PatentDe  


Dokumentenidentifikation EP1593000 24.08.2006
EP-Veröffentlichungsnummer 0001593000
Titel ELEKTROCHROMISCHE ANZEIGEEINRICHTUNG
Anmelder Ntera Ltd., Dublin, IE
Erfinder PICHOT, Francois, Dublin 14, IE;
MCATAMNEY, Colm, Ashbourne, County Meath, IE;
BACH, Udo, 78247 Hilzingen, DE
Vertreter derzeit kein Vertreter bestellt
DE-Aktenzeichen 602004001508
Vertragsstaaten AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HU, IE, IT, LI, LU, MC, NL, PT, RO, SE, SI, SK, TR
Sprache des Dokument EN
EP-Anmeldetag 30.01.2004
EP-Aktenzeichen 047067715
WO-Anmeldetag 30.01.2004
PCT-Aktenzeichen PCT/IE2004/000014
WO-Veröffentlichungsnummer 2004068231
WO-Veröffentlichungsdatum 12.08.2004
EP-Offenlegungsdatum 09.11.2005
EP date of grant 12.07.2006
Veröffentlichungstag im Patentblatt 24.08.2006
IPC-Hauptklasse G02F 1/155(2006.01)A, F, I, 20051017, B, H, EP

Beschreibung[en]

This invention relates to an electrochromic device. In particular, it relates to an electrochromic device in which the components are built up on a single substrate which need not be transparent. Such devices are often referred to as monolithic devices.

Electrochromic systems are based on colour changes that are caused by electrochemical reactions in various types of metal oxides or organic or inorganic compounds. Electrochromic devices are well known in the art. A typical electrochromic device architecture is the sandwich type architecture, which in its simplest form consists of two glass substrates on the outside and between them a counter and working electrode, an electrochromic material and an electrolyte which allows for the passage of ions. Such a device is disclosed in e.g. EP-A-1244168; Bach, U. et al, Adv. Mater. 2002, 14, No. 11, June 5 and Cummins et al, J. Phys. Chem B 2000, 104, 11449-11459. The document EP-1 244 168 A discloses the features labeled (a) to (c) in claim 1 in combination. One disadvantage of the sandwich type-architecture is that the electrochromic layer is typically viewed through a transparent substrate, such as glass which is covered with a transparent conducting layer. Transmission values for such conducting transparent substrates, e.g. glass or plastic coated with an electrically conducting material, are typically in the region of 70 - 90%. In reflective display applications, the light must pass through this layer twice when being diffusely reflected. This results in transmission losses of 19-51%, thereby limiting the maximum diffuse reflectance in the "off" state of the device to 49-81%.

WO-A-97/16838 discloses a monolithic device for solar cell applications. This device has a "classic" monolithic architecture, i.e. the working electrode layer is deposited directly onto a transparent conducting supporting substrate and is therefore the bottom layer of the device.

WO-A-01/97237 also discloses a monolithic device having a "classic" monolithic architecture where the working electrode (photoelectrode) is deposited directly onto a transparent conducting supporting substrate.

A major disadvantage of the existing monolithic devices is that they only allow deposition of electrochromic coatings onto transparent substrates, thus limiting their applications. Furthermore, pixels must be viewed through at least two layers of material, thereby adversely affecting the reflectance of the conventional devices.

It is an object of the present invention to avoid or minimise the disadvantages of the prior art.

According to the invention there is provided an electrochromic device comprising a single supporting substrate on which are disposed:

  • (a) a working electrode comprising a porous layer of an electrically conducting or semiconducting material, the working electrode comprising material which is electrochromic per se and/or at least a portion of said working electrode bearing electrochromic material;
  • (b) a counter electrode comprising a porous layer of an electrically conducting or semiconducting material;
  • (c) a layer of an electrically insulating material which is ion-permeable and which separates the working electrode and the counter electrode layers;
wherein said electrochromic material has a major surface at least a portion of which forms at least a portion of an external surface of the device.

As used herein, the term "electrochromic material" is intended to refer to a material which changes colour on the application of an electrical potential thereto.

In the device of the invention, substantially all of the major surface of the electrochromic material may form a portion of the external surface of the device. The working electrode preferably has a major surface which may be electrochromic per se or may bear electrochromic material on at least a portion thereof. The electrochromic material may substantially cover the major surface of the working electrode. The working electrode, counter electrode and insulating layers may be substantially parallel along their length. These layers may also be substantially coextensive with one another.

The supporting substrate may be formed from any suitable transparent or non-transparent material, such as glass or metal or a ceramic or plastics material. The substrate may be rendered electrically conducting by applying an electrically conducting coating to at least a portion of the internal surface thereof. The electrically conducting coating preferably comprises a doped metal oxide, such as, for example, tin oxide doped with fluorine or antimony, or indium oxide doped with tin, or a conducting polymer or metal. However, if the intrinsic sheet resistance of the material of the working electrode and/or the counter electrode is less than 10,000 ohms per square, the application of an electrically conducting coating to the substrate may not be required.

The working electrode.may be arranged so that at least a portion thereof is laterally offset from the counter electrode.

The working and counter electrodes comprise an electrically conducting or semiconducting material. A preferred electrically conducting material of the working and/or counter electrodes comprises nanoparticles of a metal oxide selected from any of the following:

  • (a) SnO2 doped with F, Cl, Sb, P As or B;
  • (b) ZnO doped with Al, In, Ga, B, F, Si, Ge, Ti, Zr or Hf;
  • (c) In2O3 doped with Sn;
  • (d) CdO;
  • (e) ZnSnO3, Zn2In2O5 , In4Sn3O12, GaInO3 or MgIn2O4 ;
  • (f) Fe2O3 doped with Sb;
  • (g) TiO2/WO3 or TiO2/MoO3 systems; and
  • (h) Fe2O3/Sb or SnO2/Sb systems;
preferably SnO2 doped with Sb.

A preferred electrically semiconducting material of the working and/or counter electrodes comprises nanoparticles of a metal oxide selected from any of the following:

TiO2, ZrO2, HfO2, CrO3, MoO3 , WO3, V2O3, V2O5, Nb2O5 SnO2 , Ta2O5, AgO, Ag2O, ZnO, SrO, FeO, Fe2O3 or NiO, or a perovskite thereof, more preferably TiO2, WO3, MoO3, ZnO or SnO2.

When the conducting or semiconducting material of the working electrode is electrochromic per se, such a material may include metal or doped metal oxides. Examples of such oxides include WO3, TiO2, antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO) and tin doped indium oxide (ITO). Alternatively and preferably, when the conducting or semiconducting material of the working electrode, which may or may not have intrinsic electrochromic properties, bears an electrochromic material, such electrochromic material is preferably selected from viologens and polymers and mixtures thereof. Suitable viologens are disclosed in WO-A-98/35267, WO-A-01/27690, WO-A-03/001288 and a copending PCT Application entitled "Electrochromic Compounds", filed on even date by the Applicant (NTera Limited). Suitable polymers include polythiophenes, polypyrroles and polyviologens.

The electrically insulating layer is preferably transparent or light-scattering and may comprise organic or inorganic material. This layer may also be porous. Such a porous layer preferably comprises a metal oxide selected from SiO2, Al2O3, ZrO and MgO, or TiO2 in the rutile form passivated with SiO2.

The inventive device may additionally comprise an ion-conducting medium. In one embodiment, the electrically insulating layer of the device may comprise an ion-conducting medium. For example, polyethylene glycol could serve as both insulator and solid electrolyte.

In another embodiment, the ion-conducting medium may be present in the device as an additional layer of solid electrolyte. In a preferred embodiment, the electrically insulating layer is porous, each of the porous layers is at least partially sealed, and the ion-conducting medium comprises a liquid electrolyte which at least partially fills the pores of the electrodes and the insulating material. The device of the invention preferably also comprises a transparent cover or top layer at least partially exposing the electrochromic material and a sealing material sealing the cover to the electrochromic device. Preferably, the sealing material seals the cover to the supporting substrate.

The liquid electrolyte, when present, preferably comprises at least one electrochemically inert salt optionally in molten form or in solution in a solvent. Examples of suitable salts include hexafluorophosphate, bis-trifluoromethanesulfonate, bis-trifluoromethylsulfonylimide, tetraalkylammonium, dialkyl-1,3-imidazolium and lithium perchlorate. Examples of suitable molten salts include trifluoromethanesulfonate, 1-ethyl,3-methyl imidazolium bis-trifluoromethylsulfonylimide and 1-propyldimethyl imidazolium bis-trifluoromethylsulfonylimide. Lithium perchlorate is particularly preferred.

The solvent may be any suitable solvent and is preferably selected from acetonitrile, butyronitrile, glutaronitrile, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methyloxazolidinone, dimethyltetrahydropyrimidinone, &ggr;-butyrolactone and mixtures thereof. Lithium perchlorate in &ggr;-butyrolactone is particularly preferred.

The device of the invention may optionally comprise an electrical current supporting layer interposed between the (semi) conducting material of the working electrode and the electrically insulating material. The electrical current supporting layer is formed from a porous, electrically conducting material which enables the transport of charge between the device components. This layer may suitably comprise indium oxide doped with tin or tin oxide doped with fluorine, or conducting polymers such as polythiophenes, polypyrroles and polyviologens.

The device of the invention may be conveniently sealed using a suitable sealing material and a transparent cover of glass or a plastics material disposed on the external surface of the layer remote from the supporting substrate.

The invention also provides a display comprising one or more devices according to the invention. A plurality of devices according to the invention may also be connected in series, forming an assembly. The device/assembly of the invention may be used in an active matrix or passive matrix or in direct drive configurations.

In the accompanying drawings, Figure 1 is a cross sectional diagram of one embodiment of a monolithic device according to the invention; Figure 2 is a cross sectional diagram of another embodiment of a monolithic device according to the invention; Figure 3 shows a plurality of the devices of Figure 2 connected in series; and Figures 4A and 4B are photographs of a top plan view of the device of Figure 2 containing three independent electrochromic pixels.

Referring to the drawings, in which like numerals represent like parts, the device of Figure 1 comprises a supporting substrate 1, which may be glass, plastic, ceramic or other suitable material. The substrate 1 bears a conducting coating or layer 2 that provides contact for a display device to external electronic controls. This layer 2 is patterned to allow for individual contact to pixels in a display and also for individual contact to working and counter electrode layers 6 and 3, respectively. The counter electrode layer 3 comprises a material porous to ions and is electrically conducting. Layer 3 is physically in contact with layer 2 and electrical current can flow between these layers. The working and counter electrodes are separated by a porous insulating layer 4. Layer 4 is porous to ions and is electrically insulating. The layer 4 is physically deposited on top of the counter electrode layer 3 and provides insulation for subsequent layers which must not be in contact with layer 3. An ion porous, electrically conducting layer 5 is physically deposited on layer 4 and is in electrical contact with layer 2. Layer 5 provides efficient electrical charge conduction to the working electrode layer/electrochromic layer 6. The major surface of the layer 6, i.e. the viewing surface, is denoted by x.

The device of Figure 2 is the same as that of Figure 1 except that the insulating layer 4 includes a via hole that allows contact between layer 2 and layer 5 such that electrical charge may be directed to the pixel.

The electrically conducting layer 5 is physically deposited on layer 4 and is in electrical contact with layer 2 by filling in the via hole.

In Figures 4A and 4B, the device is viewed through a layer of plain glass which is disposed on the external (viewing) surface of the layer 6 and sealed to the supporting substrate of the device. The seal of the device is visible as a black square. The space between the top glass plate and the substrate contains liquid electrolyte. Figure 4A shows all three pixels in the off-state (0 volt bias), while in Figure 4B the middle pixel was switched on by applying a negative bias of 1.5 V to the working electrode relative to its underlying counter electrode (not visible).

The electrochromic device of the invention has a number of advantages over existing devices:

  • It allows deposition of electrochromic coatings on a variety of substrates.
  • The supporting substrate does not need to be transparent.
  • High reflectivities in the high-reflectance state (off-state) can be reached.
  • The new architecture makes it easy to integrate the device onto circuit boards or other substrates, which already carry other electronic components. If the device is used as a display, it provides a very simple way of 'wiring' it to other display components (located on the same circuit board).
  • There is no loss of reflectivity in reflective displays.

The invention is illustrated in the following Example.

EXAMPLE

A supporting substrate in the form of glass coated with tin doped indium oxide (ITO) was patterned according to standard wet-etching techniques. Using screen-printing techniques the following layers were deposited on the substrate in the following sequence:

  • a) Sb-doped SnO2 - (nanostructured; microparticles+binder+solvent paste)
  • b) SiO2-passivated rutile (microparticles+ binder +solvent paste);
  • c) ITO (nano - to microparticles+ binder +solvent paste); and
  • d) TiO2 (nanoparticles +polymer+ binder paste).

The binder used in each of the above steps (a)-(d) was hydroxypropyl cellulose (Klucel EXF PHARM); and the solvent was terpineol (anhydrous, Fluka).

The electrically insulating layer (b) was prepared using the materials listed below according to the procedure described by Kay et al. in Solar Energy Materials and Solar Cells (1996), 44(1), pp 99 - 117.

Materials

Inorganic pigment:
Rutile TiO2; Ti-Pure Rutile R706 by DuPont. Median particle size: 0.36 µm, 3.0 % SiO2 & organic treatment.
Binder:
Hydroxypropyl cellulose (HPC); Klucel EXF PHARM.
Solvent:
Terpineol; anhydrous, purum, mixture of isomers, Fluka ordering number 86480.

The layered structure was sintered at 450°C for 30 minutes, exposed to a solution of bis-(2-phosphonoethyl)-4,4'-bipyridinium dichloride in water, rinsed, dried and sealed using an epoxy sealing ring and a top glass cover. The device was backfilled with the electrolyte lithium perchlorate in gamma-butyrolactone.

The Sb-doped SnO2 layer is used as a counter electrode, which can store or release charge and is necessary to show the electrochromic effect of the electrochromic layer. The rutile layer electrically insulates the doped SnO2 layer from the electrochromic layer and provides a 'white background' for the device. Ionic movement through this layer is facilitated due to its porous structure. The ITO layer is used as an electrical current supporting layer. It appears opaque (nearly white). Ionic movement through this layer is facilitated due to its porous structure. Its sheet resistance is lower than 1 k&OHgr;/□.

The viologen-derivatised mesoporous TiO2 layer is used as electrochromic layer.


Anspruch[de]
Elektrochromes Bauelement, das ein einzelnes Trägersubstrat (1) umfasst, auf dem Folgendes angeordnet ist: (a) eine Arbeitselektrode (6), die eine poröse Schicht aus einem elektrisch leitenden oder halbleitenden Material umfasst, wobei die Arbeitselektrode Material umfasst, das an sich elektrochrom ist und/oder wobei wenigstens ein Teil der genannten Arbeitselektrode ein elektrochromes Material trägt; (b) eine Gegenelektrode (3), die eine poröse Schicht aus einem elektrisch leitenden oder halbleitenden Material umfasst; (c) eine Schicht (4) aus einem elektrisch isolierenden Material, das ionendurchlässig ist und das die Arbeits- von der Gegenelektrodenschicht trennt; wobei das genannte elektrochrome Material eine Hauptfläche aufweist, von der wenigstens ein Teil wenigstens einen Teil einer Außenfläche des Bauelementes bildet. Bauelement nach Anspruch 1, wobei im Wesentlichen die gesamte genannte Hauptfläche einen Teil der Außenfläche des Bauelementes bildet. Bauelement nach Anspruch 1 oder 2, wobei die genannte Arbeitselektrode eine Hauptfläche hat, die an sich elektrochrom ist. Bauelement nach Anspruch 1 oder 2, wobei die genannte Arbeitselektrode eine Hauptfläche hat, von der wenigstens ein Teil elektrochromes Material trägt. Bauelement nach Anspruch 4, wobei das genannte elektrochrome Material im Wesentlichen die genannte Hauptfläche der genannten Arbeitselektrode bedeckt. Bauelement nach einem der vorherigen Ansprüche, wobei die Arbeitselektrode, die Gegenelektrode und die Isolierschichten im Wesentlichen parallel sind; und/oder wobei die Arbeitselektrode, die Gegenelektrode und die Isolierschichten im Wesentlichen koextensiv miteinander sind. Bauelement nach einem der Ansprüche 1 bis 5, wobei wenigstens ein Teil der Arbeitselektrode lateral von der Gegenelektrode versetzt ist. Bauelement nach einem der vorherigen Ansprüche, wobei das Trägersubstrat aus einem transparenten oder nichttransparenten Material gebildet ist. Bauelement nach Anspruch 8, wobei das Substrat aus Glas oder Metall oder einem Keramik- oder Plastikmaterial gebildet ist. Bauelement nach Anspruch 8 oder 9, wobei das Trägersubstrat eine elektrisch leitende Beschichtung auf wenigstens einem Teil der Innenfläche davon trägt. Bauelement nach Anspruch 10, wobei die elektrisch leitende Beschichtung ein dotiertes Metalloxid, vorzugsweise mit Fluor oder Antimon dotiertes Zinnoxid oder mit Zinn dotiertes Indiumoxid oder ein leitendes Polymer oder Metall umfasst. Bauelement nach einem der Ansprüche 1 bis 9, wobei der Eigenschichtwiderstand des Materials der Arbeitselektrode und/oder der Gegenelektrode weniger als 10.000 Ohm pro Quadrat beträgt. Bauelement nach einem der vorherigen Ansprüche, wobei die Arbeits- und/oder die Gegenelektrode ein elektrisch leitendes Material umfasst/umfassen, das Nanopartikel aus einem Metalloxid beinhaltet, das aus den Folgenden ausgewählt sind: (a) SnO2, dotiert mit F, Cl, Sb, P, As oder B; (b) ZnO, dotiert mit Al, In, Ga, B, F, Si, Ge, Ti, Zr oder Hf; (c) In2O3, dotiert mit Sn; (d) CdO; (e) ZnSnO3, Zn2In2O5, In4Sn3O12, GaInO3 oder MgIn2O4; (f) Fe2O3, dotiert mit Sb; (g) TiO2/WO3- oder TiO2/MoO3-Systeme; und (h) Fe2O3/Sb- oder SnO2/Sb-Systeme; vorzugsweise SnO2 dotiert mit Sb. Bauelement nach einem der Ansprüche 1 bis 13, wobei die Arbeits- und/oder Gegenelektrode ein elektrisch halbleitendes Material umfasst/umfassen, das Nanopartikel eines Metalloxids beinhaltet, das aus den Folgenden ausgewählt sind: TiO2, ZrO2, HfO2, CrO3, MoO3, WO3, VO, NbO, SnO2, TaO, AgO, ZnO, SrO, FeO, Fe2O3 oder NiO, oder ein Perovskit davon, vorzugsweise TiO2, WO3, MoO3, ZnO oder SnO2. Bauelement nach Anspruch 3 oder einem davon abhängigen Anspruch, wobei das elektrochrome Material der Arbeitselektrode ein Metalloxid ist, das ausgewählt ist aus WO3 und TiO2, oder ein dotiertes Metalloxid, das aus mit Antimon oder Fluor dotiertem Zinnoxid und mit Zinn dotiertem Indiumoxid ausgewählt ist. Bauelement nach Anspruch 4 oder einem davon abhängigen Anspruch, wobei das elektrochrome Material aus Viologenen und Polymeren und Gemischen davon ausgewählt ist. Bauelement nach einem der vorherigen Ansprüche, die ferner ein ionenleitendes Medium umfasst. Bauelement nach einem der vorherigen Ansprüche, wobei die elektrisch isolierende Schicht ein ionenleitendes Medium umfasst. Bauelement nach einem der Ansprüche 1 bis 17, wobei das elektrisch isolierende Material porös und jede der porösen Schichten wenigstens teilweise abgedichtet ist und wobei das ionenleitende Medium einen Flüssigelektrolyt umfasst, der die Poren der Elektroden und des Isoliermaterials wenigstens teilweise füllt. Bauelement nach einem der vorherigen Ansprüche, die ferner einen transparenten Deckel, der das genannte elektrochrome Material wenigstens teilweise exponiert, und ein Dichtungsmaterial umfasst, das den genannten Deckel auf dem genannten elektrochromen Bauelement abdichtet. Bauelement nach Anspruch 20, wobei das genannte Dichtungsmaterial den genannten Deckel auf dem genannten Trägersubstrat abdichtet. Bauelement nach einem der Ansprüche 19 bis 21, wobei das elektrisch isolierende Material ein Metalloxid umfasst, das aus SiO2, Al2O3, ZrO und MgO oder TiO2 in der mit SiO2 passivierten Rutilform ausgewählt ist. Bauelement nach einem der vorherigen Ansprüche, die ferner eine Schicht zwischen der Arbeitselektrode und den elektrisch isolierenden Schichten umfasst, die elektrischen Strom führen kann. Bauelement nach Anspruch 23, wobei die Schicht, die elektrischen Strom führen kann, mit Zinn dotiertes Indiumoxid oder mit Fluor dotiertes Zinnoxid oder ein leitendes Polymer umfasst, das aus Polythiophenen, Polypyrrolen und Polyviologenen ausgewählt ist. Display, das ein oder mehrere Bauelemente nach einem der vorherigen Ansprüche umfasst. Display nach Anspruch 25, das eine Mehrzahl von in Reihe geschalteten Bauelementen umfasst. Verwendung eines Bauelementes nach einem der Ansprüche 1 bis 24 in einer aktiven Matrix oder einer passiven Matrix oder in Direktansteuerungskonfigurationen.
Anspruch[en]
An electrochromic device comprising a single supporting substrate (1) on which are disposed: (a) a working electrode (6) comprising a porous layer of an electrically conducting or semiconducting material, the working electrode comprising material which is electrochromic per se and/or at least a portion of said working electrode bearing electrochromic material; (b) a counter electrode (3) comprising a porous layer of an electrically conducting or semiconducting material; (c) a layer (4) of an electrically insulating material which is ion-permeable and which separates the working electrode and the counter electrode layers; wherein said electrochromic material has a major surface at least a portion of which forms at least a portion of an external surface of the device. A device according to claim 1, wherein substantially all of said major surface forms a portion of the external surface of the device. A device according to claim 1 or 2, wherein said working electrode has a major surface which is electrochromic per se. A device according to claim 1 or 2, wherein said working electrode has a major surface at least a portion of which bears electrochromic material. A device according to claim 4, wherein said electrochromic material substantially covers said major surface of said working electrode. A device according to any preceding claim, wherein the working electrode, counter electrode and insulating layers are substantially parallel; and/or wherein the working electrode, counter electrode and insulating layers are substantially coextensive with one another. A device according to any of claims 1 to 5, wherein at least a portion of the working electrode is laterally offset from the counter electrode. A device according to any preceding claim, wherein the supporting substrate is formed from a transparent or non-transparent material. A device according to claim 8, wherein the substrate is formed from glass or metal or a ceramic or plastics material. A device according to claim 8 or 9, wherein the supporting substrate bears an electrically conducting coating on at least a portion of the internal surface thereof. A device according to claim 10, wherein the electrically conducting coating comprises a doped metal oxide, preferably tin oxide doped with fluorine or antimony, or indium oxide doped with tin, or a conducting polymer or metal. A device according to any of claims 1 to 9, wherein the intrinsic sheet resistance of the material of the working electrode and/or the counter electrode is less than 10,000 ohms per square. A device according to any preceding claim, wherein the working and/or counter electrodes comprise an electrically conducting material comprising nanoparticles of a metal oxide selected from any of the following: (a) SnO2 doped with F, Cl, Sb, P, As or B; (b) ZnO doped with Al, In, Ga, B, F, Si, Ge, Ti, Zr or Hf; (c) In2O3 doped with Sn; (d) CdO; (e) ZnSnO3, Zn2In2O5 , In4Sn3O12, GaInO3 or MgIn2O4 ; (f) Fe2O3 doped with Sb; (g) TiO2/WO3 or TiO2/MoO3 systems; and (h) Fe2O3/Sb or SnO2/Sb systems; preferably SnO2 doped with Sb. A device according to any of claims 1 to 13, wherein the working and/or counter electrode comprise an electrically semiconducting material comprising nanoparticles of a metal oxide selected from any of the following: TiO2, ZrO2, HfO2, CrO3, MoO3, WO3, VO, NbO, SnO2, TaO, AgO, ZnO, SrO, FeO, Fe2O3 or NiO, or a perovskite thereof, preferably TiO2, WO3, MoO3, ZnO or SnO2 . A device according to claim 3 or any claim dependent thereon, wherein the electrochromic material of the working electrode is a metal oxide selected from WO3 and TiO2 or a doped metal oxide selected from antimony or fluorine doped tin oxide and tin doped indium oxide. A device according to claim 4 or any claim dependent thereon, wherein the electrochromic material is selected from viologens and polymers and mixtures thereof. A device according to any preceding claim, further comprising an ion-conducting medium. A device according to any preceding claim, wherein the electrically insulating layer comprises an ion-conducting medium. A device according to any of claims 1 to 17, wherein the electrically insulating material is porous and each of the porous layers is at least partially sealed, and the ion-conducting medium comprises a liquid electrolyte which at least partially fills the pores of the electrodes and the insulating material. A device according to any preceding claim, further comprising a transparent cover at least partially exposing said electrochromic material and a sealing material sealing said cover to said electrochromic device. A device according to claim 20, wherein said sealing material seals said cover to said supporting substrate. A device according to any of claims 19 to 21, wherein the electrically insulating material comprises a metal oxide selected from SiO2, Al2O3, ZrO and MgO, or TiO2 in the rutile form passivated with SiO2. A device according to any preceding claim, further comprising an electrical current supporting layer interposed between the working electrode and the electrically insulating layers. A device according to claim 23, wherein the electrical current supporting layer comprises indium oxide doped with tin or tin oxide doped with fluorine, or a conducting polymer selected from polythiophenes, polypyrroles and polyviologens. A display comprising one or more devices according to any preceding claim. A display according to claim 25, comprising a plurality of devices connected in series. Use of a device according to any of claims 1 to 24 in an active matrix or passive matrix or in direct drive configurations.
Anspruch[fr]
Dispositif électrochromique comprenant un substrat de support unique (1) sur lequel sont disposées : (a) une électrode de travail (6) comprenant une couche poreuse d'une matière électriquement conductrice ou semi-conductrice, l'électrode de travail comprenant une matière qui est électrochromique en soi et/ou au moins une partie de ladite électrode de travail portant une matière électrochromique ; (b) une contre-électrode (3) comprenant une couche poreuse d'une matière électriquement conductrice ou semi-conductrice ; (c) une couche (4) d'une matière électriquement isolante qui est perméable aux ions et qui sépare les couches d'électrode de travail et de contre-électrode ; dans lequel ladite matière électrochromique a une surface principale dont au moins une partie forme au moins une partie d'une surface externe du dispositif. Dispositif selon la revendication 1, dans lequel essentiellement la totalité de ladite surface principale forme une partie de la surface externe du dispositif. Dispositif selon la revendication 1 ou 2, dans lequel ladite électrode de travail comporte une surface principale qui est électrochromique en soi. Dispositif selon la revendication 1 ou 2, dans lequel ladite électrode de travail comporte une surface principale dont au moins une partie porte une matière électrochromique. Dispositif selon la revendication 4, dans lequel ladite matière électrochromique couvre essentiellement ladite surface principale de ladite électrode de travail. Dispositif selon l'une quelconque des revendications précédentes, dans lequel l'électrode de travail, la contre-électrode et les couches isolantes sont essentiellement parallèles ; et/ou dans lequel l'électrode de travail, la contre-électrode et les couches isolantes s'étendent essentiellement dans le même sens les unes par rapport aux autres. Dispositif selon l'une quelconque des revendications 1 à 5, dans lequel au moins une partie de l'électrode de travail est décalée latéralement par rapport à la contre-électrode. Dispositif selon l'une quelconque des revendications précédentes, dans lequel le substrat de support est formé à partir d'une matière transparente ou non transparente. Dispositif selon la revendication 8, dans lequel le substrat est formé en verre ou métal ou en une matière céramique ou plastique. Dispositif selon la revendication 8 ou 9, dans lequel le substrat de support porte un revêtement électriquement conducteur sur au moins une partie de sa surface interne. Dispositif selon la revendication 10, dans lequel le revêtement électriquement conducteur comprend un oxyde métallique dopé, de préférence de l'oxyde d'étain dopé au fluor ou à l'antimoine, ou de l'oxyde d'indium dopé à l'étain, ou un polymère ou métal conducteur. Dispositif selon l'une quelconque des revendications 1 à 9, dans lequel la résistance de couche intrinsèque de la matière de l'électrode de travail et/ou de la contre-électrode est inférieure à 10000 ohms par carré. Dispositif selon l'une quelconque des revendications précédentes, dans lequel l'électrode de travail et/ou la contre-électrode comprennent une matière électriquement conductrice comprenant des nanoparticules d'un oxyde métallique sélectionné parmi les oxydes métalliques suivants : (a) SnO2 dopé au F, Cl, Sb, P, As ou B ; (b) ZnO dopé à l'Al, In, Ga, B, F, Si, Ge, Ti, Zr ou Hf ; (c) In2O3 dopé au Sn ; (d) CdO; (e) ZnSnO3, Zn2h2O5, In4Sn3O12, GaInO3 ou MgIn2O4 ; (f) Fe2O3 dopé au Sb ; (g) Systèmes TiO2/WO3 ou TiO2/MoO3 ; et (h) Systèmes Fe2O3/Sb ou SnO2/Sb ; de préférence du SnO2 dopé au Sb. Dispositif selon l'une quelconque des revendications 1 à 13, dans lequel l'électrode de travail et/ou la contre-électrode comprennent une matière électriquement semi-conductrice comprenant des nanoparticules d'un oxyde métallique sélectionné parmi les oxydes métalliques suivants : TiO2, ZrO2, HfO2, CrO3, MoO3, WO3, VO, NbO, SnO2, TaO, AgO, ZnO, SrO, FeO, Fe2O3 ou NiO, ou un pérovskite de ceux-ci, de préférence le TiO2, WO3, MoO3, ZnO ou SnO2. Dispositif selon la revendication 3 ou n'importe quelle revendication dépendant de celle-ci, dans lequel la matière électrochromique de l'électrode de travail est un oxyde métallique sélectionné parmi le WO3 et le TiO2 ou un oxyde métallique dopé sélectionné parmi l'oxyde d'étain dopé à l'antimoine ou au fluor et l'oxyde d'indium dopé à l'étain. Dispositif selon la revendication 4 ou n'importe quelle revendication dépendant de celle-ci, dans lequel la matière électrochromique est sélectionnée parmi les viologènes et polymères et mélanges de ceux-ci. Dispositif selon l'une quelconque des revendications précédentes, comprenant en outre un milieu de conduction ionique. Dispositif selon l'une quelconque des revendications précédentes, dans lequel la couche électriquement isolante comprend un milieu de conduction ionique. Dispositif selon l'une quelconque des revendications 1 à 17, dans lequel la matière électriquement isolante est poreuse et chacune des couches poreuses est au moins partiellement scellée, et le milieu de conduction ionique comprend un électrolyte liquide qui remplit au moins partiellement les pores des électrodes et la matière isolante. Dispositif selon l'une quelconque des revendications précédentes, comprenant en outre un couvercle transparent qui expose au moins partiellement ladite matière électrochromique et une matière d'étanchéité qui scelle le couvercle sur ledit dispositif électrochromique. Dispositif selon la revendication 20, dans lequel ladite matière d'étanchéité scelle ledit couvercle sur ledit substrat de support. Dispositif selon l'une quelconque des revendications 19 à 21, dans lequel la matière électriquement isolante comprend un oxyde métallique sélectionné parmi les SiO2, Al2O3, ZrO et MgO, ou TiO2 sous la forme rutile passivée au SiO2. Dispositif selon l'une quelconque des revendications précédentes, comprenant en outre une couche de support de courant électrique interposée entre l'électrode de travail et les couches électriquement isolantes. Dispositif selon la revendication 23, dans lequel la couche de support de courant électrique comprend de l'oxyde d'indium dopé à l'étain ou de l'oxyde d'étain dopé au fluor, ou un polymère conducteur sélectionné parmi les polythiophènes, les polypyrroles et les polyviologènes. Afficheur comprenant un ou plusieurs dispositifs selon l'une quelconque des revendications précédentes. Afficheur selon la revendication 25, comprenant une pluralité de dispositifs connectés en série. Utilisation d'un dispositif selon l'une quelconque des revendications 1 à 24 dans une matrice active ou une matrice passive ou en configurations de commande directe.






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