which may in fact be a superposition of layers) commonly comprise a layer based on indium oxide, generally tin-doped indium oxide better known under the abbreviation ITO. It may also be layers based on doped tin oxide, for example antimony, or based on doped zinc oxide, for example aluminum (or a mixture based on at least two of these oxides).
  • WO93 / 05438 discloses an electroconductive layer consisting of a thin metal layer, in particular based on silver, copper or aluminum, which is associated with a layer based on a metal blocker, for example the iron, zirconium, titanium, tungsten.
  • This TCO type: English abbreviation for "Conductive Transparent Oxide” is intended to be integrated into an electrochemical device of the electrochromic type in which the metal blocking layer constitutes a barrier to the diffusion of Li + ions between one of the active layers. and the metal layer.
  • WO94 / 15247 also discloses an electroconductive layer of structure similar to that previously described, which is completed by a layer based on a transparent conductive oxide such as zinc oxide, or indium oxide. doped with tin.
  • Document US5510173 and US5763063 also disclose an energy control stack structure incorporating a layer of silver or copper advantageously alloyed with a noble metal, for which protection against corrosion is obtained by means of coating of a bilayer based on In2 ⁇ 3 and diTO or ZnO2 / In2 ⁇ 3 and ITO. In the case of the use of ZnO 2, the application as an electrode is impossible because of the insulating nature of this oxide.
  • US Pat. No. 6,870,656 discloses a reflective electrode structure incorporating an electrochemically stable silver and gold alloy layer.
  • ITO layers have been particularly studied. They can be easily deposited by magnetic field assisted sputtering, either from an oxide target (non-reactive sputtering), or from an indium and tin-based target (reactive sputtering in the presence of an oxidizing agent of the oxygen type).
  • oxide target non-reactive sputtering
  • indium and tin-based target reactive sputtering in the presence of an oxidizing agent of the oxygen type
  • the aim of the invention is to obtain an assembly of electroconductive electroconductive layers to form the electrodes of the electrochemical / electrocontrollable systems of the type previously described (electrochromic, photovoltaic, electroluminescent ).
  • the subject of the invention is an electrochemical / electrically controllable device, with variable optical and / or energy properties, comprising at least one carrier substrate provided with an electroactive layer or a stack of electroactive layers arranged between an electrode called " lower "and an electrode called” upper ".
  • one at least one of the lower or upper electrodes comprises at least four layers including at least one functional metallic layer with intrinsic properties of electrical conductivity, said functional layer being associated with an electrochemical barrier layer of electroconductive material that is transparent in the visible, said electrochemical barrier layer being associated a protective layer against moisture electroconductive material transparent in the visible and said functional layer being associated with a first sub-layer of transparent electroconductive material in the visible.
  • this particular stacking structure it is possible to obtain, at lower cost, a transparent electrode having an electrochemical resistance compatible with the electrically controllable systems while having properties of high electrical conductivity, and without the use of a heat treatment in recovery.
  • the electrochemical systems have similar characteristics in terms of speed and color homogeneity to those using conventional electrodes of the prior art (mainly based on optionally doped indium oxide).
  • the electrode thus obtained is both electroconductive in its thickness and along its surface.
  • the first sub-layer is identical in nature to the electrochemical barrier layer;
  • the electrochemical barrier layer is based on zinc oxide or a mixed zinc oxide doped with another metal chosen from the family of the following metals: Al, Ga, B, Sc the zinc oxide is of the ZnOx type with x less than 1, preferably between 0.88 and 0.98, especially from 0.90 to 0.95.
  • the functional layer is based on a pure material chosen from silver, or Cu or Zn or Al or Au, or based on an alloy of this material containing in particular Al, Pt, Cu, Zn, Cd, In, Bo, Si,
  • Zr, Mo, Ni, Li, Cr, Ga, Ge, Mg, Mn, Co, SnIa moisture barrier layer is based on doped indium oxide, in particular with tin, or oxide of tin doped, especially with antimony - the first under layer is associated with a second sub-layer similar to the moisture barrier layer,
  • the term “lower” electrode means the electrode which is closest to the carrier substrate taken as reference, on which at least part of the active layers (for example all the active layers in a electrochromic system “all solid") is deposited.
  • the "upper” electrode is the one deposited on the other side, with respect to the same reference substrate.
  • the upper and / or lower electrode according to the invention has an electrical resistivity of between 10 ⁇ 10 4 and 9 ⁇ 10 5 ohm.cm, which makes its use as an electrode perfectly satisfactory.
  • the electrode in particular to reach this resistivity level, it has a total thickness of between 160 and 320 nm. In these thickness ranges, the electrode remains transparent, that is to say that it has a low light absorption. in the visible. However, it is not excluded to have much thicker layers (especially in the case where the electroactive electrochemical system functions in reflection rather than transmission), or thinner layers (especially when they are associated in electrode to another type of conductive layer, metal for example).
  • the invention can be applied to different types of electrochemical or electrically controllable systems. It is particularly interested in electrochromic systems, especially "all solid” or “all solid on polymer” or “all polymer”, or liquid crystal systems or viologen, or electroluminescent systems.
  • the electrochromic systems or glazing to which the invention can be applied are described in the aforementioned patents. They may comprise at least one carrier substrate and a stack of functional layers comprising at least successively a first electroconductive layer, an electrochemically active layer capable of reversibly inserting ions such as H + , Li + , OH "of the electrochromic anodic material type or respectively cathodic, an electrolyte layer, a second electrochemically active layer capable of reversibly inserting ions such as H + , Li + , OH "of the cathodic or anodic electrochromic material type, and a second electroconductive layer, (the term "layer” is to be understood as a single layer or a superposition of several layers, continuous or discontinuous).
  • the invention also relates to the incorporation of the electrochemical devices described in the preamble of the present application in glazings, operating in reflection (mirror) or transmission.
  • glazing is to be understood in the broad sense and includes any substantially transparent material, glass and / or polymeric material (such as polycarbonate PC or polymethyl methacrylate PMMA).
  • the carrier substrates and / or counter-substrates that is to say the substrates surrounding the active system, can be rigid, flexible or semi-flexible.
  • the glazing works in reflection, it can be used in particular as an interior mirror or as a rearview mirror.
  • the invention also relates to the various applications that can be found with these devices, glazings or mirrors: it may be a question of glazing for buildings, in particular exterior glazing, internal partitions or glazed doors). It can also be windows, roofs or internal partitions of means of transport such as trains, planes, cars, boats. It can also be display screens or display, such as projection screens, television or computer screens, touch screens. They can also be used to make glasses or camera lenses, or to protect solar panels. They can also be used as energy storage devices of the battery type, fuel cell, batteries and batteries themselves.
  • FIG. 1 a schematic sectional view of an electrochromic cell using an electrode according to the invention
  • FIG. 2 illustrates for various configurations of electrodes according to the invention their electrochemical protection.
  • FIG. 1 is deliberately very schematic and is not necessarily scaled to facilitate reading: it shows in section a "solid" electrochromic device according to the teachings of the invention comprising successively:
  • a lower electrode 2 comprising a stack of ITO / ZnO: Al / Ag / ZnO: Al / ITO layers of respective thicknesses 15 to 20 nm for 1TTO / 60 at 80 nm for ZnO: Al / 3 at 15 nm for silver / 60 to 80 nm for ZnO: A1 / 15 at 20 nm for ITTO,
  • the face of the glass 8 turned towards the PU sheet 7 is provided with a stack of thin films with a solar protection function.
  • This stack may in particular comprise two silver layers interposed by dielectric layers, in a known manner.
  • the electrochromic system 3 comprises:
  • a first layer of anodic electrochromic material EC1 of iridium oxide (hydrated) of 40 to 100 nm or of nickel oxide hydrated at 40 to 400 nm, alloyed or not with other metals (alternatively, this layer can be replaced by a layer of anodic electrochromic material made of nickel oxide from 100 to 300 nm, alloyed or not with other metals)
  • cathodic EC2 electrochrome material based on WO3 tungsten oxide of 370 nm.
  • the set of layers was deposited by magnetic field assisted sputtering.
  • the electrochromic device described above constitutes the example
  • Example 2 which is a known structure of the prior art and for which the lower and upper electrodes are based on diTO or SnO 2: F is given below.
  • the upper electrode has other conductive elements: it may be more particularly to associate the electrode to a more conductive layer that it, and / or a plurality of strips or son son.
  • a preferred embodiment of this type of electrode is to apply on the diTO layer (possibly topped with one or more other conductive layers) a network of son encrusted on the surface of a polymer sheet (which can then protect the active system and / or allow the lamination of the glass-type carrier-substrate with another glass in the case of electroactive glazing production, of the electrochromic type, for example).
  • the most reliable validation of the TCOs consists in carrying out a durability test of the electrochromic cells by exposure at 80 ° C. in the colored state.
  • the parameters representative of the deterioration of the EC glazings are the evolution of the switching time (Vcom) and the contrast (TL decored / TL ⁇ ioré)
  • this substantially takes up the structure of the stack of example 1 except as regards the nature of the lower and upper electrodes 2 and 4.
  • both comprise a stack of ITO / ZnO: Al / Ag / ZnO: Al / ITO layers of respective thicknesses 15 to 20 nm for IT ⁇ / 60 at 80 nm for ZnO: Al / 3 at 15 nm for silver / 60 to 80 nm for ZnO / 15 at 20 nm for 11TO.
  • This configuration eliminates the wire network, the conduction of the TCO being equivalent to that of the whole ITO + son.
  • TCO comprising 12 nm of Ag undergoes an oxidation cycle using a so-called 'three-electrode' assembly with a working electrode (TCO studied), a reference electrode (Electrode Saturated Calomel) and a counter electrode (glass + 500 nm ITO) immersed in a liquid electrolyte H3PO4 (orthophosphoric acid).
  • TCO studied working electrode
  • reference electrode Electrode Saturated Calomel
  • counter electrode glass + 500 nm ITO immersed in a liquid electrolyte H3PO4 (orthophosphoric acid).
  • a first family is distinguished in which the organic electroluminescent material of the thin layer consists of evaporated molecules (OLEDs), for example the AlQ complex . 3 (tris (8-hydroxyquinoline) aluminum), DPVBi (4,4 '- (diphenylvinylene biphenyl)), DMQA (dimethyl quinacridone) or DCM (4- (dicyanomethylene) -2-methyl-6- (4 dimethylaminostyryl) -4H-pyran).
  • OLEDs evaporated molecules
  • HTL HTL
  • ETL HoIe Transporting Layer
  • HIL HoIe Injection Layer
  • the organic electroluminescent material of the thin layer consists of polymers (pLEDs) such as for example PPV for poly (p ⁇ r ⁇ -phenylene vinylene), PPP (poly (p ⁇ r ⁇ -phenylene), the DO-PPP (poly (2-decyloxy-1,4-phenylene), MEH-PPV (poly [2- (2'-ethylhexyloxy) -5-methoxy-1,4-phenylene vinylene)]), CN-PPV (poly [2,5-bis (hexyloxy) -1,4-phenylene- (1-cyanovinylene)]) or PDAF (poly (dialkylfluorene), the polymer layer is also associated with a layer which promotes the injection of holes ( HIL) consisting for example of PEDT / PSS (poly (3,4-ethylene-dioxythiophene / poly (4-styrene sulfonate)),
  • HIL hole
  • the inorganic electroluminescent material of the thin layer consists of a thin layer of a phosphor for example sulfides such as for example ZnS: Mn or SrS: Ce or oxides such as Zn 2 SiO 4 : Mn, Zn 2 GeO 4 : Mn or Zn 2 Ga 2 ⁇ 4 : Mn.
  • a phosphor for example sulfides such as for example ZnS: Mn or SrS: Ce or oxides such as Zn 2 SiO 4 : Mn, Zn 2 GeO 4 : Mn or Zn 2 Ga 2 ⁇ 4 : Mn.
  • an insulating layer made from a dielectric material, typically for example Si3N 4 , BaTiOe or Al 2 O 3 / TiO 2
  • a fourth family in which the inorganic electroluminescent material consists of a thick phosphor layer such as for example ZnS: Mn or ZnS: Cu, this layer being associated with an insulating layer of dielectric material, for example BaTiOe, these layers being generally made by screen printing.
  • a thick phosphor layer such as for example ZnS: Mn or ZnS: Cu
  • this layer being associated with an insulating layer of dielectric material, for example BaTiOe, these layers being generally made by screen printing.
  • the stack of layers including the electroluminescent layer is associated with and other insulating layers, HTL, ETL, HIL, to two electrodes, (a cathode and an anode in the case of organic systems).
  • Electrodes are similar to those already envisaged for the electrocommandable electrochromic type systems described above.
  • each of the layers forming the stack of the two types of electrode is given below:
  • Electrode El 15 to 20 nm for ITTO / 60 at 80 nm for ZnO: Al / 6 at 12 nm for silver / 60 to 80 nm for ZnO: A1 / 15 at 20 nm for 11TO.
  • Electrode E2 15 to 20 nm for 1TTO / 60 to 80 nm for ZnO: A1 / 40 nm minimum for silver / 60 to 80 nm for ZnO: A1 / 15 at 20 nm for ITTO.
  • This electrode structure according to the invention is integrated within a stack of electroluminescent type according to the following configuration: E1 / (Si3N4 (300nm) / Luminophore (500nm) / Si3N4 (300nm)) / E2
  • the invention also relates to the substrate provided with at least one electrode of the type described above, independently of the electrical / electrochemical device in which it is incorporated or intended to be incorporated as well as the lower or upper electrode as such.

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention concerns an electrochemical/electrically-driven device, with variable optical and/or energetic properties, comprising at least one carrier substrate provided with an electroactive layer or a stack of electroactive layers arranged between a so-called lower electrode and a so-called upper electrode. The invention is characterized in that at least one of the lower or upper electrodes comprises at least four layers one of which at least one functional metal layer with intrinsic electrically conductive properties, said functional metal layer being associated with an electrochemical barrier layer made of electrically conductive material transparent in the visible light, said electrochemical barrier layer being associated with a protective layer against moisture made of electrically conductive material transparent in the visible light and said functional layer being associated with a first undercoat made of electrically conductive material transparent in the visible light.

Description

ELECTRODE DE DISPOSITIFS ELECTROCHIMIQUES/ELECTROCOMMANDABLES ELECTRODE OF ELECTROCHEMICAL DEVICES / ELECTROCOMMANDABLE
La présente invention a pour objet un dispositif électrochimique, et/ ou électrocommandable du type vitrage et à propriétés optiques et/ ou énergétiques variables, ou un dispositif photovoltaïque, ou encore un dispositif électroluminescent.The present invention relates to an electrochemical device, and / or electrically controllable type glazing and optical properties and / or variable energy, or a photovoltaic device, or a light emitting device.
Il y a en effet actuellement une demande accrue pour des vitrages dits " intelligents " aptes à s'adapter aux besoins des utilisateurs.There is currently an increased demand for so-called "smart" glazing able to adapt to the needs of users.
Il existe aussi une demande accrue pour les vitrages photovoltaïques, qui permettent de convertir l'énergie solaire en énergie électrique, ainsi que pour les vitrages électroluminescents qui ont des applications intéressantes dans les appareils d'affichage et en tant que surfaces éclairantes.There is also an increased demand for photovoltaic glass, which converts solar energy into electrical energy, as well as for electroluminescent glazing which has interesting applications in display devices and as illuminating surfaces.
En ce qui concerne les vitrages " intelligents ", il peut s'agir du contrôle de l'apport solaire à travers des vitrages montés en extérieur dans des bâtiments ou des véhicules du type automobile, train ou avion. Le but est de pouvoir limiter un échauffement excessif à l'intérieur des habitacles /locaux, mais uniquement en cas de fort ensoleillement.Regarding "smart" glazing, it may be the control of solar input through glazing mounted outdoors in buildings or vehicles of the car, train or plane type. The goal is to be able to limit excessive heating inside the interiors / premises, but only in case of strong sunshine.
Il peut aussi s'agir du contrôle du degré de vision à travers des vitrages, notamment afin de les obscurcir, de les rendre diffusant voire d'empêcher toute vision quand cela est souhaitable. Cela peut concerner les vitrages montés en cloisons intérieures dans les locaux, les trains, les avions ou montés en vitres latérales d'automobile. Cela concerne aussi les miroirs utilisés comme rétroviseurs, pour éviter ponctuellement au conducteur d'être ébloui, ou les panneaux de signalisation, pour que des messages apparaissent quand cela est nécessaire, ou par intermittence pour mieux attirer l'attention. Des vitrages que l'on peut rendre à volonté diffusants peuvent être utilisés quand on le souhaite comme écrans de projection.It can also be the control of the degree of vision through glazing, especially in order to obscure them, to make them diffuse or even to prevent any vision when it is desirable. This may concern glazing mounted in interior partitions in premises, trains, planes or mounted in automotive side windows. This also applies to mirrors used as mirrors, to punctually avoid the driver to be dazzled, or signs, so that messages appear when necessary, or intermittently to better attract attention. Glazes that can be rendered at will diffusers can be used when desired as screens of projection.
En variante, il peut s'agir de la génération de lumière par le vitrage afin de contrôler le niveau de luminosité ou la couleur générée.Alternatively, it may be the generation of light through the glazing to control the level of brightness or color generated.
Il existe différents systèmes électrocommandables permettant ce genre de modifications d'aspect/de propriétés thermiques.There are different electrically controllable systems that allow this kind of aspect changes / thermal properties.
Pour moduler la transmission lumineuse ou l'absorption lumineuse des vitrages, il y a les systèmes dits viologènes, comme ceux décrits dans les brevets US-5 239 406 et EP-612 826.In order to modulate the light transmission or the light absorption of the glazings, there are the so-called viologen systems, such as those described in patents US Pat. No. 5,239,406 and EP-612,826.
Pour moduler la transmission lumineuse et/ ou la transmission thermique des vitrages, il y a aussi les systèmes dits électrochromes. Ceux-ci, de manière connue, comportent généralement deux couches de matériau électrochrome séparées par une couche d'électrolyte et encadrées par deux couches électroconductrices. Chacune des couches de matériau électrochrome peut insérer réversiblement des cations et des électrons, la modification de leur degré d'oxydation suite à ces insertions /désinsertions conduisant à une modification dans ses propriétés optiques et/ ou thermiques. On peut notamment moduler leur absorption et/ ou leur réflexion dans les longueurs d'onde du visible et/ ou de l'infra-rouge. II est d'usage de ranger les systèmes électrochromes en trois catégories :To modulate the light transmission and / or the thermal transmission of the glazings, there are also so-called electrochromic systems. These, in known manner, generally comprise two layers of electrochromic material separated by an electrolyte layer and framed by two electroconductive layers. Each of the layers of electrochromic material can reversibly insert cations and electrons, the modification of their degree of oxidation following these insertions / désinsertions leading to a change in its optical and / or thermal properties. We can notably modulate their absorption and / or their reflection in the wavelengths of the visible and / or infra-red. It is customary to arrange the electrochromic systems in three categories:
- celle où l'électrolyte est sous forme d'un polymère ou d'un gel ; par exemple un polymère à conduction protonique comme ceux décrits dans les brevets EP-253 713 ou EP-670 346, ou un polymère à conduction d'ions lithium comme ceux décrits dans les brevets EP-382 623, EP-518 754 et EP-532 408 ; les autres couches du système étant généralement de nature minérale,that in which the electrolyte is in the form of a polymer or a gel; for example a proton-conductive polymer such as those described in patents EP-253 713 or EP-670 346, or a conductive polymer of lithium ions such as those described in patents EP-382 623, EP-518 754 and 532,408; the other layers of the system are generally of a mineral nature,
- celle où l'électrolyte est une couche essentiellement minérale. On désigne souvent cette catégorie sous le terme de système " tout solide ", on pourra en trouver des exemples dans les brevet EP-867 752, EP-831 360, les brevets WO.00/57243 et WO.00/71777, - celle où l'ensemble des couches est à base de polymères, catégorie que l'on désigne souvent sous le terme de système " tout polymère ".the one in which the electrolyte is an essentially mineral layer. This category is often referred to as the "all-solid" system, examples of which can be found in EP-867,752, EP-831,360, WO.00 / 57243 and WO.00 / 71777, - The one where the set of layers is based on polymers, a category that is often referred to as the "all-polymer" system.
Il existe aussi des systèmes appelés " valves optiques ". Il s'agit de films comprenant une matrice de polymère généralement réticulé dans laquelle sont dispersées des micro-gouttelettes contenant des particules qui sont capables de se placer selon une direction privilégiée sous l'action d'un champ magnétique ou électrique. Il est ainsi connu du brevet WO.93/09460 une valve optique comprenant une matrice en polyorganosilane et des particules du type polyiodure qui interceptent beaucoup moins la lumière quand le film est mis sous tension.There are also systems called "optical valves". They are films comprising a generally crosslinked polymer matrix in which are dispersed micro-droplets containing particles which are capable of being placed in a preferred direction under the action of a magnetic or electric field. It is thus known from WO.93 / 09460 an optical valve comprising a polyorganosilane matrix and polyiodide particles that intercept much less light when the film is turned on.
On peut aussi citer les systèmes dits à cristaux liquides, d'un mode de fonctionnement similaire aux précédents. Ils sont basés sur l'utilisation d'un film placé entre deux couches conductrices et à base d'un polymère dans lequel sont disposées des gouttelettes de cristaux liquides, notamment nématiques à anisotropie diélectrique positive. Les cristaux liquides, quand le film est mis sous tension, s'orientent selon un axe privilégié, ce qui autorise la vision. Hors tension, en l'absence d'alignement des cristaux, le film devient diffusant et empêche la vision. Des exemples de tels films sont décrits notamment dans les brevets européen EP-O 238 164, et américains US-4 435 047, US-4 806 922, US-4 732 456. Ce type de film, une fois feuilleté et incorporé entre deux substrats en verre, est commercialisé par la société Saint-Gobain Vitrage sous la dénomination commerciale " Priva-Lite ".We can also mention so-called liquid crystal systems, a mode of operation similar to the previous ones. They are based on the use of a film placed between two conducting layers and based on a polymer in which liquid crystal droplets, in particular nematic with positive dielectric anisotropy, are arranged. The liquid crystals, when the film is energized, are oriented along a preferred axis, which allows vision. When the crystals are not aligned, the film becomes diffused and prevents vision. Examples of such films are described in particular in European patents EP-0 238 164, and US-4,435,047, US-4,806,922, US-4,732,456. This type of film, once laminated and incorporated between two glass substrates, is marketed by Saint-Gobain Vitrage under the trade name "Priva-Lite".
On peut en fait utiliser tous les dispositifs à cristaux liquides connus sous les termes de " NCAP " (Nematic Curvilinearly Aligned Phases) ou " PDLC " (Polymer Dispersed Liquid Cristal).In fact, it is possible to use all liquid crystal devices known as "NCAP" (Nematic Curvilinearly Aligned Phases) or "PDLC" (Polymer Dispersed Liquid Crystal).
On peut également utiliser, par exemple, les polymères à cristaux liquides cholestériques, comme ceux décrits dans le brevet WO.92/ 19695. Quant aux systèmes électroluminescents, ils comportent un matériau ou un empilement de matériaux électroluminescents, organiques ou inorganiques alimenté en électricité par des électrodes. Tous ces systèmes confondus ont en commun la nécessité d'être équipés en amenées de courant venant alimenter des électrodes généralement sous forme de deux couches électroconductrices de part et d'autre de la couche ou des différentes couches active (s) du système. Ces couches électroconductrices (qui peuvent en fait être une superposition de couches) comportent communément une couche à base d'oxyde d'indium, généralement l'oxyde d'indium dopé à l'étain plus connu sous l'abréviation ITO. Il peut aussi s'agir de couches à base d'oxyde d'étain dopé, par exemple à l'antimoine, ou encore à base d'oxyde de zinc dopé, par exemple à l'aluminium (ou d'un mélange à base d'au moins deux de ces oxydes).It is also possible to use, for example, cholesteric liquid crystal polymers, such as those described in the patent WO.92 / 19695. As for the electroluminescent systems, they comprise a material or a stack of electroluminescent, organic or inorganic materials powered by electricity. electrodes. All these systems combined have in common the need to be equipped with current leads supplying electrodes generally in the form of two electroconductive layers on either side of the layer or the various active layers (s) of the system. These electroconductive layers (which may in fact be a superposition of layers) commonly comprise a layer based on indium oxide, generally tin-doped indium oxide better known under the abbreviation ITO. It may also be layers based on doped tin oxide, for example antimony, or based on doped zinc oxide, for example aluminum (or a mixture based on at least two of these oxides).
On connaît par exemple par le document WO93/ 05438 une couche électroconductrice constituée d'une fine couche métallique notamment à base d'argent, de cuivre, d'aluminium qui est associée à une couche à base d'un bloqueur métallique comme par exemple le fer, le zirconium, le titane, le tungstène. Cet empilement de type TCO : abréviation anglaise pour « Oxyde Transparent Conducteur » est destiné à être intégré dans un dispositif électrochimique de type électrochrome au sein duquel la couche de bloqueur métallique constitue une barrière à la diffusion des ions Li+ entre l'une des couches actives et la couche métallique.For example, WO93 / 05438 discloses an electroconductive layer consisting of a thin metal layer, in particular based on silver, copper or aluminum, which is associated with a layer based on a metal blocker, for example the iron, zirconium, titanium, tungsten. This TCO type: English abbreviation for "Conductive Transparent Oxide" is intended to be integrated into an electrochemical device of the electrochromic type in which the metal blocking layer constitutes a barrier to the diffusion of Li + ions between one of the active layers. and the metal layer.
On connaît par ailleurs par le document WO94/ 15247 une couche électroconductrice de structure similaire à celle précédemment décrite, qui est complétée par une couche à base d'oxyde conducteur transparent comme par exemple l'oxyde de zinc, ou l'oxyde d'indium dopé à l'étain. On connaît en outre par les documents US5510173 et US5763063, une structure d'empilement à contrôle énergétique incorporant une couche d'argent ou de cuivre avantageusement alliée avec un métal noble, pour lesquelles une protection à l'égard de la corrosion est obtenue par le revêtement d'un bicouche à base In2θ3 et diTO ou Znθ2/In2θ3 et ITO. Dans le cas de l'utilisation du Znθ2, l'application en tant électrode est impossible du fait du caractère isolant de cet oxyde. Par ailleurs, on connaît par le brevet US6870656 qui décrit une structure d'électrode réfléchissante incorporant une couche à base d'alliage d'argent et d'or électrochimiquement stable.WO94 / 15247 also discloses an electroconductive layer of structure similar to that previously described, which is completed by a layer based on a transparent conductive oxide such as zinc oxide, or indium oxide. doped with tin. Document US5510173 and US5763063 also disclose an energy control stack structure incorporating a layer of silver or copper advantageously alloyed with a noble metal, for which protection against corrosion is obtained by means of coating of a bilayer based on In2θ3 and diTO or ZnO2 / In2θ3 and ITO. In the case of the use of ZnO 2, the application as an electrode is impossible because of the insulating nature of this oxide. Furthermore, US Pat. No. 6,870,656 discloses a reflective electrode structure incorporating an electrochemically stable silver and gold alloy layer.
Quelle que soit la structure de couche électroconductrice décrite précédemment, sa tenue électrochimique n'est obtenue que lorsque cette couche électroconductrice est alliée.Whatever the electroconductive layer structure described above, its electrochemical resistance is obtained only when this electroconductive layer is alloyed.
Les couches ITO ont été particulièrement étudiées. Elles peuvent être aisément déposées par pulvérisation cathodique assistée par champ magnétique, soit à partir d'une cible d'oxyde (pulvérisation non réactive), soit à partir d'une cible à base d'indium et d'étain (pulvérisation réactive en présence d'un agent oxydant du type oxygène). Cependant, pour présenter une conductivité électrique suffisante pour l'application et pour être électrochimiquement robustes, elles nécessitent le recours à une étape de traitement thermique in situ ou en reprise (souvent au delà de 3000C).ITO layers have been particularly studied. They can be easily deposited by magnetic field assisted sputtering, either from an oxide target (non-reactive sputtering), or from an indium and tin-based target (reactive sputtering in the presence of an oxidizing agent of the oxygen type). However, to present an electrical conductivity sufficient for the application and to be electrochemically robust, they require the use of a heat treatment step in situ or recovery (often beyond 300 0 C).
Le but que se fixe l'invention est de parvenir à obtenir un assemblage de couches électroconductrices électrochimiquement robuste pour constituer les électrodes des systèmes électrochimiques /électrocommandables du type de ceux précédemment décrits (électrochromes, photovoltaïques, électroluminescents...)The aim of the invention is to obtain an assembly of electroconductive electroconductive layers to form the electrodes of the electrochemical / electrocontrollable systems of the type previously described (electrochromic, photovoltaic, electroluminescent ...)
Accessoirement, il s'agit d'atteindre cet objectif à moindre coût et en s 'affranchissant des étapes de traitement thermique et sans bouleverser les configurations connues des systèmes électrochimiques concernant l'invention. Il s'agit, plus généralement, de mettre au point des électrodes sur substrat essentiellement transparent (verre ou matériau polymère), qui soient meilleures.Incidentally, it is a question of achieving this objective at a lower cost and by dispensing with the heat treatment steps and without upsetting the known configurations of the electrochemical systems concerning the invention. It is, more generally, to develop electrodes on substantially transparent substrate (glass or polymer material), which are better.
L'invention a pour objet un dispositif électrochimique/ électrocommandable, à propriétés optiques et/ou énergétiques variables, comportant au moins un substrat porteur muni d'une couche électroactive ou d'un empilement de couches électroactives disposé(e) entre une électrode dite " inférieure " et une électrode dite " supérieure ". Selon l'invention, l'une au moins des électrodes inférieure ou supérieure comprend au moins quatre couches dont au moins une couche fonctionnelle métallique à propriétés intrinsèque de conductivité électrique, ladite couche fonctionnelle étant associée à une couche barrière électrochimique en matériau électroconducteur transparent dans le visible, ladite couche barrière électrochimique étant associée à une couche de protection contre l'humidité en matériau électroconducteur transparent dans le visible et ladite couche fonctionnelle étant associée à une première sous-couche en matériau électroconducteur transparent dans le visible. Grâce à cette structure d'empilement particulière, il est possible d'obtenir, à moindre coût, une électrode transparente présentant une tenue électrochimique compatible avec les systèmes électrocommandables tout en ayant des propriétés de conductivité électrique élevée, et ce, sans le recours à un traitement thermique en reprise. Par ailleurs, on remarque qu'avec ce type de structure d'empilement au niveau de l'électrode inférieure et éventuellement de l'électrode supérieure, les systèmes électrochimiques présentent des caractéristiques similaires en terme de vitesse et d'homogénéité de coloration à ceux utilisant des électrodes classiques de l'art antérieur (à base majoritairement d'oxyde d'indium éventuellement dopé). De plus, on remarque que l'électrode ainsi obtenue est à la fois électroconductrice dans son épaisseur et suivant sa surface.The subject of the invention is an electrochemical / electrically controllable device, with variable optical and / or energy properties, comprising at least one carrier substrate provided with an electroactive layer or a stack of electroactive layers arranged between an electrode called " lower "and an electrode called" upper ". According to the invention, one at least one of the lower or upper electrodes comprises at least four layers including at least one functional metallic layer with intrinsic properties of electrical conductivity, said functional layer being associated with an electrochemical barrier layer of electroconductive material that is transparent in the visible, said electrochemical barrier layer being associated a protective layer against moisture electroconductive material transparent in the visible and said functional layer being associated with a first sub-layer of transparent electroconductive material in the visible. Thanks to this particular stacking structure, it is possible to obtain, at lower cost, a transparent electrode having an electrochemical resistance compatible with the electrically controllable systems while having properties of high electrical conductivity, and without the use of a heat treatment in recovery. Moreover, it is noted that with this type of stack structure at the lower electrode and possibly the upper electrode, the electrochemical systems have similar characteristics in terms of speed and color homogeneity to those using conventional electrodes of the prior art (mainly based on optionally doped indium oxide). In addition, it is noted that the electrode thus obtained is both electroconductive in its thickness and along its surface.
Dans des modes de réalisation préférés de l'invention, on peut éventuellement avoir recours en outre à l'une et/ ou à l'autre des dispositions suivantes : - la première sous couche est de nature identique à la couche barrière électrochimique,In preferred embodiments of the invention, one or more of the following provisions may also be used: the first sub-layer is identical in nature to the electrochemical barrier layer;
- la couche barrière électrochimique est à base d'oxyde de zinc ou d'un oxyde mixte de zinc dopé par un autre métal choisi parmi la famille des métaux suivants : Al , Ga, B, Sc - l'oxyde de zinc est du type ZnOx avec x inférieur à 1, préférentiellement compris entre de 0,88 à 0,98, notamment de 0,90 à 0,95.the electrochemical barrier layer is based on zinc oxide or a mixed zinc oxide doped with another metal chosen from the family of the following metals: Al, Ga, B, Sc the zinc oxide is of the ZnOx type with x less than 1, preferably between 0.88 and 0.98, especially from 0.90 to 0.95.
- la couche fonctionnelle est à base d'un matériau pur choisi parmi l'argent, ou le Cu ou le Zn ou l'Ai ou l'Au ou à base d'alliage de ce matériau contenant notamment du Al, Pt, Cu, Zn, Cd, In, Bo, Si,the functional layer is based on a pure material chosen from silver, or Cu or Zn or Al or Au, or based on an alloy of this material containing in particular Al, Pt, Cu, Zn, Cd, In, Bo, Si,
Zr, Mo, Ni, Li, Cr, Ga, Ge, Mg, Mn, Co, SnIa couche barrière à l'humidité est à base d'oxyde d'indium dopé, notamment à l'étain, ou d'oxyde d'étain dopé, notamment à l'antimoine - la première sous couche est associée à une deuxième sous couche similaire à la couche barrière à l'humidité,Zr, Mo, Ni, Li, Cr, Ga, Ge, Mg, Mn, Co, SnIa moisture barrier layer is based on doped indium oxide, in particular with tin, or oxide of tin doped, especially with antimony - the first under layer is associated with a second sub-layer similar to the moisture barrier layer,
On entend au sens de l'invention par électrode " inférieure ", l'électrode qui se trouve la plus proche du substrat porteur pris en référence, sur laquelle une partie au moins des couches actives (par exemple l'ensemble des couches actives dans un système électrochrome " tout solide ") est déposée. L'électrode " supérieure " est celle déposée de l'autre côté, par rapport au même substrat de référence.For the purposes of the invention, the term "lower" electrode means the electrode which is closest to the carrier substrate taken as reference, on which at least part of the active layers (for example all the active layers in a electrochromic system "all solid") is deposited. The "upper" electrode is the one deposited on the other side, with respect to the same reference substrate.
Avantageusement, l'électrode supérieure et/ ou inférieure selon l'invention présente une résistivité électrique comprise entre 10.10 4 et 9.10 5 ohm.cm, ce qui rend son utilisation en tant qu'électrode parfaitement satisfaisanteAdvantageously, the upper and / or lower electrode according to the invention has an electrical resistivity of between 10 × 10 4 and 9 × 10 5 ohm.cm, which makes its use as an electrode perfectly satisfactory.
De préférence, notamment pour atteindre ce niveau de résistivité, elle a une épaisseur totale comprise entre 160 et 320 nm Dans ces gammes d'épaisseurs, l'électrode demeure transparente, c'est-à-dire qu'elle présente une faible absorption lumineuse dans le visible. Il n'est cependant pas exclu d'avoir des couches nettement plus épaisses (notamment dans le cas où le système électroactif du type électrochrome fonctionne en réflexion plutôt qu'en transmission), ou des couches plus fines (notamment quand elles sont associées dans l'électrode à un autre type de couche conductrice, métallique par exemple). Comme mentionné plus haut, l'invention peut s'appliquer à différents types de systèmes électrochimiques ou électrocommandables. Elle s'intéresse plus particulièrement aux systèmes électrochromes, notamment les " tout solide " ou les " tout solide sur polymère" ou les " tout polymère ", ou encore aux systèmes à cristaux liquides ou viologènes, ou encore aux systèmes électroluminescents..Preferably, in particular to reach this resistivity level, it has a total thickness of between 160 and 320 nm. In these thickness ranges, the electrode remains transparent, that is to say that it has a low light absorption. in the visible. However, it is not excluded to have much thicker layers (especially in the case where the electroactive electrochemical system functions in reflection rather than transmission), or thinner layers (especially when they are associated in electrode to another type of conductive layer, metal for example). As mentioned above, the invention can be applied to different types of electrochemical or electrically controllable systems. It is particularly interested in electrochromic systems, especially "all solid" or "all solid on polymer" or "all polymer", or liquid crystal systems or viologen, or electroluminescent systems.
Les systèmes, ou vitrages, électrochromes auxquels peut s'appliquer l'invention, sont décrits dans le brevets précités. Ils peuvent comporter au moins un substrat porteur et un empilement de couches fonctionnelles comprenant au moins successivement une première couche électroconductrice, une couche électrochimiquement active susceptible d'insérer réversiblement des ions tels que H+, Li+, OH" du type matériau électrochrome anodique ou respectivement cathodique, une couche d'électrolyte, une seconde couche électrochimiquement active susceptible d'insérer réversiblement des ions tels que H+, Li+, OH" du type matériau électrochrome cathodique ou respectivement anodique, et une seconde couche électroconductrice, (le terme de " couche " est à comprendre comme une couche unique ou une superposition de plusieurs couches, continues ou discontinues). L'invention concerne également l'incorporation des dispositifs électrochimiques décrits dans le préambule de la présente demande dans des vitrages, fonctionnant en réflexion (miroir) ou en transmission. Le terme " vitrage " est à comprendre au sens large et englobe tout matériau essentiellement transparent, en verre et/ ou en matériau polymère (comme du polycarbonate PC ou du polymétacrylate de méthyle PMMA). Les substrats porteurs et/ou contre-substrats, c'est-à-dire les substrats encadrant le système actif, peuvent être rigides, flexibles ou semi-flexibles.The electrochromic systems or glazing to which the invention can be applied are described in the aforementioned patents. They may comprise at least one carrier substrate and a stack of functional layers comprising at least successively a first electroconductive layer, an electrochemically active layer capable of reversibly inserting ions such as H + , Li + , OH "of the electrochromic anodic material type or respectively cathodic, an electrolyte layer, a second electrochemically active layer capable of reversibly inserting ions such as H + , Li + , OH "of the cathodic or anodic electrochromic material type, and a second electroconductive layer, (the term "layer" is to be understood as a single layer or a superposition of several layers, continuous or discontinuous). The invention also relates to the incorporation of the electrochemical devices described in the preamble of the present application in glazings, operating in reflection (mirror) or transmission. The term "glazing" is to be understood in the broad sense and includes any substantially transparent material, glass and / or polymeric material (such as polycarbonate PC or polymethyl methacrylate PMMA). The carrier substrates and / or counter-substrates, that is to say the substrates surrounding the active system, can be rigid, flexible or semi-flexible.
Si le vitrage fonctionne en réflexion, il peut notamment être utilisé comme miroir d'intérieur ou comme rétroviseur. L'invention concerne également les diverses applications que l'on peut trouver à ces dispositifs, vitrages ou miroirs : il peut s'agir de faire des vitrages pour bâtiment, notamment des vitrages extérieurs, des cloisons internes ou des portes vitrées). Il peut aussi s'agir de fenêtres, toits ou cloisons internes de moyens de transport comme des trains, avions, voitures, bateaux. Il peut aussi s'agir d'écrans de visualisation ou d'affichage, comme des écrans de projection, des écrans de télévision ou d'ordinateur, des écrans tactiles. On peut aussi les utiliser pour faire des lunettes ou des objectifs d'appareil photo, ou encore pour protéger des panneaux solaires. On peut aussi les utiliser comme dispositifs de stockage d'énergie du type batterie, pile à combustible, batteries et piles elles-mêmes.If the glazing works in reflection, it can be used in particular as an interior mirror or as a rearview mirror. The invention also relates to the various applications that can be found with these devices, glazings or mirrors: it may be a question of glazing for buildings, in particular exterior glazing, internal partitions or glazed doors). It can also be windows, roofs or internal partitions of means of transport such as trains, planes, cars, boats. It can also be display screens or display, such as projection screens, television or computer screens, touch screens. They can also be used to make glasses or camera lenses, or to protect solar panels. They can also be used as energy storage devices of the battery type, fuel cell, batteries and batteries themselves.
L'invention sera maintenant décrite plus en détails à l'aide d'exemples non limitatifs et de figures :The invention will now be described in more detail using non-limiting examples and figures:
- La figure 1 : une vue schématique en coupe d'une cellule électrochrome utilisant une électrode conforme à l'invention, - la figure 2 illustre pour diverses configurations d'électrodes selon l'invention leur protection électrochimique.- Figure 1: a schematic sectional view of an electrochromic cell using an electrode according to the invention; - Figure 2 illustrates for various configurations of electrodes according to the invention their electrochemical protection.
La figure 1 est volontairement très schématique et n'est pas nécessairement à l'échelle pour en faciliter la lecture : elle représente en coupe un dispositif électrochrome " tout solide " selon les enseignements de l'invention comprenant successivement :FIG. 1 is deliberately very schematic and is not necessarily scaled to facilitate reading: it shows in section a "solid" electrochromic device according to the teachings of the invention comprising successively:
- un substrat de verre silico-sodo-calcique 1 clair de 2, 1 mm d'épaisseur,a clear silico-soda-lime glass substrate 1, 2 mm thick,
- une électrode inférieure 2 comportant un empilement de couches du type ITO/ZnO :Al/Ag/ZnO :A1/ITO d'épaisseurs respectives 15 à 20 nm pour 1TTO/60 à 80 nm pour le ZnO :Al/3 à 15 nm pour l'argent/ 60 à 80 nm pour le ZnO :A1/ 15 à 20 nm pour ITTO,a lower electrode 2 comprising a stack of ITO / ZnO: Al / Ag / ZnO: Al / ITO layers of respective thicknesses 15 to 20 nm for 1TTO / 60 at 80 nm for ZnO: Al / 3 at 15 nm for silver / 60 to 80 nm for ZnO: A1 / 15 at 20 nm for ITTO,
- une électrode supérieure 4 à base diTO ou de Snθ2 :Fan upper electrode 4 based on diTO or SnO 2: F
- un système électrochrome 3 dont la structure est décrite ci après - une feuille 7 de PU permet de feuilleter le verre 1 à un autre verrean electrochromic system 3, the structure of which is described below, a sheet 7 of PU making it possible to flick the glass 1 to another glass
8 de mêmes caractéristiques que le verre 1. Optionnellement, la face du verre 8 tournée vers la feuille de PU 7 est munie d'un empilement de couches minces à fonction de protection solaire. Cet empilement peut notamment comporter deux couches d'argent intercalées par des couches en diélectrique, de façon connue.8 of the same characteristics as glass 1. Optionally, the The face of the glass 8 turned towards the PU sheet 7 is provided with a stack of thin films with a solar protection function. This stack may in particular comprise two silver layers interposed by dielectric layers, in a known manner.
Le système électrochrome 3 comprend :The electrochromic system 3 comprises:
- une première couche de matériau électrochrome anodique ECl en oxyde d'iridium (hydraté) de 40 à 100 nm ou d'oxyde de nickel hydraté de 40 à 400 nm, alliée ou non à d'autres métaux, (en variante, cette couche peut être remplacée par une couche de matériau électrochrome anodique en oxyde de nickel de 100 à 300 nm, alliée ou non à d'autres métaux)a first layer of anodic electrochromic material EC1 of iridium oxide (hydrated) of 40 to 100 nm or of nickel oxide hydrated at 40 to 400 nm, alloyed or not with other metals (alternatively, this layer can be replaced by a layer of anodic electrochromic material made of nickel oxide from 100 to 300 nm, alloyed or not with other metals)
- une couche en oxyde de tungstène de 100 nm,a layer of tungsten oxide of 100 nm,
- une seconde couche en oxyde de tantale hydraté ou d'oxyde de silice hydraté ou d'oxyde de zirconium hydraté de 100 nm, ces deux dernières couches formant une couche à fonction électrolyte ELa second layer of hydrated tantalum oxide or of hydrated silica oxide or of hydrated zirconium oxide of 100 nm, these last two layers forming an electrolyte-functional layer EL
- une seconde couche de matériau électrochrome EC2 cathodique à base d'oxyde de tungstène WO3 de 370 nm, L'ensemble des couches a été déposé par pulvérisation cathodique assistée par champ magnétique.a second layer of cathodic EC2 electrochrome material based on WO3 tungsten oxide of 370 nm. The set of layers was deposited by magnetic field assisted sputtering.
Le dispositif électrochrome décrit précédemment constitue l'exempleThe electrochromic device described above constitutes the example
1.1.
On donne ci-après l'exemple 2 qui est une structure connue de l'art antérieur et pour laquelle les électrodes tant inférieure que supérieure sont à base diTO ou de Snθ2 :FExample 2 which is a known structure of the prior art and for which the lower and upper electrodes are based on diTO or SnO 2: F is given below.
EXEMPLE 2 (comparatif = standard EC) le vitrage électrochrome EC est de composition identique à l'exemple 1 à ceci près que - l'électrode inférieure 2 est à base diTO (oxyde d'indium dopé à l'étain) deEXAMPLE 2 (comparative = EC standard) the electrochromic glazing EC is of composition identical to example 1 except that the lower electrode 2 is based on diTO (indium oxide doped with tin) of
500 nm, déposé à chaud (3500C) En variante, l'électrode supérieure comporte d'autres éléments conducteurs: il peut s'agir plus particulièrement d'associer l'électrode à une couche plus conductrice qu'elle, et/ ou à une pluralité de bandes ou de fils conducteurs. On se reportera pour plus de détails au brevet WO- 00/57243 précité pour la mise en œuvre de telles électrodes multi- composantes. Un mode de réalisation préféré de ce type d'électrode consiste à appliquer sur la couche diTO (éventuellement surmontée d'une ou plusieurs autres couches conductrices) un réseau de fils conducteurs incrustés à la surface d'une feuille de polymère (qui pourra alors protéger le système actif et/ ou permettre le feuilletage du substrat-porteur du type verre avec un autre verre dans le cas d'une fabrication de vitrage électroactif, du type électrochrome par exemple).500 nm, deposited under heat (350 ° C.) Alternatively, the upper electrode has other conductive elements: it may be more particularly to associate the electrode to a more conductive layer that it, and / or a plurality of strips or son son. Reference is made to the above-mentioned patent WO 00/57243 for the implementation of such multi-component electrodes. A preferred embodiment of this type of electrode is to apply on the diTO layer (possibly topped with one or more other conductive layers) a network of son encrusted on the surface of a polymer sheet (which can then protect the active system and / or allow the lamination of the glass-type carrier-substrate with another glass in the case of electroactive glazing production, of the electrochromic type, for example).
Des tests comparatifs ont été effectués sur les deux cellules électrochromes des exemples 1 et 2.Comparative tests were carried out on the two electrochromic cells of Examples 1 and 2.
La validation la plus fiable des TCO consiste à effectuer un test de durabilité des cellules électrochromes par une exposition à 800C à l'état coloré. Dans ce cadre, les paramètres représentatifs de la dégradation des vitrages EC sont l'évolution le temps de commutation (Vcom) et le contraste (TL décoioré/TL∞ioré)The most reliable validation of the TCOs consists in carrying out a durability test of the electrochromic cells by exposure at 80 ° C. in the colored state. In this context, the parameters representative of the deterioration of the EC glazings are the evolution of the switching time (Vcom) and the contrast (TL decored / TL∞ioré)
Le tableau ci-dessus indique que le temps de commutation (Vcom) ainsi que le contraste, subissent une évolution similaire sur l'échantillon standard (avec électrode inférieure de 500 nm diTO à chaud) et sur l'échantillon incorporant le TCO multicouche. L'utilisation du TCO multicouche est donc parfaitement compatible avec une utilisation en vitrages électrochromes.The above table indicates that the switching time (Vcom) as well as the contrast, undergo a similar evolution on the standard sample (with hot dioid 500 nm lower electrode) and on the sample incorporating the multilayer TCO. The use of the multilayer TCO is therefore perfectly compatible with a use in electrochromic glazings.
Mesure optiqueOptical measurement
Les résultats optiques montrent (pour un TCO incorporant une couche d'Ag de 12 nm d'épaisseur) une perte en TL ainsi qu'une augmentation de la réflexion. Cette absorption lumineuse plus importante est parfaitement acceptable pour l'application pour toits automobile, pour laquelle le niveau de TL attendu par le client est au plus de 40%. On donne ci-après d'autres exemples illustrant d'autres modes de réalisation de l'invention. Exemple 3The optical results show (for a TCO incorporating an Ag layer 12 nm thick) a loss in TL as well as an increase in reflection. This higher light absorption is perfectly acceptable for the automotive roof application, for which the level of TL expected by the customer is at most 40%. Other examples illustrating other embodiments of the invention are given below. Example 3
Selon une variante de l'invention faisant l'objet de l'exemple 3, celle- ci reprend sensiblement la structure de l'empilement de l'exemple 1 sauf en ce qui concerne la nature des électrodes inférieure 2 et supérieure 4. En effet, l'une et l'autre comportent un empilement de couches du type ITO/ZnO :Al/Ag/ZnO :A1/ITO d'épaisseurs respectives 15 à 20 nm pour ITΓΌ/60 à 80 nm pour le ZnO :Al/3 à 15 nm pour l'argent/ 60 à 80 nm pour le ZnO/ 15 à 20 nm pour 11TO. Cette configuration permet de s'affranchir du réseau de fils, la conduction du TCO étant équivalente à celle de l'ensemble ITO + fils.According to a variant of the invention which is the subject of example 3, this substantially takes up the structure of the stack of example 1 except as regards the nature of the lower and upper electrodes 2 and 4. both comprise a stack of ITO / ZnO: Al / Ag / ZnO: Al / ITO layers of respective thicknesses 15 to 20 nm for ITΓΌ / 60 at 80 nm for ZnO: Al / 3 at 15 nm for silver / 60 to 80 nm for ZnO / 15 at 20 nm for 11TO. This configuration eliminates the wire network, the conduction of the TCO being equivalent to that of the whole ITO + son.
On donne ci-après d'autres exemples de réalisation de l'invention Le tableau ci-dessous regroupe les caractéristiques électriques et optiques de différents TCO multicouches répondant à des applications diverses.Other embodiments of the invention are given below. The table below groups together the electrical and optical characteristics of various multilayer TCOs that meet various applications.
Dans le précédent tableau : etot : épaisseur totale, p : résistivité effective de l'empilement et R carré = p/etot en Ω/carré. En outre TL : transmission lumineuse en %, RL : réflexion lumineuse, Abs = 100- RL - TL Les inventeurs se sont aperçu que la protection électrochimique de la couche fonctionnelle est déterminée par l'épaisseur de la couche barrière électrochimique. Les inventeurs ont ainsi pu déterminer qu'une épaisseur minimale de 60 nm de ZnO :A1 est nécessaire pour protéger l'Ag. Ceci est illustré sur la figure 2 ou un TCO comprenant 12 nm d'Ag subi un cycle d'oxydation à l'aide d'un montage dit 'à trois électrodes' avec une électrode travail (TCO étudié), une électrode référence (Electrode au Calomel Saturé) et une contre-électrode (verre + 500 nm ITO) plongées dans un électrolyte liquide H3PO4 (acide orthophosphorique ).In the previous table: etot: total thickness, p: effective resistivity of the stack and R squared = p / etot in Ω / square. In addition TL: light transmission in%, RL: light reflection, Abs = 100-RL-TL The inventors have found that the electrochemical protection of the functional layer is determined by the thickness of the electrochemical barrier layer. The inventors have thus been able to determine that a minimum thickness of 60 nm of ZnO: Al is necessary to protect the Ag. This is illustrated in FIG. 2 where a TCO comprising 12 nm of Ag undergoes an oxidation cycle using a so-called 'three-electrode' assembly with a working electrode (TCO studied), a reference electrode (Electrode Saturated Calomel) and a counter electrode (glass + 500 nm ITO) immersed in a liquid electrolyte H3PO4 (orthophosphoric acid).
Selon une autre variante de réalisation destinée particulièrement à une utilisation avec un système électrocommandable de type électroluminescent :According to another embodiment particularly intended for use with an electroluminesible electroluminescent type system:
On distingue une première famille dans laquelle le matériau électroluminescent organique de la couche mince est constitué à partir de molécules évaporées (OLEDs) comme par exemple le complexe d'AlQ.3 (tris(8-hydroxyquinoline) aluminium), le DPVBi (4,4'-(diphényl vinylène biphényl)), le DMQA (diméthyl quinacridone) ou le DCM (4- (dicyanométhylène)-2-méthyl-6-(4-diméthylaminostyryl)-4H-pyran) . Dans ce cas, on associe au niveau de chacune des faces de la couche mince des couches supplémentaires favorisant le transport des porteurs électriques (trous et électrons), ces couches supplémentaires sont respectivement appelées " HTL " et " ETL " pour " HoIe Transporting Layer " et Electron Transporting Layer ". De plus, afin d'améliorer l'injection des trous au niveau de la couche HTL, cette dernière est associée à une couche appelée " HIL " pour " HoIe Injection Layer " constituée par exemple de phtalocyanine de cuivre ou de zinc,A first family is distinguished in which the organic electroluminescent material of the thin layer consists of evaporated molecules (OLEDs), for example the AlQ complex . 3 (tris (8-hydroxyquinoline) aluminum), DPVBi (4,4 '- (diphenylvinylene biphenyl)), DMQA (dimethyl quinacridone) or DCM (4- (dicyanomethylene) -2-methyl-6- (4 dimethylaminostyryl) -4H-pyran). In this case, there are associated at the level of each of the faces of the thin layer additional layers favoring the transport of electrical carriers (holes and electrons), these additional layers are respectively called "HTL" and "ETL" for "HoIe Transporting Layer" and Electron Transporting Layer "In addition, to improve the injection of holes in the HTL layer, the latter is associated with a layer called "HIL" for "HoIe Injection Layer" consisting for example of phthalocyanine copper or zinc,
Une seconde famille dans laquelle le matériau électroluminescent organique de la couche mince est constitué à partir de polymères (pLEDs) comme par exemple le PPV pour poly(pαrα-phénylène vinylène), le PPP (poly(pαrα-phénylène), le DO-PPP (poly(2-décyloxy-l,4-phénylène), le MEH- PPV (poly[2-(2'-éthylhexyloxy)-5-méthoxy-l,4-phénylène vinylène)]), le CN- PPV (poly[2,5-bis(hexyloxy)-l,4-phénylène-(l-cyanovinylène)]) ou les PDAF (poly(dialkylfluorène), la couche de polymère est associée également à une couche qui favorise l'injection des trous (HIL) constituée par exemple du PEDT/PSS (poly (3,4-ethylène-dioxythiophène/ poly(4-styrène sulfonate)),A second family in which the organic electroluminescent material of the thin layer consists of polymers (pLEDs) such as for example PPV for poly (pαrα-phenylene vinylene), PPP (poly (pαrα-phenylene), the DO-PPP (poly (2-decyloxy-1,4-phenylene), MEH-PPV (poly [2- (2'-ethylhexyloxy) -5-methoxy-1,4-phenylene vinylene)]), CN-PPV (poly [2,5-bis (hexyloxy) -1,4-phenylene- (1-cyanovinylene)]) or PDAF (poly (dialkylfluorene), the polymer layer is also associated with a layer which promotes the injection of holes ( HIL) consisting for example of PEDT / PSS (poly (3,4-ethylene-dioxythiophene / poly (4-styrene sulfonate)),
Une troisième famille dans laquelle le matériau électroluminescent inorganique de la couche mince est constitué d'une couche mince d'un luminophore par exemple de sulfures tel que par exemple ZnS : Mn ou du SrS :Ce ou d'oxydes tel que Zn2SiO4:Mn, Zn2GeO4:Mn ou Zn2Ga2θ4:Mn. Dans ce cas, on associe à chacune des faces de la couche mince électroluminescente, une couche isolante réalisée à partir d'un matériau diélectrique, classiquement par exemple du Si3N4 , du BaTiOe ou du Al2O3/TiO2 A third family in which the inorganic electroluminescent material of the thin layer consists of a thin layer of a phosphor for example sulfides such as for example ZnS: Mn or SrS: Ce or oxides such as Zn 2 SiO 4 : Mn, Zn 2 GeO 4 : Mn or Zn 2 Ga 2 θ 4 : Mn. In this case, one associates with each of the faces of the thin electroluminescent layer, an insulating layer made from a dielectric material, typically for example Si3N 4 , BaTiOe or Al 2 O 3 / TiO 2
Une quatrième famille dans laquelle le matériau électroluminescent inorganique est constitué d'une couche épaisse de luminophore tel que par exemple du ZnS:Mn ou du ZnS :Cu, cette couche étant associée à une couche isolante en matériau diélectrique par exemple de BaTiOe, ces couches étant généralement réalisées par sérigraphie.A fourth family in which the inorganic electroluminescent material consists of a thick phosphor layer such as for example ZnS: Mn or ZnS: Cu, this layer being associated with an insulating layer of dielectric material, for example BaTiOe, these layers being generally made by screen printing.
Quel que soit le type du système électroluminescent, organique ou inorganique, en couches minces ou épaisses, l'empilement de couches comprenant notamment la couche électroluminescente, est associé de part et d'autre des couches isolantes, HTL, ETL, HIL, à des deux électrodes, (une cathode et une anode dans le cas des systèmes organiques).Whatever the type of electroluminescent system, organic or inorganic, in thin or thick layers, the stack of layers including the electroluminescent layer, is associated with and other insulating layers, HTL, ETL, HIL, to two electrodes, (a cathode and an anode in the case of organic systems).
Ces électrodes sont similaires à celles déjà envisagées pour les systèmes électrocommandables de type électrochromes décrits précédemment.These electrodes are similar to those already envisaged for the electrocommandable electrochromic type systems described above.
Néanmoins, il peut être nécessaire de rendre réfléchissantes l'une de ces électrodes et pour ce faire on augmente l'épaisseur de la couche fonctionnelle à propriétés de conductivité électrique. On donne ci-après les épaisseurs de chacune des couches formant l'empilement des deux types d'électrode :Nevertheless, it may be necessary to make one of these electrodes reflective and to this end the thickness of the functional layer with electrical conductivity properties is increased. The thicknesses of each of the layers forming the stack of the two types of electrode are given below:
Electrode El : 15 à 20 nm pour ITTO/ 60 à 80 nm pour le ZnO :Al/6 à 12 nm pour l'argent/ 60 à 80 nm pour le ZnO :A1/ 15 à 20 nm pour 11TO. Electrode E2 : 15 à 20 nm pour 1TTO/60 à 80 nm pour le ZnO :A1/4O nm minimum pour l'argent/ 60 à 80 nm pour le ZnO :A1/ 15 à 20 nm pour ITTO.Electrode El: 15 to 20 nm for ITTO / 60 at 80 nm for ZnO: Al / 6 at 12 nm for silver / 60 to 80 nm for ZnO: A1 / 15 at 20 nm for 11TO. Electrode E2: 15 to 20 nm for 1TTO / 60 to 80 nm for ZnO: A1 / 40 nm minimum for silver / 60 to 80 nm for ZnO: A1 / 15 at 20 nm for ITTO.
Cette structure d'électrode selon l'invention est intégrée au sein d'un empilement de type électroluminescent selon la configuration suivante : El /(Si3N4(300nm)/Luminophore(500nm)/Si3N4(300nm))/E2This electrode structure according to the invention is integrated within a stack of electroluminescent type according to the following configuration: E1 / (Si3N4 (300nm) / Luminophore (500nm) / Si3N4 (300nm)) / E2
L'invention concerne aussi le substrat muni d'au moins une électrode du type décrit plus haut, indépendamment du dispositif électrique/ électrochimique dans lequel elle est incorporée ou destinée à être incorporée ainsi que l'électrode inférieure ou supérieure en tant que telle. The invention also relates to the substrate provided with at least one electrode of the type described above, independently of the electrical / electrochemical device in which it is incorporated or intended to be incorporated as well as the lower or upper electrode as such.

Claims

REVENDICATIONS
1. Dispositif électrochimique/ électrocommandable, à propriétés optiques et/ou énergétiques variables, comportant au moins un substrat porteur muni d'une couche électroactive ou d'un empilement de couches électroactives disposé(e) entre une électrode dite " inférieure " et une électrode dite " supérieure ", caractérisé en ce que l'une au moins des électrodes inférieure ou supérieure comprend au moins quatre couches dont au moins une couche fonctionnelle métallique à propriétés intrinsèque de conductivité électrique, ladite couche fonctionnelle étant associée à une couche barrière électrochimique en matériau électroconducteur transparent dans le visible, ladite couche barrière électrochimique étant associée à une couche de protection contre l'humidité en matériau électroconducteur transparent dans le visible et ladite couche fonctionnelle étant associée à une première sous-couche en matériau électroconducteur transparent dans le visible, la couche fonctionnelle étant à base d'un matériau pur choisi parmi l'argent, ou le Cu ou le Zn ou l'Ai ou l'Au.An electrochemical / electrically controllable device, with variable optical and / or energy properties, comprising at least one carrier substrate provided with an electroactive layer or a stack of electroactive layers arranged between a so-called "lower" electrode and an electrode so-called "upper", characterized in that at least one of the lower or upper electrodes comprises at least four layers including at least one functional metallic layer with intrinsic properties of electrical conductivity, said functional layer being associated with an electrochemical barrier layer of material electroconductive transparent in the visible, said electrochemical barrier layer being associated with a protective layer against moisture electroconductive material transparent in the visible and said functional layer being associated with a first sub-layer of electroconductive material transparent in the visible, the functional layer being based on a pure material selected from silver, or Cu or Zn or Al or Au.
2. Dispositif électrochimique selon la revendication 1, caractérisé en ce que la première sous couche est de nature identique à la couche barrière électrochimique.2. Electrochemical device according to claim 1, characterized in that the first sublayer is identical in nature to the electrochemical barrier layer.
3. Dispositif électrochimique selon la revendication 1 ou la revendication 2, caractérisé en ce que la couche barrière électrochimique est à base d'oxyde de zinc ou d'un oxyde mixte de zinc dopé par un autre métal choisi parmi la famille des métaux suivants : Al , Ga, B, Sc3. Electrochemical device according to claim 1 or claim 2, characterized in that the electrochemical barrier layer is based on zinc oxide or a mixed zinc oxide doped with another metal selected from the family of the following metals: Al, Ga, B, Sc
4. Dispositif électrochimique selon l'une quelconque des revendications précédentes, caractérisé en ce que l'oxyde de zinc est du type ZnOx avec x inférieur à 1, préférentiellement compris entre de 0,88 à 0,98, notamment de 0,90 à 0,95. 4. Electrochemical device according to any one of the preceding claims, characterized in that the zinc oxide is ZnOx type with x less than 1, preferably between 0.88 to 0.98, in particular from 0.90 to 0.95.
5. Dispositif électrochimique selon l'une quelconque des revendications précédentes, caractérisé en ce que la couche barrière à l'humidité est à base d'oxyde d'indium dopé, notamment à l'étain, ou d'oxyde d'étain dopé, notamment à l'antimoine. 5. Electrochemical device according to any one of the preceding claims, characterized in that the moisture barrier layer is based on doped indium oxide, in particular tin, or doped tin oxide, especially antimony.
6. Dispositif électrochimique selon l'une quelconque des revendications précédentes, caractérisé en ce que la première sous couche est associée à une deuxième sous couche similaire à la couche barrière à l'humidité.6. Electrochemical device according to any one of the preceding claims, characterized in that the first sub-layer is associated with a second sub-layer similar to the moisture barrier layer.
7. Dispositif selon l'une des revendications précédentes, caractérisé en ce que l'électrode supérieure (4) comprend, outre la couche à base d'oxyde d'indium dopé (5), au moins une autre couche électroconductrice et/ ou une pluralité de bandes conductrices ou de fils conducteurs (6).7. Device according to one of the preceding claims, characterized in that the upper electrode (4) comprises, in addition to the doped indium oxide layer (5), at least one other electroconductive layer and / or a plurality of conductive strips or conductive wires (6).
8. Dispositif selon l'une des revendications précédentes, caractérisé en ce qu'il s'agit d'un système électrochrome, notamment un système électrochrome " tout solide " ou un système électrochrome " tout solide " sur polymère ou un système électrochrome " tout polymère ", d'un système à cristaux liquides ou d'un système viologène, ou d'un système électroluminescent.8. Device according to one of the preceding claims, characterized in that it is an electrochromic system, including an electrochromic system "all solid" or an electrochromic system "all solid" polymer or an electrochromic system "all polymer ", a liquid crystal system or a viologen system, or a light emitting system.
9- Electrode destinée à être intégrée au sein du dispositif électrochimique selon l'une quelconque des revendications 1 à 8, caractérisée en ce qu'elle comprend un empilement de couches du type ITO/ZnO :Al/Ag/ZnO :A1/ITO.9- Electrode intended to be integrated within the electrochemical device according to any one of claims 1 to 8, characterized in that it comprises a stack of layers of the type ITO / ZnO: Al / Ag / ZnO: A1 / ITO.
10- Electrode selon la revendication 9, caractérisée en ce que l'épaisseur de la couche d'argent est comprise entre 3 à 15 nm, préférentiellement comprise entre 6 à 12 nm.10- Electrode according to claim 9, characterized in that the thickness of the silver layer is between 3 to 15 nm, preferably between 6 to 12 nm.
11- Electrode selon la revendication 9, caractérisée en ce que l'épaisseur de la couche d'argent est comprise entre 30 à 50 nm.11- Electrode according to claim 9, characterized in that the thickness of the silver layer is between 30 to 50 nm.
12- Electrode selon la revendication 9, caractérisée en ce que l'épaisseur de la couche de ZnO est comprise entre 60 et 150 nm. 12- Electrode according to claim 9, characterized in that the thickness of the ZnO layer is between 60 and 150 nm.
13- Electrode selon la revendication 9, caractérisée en ce que l'épaisseur de la couche diTO est comprise entre 10 et 30 nm et préférentiellement 15 et 20 nm.13- Electrode according to claim 9, characterized in that the thickness of the diTO layer is between 10 and 30 nm and preferably 15 and 20 nm.
14. Vitrage caractérisé en ce qu'il incorpore le dispositif selon l'une des revendications 1 à 8.14. Glazing characterized in that it incorporates the device according to one of claims 1 to 8.
15. Miroir, notamment rétroviseur, caractérisé en ce qu'il incorpore le dispositif selon l'une des revendications 1 à 8 avec une épaisseur de la couche fonctionnelle d'au moins 40 nm.15. Mirror, in particular mirror, characterized in that it incorporates the device according to one of claims 1 to 8 with a thickness of the functional layer of at least 40 nm.
16. Utilisation du dispositif selon l'une des revendications 1 à 8 ou du vitrage selon la revendication 14 pour faire des vitrages pour bâtiment, des vitrages équipant des cloisons internes ou fenêtres ou toits ou équipant des moyens de transport du type avion, train, voiture, bateau, des écrans de visualisation/ d'affichage comme des écrans d'ordinateur ou de télévision ou des écrans de projection, des écrans tactiles, pour faire des lunettes ou des objectifs d'appareils photographiques ou des protections de panneaux solaires, ou des surfaces éclairantes. 16. Use of the device according to one of claims 1 to 8 or glazing according to claim 14 for making glazing for building, glazing equipping internal partitions or windows or roofs or equipping means of transport of the airplane type, train, car, boat, display / display screens such as computer or television screens or projection screens, touch screens, for making glasses or camera lenses or solar panel protections, or illuminating surfaces.
17. Procédé d'obtention du dispositif selon l'une des revendications17. Method for obtaining the device according to one of the claims
1 à 8, caractérisé en ce qu'on dépose l'une au moins des couches formant l'électrode inférieure ou supérieure est obtenue par pulvérisation cathodique assistée par champ magnétique, notamment à température ambiante. 1 to 8, characterized in that the deposited at least one of the layers forming the lower or upper electrode is obtained by magnetic field assisted sputtering, especially at room temperature.
EP06794447A 2005-05-27 2006-05-22 Electrodes of electrochemical/electrically-driven devices Withdrawn EP1883856A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0551391A FR2886419B1 (en) 2005-05-27 2005-05-27 ELECTRODE OF ELECTROCHEMICAL DEVICES / ELECTROCOMMANDABLE
PCT/FR2006/050465 WO2007000542A2 (en) 2005-05-27 2006-05-22 Electrode de dispositifs electrochimiques/electrocommandables

Publications (1)

Publication Number Publication Date
EP1883856A2 true EP1883856A2 (en) 2008-02-06

Family

ID=35406982

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06794447A Withdrawn EP1883856A2 (en) 2005-05-27 2006-05-22 Electrodes of electrochemical/electrically-driven devices

Country Status (8)

Country Link
US (1) US8259380B2 (en)
EP (1) EP1883856A2 (en)
JP (1) JP2008542804A (en)
KR (1) KR20080011401A (en)
CN (1) CN101218536A (en)
FR (1) FR2886419B1 (en)
RU (1) RU2411560C2 (en)
WO (1) WO2007000542A2 (en)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2904123B1 (en) * 2006-07-21 2008-09-12 Saint Gobain ELECTROCHEMICAL / ELECTROCOMMANDABLE DEVICE OF THE WINDOW TYPE AND HAVING VARIABLE OPTICAL AND / OR ENERGY PROPERTIES.
FR2904704B1 (en) * 2006-08-04 2008-12-05 Saint Gobain ELECTROCHEMICAL DEVICE, AND / OR ELELCTROCOMMANDABLE OF THE GLAZING TYPE AND HAVING VARIABLE OPTICAL AND / OR ENERGY PROPERTIES
JP5353191B2 (en) * 2008-11-05 2013-11-27 東ソー株式会社 Laminated transparent conductive film and method for producing the same
US11599003B2 (en) 2011-09-30 2023-03-07 View, Inc. Fabrication of electrochromic devices
US9007674B2 (en) 2011-09-30 2015-04-14 View, Inc. Defect-mitigation layers in electrochromic devices
DE102009026148A1 (en) * 2009-07-10 2011-01-13 Saint-Gobain Sekurit Deutschland Gmbh & Co. Kg Electrochromic layer structure and method for its production
US10303035B2 (en) 2009-12-22 2019-05-28 View, Inc. Self-contained EC IGU
US10802371B2 (en) 2011-12-12 2020-10-13 View, Inc. Thin-film devices and fabrication
US12061402B2 (en) 2011-12-12 2024-08-13 View, Inc. Narrow pre-deposition laser deletion
US11865632B2 (en) 2011-12-12 2024-01-09 View, Inc. Thin-film devices and fabrication
KR20220120709A (en) 2011-12-12 2022-08-30 뷰, 인크. Thin-film devices and fabrication
US20210394489A1 (en) 2011-12-12 2021-12-23 View, Inc. Thin-film devices and fabrication
DE102012101004A1 (en) * 2012-02-08 2013-08-08 Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG Electrode for use in electrochemical measuring systems
FR2991786B1 (en) 2012-06-08 2014-06-20 Saint Gobain PROJECTION SCREEN OPERATING IN REFLECTION INCLUDING VARIABLE LUMINOUS DIFFUSION SYSTEM
EP3842613A1 (en) 2012-08-23 2021-06-30 View, Inc. Photonic powered electrochromic devices
US20150093500A1 (en) * 2013-09-30 2015-04-02 Intermolecular, Inc. Corrosion-Resistant Silver Coatings with Improved Adhesion to III-V Materials
CN103981535A (en) * 2014-04-29 2014-08-13 天津大学 Catalytic electrode for photolysis of water to prepare hydrogen and preparation method thereof
JP6452734B2 (en) 2014-06-17 2019-01-16 セイジ・エレクトロクロミクス，インコーポレイテッド Moisture resistant electrochromic device
US11114742B2 (en) 2014-11-25 2021-09-07 View, Inc. Window antennas
CN107533267A (en) 2015-03-20 2018-01-02 唯景公司 Switch low defect electrochromic more quickly
CN109121433A (en) * 2016-05-09 2019-01-01 Sage电致变色显示有限公司 Comprising for preventing the device of Ion transfer electrochromic device and and forming method thereof
CA3034630A1 (en) 2016-08-22 2018-03-01 View, Inc. Electromagnetic-shielding electrochromic windows
US11320713B2 (en) 2017-02-16 2022-05-03 View, Inc. Solar power dynamic glass for heating and cooling buildings
CN108766261A (en) * 2018-05-24 2018-11-06 上海九山电子科技有限公司 A kind of in-vehicle display system and automobile
CN113940014A (en) 2019-05-09 2022-01-14 唯景公司 Antenna system for controlled coverage in buildings
EP4004641B1 (en) * 2019-07-31 2024-10-09 View, Inc. Faster switching electrochromic devices
JP2022086460A (en) * 2020-11-30 2022-06-09 株式会社リコー Electrochromic device and electrochromic light control lens
CN113284957B (en) 2021-04-21 2022-09-23 华为技术有限公司 Solar cell and electronic device
CN113189822A (en) * 2021-04-23 2021-07-30 广东省科学院新材料研究所 Electrochromic device and preparation method thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5321544A (en) * 1991-09-04 1994-06-14 Sun Active Glass Electrochromics, Inc. Electrochromic structures and methods
JPH09221340A (en) * 1996-02-09 1997-08-26 Nippon Sheet Glass Co Ltd Substrate with transparent conductive film
GB9603851D0 (en) * 1996-02-23 1996-04-24 Pilkington Plc Electrochromic devices
WO1998004406A1 (en) * 1996-07-26 1998-02-05 Asahi Glass Company Ltd. Transparent conductive film and method for forming transparent electrode
JPH1170610A (en) * 1996-07-26 1999-03-16 Asahi Glass Co Ltd Transparent conductive film and formation of transparent electrode
JPH10282907A (en) * 1997-04-10 1998-10-23 Toppan Printing Co Ltd Electrode substrate
FR2791147B1 (en) * 1999-03-19 2002-08-30 Saint Gobain Vitrage ELECTROCHEMICAL DEVICE OF THE ELECTROCOMMANDABLE DEVICE TYPE WITH VARIABLE OPTICAL AND / OR ENERGY PROPERTIES
US6822158B2 (en) * 2002-03-11 2004-11-23 Sharp Kabushiki Kaisha Thin-film solar cell and manufacture method therefor
FR2857617B1 (en) * 2003-07-16 2006-10-27 Saint Gobain FUNCTIONALIZED SAFETY GLAZING
US7626748B2 (en) * 2005-03-01 2009-12-01 Bijan Radmard Gel polymers containing ionic liquids
FR2893427B1 (en) * 2005-11-16 2008-01-04 Saint Gobain ELECTROCHEMICAL SYSTEM ON PLASTIC

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007000542A2 *

Also Published As

Publication number Publication date
WO2007000542A2 (en) 2007-01-04
JP2008542804A (en) 2008-11-27
FR2886419B1 (en) 2009-07-31
US8259380B2 (en) 2012-09-04
RU2007149344A (en) 2009-07-10
FR2886419A1 (en) 2006-12-01
US20080190759A1 (en) 2008-08-14
RU2411560C2 (en) 2011-02-10
CN101218536A (en) 2008-07-09
KR20080011401A (en) 2008-02-04
WO2007000542A3 (en) 2007-04-12

Similar Documents

Publication Publication Date Title
EP1883856A2 (en) Electrodes of electrochemical/electrically-driven devices
EP2084574B1 (en) High electric conductivity transparent layer with a metallic grid having an optimised electrochemical resistance
EP1451634B1 (en) Electrochemical/electro-controllable device electrode
EP2307926B1 (en) Electrochromic device with controlled infrared reflection
EP2047325B1 (en) Glass type electrochemical/ electrically controllable device with variable optical and/or energetic characteristic
EP1952194B1 (en) Electrochromic system on a plastic substrate
FR2904704A1 (en) ELECTROCHEMICAL DEVICE, AND / OR ELELCTROCOMMANDABLE OF THE GLAZING TYPE AND HAVING VARIABLE OPTICAL AND / OR ENERGY PROPERTIES
FR2857617A1 (en) Functionalized safety window for vehicles and buildings consists of at least one active system and at least one polymer film arranged between two rigid substrates
JP2008542804A5 (en)
WO2000057243A1 (en) Electrochemical device, such as an electrically controlled system with variable optical and/or energy properties
EP1509810A2 (en) Electrically-operated device with variable optical and/or energetic properties
EP2263118A2 (en) Electrochromic device including a meshing
WO2006018568A2 (en) Non-oxidised electrolyte electrochemical system
EP2649489A1 (en) Electrochemical device with electrocontrollable optical transmission and/or energy-related properties
FR2908228A1 (en) Electrically conductive layer for windows comprises a metal grille with a coating for electrochemical protection
EP2649488A1 (en) Electrochemical device with electrocontrollable optical transmission and/or enegy-related properties
WO2010004158A1 (en) Insulating electrode for electrochemical device

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20071113

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20080529

DAX Request for extension of the european patent (deleted)
APBK Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNE

APBN Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2E

APBR Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3E

APAV Appeal reference deleted

Free format text: ORIGINAL CODE: EPIDOSDREFNE

APBT Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9E

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20131203