Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/08—Oxides
  • C23C14/085—Oxides of iron group metals
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C19/00—Alloys based on nickel or cobalt
  • C22C19/03—Alloys based on nickel or cobalt based on nickel
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/34—Sputtering
  • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
  • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
• • 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
  • G02F1/1514—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 characterised by the electrochromic material, e.g. by the electrodeposited material
  • G02F1/1523—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
  • G02F1/1524—Transition metal compounds

Definitions

• the invention relates to electrochemical devices, and in particular electrocontrollable systems with variable optical and / or energy properties of the glazing or electrochromic mirror type.
• Electrochromic systems in a known manner, comprise a layer of an electrochromic material capable of reversibly and simultaneously inserting ions and electrons and whose oxidation states corresponding to the inserted and uninserted states are of distinct coloration, one of the states exhibiting one light transmission higher than the other, the insertion or removal reaction being controlled by an adequate power supply.
• the electrochromic material usually based on tungsten oxide, must thus be brought into contact with an electron source such as a transparent electroconductive layer and with a source of ions (cations or anions) such as 'an ion conductive electrolyte.
• a counter-electrode must also be associated with the layer of electrochromic material capable of reversibly inserting ions, symmetrically with respect to the layer of material. electrochromic, so that, macroscopically, the electrolyte appears as a simple medium for ions.
• the counter-electrode must consist of either a neutral layer in coloring, or at least transparent or little colored when the electrochromic layer is in the colored state. Since tungsten oxide is a cathodic electrochromic material, that is to say that its colored state corresponds to the most reduced state, an anodic electrochromic material based on nickel oxide or iridium oxide is generally used for the counter electrode. He has It has also been proposed to use an optically neutral material in the oxidation states concerned, such as for example cerium oxide or organic materials such as electronic conductive polymers
• the electrolyte is in the form of a polymer or a gel, for example a proton-conducting polymer such as those described in European patents EP-0 253 713 and EP-0 670,346, or a lithium ion conduction polymer such as those described in patents EP-0 382 623, EP-0 518 754 or EP-0 532 408, ⁇ - * - either the electrolyte is a mineral layer , an ionic conductor but electronically insulating, we then speak of “all-solid” electrochromic systems.
• European patent applications EP-0 867 752 and EP-0 831 360 for the description of an “all-solid” electrochromic system, reference may be made to European patent applications EP-0 867 752 and EP-0 831 360.
• the present invention particularly relates to obtaining layers of anodic electrochromic material based on nickel oxide capable of being part of such electrochromic systems.
• nickel oxide is known to have such a property, and described as such in particular in patent EP-0 373 020 B1.
• this material has a drawback: obtaining it in the form of a thin layer by a standard vacuum deposition process, reactive sputtering assisted by magnetic field, poses certain difficulties: since nickel is ferromagnetic, using a standard nickel target and a standard magnet, the magnetic field developed on the surface of the target is weak, resulting in a low deposition speed and poor exploitation of the target. This type of material was also studied in the patent application
• W098 / 14824 in an application to electrochromic mirrors there are studied nickel oxides alloyed with another metal such as vanadium, chromium, manganese, iron or cobalt, this modification of composition being said to improve the functionality of the mirror , give it a more uniform color especially.
• the invention therefore aims to remedy these drawbacks, in particular by proposing a new method of obtaining nickel oxide with anodic electrochromic property, a method of obtaining which is in particular faster, more profitable, easier to implement. without compromising the functionality sought in nickel oxide.
• This “functionality” aims in particular at its stability, its durability in operation in an electrochromic system, very particularly of the H + or Li + conduction type and of the “all-solid” type, its transparency in the discolored state, when it occurs. in a thin layer.
• the invention firstly relates to an essentially metallic target of sputtering device, preferably assisted by magnetic field, in particular in a reactive atmosphere in the presence of oxygen to obtain the corresponding metallic oxide in a thin layer, said target mainly comprising nickel and being alloyed with at least one other minority element in order to reduce or even eliminate its ferromagnetic character, while best preserving the optical and / or electrochemical properties of the layer of alloyed nickel oxide obtained from this target.
• the invention thus makes an advantageous compromise by making it possible to obtain, by reactive spraying, layers based on nickel oxide with much higher speeds and better profitability of the target, without degrading their functionality, by adding to the targets carefully chosen elements.
• the maximum effect in terms of productivity gain is achieved by completely eliminating the ferromagnetic nature of nickel, but we can choose to simply decrease it, by modulating adequately the chemical nature of the added element and the quantity of this element incorporated into the target.
• the proportion in the alloy of this or these mineral elements remains at most 20 atomic% with respect to the nickel assembly + mineral element (s), preferably in particular at most 18 % and for example between 3 and 15%.
• nickel oxide includes nickel oxide which can be, to varying degrees, hydrate and / or hydroxyl and / or protonated (and optionally nitrided). Likewise, the stoichiometry between nickel and oxygen can generally vary in a Ni / O ratio varying between 1 and Vi. It can be considered that nickel is however generally predominantly at the degree of oxidation + 2.
• a first variant consists in that this minority element (hereinafter referred to as the “additive” for the sake of brevity) is a metal whose oxide is an electrochromic material with anodic coloring. It can in particular be at least one of the following metals: Ir, Ru, Rh. Ideally, this is moreover particularly the case for iridium, the corresponding oxides have an identical operating voltage range or similar to that of nickel oxide: far from disturbing the functionality of nickel oxide, the additive makes it possible to keep it intact and even possibly to increase its capacity for reversible insertion of ions. One can even, then, consider reducing the thickness of the layer while keeping the same level of optical / energetic modification as a thicker layer of nickel oxide.
• a second variant consists in that the additive is a metal whose oxide is an electrochromic material with cathodic coloring. It can in particular be at least one of the following metals: Mo, W, Re, Sn, In, Bi. It may seem paradoxical and likely to cause disturbances to introduce such a material into nickel oxide. In fact, it has been found that the oxides of the aforementioned metals have cathodic ion insertion capacities in operating voltage ranges well outside the potentials reached by nickel oxide used as an anodic electrochromic material.
• these additives which are effectively found in oxidized form in nickel oxide are inert and remain colorless when the nickel oxide undergoes variations in coloring by tensioning; these additives are neutralized when the active system is in operation and do not reduce its level of light transmission in the discolored state.
• their presence tends to decrease the ionic insertion capacity of the layer as a whole, and it is then possible, if necessary, to increase its thickness a little to compensate for this phenomenon, a measure also possible for all of the following variants.
• a third variant consists in that the additive is made of a metal, an alkaline earth metal or a semiconductor in which the hydrated and / or hydroxylated oxide is a proton conductor. It can in particular be at least one of the following elements: Ta, Zn, Zr, Al, Si, Sb, U, Be, Mg, Ca, Y. These materials in oxidized form have no significant electrochromic properties .
• a fourth variant consists in that the additive is an element whose oxide is hydroscopic, a characteristic which is again advantageous when an electrochromic system operating in ionic insertion / de-insertion, and very particularly cationic of the proton type, is concerned.
• They are typically alkalis, in particular Li, Na, K, Rb, Cs.
• these materials have been found to improve the stability of nickel oxide when it acts as an anodic electrochromic material in an electrochromic system, especially when nickel oxide is hydrated / hydroxylated, probably by promoting the retention of the water contained in the layer.
• the preferred embodiments of the target of the invention are the Ni / Si, Ni / Ai, Ni / Sn, Ni / W, Ni / Zn, Ni / Ta and Ni / Y alloys, the first three alloys being the least expensive to manufacture.
• the fabrication of the alloy targets is carried out in a known manner in this field of vacuum deposition, for example by hot sintering of the metal powders to be alloyed.
• the subject of the invention is also the method of manufacturing a thin layer based on alloyed nickel oxide, optionally hydrated and / or hydroxylated and / or protonated and / or nitrided, and which uses the sputtering technique assisted by magnetic field in reactive oxidizing atmosphere from the target described above.
• the invention also relates to the use of this method for manufacturing an anodic electrochromic material in a thin layer based on said oxide.
• the subject of the invention is also the electrochemical device comprising at least one carrier substrate provided with a stack of functional layers including at least one electrochemically active layer capable of reversibly and simultaneously inserting ions of the H + , Li + type ,
• This oxide can be obtained from targets whose composition has been defined in the four variants described above. It can also be noted that, as a general rule, the atomic proportion of the additive (s) relative to nickel in the alloy of the target is generally close to the atomic proportion of the additive relative to nickel in the oxide layer. obtained from the target considered.
• the layers according to the invention therefore do not in principle have a sheet structure with an Li-type intercalation compound between the sheets, but a generally amorphous structure with a homogeneous distribution in grains.
• the layer may be based on nickel oxide, optionally hydrated / hydroxylated and / or nitrided, alloyed with at least one additive, the oxide of which is an anodic electrochromic material such as Ir, Ro, Rh, or alloyed with at least one metal, the l oxide is a cathodic electrochromic material, such as Mo, W, Re, Sn, In, Bi, or alloyed with at least one alkaline earth metal or semiconductor whose hydrated and / or hydroxylated oxide is a proton conductor such as Ta , Zn, Zr, Al, Si, Sb, U, Mg, La, Y.
• an additive whose oxide is hygroscopic like an alkali such as Li, Na, K, Rb, Cs.
• the term “ally” has the following meaning: the additive in question is associated with nickel oxide in the form of oxide. This oxide can find in the form of a matrix made of microdomains of nickel oxide within which there are microdomains based on the oxide of the additive in question. It may also be in the presence of a true mixed oxide, in which nickel atoms are substituted by atoms of the additive in question.
• Preferred embodiments are N ⁇ S ⁇ x O y , N ⁇ Al x O y , N ⁇ Sn x O y , N ⁇ W x O y ,
• the layers obtained can be hydrated and / or hydroxylated and / or protonated and / or mtrurated, and that the control of the degree of hydration, protonation and / or hydroxylation and / or nitriding of the layer is done in particular by appropriately adjusting the sputtering deposition parameters, for example by adapting the composition of the reactive atmosphere during deposition (as was envisaged in particular for the electrolyte layers in patent EP-0 831 360 ).
• the reactive atmosphere may in particular contain a certain quantity of molecules of which at least one of the atoms is nitrogen.
• the invention also relates to the use of these electrochemical devices so that they form part of electrochromic glazing.
• These glazings can equip buildings as exterior glazing or internal partitions or in glazed doors. They can also be fitted to any means of transport such as trains, boats, planes, cars, trucks, as side windows, car roofs, etc. They can also be used in viewing screen glazing such as computer or television screens, touch screen, in glasses, camera lenses, solar panel protections. They can also be used as a mirror, for example to make anti-glare vehicle mirrors (by sufficiently thickening one of the electrically conductive layers and / or by adding an opaque coating). They can also be used to make energy storage devices of the battery type. Other details and advantageous characteristics of the invention emerge below from various nonlimiting embodiments.
• the glazing has the following sequence:
• the glass (1) is a standard clear silica-soda-lime glass
• the fluorine-doped tin oxide layer (2) is the first transparent electroconductive layer obtained in a known manner by CVD,
• NiO x H y layer (3) is the counter-electrode, the anodic electrochromic material of the system, obtained by sputtering in the presence of a reactive atmosphere Ar / 0 2 / H 2 from a nickel target about 99.95 atomic% nickel;
• the layer (4) in W0 3 , (5) in Ta 2 0 5 forming the electrolyte, are deposited in a known manner by sputtering from target of W and Ta,
• the layer (7) of indium oxide doped with tin is the second transparent electroconductive layer, also deposited in a known manner by sputtering from a target of indium tin alloy.
• This glazing works by transferring protons from one electrochromic layer to another, by modifying the potential difference generated across the glazing appropriately.
• NiO x H y layer (3) is obtained in a difficult manner. Its deposition rate is only 4 nm. m / minute. The target is not used regularly (its use rate is less than 5%).
• NiSi z O x H y 250 nm thick obtained by sputtering in a reactive atmosphere Ar / 0 2 / H 2 from a target made of Ni / Si alloy in an atomic proportion of approximately 10% of Si by compared to Ni + Si.
• NiW z O x H y 250 nm thick obtained as above but from of an Ni / W alloy target in an atomic proportion of W relative to Ni + W of approximately 7%.
• Table 1 indicates the deposition rates v of the nickel oxide-based layers obtained in accordance with the three preceding examples, rates expressed in nm. m / minutes (for a deposit at 3.5 W / cm 2 ):
• Table 1 The glasses coated with the layers described above are provided with current leads connected in a known manner to a voltage generator. They are then laminated to a second glass identical to the first by means of a 1.25 mm thick polyurethane sheet.
• the three laminated glazings then underwent a coloring / discoloration cycle (coloring by imposing on the terminals a voltage of approximately ⁇ 1.2 V, and discoloration by imposing on the terminals a voltage of approximately 0.8 V).
• the values of light transmission T L in% were then measured, of a * and b * in the colorimetry system (L, a * , b * ) in light transmission, and of energy transmission T E in% (reference for the T measurements: illuminant D 65 ), and this when the glazing is colored (“coloring”) then discolored (“discoloration”).
• Table 2 below consolidates all these data for the three glazings:
• the modifications made to the electrochromic material based on nickel oxide do not affect the performance thereof: the ranges of light transmission and energy transmission achieved with examples 2 and 3 according to the invention are almost identical. to those of Comparative Example 1, and the colorimetric aspect in transmission is not significantly modified either.
• the deposition rates of the layers based on nickel oxide according to the invention are at least five times higher than the deposition rate of a layer based on standard nickel oxide.

Landscapes

• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Nonlinear Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Crystallography & Structural Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
• Physical Vapour Deposition (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Related Child Applications (2)

Publications (1)

Family

ID=9545804

Family Applications (1)

Country Status (5)

Cited By (10)

Families Citing this family (5)

Citations (4)

Family Cites Families (7)

• 1999
  • 1999-05-20 FR FR9906408A patent/FR2793888B1/fr not_active Expired - Fee Related
• 2000
  • 2000-05-19 EP EP00931328A patent/EP1109945A1/fr not_active Withdrawn
  • 2000-05-19 KR KR1020017000771A patent/KR100686611B1/ko not_active IP Right Cessation
  • 2000-05-19 WO PCT/FR2000/001388 patent/WO2000071777A1/fr active IP Right Grant
  • 2000-05-19 JP JP2000620150A patent/JP5005854B2/ja not_active Expired - Fee Related

Patent Citations (4)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events