Processes for preparing metal oxide layers or ion-conductive layers utilizing plasma, and associated materials and devices

Abstract

Processes for preparing metal oxide layers utilizing plasma are disclosed. An example process includes applying a first solution to a first substrate. The first solution includes one or more first metal precursors. The one or more first metal precursors are exposed to first plasma to form on the first substrate one or more first metal oxide layers including the one or more first metal oxides. A second solution is applied to a second substrate. The second solution includes one or more second metal precursors. The one or more second metal precursors are exposed to second plasma to form on the second substrate one or more second metal oxide layers including the one or more second metal oxides. An ion-conducting interlayer is positioned between the one or more first metal oxide layers and the one or more second metal oxide layers to form an assembly, and the assembly is laminated.

Description

PROCESSES FOR PREPARING METAL OXIDE LAYERS OR ION-CONDUCTIVE LAYERS UTILIZING PLASMA, AND ASSOCIATED MATERIALS AND DEVICESTECHNICAL FIELD

[0001] The present disclosure relates in general to metal oxide layers and ion-conductive layers of electrochromic devices or electrochemical devices, and in particular to processes for preparing metal oxide layers or ion-conductive layers for electrochromic devices or electrochemical devices utilizing plasma.BACKGROUND

[0002] “Smart windows” or “smart glass” may refer to devices where the colour and the amount of light transmission or reflection of the device may be altered by electronic switching. When the bias is electrical in nature (for example, a voltage is applied), the devices may be referred to as electrochromic (EC) devices. These devices may be used for variable transmission windows for use in buildings and transportation (automobiles, aeroplanes, passenger trains, boats such as ferries, etc.), displays and automotive mirrors for controlling reflectivity. By adjusting the transmission of the windows, the solar energy that is transmitted through the window may also change.

[0003] Windows are widely regarded to be one of the least efficient components of a building envelope. Heating, ventilating, and air conditioning (HVAC) and lighting in buildings account for greater than 30 percent of global primary energy consumption, and up to half of this energy can be lost through windows. This energy loss results in high greenhouse gas (GHG) emissions and costs for building owners. The use of electrochromic windows in residential and commercial buildings may result in buildings with improved energy efficiency. Electrochromic windows can lower building heating, cooling and lighting needs by about 20%. In addition, electrochromic windows may provide shade, glare reduction, and provide other benefits, such as improved worker productivity.

[0004] Electrochromic glass (also known as electrochromic glazing) in the automotive industry may be used in small surface rear-view and side-mirrors. The automotive industry is interested in expanding the products into sunroofs and side windows to improve the passenger experience (particularly as ridesharing puts more passengers in the back seat). Air conditioning and heating systems cool, heat, and ventilate the interior of vehicles. These air conditioning and heating systems may be electrically powered, and their use can particularly reduce electric vehicle (EV) range by 30-40%, depending upon the airconditioning and heating systems, the climate, and the driving cycle. Electrochromic windows can help manage the interior climate of vehicles, thus reducing air conditioning and heating usage, and extending the range of EVs. Therefore, when used in transportation, electrochromic windows may result in vehicles with improved energy efficiency.

[0005] The overall configuration of an electrochromic device may comprise an anode and a cathode supported on transparent conductive substrates and an ion-conducting (electrolyte) layer positioned between the anode and cathode. The anode, cathode, or both may include (an) electrochromic material(s).

[0006] Sputtering, an in vacuo physical vapour deposition method (including in de magnetron, electron beam and radio frequency) is a widely used method of thin film and coating deposition in the electrochromic industry today, and has been for the past 30 years. While very versatile, sputtering requires a vacuum chamber and high energy to operate, and is also known to produce pinholes.

[0007] For larger rigid substrates, the sputtering method requires vacuum systems that scale to the size of the desired product. As the vacuum chamber size increases, the capital cost rises, the time to bring the system to operating condition increases with the volumetric size of the chamber, the cost of the sputtering target, required components and power source increases, and the power required to obtain sufficiently high deposition rates scales with the size of the sputtering target.

[0008] Alternative metal oxide film synthesis techniques that have been tried include evaporation, chemical vapour deposition, electrodeposition, sol-gel techniques, laser ablation, and thermal deposition, but drawbacks such as cost, scalability, and obtaining the desired mixed metal oxide compositions have prevented these techniques from replacing sputtering as the industry standard.

[0009] Plasma treatments may be used to alter the surface properties of materials. The surface treatment can etch and clean surfaces, or function to activate a surface and improve surface adhesion properties of a material prior to bonding with coatings or adhesives, for example. Thin films may be formed with plasma treatment, but the process often requires a carrier gas, vapour deposition, and / or a pressure or vacuum chamber.

[0010] No admission is necessarily intended, nor should be construed, that any of the preceding information constitutes prior art.SUMMARY

[0011] In some aspects, the techniques described herein relate to a process for manufacturing an electrochromic laminated glass unit, the process including: receiving a first indication of a first amount of a first solution to be applied to a first transparent conductive glass substrate, the first solution including one or more first metal precursors, the one or more first metal precursors to be converted into one or more first metal oxides upon exposure to plasma; applying the first amount of the first solution to the first transparent conductive glass substrate; exposing the one or more first metal precursors to first plasma to form one or more first metal oxide layers on the first transparent conductive glass substrate, the one or more first metal oxide layers including the one or more first metal oxides; receiving a second indication of a second amount of a second solution to be applied to a second transparent conductive glass substrate, the second solution including one or more second metal precursors, the one or more second metal precursors to be converted into one or more second metal oxides upon exposure to plasma; applying the second amount of the second solution on the second transparent conductive glass substrate; exposing the one or more second metal precursors to second plasma to form one or more second metal oxide layers on the second transparent conductive glass substrate, the one or more second metal oxide layers including the one or more second metal oxides; positioning an ion-conducting interlayer between the one or more first metal oxide layers on the first transparent conductive glass substrate and the one or more second metal oxide layers on the second transparent conductive glass substrate to form a pre-laminated unit; and laminating the prelaminated unit to form an electrochromic laminated glass unit, wherein the one or more first metal oxide layers are not subjected to annealing after the one or more first metal oxide layers are formed and prior to laminating the pre-laminated unit to form the electrochromic laminated glass unit, and the one or more second metal oxide layers are not subjected to annealing after the one or more second metal oxide layers are formed and prior to laminating the pre-laminated unit to form the electrochromic laminated glass unit.

[0012] In some aspects, the techniques described herein relate to a process wherein receiving the first indication of the first amount of the first solution to be placed on the first transparent conductive glass substrate includes receiving a number of layers of the first solution to be applied to the first transparent conductive glass substrate, and applying the first amount of the first solution to the first transparent conductive glass substrate includes applying the number of layers of the first solution to the first transparent conductive glass substrate.

[0013] In some aspects, the techniques described herein relate to a process wherein receiving the first indication of the first amount of the first solution to be placed on the first transparent conductive glass substrate includes receiving a specified thickness of the one or more first metal oxide layers to be formed on the first transparent conductive glass substrate when a conversion of the one or more first metal precursors to the one or more first metal oxides is complete, and applying the first amount of the first solution to the first transparent conductive glass substrate includes applying the first amount of the first solution that is sufficient to form the one or more first metal oxide layers of the specified thickness.

[0014] In some aspects, the techniques described herein relate to a process wherein applying the first amount of the first solution to the first transparent conductive glass substrate includes applying multiple layers of the first solution to the first transparent conductive glass substrate, and exposing the one or more first metal precursors to the first plasma includes exposing each layer of the multiple layers to the first plasma.

[0015] In some aspects, the techniques described herein relate to a process wherein applying the first amount of the first solution to the first transparent conductive glass substrate includes applying multiple layers of the first solution to the first transparent conductive glass substrate, and exposing the one or more first metal precursors to the first plasma includes exposing fewer layers than a total number of the multiple layers to the first plasma.

[0016] In some aspects, the techniques described herein relate to a process, further including exposing at least some of the one or more first metal precursors to ultraviolet or near-infrared electromagnetic radiation to convert at least some of the one or more first metal precursors into at least some of the one or more first metal oxides.

[0017] In some aspects, the techniques described herein relate to a process, further including: monitoring a conversion of the one or more first metal precursors into the one or more first metal oxides; determining that the conversion of the one or more first metal precursors into the one or more first metal oxides is incomplete; and repeating exposing the one or more first metal precursors to the first plasma and monitoring the conversion of the one or more first metal precursors into the one or more first metal oxides until a determination is made that the conversion of the one or more first metal precursors into the one or more first metal oxides is complete, thereby forming the one or more first metal oxide layers on the first transparent conductive glass substrate.

[0018] In some aspects, the techniques described herein relate to a process wherein monitoring the conversion of the one or more first metal precursors into the one or more first metal oxides includes utilizing spectroscopy to monitor the conversion of the one or more first metal precursors into the one or more first metal oxides.

[0019] In some aspects, the techniques described herein relate to a process wherein the one or more first metal precursors include one or more ligands, utilizing spectroscopy includes utilizing spectroscopy to detect signals corresponding to the one or more ligands, and determining that the conversion of the one or more first metal precursors into the one or more first metal oxides is incomplete includes determining that the signals indicate that the one or more ligands have not reached a threshold level.

[0020] In some aspects, the techniques described herein relate to a process wherein exposing the one or more first metal precursors to the first plasma includes rastering the one or more first metal precursors using plasma emitted from a plasma nozzle positioned above the first transparent conductive glass substrate.

[0021] In some aspects, the techniques described herein relate to a process wherein rastering the one or more first metal precursors using the plasma emitted from the plasma nozzle includes moving the plasma nozzle at a rate of from about 100 millimeters (mm) per second to about 520 mm per second.

[0022] In some aspects, the techniques described herein relate to a process wherein the plasma nozzle is positioned from about 10 mm to about 260 mm above the first transparent conductive glass substrate.

[0023] In some aspects, the techniques described herein relate to a process wherein exposing the one or more first metal precursors to the first plasma includes exposing the one or more first metal precursors to at least one of blown ion plasma and flame plasma.

[0024] In some aspects, the techniques described herein relate to a process wherein applying the first amount of the first solution to the first transparent conductive glass substrate includes utilizing one or more of spin coating, spray coating, ultrasonic spray coating, slot die coating, curtain coating, painting, and dip coating to apply the first amount of the first solution to the first transparent conductive glass substrate.

[0025] In some aspects, the techniques described herein relate to a process, further including: dissolving the one or more first metal precursors in one or more first solvents toform the first solution; and dissolving the one or more second metal precursors in one or more second solvents to form the second solution.

[0026] In some aspects, the techniques described herein relate to an electrochromic laminated glass unit manufactured according to the techniques described herein.

[0027] In some aspects, the techniques described herein relate to a process including: applying a first solution to a first conductive substrate, the first solution including one or more first metal precursors that may be converted into one or more first metal oxides upon exposure to plasma; exposing the one or more first metal precursors to first plasma to form one or more first metal oxide layers on the first conductive substrate, the one or more first metal oxide layers including the one or more first metal oxides; exposing the one or more first metal oxide layers to a first temperature of from about 30 °C to about 300 °C for about 15 minutes to about 60 minutes to anneal the one or more first metal oxide layers; applying a second solution to a second conductive substrate, the second solution including one or more second metal precursors that may be converted into one or more second metal oxides upon exposure to plasma; exposing the one or more second metal precursors to second plasma to form one or more second metal oxide layers on the second conductive substrate, the one or more second metal oxide layers including the one or more second metal oxides; exposing the one or more second metal oxide layers to a second temperature of from about 30 °C to about 300 °C for about 15 minutes to about 60 minutes to anneal the one or more second metal oxide layers; positioning an ion-conducting interlayer between the one or more first metal oxide layers on the first conductive substrate and the one or more second metal oxide layers on the second conductive substrate to form an assembly; and laminating the assembly.

[0028] In some aspects, the techniques described herein relate to a process, further including: receiving a first number of layers of the first solution to be applied to the first conductive substrate; and receiving a second number of layers of the second solution to be applied to the second conductive substrate, wherein applying the first solution to the first conductive substrate includes applying the first number of layers of the first solution to the first conductive substrate and applying the second solution to the second conductive substrate includes applying the second number of layers of the second solution to the second conductive substrate.

[0029] In some aspects, the techniques described herein relate to a process, further including: receiving a first specified thickness of the one or more first metal oxide layers to be formed on the first conductive substrate when a first conversion of the one or more firstmetal precursors to the one or more first metal oxides is complete; and receiving a second specified thickness of the one or more second metal oxide layers to be formed on the second conductive substrate when a second conversion of the one or more second metal precursors to the one or more second metal oxides is complete, wherein applying the first solution to the first conductive substrate includes applying a first amount of the first solution that is sufficient to form the one or more first metal oxide layers of the first specified thickness, and applying the second solution to the second conductive substrate includes applying a second amount of the second solution that is sufficient to form the one or more second metal oxide layers of the second specified thickness.

[0030] In some aspects, the techniques described herein relate to a process wherein the one or more first metal oxide layers are one or more cathodic electrochromic layers, the one or more first metal oxides include one or more of WOx, WNbOx, TiWOx, and LiWOx, the one or more second metal oxide layers are one or more anodic electrochromic layers, and the one or more second metal oxides include one or more of NiOx, LiNiOx, NiNbOx, NiNbLiOx, NiAILiOx, NiCeOx, NiCeLiOx, and VOx.

[0031] In some aspects, the techniques described herein relate to a process wherein at least one of the one or more first metal oxide layers and the one or more second metal oxide layers is one or more doped metal oxide layers that are doped using a dopant atom that is one or more of niobium, aluminum, lithium, tantalum, molybdenum, cerium, cobalt and titanium.

[0032] In some aspects, the techniques described herein relate to a process wherein at least one of the one or more first metal precursors and the one or more second metal precursors include one or more of tungsten (VI) chloride, tungsten (VI) isopropoxide, vanadium (III) chloride, nickel (II) nitrate hexahydrate, tantalum (V) ethoxide, niobium (IV) 2- ethylhexanoate, niobium (V) ethoxide, nickel (II) 2-ethylhexanoate, lithium methoxide, lithium ethoxide, lithium 2-ethylhexanoate, lithium trimethylsilanolate, and molybdenum (IV) 2- ethylhexanoate.

[0033] In some aspects, the techniques described herein relate to a process wherein both the first conductive substrate and the second conductive substrate are non-rigid.

[0034] In some aspects, the techniques described herein relate to an electrochromic device manufactured according to the techniques described herein.

[0035] In some aspects, the techniques described herein relate to a process including: applying a first solution to a first substrate, the first solution including one or more first metalprecursors that may be converted into one or more first metal oxides upon exposure to plasma; exposing the one or more first metal precursors to first plasma to form one or more first metal oxide layers on the first substrate, the one or more first metal oxide layers including the one or more first metal oxides; applying a second solution to a second substrate, the second solution including one or more second metal precursors that may be converted into one or more second metal oxides upon exposure to plasma; exposing the one or more second metal precursors to second plasma to form one or more second metal oxide layers on the second substrate, the one or more second metal oxide layers including the one or more second metal oxides; positioning an ion-conducting interlayer between the one or more first metal oxide layers and the one or more second metal oxide layers to form an assembly; and laminating the assembly.

[0036] In some aspects, the techniques described herein relate to a process, further including: annealing the one or more first metal oxide layers; and annealing the one or more second metal oxide layers.

[0037] In some aspects, the techniques described herein relate to a process wherein the one or more first metal oxide layers are not subjected to annealing after the one or more first metal oxide layers are formed and prior to laminating the assembly, and the one or more second metal oxide layers are not subjected to annealing after the one or more second metal oxide layers are formed and prior to laminating the assembly.

[0038] In some aspects, the techniques described herein relate to an electrochemical device manufactured according to the techniques described herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The particular arrangements shown in the Figures should not be viewed as limiting. It should be understood that the illustrated elements, including the shape, size and scale, may not necessarily be drawn in actual proportion to each other.

[0040] Further features and advantages of the present disclosure will become apparent from the following detailed description, taken in combination with the appended drawings, in which:

[0041] Fig. 1 is a schematic depiction of an electrochromic device according to some embodiments.

[0042] Fig. 2 is a schematic depiction of another electrochromic device according to various embodiments.

[0043] Fig. 3 is a graph showing the change in CIE Y transmittance for the bleached and colored states over repeated cycles for the electrochromic device obtained in Example 4.

[0044] Fig. 4 is a graph showing the change in CIE Y transmittance for the bleached and colored states over repeated cycles for the electrochromic device obtained in Example 5.

[0045] Fig. 5A is a flow diagram depicting a process for manufacturing an electrochromic laminated glass unit according to some embodiments.

[0046] Fig. 5B is a flow diagram depicting a process for manufacturing an electrochromic device according to various embodiments.

[0047] Fig. 5C is a flow diagram depicting another process for manufacturing an electrochromic device according to some embodiments.

[0048] Fig. 6A is a schematic representation of a curved electrochromic device that may be manufactured according to various embodiments of processes described herein.

[0049] Fig. 6B is a schematic representation of a flat electrochromic device that may be manufactured according to various embodiments of processes described herein.

[0050] Throughout the drawings, like reference numerals will be understood to refer to like parts, components, and structures.DETAILED DESCRIPTION

[0051] In various embodiments, the term “amorphous” may refer to a chemical composition without long-range order, detectable by X-ray powder diffraction, in its atomic structure.

[0052] In various embodiments, the term “crystalline” may refer to a chemical composition with long-range order, detectable by X-ray powder diffraction, in its atomic structure.

[0053] In various embodiments, the term “excited gas” may refer to a plasma.

[0054] In various embodiments, the term “plasma” may refer to a state or matter composed of a gaseous mixture of ions and free electrons, wherein the ionized gaseous substance becomes electrically conductive.

[0055] In various embodiments, the term “electrochromic device” may refer to an electrochemical device comprising a substrate, an anodic electrode, a cathodic electrode, an ion-conductive layer, and charge-balancing ions that are capable of transitioning transparency from a colored state (that is, low transmittance of light through the window) to a transparent state (that is, high transmittance of light through the window), and / or from a transparent state to a colored state, through the use of an applied electrical bias. The “transparent” state may also be referred to as a “bleached” state.

[0056] In various embodiments, the term “electrochromic layer” may refer to a layer that alters the optical color or opacity of a surface when a voltage is applied.

[0057] In various embodiments, the term “electrochromic mirror” may refer to an electrochromic device with a mirror or other reflective layer adhered to the electrochromic device.

[0058] In various embodiments, the term “ion-storage layer” may refer to an electrochemically-active layer of solid-state inorganic material in which ions can move in and out of its structure via a process called insertion (intercalation) or extraction (deintercalation). In various embodiments, the ion-storage layer is positioned in between an electrically- conductive layer and an ion-conductive layer.

[0059] In various embodiments, the term “anodic electrochromic layer” may refer to a layer comprising a solid-state inorganic electrochromic material that transitions to its coloured state when ions are extracted out of it. In various embodiments, the anodic electrochromiclayer is positioned in between an electrically-conductive layer and a solid-state, ion- conductive electrolyte layer within an electrochromic device.

[0060] In various embodiments, the term “cathodic electrochromic layer” may refer to a layer comprising a solid-state inorganic electrochromic material that transitions to its colored state when ions are inserted into it. In various embodiments, the cathodic electrochromic layer is positioned in between an electrically-conductive layer and an ion-conducting layer within an electrochromic device.

[0061] In various embodiments, the term “ligand” may refer to any chemical group coordinated, chemically bonded or ionically bonded to a metal or metalloid. Ligand examples include, but are not limited to, chloride, bromide, nitrate, 2-ethylhexanoate, ethoxide, butoxide, isopropoxide and acetylacetonate.

[0062] In various embodiments, the term “precursor” may describe any chemical containing a metal that is deposited onto a substrate or layer and then converted into a metal oxide or mixed metal oxide. Precursor examples include, but are not limited to, inorganic chloride, inorganic nitrate, inorganic alkanoate, inorganic 2-ethylhexanoate, inorganic ethoxide, inorganic butoxide, inorganic isopropoxide, inorganic propoxide, and inorganic acetylacetonate, wherein the inorganic cation may be any of the metals, semiconductors, and / or metalloids identified above.

[0063] In various embodiments, the term “sputtering” may refer to a physical vapour deposition technique conducted under vacuum whereby a solid target material is exposed to high energy that ejects atoms of the material, and those atoms are subsequently deposited onto a substrate.

[0064] In various embodiments, the term “support” may refer to a mechanically supportive material upon which additional functional layers may be positioned or placed. Suitable support materials include any substrates (for example, transparent conductive glasses, transparent conductive plastics, transparent conductive polymers (for example, polyethylene terephthalate (PET))) or substrate-supported electrodes.

[0065] In various embodiments, the term “substrate” may refer to an underlying material or layer upon which additional functional layers are assembled. A substrate may be considered a type of support.

[0066] In various embodiments, the term “electrode” may refer to a solid-state, layered structure comprising an electrically conductive layer and an electrochemically-active layer in contact with each other.

[0067] In various embodiments, the term “substrate-supported electrode” may refer to an electrode that is connected to the substrate. The electrically conductive layer may be positioned between the substrate and an electrochemically active layer. A substrate- supported electrode may be considered a type of support.

[0068] In various embodiments, the term “electrochemical device” may refer to a device capable of either generating electrical energy from chemical reactions or using electrical energy to cause chemical reactions. An electrochemical device may include two electron conductors (electrodes) separated by an ionic conductor (electrolyte) and linked by an electron conductor.

[0069] In various embodiments, the term “electrochemically active layer” may refer to a solid-state inorganic material positioned in between the electrically conductive layer and the ion-conductive electrolyte layer within an electrochemical cell. This material undergoes either reduction or oxidation during the galvanic or voltaic operation of the cell.

[0070] In various embodiments, the term “electrically conductive layer” may refer to a material with a high electrical conductivity that is in contact with the electrochemically active layer. This material may provide an electrical connection from an external source to the electrochemically active layer.

[0071] In various embodiments, the term “busbar” may refer to a metal or metallic strip, bar, wires, or other suitable structure that distributes electrical connections and reduces electrical resistance between two areas.

[0072] In various embodiments, the term “protective layer” may refer to a material that protects underlying layers from physical damage, dust, environmental conditions, operating conditions and moisture.

[0073] In various embodiments, the term “rastered” may refer to a scan pattern in which an area is scanned from side to side in lines from top to bottom, or some variation thereof.

[0074] Atmospheric plasma may be utilized to change the properties and composition of films. However, formation of large format, optically acceptable (low haze, high uniformity) functional thin films and with excellent adhesion has not been demonstrated.

[0075] The present disclosure describes methods of using plasma for fabricating metal oxide or mixed metal oxide layers for electrochemical devices and methods for manufacturing electrochemical devices with metal oxide or mixed metal oxide layers. In some embodiments, the plasma treatment is a process wherein a gas between two electrodes at, or near, atmospheric pressure, is excited by exposure to a high-frequency electric field between the electrodes. A metal precursor film is applied to a support, and is then exposed to the excited gas to produce the metal oxide or mixed metal oxide layer from the precursor film. The method of manufacture uses solution-processable precursors to enable precise composition control and lower cost manufacturing than existing techniques. Also described are methods of using plasma for fabricating ion-conductive electrolyte layers and methods for manufacturing electrochemical devices with ion-conductive electrolyte layers.

[0076] Electrochromic films may be annealed to enhance their physical, chemical, or optical properties. One advantage of the described methods is that they allow for an annealing step to be omitted in a process for manufacturing an electrochromic device, or for the annealing step to be carried out at a lower temperature or for a shorter period of time than a typical annealing step. The use of plasma to convert metal precursors to metal oxides may partially or completely achieve the same results (for example, improving crystallinity, enhancing adhesion, or improving transparency or light-absorption) as an annealing step. Accordingly, manufacturing of electrochromic devices may be simplified or streamlined by inclusion of embodiments of the described methods, thereby reducing costs or increasing productivity.

[0077] U.S. Patent Publication No. US20200165161 A1 , the publication of U.S. Patent Application No. 16 / 632,636, titled “PHOTODEPOSITION OF METAL OXIDES FOR ELECTROCHROMIC DEVICES,” describes photodeposition techniques for generating metal oxides and mixed-metal oxides for making electrochromic layers and devices using ultraviolet irradiation, near infrared irradiation, ozone, or a combination thereof. The entire disclosure of U.S. Patent Publication No. US20200165161A1 is incorporated herein by reference in jurisdictions allowing such incorporation.

[0078] Plasma, such as blown ion plasma and flame plasma, relies on the high speed discharge of ions. Atmospheric plasma is commonly used on conductive and non-conductive surfaces to etch or clean the surface, and to improve surface adhesion properties prior to bonding with inks, coatings, adhesives, etc. The technique permits integration into an in-line production system.

[0079] In some embodiments, an electrochromic film is prepared by coating a substrate with a solution that includes one or more metal precursors, thereby forming a film on a substrate. Then, the film is subjected to plasma to convert the one or more metal precursors to the desired amorphous or crystalline metal oxide or mixed-metal oxide layer. To produce a multilayer thin film, the coating and plasma steps may be repeated multiple times.

[0080] In various embodiments, a solid-state ion conducting film is prepared by coating a substrate-supported electrode (such as an anode or cathode) with a solution that includes one or more metal precursors, thereby forming a film on the substrate. Then, the film is subjected to atmospheric plasma to convert the one or more metal precursors to a desired amorphous or crystalline metal oxide or mixed-metal oxide layer. To produce a multilayer thin film, the coating and plasma steps may be repeated multiple times.

[0081] In some embodiments, the substrate or substrate-supported electrode coated with the film is placed under a plasma stream and is moved under the plasma nozzle or nozzles (described as a single plasma nozzle herein for brevity) from which the plasma stream is emitted. In other embodiments, the substrate or substrate-supported electrode remains stationary, and the plasma nozzle moves over the substrate or substrate-supported electrode to treat the entire precursor film.

[0082] In various embodiments, the plasma nozzle is moved over the surface of the substrate or the substrate-supported electrode at a rate of between about 15 millimeters per second (mm / s) and about 510 mm / s. In some embodiments, the plasma nozzle is moved over the surface of the substrate or the substrate-supported electrode at a rate of between about 255 mm / s and about 508 mm / s. In some embodiments, both the substrate or the substrate-supported electrode and the plasma nozzle are moved.

[0083] In some embodiments, the plasma nozzle is moved over the surface of the substrate or the substrate-supported electrode between 15 and 350 passes. In some embodiments, the plasma nozzle is moved over the surface of the substrate or substrate- supported electrode between 250 and 350 passes.

[0084] In various embodiments, the gap between the plasma nozzle head(s) and the substrate or the substrate-supported electrode is between about 5 mm and about 100 mm. In some embodiments, the plasma nozzle head(s) and the substrate or substrate-supported electrode is between about 9.5 mm and about 55 mm.

[0085] In some embodiments, the plasma nozzle has a sweep width of about 150 mm. In other embodiments, the plasma nozzle has a sweep width of about 250 mm. In some embodiments, the plasma nozzle has a sweep width of about 500 mm.

[0086] In various embodiments, the plasma nozzle is moved over the surface of the substrate or the substrate-supported electrode in two (2) to six (6) sequential steps. Each sequential step may have its own number of passes, distance between the plasma nozzle and the substrate or the substrate-supported electrode, and rate at which the plasma nozzle passes over the substrate or the substrate-supported electrode.

[0087] In some embodiments, a thermocouple positioned at the surface of the substrate or the substrate-supported electrode may be utilized to measure the temperature during plasma exposure. In some embodiments, during plasma exposure, the thermocouple reads between about 100 °C and about 650 °C. In various embodiments, during plasma exposure, the thermocouple reads between about 140 °C and about 200 °C.

[0088] In some embodiments, the precursor film is formed from multiple layers or applications of metal precursor-containing solution and is subjected to plasma between each layer or application of the metal precursor-containing solution. In some embodiments, the precursor film is formed from multiple layers or applications of metal precursor-containing solution and is subjected to plasma only after all layers or applications of the metal precursor-containing solution have been applied. In some embodiments, the precursor film is composed of multiple layers or applications of metal precursor-containing solution and is subjected to plasma after every second, third, or fourth layer or application of the metal precursor-containing solution has been applied. In various embodiments, the precursor film is composed of multiple layers and is subjected to plasma after every fifth, sixth or seventh layer of the metal precursor-containing solution has been applied. In some embodiments, the plasma step may be alternated with a photodeposition or thermal or chemical reaction step.

[0089] In certain embodiments, the metal oxide layer or layers undergo an annealing step in an oven in atmospheric air at temperatures ranging from about 30 °C to about 600 °C. In some embodiments, the metal oxide layer or layers may undergo an annealing step, for example, at a temperature of from about 30 °C to about 300 °C. In certain embodiments, the metal oxide layer or layers undergoes an annealing step in an oven in atmospheric air at temperatures ranging from about 30 to about 300 °C for about 15 minutes to about 1 hour. In some embodiments, the metal oxide layer or layers undergo an annealing step at about 50 °C for about 15 minutes to about 1 hour. In some embodiments, the metal oxide layer or layers undergo an annealing step at about 100 °C for about 15 minutes to about 1 hour. Insome embodiments, the metal oxide layer or layers undergo an annealing step at about 200 °C for about 15 minutes to about 1 hour. In some embodiments, the metal oxide layer or layers undergo an annealing step at about 300 °C for about 15 minutes to about 1 hour. In some embodiments, the metal oxide layer or layers undergo an annealing step at about 350 °C for about 15 minutes to about 1 hour. In some embodiments, the metal oxide layer or layers undergo an annealing step at about 400 °C for about 15 minutes to about 1 hour. In some embodiments, the metal oxide layer or layers undergo an annealing step at about 450 °C for about 15 minutes to about 1 hour.

[0090] The active electrochromic and solid-state ion conducting layers fabricated by the methods described herein may be formed from an initial solution. A solution is a liquid material that includes one or more inorganic or organometallic precursors. This solution may be prepared by dissolving a metal precursor or precursors into a compatible solvent and then applying the solution to the surface of the support (for example, a substrate or substrate-supported electrode). Upon drying, a layer of the desired precursor or precursors is formed on the support. Examples of compatible solvents include but are not limited to water, methanol, ethanol, isopropanol, acetone, hexane and methyl isobutyl ketone, propylene glycol methyl ether acetate (PGMEA), ethyl acetate, acetonitrile, ethylene glycol, tetrahydrofuran (THF), toluene, and N-methylpyrrolidone. Any solvent can be used any as long as it is a solvent which can dissolve the metal precursor or precursors and which will evaporate before or during atmospheric plasma treatment from the support leaving behind the metal precursor or precursors.

[0091] In some embodiments, a majority of the solvent may evaporate prior to or during application of the solution to the support, leaving behind a significantly reduced amount of solvent in the solution that has been applied to the support. In other embodiments, less than a majority of the solvent may evaporate prior to or during application of the solution to the support.

[0092] Precursors suitable for use in the various processes described herein include any inorganic or organometallic compound that can be converted to the corresponding oxide upon exposure to photodeposition. Suitable precursors include, but are not limited to, an inorganic chloride, an inorganic nitrate, an organometallic 2-ethylhexanoate, an organometallic butoxide, an organometallic ethoxide, an organometallic methoxide, an organometallic isopropoxide, an organometallic acetylacetonate, an organometallic silanolate, an organometallic oxalate, or mixtures thereof. Examples of precursors include, but are not limited to, tungsten (VI) chloride, tungsten (VI) isopropoxide, vanadium (III) chloride, nickel (II) nitrate hexahydrate, tantalum (V) ethoxide, niobium (IV) 2-ethylhexanoate, niobium (V) ethoxide, nickel (II) 2-ethylhexanoate, lithium methoxide, lithium ethoxide, lithium 2-ethylhexanoate, lithium trimethylsilanolate, and molybdenum (IV) 2- ethylhexanoate.

[0093] Initial application of the solution to the substrate or substrate-supported electrode can be performed using a variety of methods including spin coating, spray coating, ultrasonic spray coating, slot die coating, curtain coating, painting, dip coating, or other suitable methods.

[0094] In some embodiments, where precursors comprise organic ligands, formation of the desired metal oxide can be monitored by infrared (IR) or Fourier transform infrared (FTIR) spectroscopy, as loss of ligands from the precursor gives rise to a loss of ligand signal in the infrared spectrum.

[0095] For precursors which cannot be tracked by infrared spectroscopy, including but not limited to metal chloride salts, X-ray fluorescence (XRF) spectroscopy can be used to monitor the transformation to a metal oxide.

[0096] In some embodiments, the electrochromic layers are used in an electrochromic device. In some embodiments, the ion-conductive layer is used in an electrochemical device. In some embodiments, both the electrochromic layers and the ion-conductive layer are used in an electrochromic device.

[0097] Fig. 1 schematically depicts an electrochromic device 100 that may be prepared using the processes described herein. The electrochromic device 100 is depicted as connected to an external power source or control electronics and software 108. The electrochromic device includes a first substrate 101 , a first conductive layer 102, an anodic electrochromic layer 103 (which may also be referred to as an ion-storage layer), an ion- conductive electrolyte layer 104 (which may also be referred to as an ion-conductive or ionconducting interlayer or layer or as an interlayer), a cathodic electrochromic layer 105, a second conductive layer 106, and a second substrate 107. The first substrate 101 and the second substrate 107 may provide a base structure for the other layers as well as function to protect the other layers. The first conductive layer 102 and the second conductive layer 106 may provide a means for conducting charge to and from the anodic electrochromic layer 103 and the cathodic electrochromic layer 105, respectively, from the external power source or control electronics and software 108.

[0098] The ion-conductive electrolyte layer 104 may provide a means to transport ions between the anodic electrochromic layer 103 and the cathodic electrochromic layer 105. Invarious embodiments, the order of the layers may be reversed with respect to the first substrate 101 and the second substrate 107. That is, the layers may be in the following order: first substrate 101 , first conductive layer 102, cathodic electrochromic layer 105, ion- conductive electrolyte layer 104, anodic electrochromic layer 103, second conductive layer 106, and second substrate 107. In some embodiments, additional protective and functional layer(s) may also optionally be applied. The thickness of the layers of the device, including the shape, size, and scale of layers may not necessarily be drawn to scale or in actual proportion to each other, but is represented for clarity.

[0099] When a voltage is applied across the electrodes, an electric field is generated within the insulating electrochromic material, which can cause migration of ions to or from the electrochromic material, producing colour changes in that electrochromic material (for example, from colourless to a coloured state, when it is switched from one electrochromic state to another). By reversing the applied bias, the electrochromic material can be switched back, for example, from a coloured to colourless (or to its bleached state). The electrochromic material may also be coloured initially, and switch to a colourless state with applied voltage, and then switched back to the coloured state by reversing the applied bias. (For example, tungsten oxide-based materials colour with ion insertion, whereas nickel oxide-based materials colour with ion extraction)

[0100] Each of the first substrate 101 and the second substrate 107 may be made of transparent materials. Each of the first substrate 101 and the second substrate 107 may include, but are not limited to glass, plastic, or polymers. Each of the first substrate 101 and the second substrate 107 should have suitable optical, electrical, thermal, and mechanical properties for the desired application. In some embodiments, the first substrate 101 and the second substrate 107 include materials that are selected from the group consisting of glass, polyethylene terephthalate (PET), polycarbonate, polyethylene naphthalate (PEN), polyvinyl butyral (PVB), polymethyl methacrylate (PMMA), acrylic, transparent acrylonitrile butadiene styrene (ABS), methyl methacrylate acrylonitrile butadiene styrene (MABS), polyvinyl chloride (PVC), amorphous copolyester (PETG), general purpose polystyrene, styrene acrylonitrile resin (SAN), styrene methyl methacrylate (SMMA), fluorinated ethylene propylene (FEP), transparent polypropylene, ionomer resin, polyethylene (PE), cyclic olefin copolymers, thermoplastic polyurethane (TPU), and liquid silicone rubber (LSR). In various embodiments, the first substrate 101 and the second substrate 107 include materials that are selected from the group consisting of glass, polyethylene terephthalate (PET), polycarbonate, polyethylene naphthalate (PEN), polyvinyl butyral (PVB), polymethyl methacrylate (PMMA), acrylic, and polyvinyl chloride (PVC).

[0101] If the first substrate 101 and the second substrate 107 include glass, they may further include a sodium barrier layer. The first substrate 101 and the second substrate 107 may be of the same material or different materials. In some embodiments, both the first substrate 101 and the second substrate 107 include glass. In some embodiments, both the first substrate 101 and the second substrate 107 include tempered glass or heat strengthened glass. In various embodiments, both the first substrate101 and the second substrate 107 include polycarbonate. In some embodiments, the first substrate 101 and the second substrate 107 include different materials. For example, the first substrate 101 may include glass and the second substrate 107 may include polycarbonate or polyethylene terephthalate.

[0102] In some embodiments, the first substrate 101 and the second substrate 107 are flat, resulting in a planar electrochromic device. In various embodiments, the first substrate 101 and the second substrate 107 are singly curved, doubly curved (or compound curved), or complexly curved, resulting in a singly curved, doubly curved (or compound curved) or complexly curved electrochromic device.

[0103] In contact with the first substrate 101 and the second substrate 107 are the first conductive layer 102 and the second conductive layer 106, respectively. Each of the first conductive layer 102 and the second conductive layer 106 may be a coating or coatings that include a transparent conductive oxide (TCO). The coating or coatings should provide sufficient conductance for the electrochromic device 100. In embodiments where the electrochromic device 100 may allow light to pass, such as an electrochromic window, the coating or coatings should also not appreciably interfere with the transmission of light. The coating or coatings may include the same material or different materials. In embodiments where the coating or coatings includes a TCO, the transparent conductive coating may include fluorine tin oxide (FTO), indium tin oxide (ITO), aluminum zinc oxide (AZO), silver mesh, silver nanowires, silver nanoparticles, carbon nanotubes, carbon black, graphene, conductive polymers, or a combination of two or more thereof. In various embodiments, the coating or coatings includes FTO or ITO.

[0104] The anodic electrochromic layer 103 and the cathodic electrochromic layer 105 may exhibit a high color contrast between their colored and bleached states and may have rapid conversion between coloured and bleached states. Moreover, the anodic electrochromic layer 103 and the cathodic electrochromic layer 105 may be capable of switching at low applied voltage and may show excellent reversibility with cycling between states.

[0105] There are different types of electrochromic materials including organic chromophores and surface-confined electrochromic layers, such as metal oxides. The majority of the architectural electrochromic windows on the market today employ metal oxides, as the metal oxides are more durable than their organic counterparts, and generally switch more uniformly when used on larger area windows. Generating active metal oxide or mixed-metal oxide layers is an important step in the manufacture of electrochromic devices.

[0106] In some embodiments, the anodic electrochromic layer 103 and the cathodic electrochromic layer 105 each include metal oxides selected from the group consisting of NiOx, WOx, MoOx, TiOx, TaOx, VOx, NbOx, CoOx, IrOx, MnOx, FeOx, LiNiOx, WNbOx, TiWOx, LiWOx, NiNbOx, NiNbLiOx, NiAILiOx, NiCeOx, NiCel_iOx,or one or more combinations thereof. In some embodiments, the cathodic electrochromic layer 105 includes WOx, WNbOx, TiWOx, LiWOx, or one or more combinations thereof. In some embodiments, the anodic electrochromic layer 103 includes NiOx, LiNiOx, NiNbOx, NiNbLiOx, NiAILiOx, NiCeOx, NiCeLiOx, VOx, or one or more combinations thereof. In some embodiments, the cathodic electrochromic layer 105 is predominantly composed of tungsten oxide. In some embodiments, the anodic electrochromic layer 103 is predominantly composed of nickel oxide.

[0107] In some embodiments, the anodic electrochromic layer 103 or the cathodic electrochromic layer 105 is a doped metal oxide layer and the dopant atom is selected from niobium, aluminum, lithium, tantalum, molybdenum, cerium, cobalt and titanium.

[0108] The processes described herein may be utilized to form one or more metal oxide layers to a specified thickness, according to requirements. In some embodiments, the one or more metal oxide layers has an average thickness of about 10 nm to about 2000 nm. In some embodiments, the one or more metal oxide layers has an average thickness of about 100 nm to about 800 nm. In some embodiments, the average thickness of the one or more metal oxide layers is about 200 nm to about 700 nm.

[0109] In various embodiments, an additional layer is added to the anodic electrochromic layer 103 on the first substrate 101. In some embodiments, an additional layer is added to the cathodic electrochromic layer 105 on the second substrate 107. The additional layer may be applied before or after the anodic electrochromic layer 103 or the cathodic electrochromic layer 105. In various embodiments, this additional layer is a barrier layer. In some embodiments, this additional barrier layer includes niobium oxide, lithium oxide, titanium oxide, cerium oxide, indium oxide, tantalum oxide, aluminum oxide, or a mixture thereof. Invarious embodiments, the barrier layer includes niobium oxide, lithium oxide, indium oxide, aluminum oxide, or a mixture thereof.

[0110] The additional layer may be made by plasma, such as atmospheric plasma. In some embodiments, another technique, such as a photodeposition or thermal or chemical reaction, may be used to form the additional layer in addition to or instead of using plasma.

[0111] In the electrochromic device 100 of Fig. 1 , the anodic electrochromic layer 103 and the cathodic electrochromic layer 105 are separated by and in contact with the ion- conductive electrolyte layer 104. One function of the ion-conductive electrolyte layer 104 in the electrochromic device 100 is to allow ions and current to travel between the anodic electrochromic layer 103 and the cathodic electrochromic layer 105. The ion-conductive electrolyte layer 104 may be liquid, semi-solid, or solid. In some embodiments, the ion- conductive electrolyte layer 104 includes a gel, a gel polymer, or a polymer. In some embodiments, the ion-conductive electrolyte layer 104 includes a solid-state, ion-conducting material.

[0112] Fig. 2 schematically depicts another electrochromic device 200 that may be prepared using the processes described herein. The electrochromic device 200 is depicted as connected to an external power source or control electronics and software 208. The electrochromic device 200 includes a substrate 201 , a first conductive layer 202, an anodic electrochromic layer 203 (which may also be referred to as an ion-storage layer), an ion- conductive electrolyte layer 204 (which may also be referred to as an ion-conductive or ionconducting interlayer or layer or as an interlayer), a cathodic electrochromic layer 205, and a second conductive layer 206. The substrate 201 may provide a base structure for the other layers as well as function to protect the other layers on one side. The first conductive layer 202 and the second conductive layer 206 may provide a means for conducting electric charge to and from the anodic electrochromic layer 203 and the second conductive layer 206 from the external power source or control electronics and software 208.

[0113] The ion-conductive electrolyte layer 204 may provide a means to transport ions between the anodic electrochromic layer 203 and the cathodic electrochromic layer 205. In various embodiments, the order of the layers may be reversed with respect to the substrate201 . That is, the layers may be in the following order: substrate 201 , first conductive layer202, cathodic electrochromic layer 205, ion-conductive electrolyte layer 204, anodic electrochromic layer 203, and second conductive layer 206. In some embodiments, additional protective and functional layer(s) may also optionally be applied. The thickness of the layers of the electrochromic device 200, including the shape, size, and scale of layersmay not necessarily be drawn to scale or in actual proportion to each other, but is represented for clarity.

[0114] As depicted in Fig 2, the ion-conductive electrolyte layer 204 may function as a conductive pathway for the migration of cations passing from one electrode to the other electrode and as an electrical insulator between the two electrodes to prevent short-circuiting of the electrochromic device 200. The materials that may be utilized for the electrochromic device 200 in Fig. 2 may be similar to those described for the electrochromic device 100 in Fig. 1 for the anodic electrochromic layer 203 and the cathodic electrochromic layer 205. One difference from the electrochromic device 100 may be in the material of the ion- conductive electrolyte layer 204. In some embodiments, the ion-conductive electrolyte layer 204 may be semi-solid or solid.

[0115] Solid-state ion-conductive electrolyte layers include mobile ions as well as metal and nonmetal ions. A number of cations and anions have been shown to be mobile in solid- state ion-conductors, including H+, Li+, Na+, K+, Cu+, Ag+, Mg2+, Zn2+, AI3+, F-, CI-, and O2-. The lithium-ion conduction properties of inorganic, solid-state layers may be of specific importance to solid-state Li-ion batteries and electrochromic windows.

[0116] Solid-state electrochromic devices commonly use solid-state, ion-conductive electrolyte layers. In accordance with some embodiments, solid-state ion-conductive materials may be prepared utilizing the processes described herein. In some embodiments, the ion-conductive electrolyte layer 204 includes a single metal oxide, a mixed metal oxide, or a doped metal oxide selected from the group consisting of NbOx, TaOx, SiOx, AIOx, LiTaOx, LiNbOx, LaTiOx, SrZrOx, ZrOx, YOx, LiLaTiOx, LiWOx, LiSiOx, LiAISiOx, LiSiGeOx, LiGeOx, LiOx, LiAIOx, LiZnOx, or one or more combinations thereof. In some embodiments, the ion-conductive electrolyte layer 204 includes at least one of NbOx, TaOx, and LiNbOx.

[0117] In some embodiments, the ion-conductive electrolyte layer 204 includes multiple layers and is subjected to plasma between each layer. In various embodiments, the ion- conductive electrolyte layer 204 includes multiple layers and is subjected to plasma after all layers of the solution containing one or more metal precursors have been applied. In some embodiments, the ion-conductive electrolyte layer 204 includes multiple layers and is subjected to plasma after every second, third, or fourth layer of the solution containing one or more metal precursors has been applied. In various embodiments, the ion-conductive electrolyte layer 204 includes multiple layers and is subjected to plasma after every fifth, sixth or seventh layer of the solution containing one or more metal precursors has beenapplied. In some embodiments, the plasma step may be alternated with a photodeposition or thermal or chemical reaction step.

[0118] Embodiments of the processes described herein may be utilized to form a solid- state ion-conductive electrolyte layer to a specified thickness, according to requirements. In some embodiments, the solid-state ion-conducting layer is an average thickness of about 5 nm to about 1000 nm. In various embodiments, the average thickness of the solid-state ionconducting layer is about 20 nm to about 600 nm. In some embodiments, the average thickness of the solid-state ion-conducting layer is about 100 nm to about 400 nm.

[0119] The processes described herein may be utilized in the manufacture of various electrochemical devices, such as electrochromic devices, fuel cells, batteries, electrolyzers, supercapacitors, and sensors. Examples of electrochromic devices include, but are not limited to, electrochromic windows (for example, architectural windows, automotive windows, aircraft cabin windows, windows on marine vessels, etc.), electrochromic sunroofs, electrochromic mirrors (for example, rear-view or side-view vehicle mirrors that automatically darken to reduce glare from headlights of behind vehicles), electrochromic displays, electrochromic eyewear (for example, adaptive googles or sunglasses), electrochromic curtains or blinds, electrochromic panels for building facades, electrochromic indicators, wearable electrochromic textiles (for example, clothing with color-changing properties), electrochromic panels or artworks, and electrochromic devices for privacy control (for example, privacy glass in conference rooms).

[0120] Examples of electrochromic devices may also include devices prior to final assembly or operation of the example electrochromic devices in the preceding paragraph. For example, an electrochromic laminated glass unit, which may include an anodic electrode, an ion-conductive interlayer, and a cathodic electrode that are assembled together in a lamination process, is an electrochromic device. As another example, an electrochromic insulated glass unit includes an electrochromic laminated glass unit assembled with one or more glass panes separated by a gap between the electrochromic laminated glass unit and the one or more glass panes. Other examples of electrochromic devices will be apparent.

[0121] Specific examples are described. It will be understood that the following examples are intended to describe various embodiments and are not intended to be limiting in any way. It will be understood that certain aspects of the disclosed processes can be arranged and combined in a wide variety of different configurations, all of which are contemplated herein.EXAMPLESExample 1 - Preparation of Vanadium Oxide Electrochromic Films via Atmospheric Plasma

[0122] In this example, fluorine-doped tin oxide (FTO) coated glass substrates (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) were cut into 10 cm by 10 cm squares and cleaned with sequential sonication in the following solutions for 15 minutes each: Extran® 300 detergent (VWR, Mississauga, ON, Canada); deionized H2O; acetone (VWR, Mississauga, ON, Canada); and 2-propanol (VWR, Mississauga, ON, Canada). The FTO coated glass substrates were dried, and the surface was rastered with atmospheric plasma for one minute. For the precursor solution, ethanol (VWR, Mississauga, ON, Canada) was added to vanadium (III) chloride (VCI3 , Sigma Aldrich, Oakville, ON, Canada) to make a 0.025 M solution. This solution was filtered and spray-coated onto a FTO coated glass substrate (Pilkington, Toledo, OH, USA) yielding a transparent film on the FTO coated glass substrate. The FTO coated glass substrate was then placed under blown ion plasma, (power = 500W; height = 2cm; Arm speed = 20 mm / s; line spacing = 5 mm) for conversion of the precursor to form VOx. The entire sample area was then rastered under the plasma twice before applying another coat of precursor. The cast thin film changed from colourless to yellow and was converted to a thin film made of a metal oxide, VOx in this case. The spray I plasma process was repeated four (4) times. Precursor conversion was followed by X-ray fluorescence (XRF) spectroscopy, and was considered complete when counts corresponding to the precursor chloride ligand disappeared or reached a baseline level. The data in Table 1 shows a decrease in the chloride values after the film is subjected to blown ion plasma treatment after each precursor layer.Table 1Example 2 - Preparation of Tungsten Oxide Electrochromic Films via Atmospheric Plasma

[0123] In this example, fluorine-doped tin oxide (FTO) coated glass substrates (TEC 10;10 Q / sq) (Pilkington, Toledo, OH, USA) were cut into 10 cm by 10 cm squares and cleanedwith sequential sonication in the following solutions for 15 minutes each: Extran® 300 detergent (VWR, Mississauga, ON, Canada); deionized H2O; acetone (VWR, Mississauga, ON, Canada); and 2-propanol (VWR, Mississauga, ON, Canada). The FTO coated glass substrates were dried, and the surface was rastered with atmospheric plasma for one minute. For the precursor solution, 2-propanol (VWR, Mississauga, ON, Canada) was added to tungsten (VI) chloride (WCI6, Sigma Aldrich, Oakville, ON, Canada) to make a 0.05 M solution. This solution was filtered and spray-coated onto an FTO coated glass substrate yielding a blue film on the FTO coated glass substrate. The FTO coated glass substrate was then placed under blown ion plasma, (power = 500W; height = 2 cm; Arm speed = 40 mm / s; line spacing = 10 mm) for conversion of the precursor to form WOx. Seven layers of precursor were applied before the entire sample area was rastered under the plasma nozzle once. The cast thin film turned from blue to colourless and was converted to a thin film made of a metal oxide, WOx in this case. Precursor conversion is followed by X-ray fluorescence (XRF) spectroscopy. The data in Table 2 shows the chloride count remained higher than baseline when film was subjected to blown ion plasma treatment after every 7 precursor layers.Table 2.Example 3 - Preparation of Tungsten Oxide Electrochromic Films via Atmospheric Plasma

[0124] In this example, fluorine-doped tin oxide (FTO) coated glass substrates (TEC 10;10 Q / sq) (Pilkington, Toledo, OH, USA) were cut into 10 cm by 10 cm squares and cleaned with sequential sonication in the following solutions for 15 minutes each: Extran® 300 detergent (VWR, Mississauga, ON, Canada); deionized H2O; acetone (VWR, Mississauga, ON, Canada); and 2-propanol (VWR, Mississauga, ON, Canada). The FTO coated glass substrates were dried, and the surface was rastered with atmospheric plasma for one minute. For the precursor solution, 2-propanol ((VWR, Mississauga, ON, Canada) was added to tungsten (VI) chloride (WCI6, Sigma Aldrich, Oakville, ON, Canada) to make a 0.05 M solution. This solution was filtered and spray-coated onto an FTO coated glass substrateyielding a blue film on the substrate. The FTO coated glass substrate was then placed under blown ion plasma, (power = 500W; height = 2 cm; Arm speed = 40 mm / s; line spacing = 10 mm) for conversion of the precursor to form WOx. The entire sample area was rastered under the plasma once before applying another coat of precursor. The cast thin film turned from blue to colourless and was converted to a thin film made of a metal oxide, WOx in this case. A single layer of tungsten precursor was applied before the plasma step. The spray I plasma process was repeated seven times. Precursor conversion was followed by X-ray fluorescence (XRF) spectroscopy, and was considered complete when counts corresponding to the precursor chloride ligand had disappeared or reached a baseline level. The data in Table 3 shows a decrease in the chloride values after the film is subjected to blown ion plasma treatment after each precursor layer.Table 3.Example 4 - Example of Electrochemical Switching of Electrochromic Device Made Using Electrochromic Material Made via Atmospheric Plasma (subjected to plasma after 7 precursor layers)

[0125] In this example, an electrochromic WOx film prepared as described in Example 2 was incorporated into a liquid electrochromic device with a structure of FTO / WOx / LiCIO4 in PC / FTO. In this example, the WOx film was the only film prepared via atmospheric plasma treatment.

[0126] The fluorine-doped tin oxide (FTO) coated glass substrates (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) were cut into 10 cm by 10 cm squares and cleaned with sequential sonication in the following solutions for 15 minutes each: Extran® 300 detergent (VWR, Mississauga, ON, Canada); deionized H2O; acetone (VWR, Mississauga, ON, Canada); and 2-propanol (VWR, Mississauga, ON, Canada). The FTO coated glass substrates were dried, and the surface was rastered with atmospheric plasma for 1 min.

[0127] Two edges of a cleaned piece of a FTO coated glass substrate were masked with Kapton(™) tape, and then the piece was coated with WOx as described in Example 2. After coating, the piece was cut into four 5 cm by 5 cm pieces. The Kapton(™) tape was removed to expose bare FTO coated glass substrate. One of the 5 cm by 5 cm pieces was used. Copper tape busbars were attached to the bare FTO coated glass substrate and silver paint (Ted Pella, Redding, CA, USA) was applied along the edges of the copper tape where it was in contact with the FTO coated glass substrate.

[0128] A 5 cm by 5 cm piece of FTO coated glass substrate (Pilkington, Toledo, OH, USA) that was not coated was used as the anode. Copper tape busbars were attached to the bare FTO coated glass substrate near an edge and silver paint (Ted Pella, Redding, CA, USA) was applied along the edges of the copper tape where it was in contact with the FTO coated glass substrate.

[0129] Double sided 3M(™) VHB(™) tape (4910, 1 / 2", 40 mil) was applied to the perimeter of one of the coated electrodes, and the two electrodes were sandwiched together, coated sides facing each other. The VHB(™) tape was wide enough to cover the busbar so as to prevent liquid electrolyte from coming into contact with them. Edges were pressed together to ensure a good seal.

[0130] A 1 M solution of battery grade lithium perchlorate (LiCIO4, Sigma Aldrich, Oakville, ON, Canada) in anhydrous propylene carbonate (PC, Sigma Aldrich, Oakville, ON, Canada) was injected into the cell using a syringe and blunt needle. This was done carefully to prevent air bubbles within the device. A second blunt needle was inserted on the opposite side to act as a vent while injecting the electrolyte. Once filled, the needles were removed.

[0131] The electrochromic performance of the electrochromic device described was tested via a coupled UV-Vis spectroscopy - electrochemistry set up. The working electrode potentiostat lead was connected to the copper tape busbar that was in contact with the FTO coated glass substrate on the coated WOx electrode. The counter electrode and reference electrode were connected to a copper tape busbar that was attached to the bare FTO coated glass substrate on the anode side. The switching times of the device (from bleached to colored and colored to bleached) were measured by applying alternating consecutive - 3.3 and + 2.5 voltages to the device at 180 second intervals. The change in transmittance at CIE-Y scale for the electrochromic device as a function of time was recorded. Fig. 3 is a graph 300 showing the change in CIE Y transmittance for the bleached and colored states over 10 switching cycles for the electrochromic device obtained in Example 4.Example 5 - Example of Electrochemical Switching of Electrochromic Device Made Using Electrochromic Material Made via Atmospheric Plasma (subjected to plasma after each precursor layers)

[0132] In this example, an electrochromic WOx film prepared as described in Example 3 was incorporated into a liquid electrochromic device with a structure of FTO / WOx / LiCIO4 in PC / VOx / FTO. In this example, the WOx film was the only film prepared via atmospheric plasma treatment.

[0133] The fluorine-doped tin oxide (FTO) coated glass substrates (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) were cut into 10 cm by 10 cm squares and cleaned with sequential sonication in the following solutions for 15 minutes each: Extran® 300 detergent (VWR, Mississauga, ON, Canada); deionized H2O; acetone (VWR, Mississauga, ON, Canada); and 2-propanol (VWR, Mississauga, ON, Canada). The FTO coated glass substrate substrates were dried and the surface was rastered with atmospheric plasma for 1 min.

[0134] Two edges of a cleaned piece of FTO coated glass substrate were masked with Kapton(™) tape, and then the piece was coated with WOx as described in Example 3. After coating, the piece was cut into four 5 cm by 5 cm pieces. The Kapton tape was removed to expose bare FTO. One of the 5 cm by 5 cm pieces was used. Copper tape busbars were attached to the bare FTO and silver paint (Ted Pella, Redding, CA, USA) was applied along the edges of the copper tape where it was in contact with the FTO coated glass substrate.

[0135] A 5 cm x 5 cm piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) coated with VOx prepared via an alternate method that had a Kapton(™) mask along one edge was used as the anode. The Kapton tape mask was removed, and copper tape busbars were attached to the bare FTO coated glass substrate near an edge, and silver paint (Ted Pella, Redding, CA, USA) was applied along the edges of the copper tape where it was in contact with the FTO coated glass substrate.

[0136] Double sided 3M(™) VHB(™) tape (4910, 1 / 2", 40 mil) was applied to the perimeter of one of the coated electrodes, and the two electrodes were sandwiched together, coated sides facing each other. The VHB tape was wide enough to cover the busbar so as to prevent liquid electrolyte from coming into contact with the busbars. Edges were pressed together to ensure a good seal.

[0137] A 1 M solution of battery grade lithium perchlorate (LiCIO4, Sigma Aldrich, Oakville, ON, Canada) in anhydrous propylene carbonate (PC, Sigma Aldrich, Oakville, ON, Canada)was injected into the cell using a syringe and blunt needle. This was done carefully to prevent air bubbles within the device. A second blunt needle was inserted on the opposite side to act as a vent while injecting the electrolyte. Once filled, the needles were removed.

[0138] The electrochromic performance of the electrochromic device described was tested via a coupled UV-Vis spectroscopy - electrochemistry set up. The working electrode potentiostat lead was connected to the copper tape busbar that was in contact with the FTO on the coated WOx electrode. The counter electrode and reference electrode were connected to a copper tape busbar that was attached to the bare FTO on the VOx (anode) side. The switching times of the device (from bleached to colored and colored to bleached) were measured by applying alternating consecutive - 3.0 and + 1 .5 voltages to the device at 180s intervals. The change in transmittance at CIE-Y scale for the electrochromic device as a function of time was recorded. Fig. 4 is a graph 400 showing the change in CIE Y transmittance for the bleached and colored states over ten switching cycles for the electrochromic device obtained in Example 5.

[0139] Fig. 5A is a flow diagram depicting a process 500 for manufacturing an electrochromic laminated glass unit according to some embodiments. The process 500 includes a step 502 in which a first indication of a first amount of a first solution to be applied to a first transparent conductive glass substrate is received. The first solution includes one or more first metal precursors that are to be converted into one or more first metal oxides upon exposure to plasma. At a step 504 the first amount of the first solution is applied to the first transparent conductive glass substrate.

[0140] In some embodiments, receiving the first indication of the first amount of the first solution to be placed on the first transparent conductive glass substrate includes receiving a number of layers of the first solution to be applied to the first transparent conductive glass substrate. Furthermore, applying the first amount of the first solution to the first transparent conductive glass substrate includes applying the number of layers of the first solution to the first transparent conductive glass substrate.

[0141] In various embodiments, receiving the first indication of the first amount of the first solution to be placed on the first transparent conductive glass substrate includes receiving a specified thickness of one or more first metal oxide layers to be formed on the first transparent conductive glass substrate when a conversion of the one or more first metal precursors to the one or more first metal oxides is complete. Furthermore, applying the first amount of the first solution to the first transparent conductive glass substrate includesapplying the first amount of the first solution that is sufficient to form the one or more first metal oxide layers of the specified thickness.

[0142] In some embodiments, applying the first amount of the first solution to the first transparent conductive glass substrate includes utilizing one or more of spin coating, spray coating, ultrasonic spray coating, slot die coating, curtain coating, painting, and dip coating to apply the first amount of the first solution to the first transparent conductive glass substrate. Similarly, applying the second amount of the second solution to the second transparent conductive glass substrate includes utilizing one or more of spin coating, spray coating, ultrasonic spray coating, slot die coating, curtain coating, painting, and dip coating to apply the second amount of the second solution to the second transparent conductive glass substrate.

[0143] At a step 506 the one or more first metal precursors are exposed to first plasma to form one or more first metal oxide layers on the first transparent conductive glass substrate. The one or more first metal oxide layers include the one or more first metal oxides. In various embodiments, exposing the one or more first metal precursors to the first plasma includes rastering the one or more first metal precursors using plasma emitted from a plasma nozzle positioned above the first transparent conductive glass substrate. Rastering the one or more first metal precursors using the plasma emitted from the plasma nozzle may include moving the plasma nozzle at a rate of from about 100 millimeters (mm) per second to about 520 mm per second. The plasma nozzle may be positioned from about 10 mm to about 260 mm above the first transparent conductive glass substrate.

[0144] In various embodiments, exposing the one or more first metal precursors to the first plasma includes exposing the one or more first metal precursors to at least one of blown ion plasma and flame plasma. Similarly, exposing the one or more second metal precursors to the second plasma includes exposing the one or more second metal precursors to at least one of blown ion plasma and flame plasma.

[0145] In some embodiments, applying the first amount of the first solution to the first transparent conductive glass substrate includes applying multiple layers of the first solution to the first transparent conductive glass substrate, and exposing the one or more first metal precursors to the first plasma includes exposing each layer of the multiple layers to the first plasma. In various embodiments, applying the first amount of the first solution to the first transparent conductive glass substrate includes applying multiple layers of the first solution to the first transparent conductive glass substrate, and exposing the one or more first metalprecursors to the first plasma includes exposing fewer layers than a total number of the multiple layers to the first plasma.

[0146] At a step 508 a second indication of a second amount of a second solution to be applied to a second transparent conductive glass substrate is received. The second solution includes one or more second metal precursors that are to be converted into one or more second metal oxides upon exposure to plasma. At a step 510 the second amount of the second solution is applied to the second transparent conductive glass substrate. At a step 512 the one or more second metal precursors are exposed to second plasma to form one or more second metal oxide layers on the second transparent conductive glass substrate. The one or more second metal oxide layers include the one or more second metal oxides.

[0147] At a step 514 a conversion of the one or more first metal precursors into the one or more first metal oxides is monitored or a conversion of the one or more second metal precursors into the one or more second metal oxides is monitored. At a step 516 the conversion of the one or more first metal precursors into the one or more first metal oxides is determined to be incomplete or the conversion of the one or more second metal precursors into the one or more second metal oxides is determined to be incomplete.

[0148] At a step 518 the exposing of the one or more first metal precursors to the first plasma or the exposing of the one or more second metal precursors to the second plasma and the monitoring of the conversion of the one or more first metal precursors into the one or more first metal oxides or the monitoring of the conversion of the one or more second metal precursors into the one or more second metal oxides is repeated until a determination is made that the conversion of the one or more first metal precursors into the one or more first metal oxides is complete or a determination is made that the conversion of the one or more second metal precursors into the one or more second metal oxides is complete, thereby forming the one or more first metal oxide layers on the first transparent conductive glass substrate or the one or more second metal oxide layers on the second transparent conductive glass substrate.

[0149] In some embodiments, monitoring the conversion of the one or more first metal precursors into the one or more first metal oxides includes utilizing spectroscopy to monitor the conversion of the one or more first metal precursors into the one or more first metal oxides. Similarly, monitoring the conversion of the one or more second metal precursors into the one or more second metal oxides includes utilizing spectroscopy to monitor the conversion of the one or more second metal precursors into the one or more second metal oxides.

[0150] In various embodiments where the one or more first metal precursors include one or more ligands, utilizing spectroscopy includes utilizing spectroscopy to detect signals corresponding to the one or more ligands, and determining that the conversion of the one or more first metal precursors into the one or more first metal oxides is incomplete includes determining that the signals indicate that the one or more ligands have not reached a threshold level. Similarly, where the one or more second metal precursors include one or more ligands, utilizing spectroscopy includes utilizing spectroscopy to detect signals corresponding to the one or more ligands, and determining that the conversion of the one or more second metal precursors into the one or more second metal oxides is incomplete includes determining that the signals indicate that the one or more ligands have not reached a threshold level.

[0151] At a step 520 an ion-conducting interlayer is positioned between the one or more first metal oxide layers on the first transparent conductive glass substrate and the one or more second metal oxide layers on the second transparent conductive glass substrate to form a pre-laminated unit. At a step 522 the pre-laminated unit is laminated to form an electrochromic laminated glass unit.

[0152] One aspect of the process 500 is that the one or more first metal oxide layers are not subjected to annealing after the one or more first metal oxide layers are formed and prior to laminating the pre-laminated unit to form the electrochromic laminated glass unit, and the one or more second metal oxide layers are not subjected to annealing after the one or more second metal oxide layers are formed and prior to laminating the pre-laminated unit to form the electrochromic laminated glass unit. That is, the one or more first metal oxide layers are not exposed to a temperature above about room temperature (approximately 20 °C to approximately 25 °C) after the process of exposing the one or more first metal precursors to the first plasma is complete and before the pre-laminated unit is exposed to the temperatures and pressures of the lamination process. Similarly, the one or more second metal oxide layers are not exposed to a temperature above about room temperature after the process of exposing the one or more second metal precursors to the second plasma is complete and before the pre-laminated unit is exposed to the temperatures and pressures of the lamination process.

[0153] The process 500 may include steps not depicted in Fig. 5A. For example, the process 500 may include a step of dissolving the one or more first metal precursors in one or more first solvents to form the first solution and dissolving the one or more second metal precursors in one or more second solvents to form the second solution. Similarly, the process 500 may include a step of exposing at least some of the one or more first metalprecursors to ultraviolet or near-infrared electromagnetic radiation to convert at least some of the one or more first metal precursors into at least some of the one or more first metal oxides or exposing at least some of the one or more second metal precursors to ultraviolet or nearinfrared electromagnetic radiation to convert at least some of the one or more second metal precursors into at least some of the one or more second metal oxides.

[0154] Fig. 5B is a flow diagram depicting a process 540 for manufacturing an electrochromic device according to various embodiments. The process 540 includes a step 542 of in which a first number of layers of a first solution to be applied to a first conductive substrate or a first specified thickness of the one or more first metal oxide layers to be formed on the first conductive substrate is received. At a step 544 a second number of layers of a second solution to be applied to a second conductive substrate or a second specified thickness of the one or more second metal oxide layers to be formed on the second conductive substrate is received.

[0155] At a step 546 the first solution is applied to the first conductive substrate. The first solution includes one or more first metal precursors that may be converted into one or more first metal oxides upon exposure to plasma. In some embodiments, applying the first solution to the first conductive substrate includes applying the first number of layers of the first solution to the first conductive substrate or applying a first amount of the first solution that is sufficient to form the one or more first metal oxide layers of the first specified thickness.

[0156] At a step 548 the one or more first metal precursors are exposed to first plasma to form one or more first metal oxide layers on the first conductive substrate. The one or more first metal oxide layers include the one or more first metal oxides. At a step 550 the one or more first metal oxide layers are exposed to a first temperature of from about 30 °C to about 300 °C for about 15 minutes to about 60 minutes to anneal the one or more first metal oxide layers.

[0157] At a step 552 the second solution is applied to the second conductive substrate. The second solution includes one or more second metal precursors that may be converted into one or more second metal oxides upon exposure to plasma. In some embodiments, applying the second solution to the second conductive substrate includes applying the second number of layers of the second solution to the second conductive substrate or applying a second amount of the second solution that is sufficient to form the one or more second metal oxide layers of the second specified thickness.

[0158] At a step 554 the one or more second metal precursors are exposed to second plasma to form one or more second metal oxide layers on the second conductive substrate. The one or more second metal oxide layers include the one or more second metal oxides. At a step 556 the one or more second metal oxide layers are exposed to a second temperature of from about 30 °C to about 300 °C for about 15 minutes to about 60 minutes to anneal the one or more second metal oxide layers.

[0159] At a step 558 an ion-conducting interlayer is positioned between the one or more first metal oxide layers on the first conductive substrate and the one or more second metal oxide layers on the second conductive substrate to form an assembly. At a step 560 the assembly is laminated.

[0160] In various embodiments where the one or more first metal oxide layers are one or more cathodic electrochromic layers, the one or more first metal oxides may include one or more of WOx, WNbOx, TiWOx, and LiWOx. In various embodiments where the one or more second metal oxide layers are one or more anodic electrochromic layers, the one or more second metal oxides may include one or more of NiOx, LiNiOx, NiNbOx, NiNbLiOx, NiAILiOx, NiCeOx, NiCeLiOx, and VOx.

[0161] In some embodiments, at least one of the one or more first metal oxide layers and the one or more second metal oxide layers is one or more doped metal oxide layers that are doped using a dopant atom that is one or more of niobium, aluminum, lithium, tantalum, molybdenum, cerium, cobalt and titanium.

[0162] In various embodiments, at least one of the one or more first metal precursors and the one or more second metal precursors include one or more of tungsten (VI) chloride, tungsten (VI) isopropoxide, vanadium (III) chloride, nickel (II) nitrate hexahydrate, tantalum (V) ethoxide, niobium (IV) 2-ethylhexanoate, niobium (V) ethoxide, nickel (II) 2- ethylhexanoate, lithium methoxide, lithium ethoxide, lithium 2-ethylhexanoate, lithium trimethylsilanolate, and molybdenum (IV) 2-ethylhexanoate.

[0163] In some embodiments, both the first conductive substrate and the second conductive substrate are non-rigid. In other embodiments, both the first conductive substrate and the second conductive substrate are rigid.

[0164] Fig. 5C is a flow diagram depicting another process 580 for manufacturing an electrochromic device according to some embodiments. The process 580 includes a step 582 in which a first solution is applied to a first substrate. The first solution includes one or more first metal precursors that may be converted into one or more first metal oxides uponexposure to plasma. At a step 584 the one or more first metal precursors are exposed to first plasma to form one or more first metal oxide layers on the first substrate. The one or more first metal oxide layers include the one or more first metal oxides. At a step 586 the one or more first metal oxide layers are annealed.

[0165] At a step 588, a second solution is applied to a second substrate. The second solution includes one or more second metal precursors that may be converted into one or more second metal oxides upon exposure to plasma. At a step 590 the one or more second metal precursors are exposed to second plasma to form one or more second metal oxide layers on the second substrate. The one or more second metal oxide layers include the one or more second metal oxides. At a step 592 the one or more second metal oxide layers are annealed.

[0166] At a step 594 an ion-conducting interlayer is positioned between the one or more first metal oxide layers and the one or more second metal oxide layers to form an assembly. At a step 596 the assembly is laminated.

[0167] In some embodiments, the process 580 does not include step 586 and step 592 - the steps of annealing the one or more first metal oxide layers and the one or more second metal oxide layers. In such embodiments, the one or more first metal oxide layers and the one or more second metal oxide layers are not subjected to annealing after the one or more first metal oxide layers are formed and the one or more second metal oxide layers are formed and prior to laminating the assembly.

[0168] It will be appreciated that each of the process 500, the process 540, and the process 580 may include variations, differences, or additional aspects of other processes described herein. For example, each of the process 500, the process 540, and the process 580 may include steps for forming an ion-conducting interlayer or an electrolyte layer. As another example, each of the process 500, the process 540, and the process 580 may utilize any of the metal precursors or any of the solvents described herein.

[0169] Fig. 6A is a schematic representation of a curved electrochromic device 600 that may be manufactured according to various embodiments of processes described herein. The curved electrochromic device 600 may be a curved electrochromic window such as a sunroof, a windshield, or a window for an automobile.

[0170] The curved electrochromic device 600 includes a first pane of conductive glass 601 and a second pane of conductive glass 607. The first pane of conductive glass 601 and the second pane of conductive glass 607 may be transparent conductive oxide (TCO) glass thatis coated with a metal coating that makes the glass electrically conductive. The metal coating may include indium tin oxide (ITO) or fluorine-doped tin oxide (FTO). The curved electrochromic device 600 also includes an anodic electrochromic layer 603 and a cathodic electrochromic layer 605. The curved electrochromic device 600 also includes an ionconducting layer 604, which may be referred to as an electrolyte layer or an interlayer, positioned between the anodic electrochromic layer 603 and the cathodic electrochromic layer 605. The anodic electrochromic layer 603, the cathodic electrochromic layer 605, or the ion-conducting layer 604 may be formed according to various embodiments of the processes described herein.

[0171] The curved electrochromic device 600 also includes a first seal 609a and a second seal 609b positioned around a perimeter of the ion-conducting layer 604, and a first bus bar 610a positioned proximate to the conductive glass 601 and a second bus bar 610b positioned proximate to the conductive glass 607. The first seal 609a and the second seal 609b may function to prevent or reduce ingress of water or other contaminants. In certain embodiments of the curved electrochromic device 600, if no electrical bias is applied, ions (for example, lithium ions) are stored in the anodic electrochromic layer 603 and the curved electrochromic device 600 is in a transparent state. If an electrical bias is applied to the first bus bar 610a and the second bus bar 610b, ions (for example, lithium ions) migrate from the anodic electrochromic layer 603 across the ion-conducting layer 604 to be stored in the cathodic electrochromic layer 605, and the curved electrochromic device 600 transitions to a coloured state. The curved electrochromic device 600 may include other components not illustrated in Fig. 6A.

[0172] Fig. 6B is a schematic representation of a flat electrochromic device 650 that may be manufactured according to various embodiments of processes described herein. The flat electrochromic device 650 may be an electrochromic insulated glass unit to be assembled in a window frame and installed in a building such as a home or an office building.

[0173] The flat electrochromic device 650 includes a first pane of conductive glass 651 and a second pane of conductive glass 657. The first pane of conductive glass 651 and the second pane of conductive glass 657 may be transparent conductive oxide (TCO) glass that is coated with a metal coating that makes the glass electrically conductive. The metal coating may include indium tin oxide (ITO) or fluorine-doped tin oxide (FTO). The flat electrochromic device 650 also includes an anodic electrochromic layer 653 and a cathodic electrochromic layer 655. The flat electrochromic device 650 also includes an ion-conducting layer 654, which may be referred to as an electrolyte layer or an interlayer, positioned between the anodic electrochromic layer 653 and the cathodic electrochromic layer 655. Theanodic electrochromic layer 653, the cathodic electrochromic layer 655, or the ionconducting layer 654 may be formed according to embodiments of the processes described herein.

[0174] The flat electrochromic device 650 also includes a first seal 659 and a second seal 662. The first seal 659 and the second seal 662 may function to prevent or reduce ingress of water or other contaminants into the flat electrochromic device 650. The flat electrochromic device 650 also includes a third pane of glass 661 and a spacer 663 positioned between the second pane of conductive glass 657 and the third pane of glass 661 . The spacer 663 may be aluminum or another suitable material. The flat electrochromic device 650 may include other components not illustrated in Fig. 6B, such as bus bars or other electrical connectors or coatings.

[0175] In certain embodiments of the flat electrochromic device 650, if no electrical bias is applied, ions (for example, lithium ions) are stored in the anodic electrochromic layer 653 and the flat electrochromic device 650 is in a transparent state. If an electrical bias is applied to the flat electrochromic device 650, ions (for example, lithium ions) migrate from the anodic electrochromic layer 653 across the ion-conducting layer 654 to be stored in the cathodic electrochromic layer 655, and the flat electrochromic device 650 transitions to a coloured state.

[0176] The processes described herein may result in one or more metal oxide layers containing one or more metal oxides formed on a substrate. The one or more metal oxide layers may be referred to as a single metal oxide layer or as a metal oxide film. It is to be understood that the metal oxide layers may include one or more metal oxides, which may be referred to as mixed metal oxides.

[0177] The following are additional examples of processes, compositions, and devices according to various embodiments.

[0178] In some aspects, the techniques described herein relate to a process for forming an active layer for use in an electrochromic device, the process including the steps of: (a) providing a support; (b) solution-coating the support with a liquid material of one or more inorganic or organometallic precursors, wherein the inorganic or organometallic precursor is a metal-containing molecule that is converted to a metal oxide upon exposure to atmospheric plasma; and (c) exposing the coated support to atmospheric plasma to convert the one or more metal precursors to a metal oxide film on the support, thereby forming the active layer.

[0179] In some aspects, the techniques described herein relate to a process, wherein steps (b) and (c) are repeated until a desired thickness of the metal oxide film is achieved to form the active layer.

[0180] In some aspects, the techniques described herein relate to a process, wherein step (b) is repeated more than once before step (c) occurs.

[0181] In some aspects, the techniques described herein relate to a process, wherein the electrochromic device includes: a first electrode including a first electrochromic material, a second electrode including a second electrochromic material, and an ion-conductor layer for conducting ions between said first electrode and second electrode.

[0182] In some aspects, the techniques described herein relate to a process, wherein the atmospheric plasma is selected from blown ion plasma and flame plasma.

[0183] In some aspects, the techniques described herein relate to a process wherein the plasma nozzle moves at a rate of between about 15 mm / s and about 510 mm / s.

[0184] In some aspects, the techniques described herein relate to a process wherein the plasma nozzle moves at a rate of between 255 mm / s and 508 mm / s.

[0185] In some aspects, the techniques described herein relate to a process wherein the gap between the plasma nozzle head and the substrate or substrate-supported electrode is between about 5 mm and about 100 mm.

[0186] In some aspects, the techniques described herein relate to a process wherein the gap between the plasma nozzle head and the substrate or substrate-supported electrode is between about 9.5 mm and about 55 mm.

[0187] In some aspects, the techniques described herein relate to a process, wherein the active layer is an electrochromic metal oxide layer

[0188] In some aspects, the techniques described herein relate to a process, wherein the electrochromic metal oxide layers are selected from the group consisting of NiOx, WOx, MoOx, TiOx, TaOx, VOx, NbOx, CoOx, IrOx, MnOx, FeOx, LiNiOx, WNbOx, TiWOx, LiWOx, NiNbOx, NiNbLiOx, NiCeOx, NiCeLiOx, NiAILiOx, or a combination thereof.

[0189] In some aspects, the techniques described herein relate to a method, wherein the cathodic electrochromic layer is selected from WOx, WNbOx, TiWOx, LiWOx, or combinations thereof.

[0190] In some aspects, the techniques described herein relate to a method, wherein anodic electrochromic layer includes NiOx, LiNiOx, NiNbOx, NiNbLiOx, NiAILiOx, NiCeOx, NiCeLiOx, VOx, or combinations thereof.

[0191] In some aspects, the techniques described herein relate to a method, wherein the electrochromic metal oxide layer is a doped metal oxide, and the dopant atom is selected from niobium, aluminum, lithium, tantalum, molybdenum, cerium, cobalt and titanium.

[0192] In some aspects, the techniques described herein relate to a process, wherein the cathodic electrochromic metal oxide layer is majority composed of tungsten oxide.

[0193] In some aspects, the techniques described herein relate to a process, wherein the anodic electrochromic metal oxide layer is majority composed of nickel oxide.

[0194] In some aspects, the techniques described herein relate to a method, including the further step of providing said first electrochromic layer with an additional layer, and / or providing said second electrochromic layer with an additional layer.

[0195] In some aspects, the techniques described herein relate to a method, wherein said additional layer is a barrier layer included of niobium oxide, lithium oxide, titanium oxide, indium oxide, cerium oxide, tantalum oxide, aluminum oxide, or a mixture thereof.

[0196] In some aspects, the techniques described herein relate to a method, wherein said additional layer is a barrier layer included of niobium oxide, lithium oxide, indium oxide, aluminum oxide or a combination thereof.

[0197] In some aspects, the techniques described herein relate to a process 10 to 16, wherein the electrochromic layers have an average thickness of between 10 nm and 2000 nm.

[0198] In some aspects, the techniques described herein relate to a process 10 to 16, wherein the electrochromic layers have an average thickness of between 100 nm and 800 nm.

[0199] In some aspects, the techniques described herein relate to a process 10 to 16, wherein the electrochromic layers have an average thickness of between 200 nm and 700 nm.

[0200] In some aspects, the techniques described herein relate to a process, wherein the active layer is an ion-conductive inorganic layer.

[0201] In some aspects, the techniques described herein relate to a process, wherein the ion-conductive inorganic layer includes a metal oxide selected from the group consisting of NbOx, TaOx, SiOx, AIOx, LiTaOx, LiNbOx, LaTiOx, SrZrOx, ZrOx, YOx, LiLaTiOx, LiWOx, LiSiOx, LiAISiOx, LiSiGeOx, LiGeOx, LiOx, LiAIOx, LiZnOx, or a combination thereof.

[0202] In some aspects, the techniques described herein relate to a process, wherein the metal oxide film includes at least one of NbOx, TaOx, and LiNbOx.

[0203] In some aspects, the techniques described herein relate to a process 23 to 25, wherein the ion-conductive inorganic layer has an average thickness between 5 nm and 1000 nm.

[0204] In some aspects, the techniques described herein relate to a process according claims 23 to 25, wherein the ion-conductive inorganic layer has an average thickness of between about 20 nm and about 600 nm.

[0205] In some aspects, the techniques described herein relate to a process according claims 23 to 25, wherein the ion-conductive inorganic layer has an average thickness of between about 100 nm and about 400 nm.

[0206] In some aspects, the techniques described herein relate to a process, wherein the liquid material of one or more inorganic or organometallic precursors include one or more of an inorganic chloride, an inorganic nitrate, an organometallic 2-ethylhexanoate, an organometallic butoxide, an organometallic ethoxide, an organometallic methoxide, an organometallic isopropoxide, an organometallic acetylacetonate, an organometallic silanolate, an organometallic oxalate, or mixtures thereof.

[0207] In some aspects, the techniques described herein relate to a process, wherein the active metal oxide film is annealed after step (c).

[0208] In some aspects, the techniques described herein relate to a process, wherein the annealing step is carried out at a temperature of about 30° C to about 600° C, such as about 30° C to about 300° C.

[0209] In some aspects, the techniques described herein relate to a process, wherein the annealing step is carried out at a temperature of about 50° C.

[0210] In some aspects, the techniques described herein relate to a process, wherein the annealing step is carried out at a temperature of about 100° C.

[0211] In some aspects, the techniques described herein relate to a process, wherein the annealing step is carried out at a temperature of about 200° C.

[0212] In some aspects, the techniques described herein relate to a process, wherein the annealing step is carried out at a temperature of about 300° C.

[0213] In some aspects, the techniques described herein relate to a process, wherein the annealing step is carried out at a temperature of about 350° C.

[0214] In some aspects, the techniques described herein relate to a process, wherein the annealing step is carried out at a temperature of about 400° C.

[0215] In some aspects, the techniques described herein relate to a method 30 to 37, wherein the annealing step is carried out for about 15 minutes to about 1 hour.

[0216] In some aspects, the techniques described herein relate to a process, wherein the support is a planar substrate.

[0217] In some aspects, the techniques described herein relate to a process, wherein the support is a singly curved, doubly curved, or complexly curved substrate.

[0218] In some aspects, the techniques described herein relate to a process, wherein the support is a transparent conductive substrate.

[0219] In some aspects, the techniques described herein relate to a process, wherein the transparent conductive substrate is formed of a transparent material coated with a conductive film.

[0220] In some aspects, the techniques described herein relate to a process, wherein the transparent material is selected from the group consisting of glass, polyethylene terephthalate (PET), polycarbonate, polyethylene naphthalate (PEN), polyvinyl butyral (PVB), polymethyl methacrylate (PMMA), acrylic, transparent acrylonitrile butadiene styrene (ABS), methyl methacrylate acrylonitrile butadiene styrene (MABS), polyvinyl chloride (PVC), amorphous copolyester (PETG), general purpose polystyrene, styrene acrylonitrile resin (SAN), styrene methyl methacrylate (SMMA), fluorinated ethylene propylene (FEP), transparent polypropylene, ionomer resin, polyethylene (PE), cyclic olefin copolymers, thermoplastic polyurethane (TPU),or liquid silicone rubber (LSR).

[0221] In some aspects, the techniques described herein relate to a process, wherein the transparent substrates are selected from the group consisting of glass, polyethyleneterephthalate (PET), polycarbonate, polyethylene naphthalate (PEN), polyvinyl butyral (PVB), polymethyl methacrylate (PMMA), acrylic, or polyvinyl chloride (PVC).

[0222] In some aspects, the techniques described herein relate to a process, wherein the transparent conductive substrate is a substrate coated with fluorine tin oxide (FTO), indium tin oxide (ITO), aluminum zinc oxide (AZO), silver mesh, silver nanowires, silver nanoparticles, carbon nanotubes, carbon black, graphene, conductive polymers or a mixture of two or more thereof.

[0223] In some aspects, the techniques described herein relate to a process, wherein the conductive substrate is a substrate coated with fluorine tin oxide (FTO) or indium tin oxide (ITO).

[0224] In some aspects, the techniques described herein relate to a process, wherein the support is a substrate-supported electrode.

[0225] In some aspects, the techniques described herein relate to a process, wherein the substrate-supported electrode is a transparent conductive substrate combined with an electrochromic layer.

[0226] In some aspects, the techniques described herein relate to a method, wherein the device is used as an electrochromic sunroof.

[0227] In some aspects, the techniques described herein relate to a method, wherein the device is used as an electrochromic window.

[0228] While particular elements, embodiments and applications have been shown and described, it will be understood, of course, that the claims are not limited thereto since modifications may be made by those skilled in the art without departing from the spirit and scope of the present disclosure, particularly in light of the foregoing teachings. Such modifications are to be considered within the purview and scope of the claims appended hereto.

[0229] While specific examples are described above for illustrative purposes, various equivalent modifications are possible. For example, while processes or blocks are presented in a given order, alternative implementations may perform routines having steps, or employ systems having blocks, in a different order, and some processes or blocks may be deleted, moved, added, subdivided, combined, and / or modified to provide alternative or subcombinations. Each of these processes or blocks may be implemented in a variety of different ways. Also, while processes or blocks are at times shown as being performed inseries, these processes or blocks may instead be performed or implemented concurrently or in parallel or may be performed at different times. Further any specific numbers noted herein are only examples: alternative implementations may employ differing values or ranges.

[0230] Throughout this specification, plural instances may implement components, operations, or structures described as a single instance. Structures and functionality presented as separate components in example configurations may be implemented as a combined structure or component. Similarly, structures and functionality presented as a single component may be implemented as separate components. These and other variations, modifications, additions, and improvements fall within the scope of the subject matter herein. Furthermore, any specific numbers noted herein are only examples: alternative implementations may employ differing values or ranges.

[0231] Components may be described or illustrated as contained within or connected with other components. Such descriptions or illustrations are examples only, and other configurations may achieve the same or similar functionality. Components may be described or illustrated as “coupled,” “couplable,” “operably coupled,” “communicably coupled” and the like to other components. Such description or illustration should be understood as indicating that such components may cooperate or interact with each other, and may be in direct or indirect physical, electrical, or communicative contact with each other.

[0232] Components may be described or illustrated as “configured to,” “adapted to,” “operative to,” “configurable to,” “adaptable to,” “operable to” and the like. Such description or illustration should be understood to encompass components both in an active state and in an inactive or standby state unless required otherwise by context.

[0233] The use of “or” in this disclosure is not intended to be understood as an exclusive “or.” Rather, “or” is to be understood as including “and / or.” For example, the phrase “providing products or services” is intended to be understood as having several meanings: “providing products,” “providing services,” and “providing products and services.”

[0234] It may be apparent that various modifications may be made, and other embodiments may be used without departing from the broader scope of the discussion herein. For example, although an electrochromic window is described as being in a transparent state in the absence of an electrical bias, the electrochromic window may be in a coloured state in the absence of an electrical bias. Therefore, these and other variations upon the example embodiments are intended to be covered by the disclosure herein.

Claims

CLAIMSI / We claim:

1. A process for manufacturing an electrochromic laminated glass unit, the process comprising: receiving a first indication of a first amount of a first solution to be applied to a first transparent conductive glass substrate, the first solution including one or more first metal precursors, the one or more first metal precursors to be converted into one or more first metal oxides upon exposure to plasma; applying the first amount of the first solution to the first transparent conductive glass substrate; exposing the one or more first metal precursors to first plasma to form one or more first metal oxide layers on the first transparent conductive glass substrate, the one or more first metal oxide layers including the one or more first metal oxides; receiving a second indication of a second amount of a second solution to be applied to a second transparent conductive glass substrate, the second solution including one or more second metal precursors, the one or more second metal precursors to be converted into one or more second metal oxides upon exposure to plasma; applying the second amount of the second solution on the second transparent conductive glass substrate; exposing the one or more second metal precursors to second plasma to form one or more second metal oxide layers on the second transparent conductive glass substrate, the one or more second metal oxide layers including the one or more second metal oxides; positioning an ion-conducting interlayer between the one or more first metal oxide layers on the first transparent conductive glass substrate and the one or more second metal oxide layers on the second transparent conductive glass substrate to form a pre-laminated unit; and laminating the pre-laminated unit to form an electrochromic laminated glass unit, wherein the one or more first metal oxide layers are not subjected to annealing after the one or more first metal oxide layers are formed and prior to laminating the pre-laminated unit to form the electrochromic laminated glass unit, and the one or more second metal oxide layers are not subjected to annealing after the one or more second metal oxide layers are formed and prior to laminating the pre-laminated unit to form the electrochromic laminated glass unit.

2. The process of claim 1 wherein receiving the first indication of the first amount of the first solution to be placed on the first transparent conductive glass substrate includes receiving a number of layers of the first solution to be applied to the first transparent conductive glass substrate, and applying the first amount of the first solution to the first transparent conductive glass substrate includes applying the number of layers of the first solution to the first transparent conductive glass substrate.

3. The process of claim 1 wherein receiving the first indication of the first amount of the first solution to be placed on the first transparent conductive glass substrate includes receiving a specified thickness of the one or more first metal oxide layers to be formed on the first transparent conductive glass substrate when a conversion of the one or more first metal precursors to the one or more first metal oxides is complete, and applying the first amount of the first solution to the first transparent conductive glass substrate includes applying the first amount of the first solution that is sufficient to form the one or more first metal oxide layers of the specified thickness.

4. The process of claim 1 wherein applying the first amount of the first solution to the first transparent conductive glass substrate includes applying multiple layers of the first solution to the first transparent conductive glass substrate, and exposing the one or more first metal precursors to the first plasma includes exposing each layer of the multiple layers to the first plasma.

5. The process of claim 1 wherein applying the first amount of the first solution to the first transparent conductive glass substrate includes applying multiple layers of the first solution to the first transparent conductive glass substrate, and exposing the one or more first metal precursors to the first plasma includes exposing fewer layers than a total number of the multiple layers to the first plasma.

6. The process of claim 1 , further comprising exposing at least some of the one or more first metal precursors to ultraviolet or near-infrared electromagnetic radiation to convert at least some of the one or more first metal precursors into at least some of the one or more first metal oxides.

7. The process of claim 1 , further comprising: monitoring a conversion of the one or more first metal precursors into the one or more first metal oxides; determining that the conversion of the one or more first metal precursors into the one or more first metal oxides is incomplete; andrepeating exposing the one or more first metal precursors to the first plasma and monitoring the conversion of the one or more first metal precursors into the one or more first metal oxides until a determination is made that the conversion of the one or more first metal precursors into the one or more first metal oxides is complete, thereby forming the one or more first metal oxide layers on the first transparent conductive glass substrate.

8. The process of claim 7 wherein monitoring the conversion of the one or more first metal precursors into the one or more first metal oxides includes utilizing spectroscopy to monitor the conversion of the one or more first metal precursors into the one or more first metal oxides.

9. The process of claim 8 wherein the one or more first metal precursors include one or more ligands, utilizing spectroscopy includes utilizing spectroscopy to detect signals corresponding to the one or more ligands, and determining that the conversion of the one or more first metal precursors into the one or more first metal oxides is incomplete includes determining that the signals indicate that the one or more ligands have not reached a threshold level.

10. The process of claim 1 wherein exposing the one or more first metal precursors to the first plasma includes rastering the one or more first metal precursors using plasma emitted from a plasma nozzle positioned above the first transparent conductive glass substrate.11 . The process of claim 10 wherein rastering the one or more first metal precursors using the plasma emitted from the plasma nozzle includes moving the plasma nozzle at a rate of from about 100 millimeters (mm) per second to about 520 mm per second.

12. The process of claim 10 wherein the plasma nozzle is positioned from about 10 mm to about 260 mm above the first transparent conductive glass substrate.

13. The process of claim 1 wherein exposing the one or more first metal precursors to the first plasma includes exposing the one or more first metal precursors to at least one of blown ion plasma and flame plasma.

14. The process of claim 1 wherein applying the first amount of the first solution to the first transparent conductive glass substrate includes utilizing one or more of spin coating, spray coating, ultrasonic spray coating, slot die coating, curtain coating, painting, and dip coating to apply the first amount of the first solution to the first transparent conductive glass substrate.

15. The process of claim 1 , further comprising: dissolving the one or more first metal precursors in one or more first solvents to form the first solution; and dissolving the one or more second metal precursors in one or more second solvents to form the second solution.

16. The electrochromic laminated glass unit manufactured according to the process of any of claims 1 to 15.

17. A process comprising: applying a first solution to a first conductive substrate, the first solution including one or more first metal precursors that may be converted into one or more first metal oxides upon exposure to plasma; exposing the one or more first metal precursors to first plasma to form one or more first metal oxide layers on the first conductive substrate, the one or more first metal oxide layers including the one or more first metal oxides; exposing the one or more first metal oxide layers to a first temperature of from about 30 °C to about 300 °C for about 15 minutes to about 60 minutes to anneal the one or more first metal oxide layers; applying a second solution to a second conductive substrate, the second solution including one or more second metal precursors that may be converted into one or more second metal oxides upon exposure to plasma; exposing the one or more second metal precursors to second plasma to form one or more second metal oxide layers on the second conductive substrate, the one or more second metal oxide layers including the one or more second metal oxides; exposing the one or more second metal oxide layers to a second temperature of from about 30 °C to about 300 °C for about 15 minutes to about 60 minutes to anneal the one or more second metal oxide layers; positioning an ion-conducting interlayer between the one or more first metal oxide layers on the first conductive substrate and the one or more second metal oxide layers on the second conductive substrate to form an assembly; and laminating the assembly.

18. The process of claim 17, further comprising: receiving a first number of layers of the first solution to be applied to the first conductive substrate; andreceiving a second number of layers of the second solution to be applied to the second conductive substrate, wherein applying the first solution to the first conductive substrate includes applying the first number of layers of the first solution to the first conductive substrate and applying the second solution to the second conductive substrate includes applying the second number of layers of the second solution to the second conductive substrate.

19. The process of claim 17, further comprising: receiving a first specified thickness of the one or more first metal oxide layers to be formed on the first conductive substrate when a first conversion of the one or more first metal precursors to the one or more first metal oxides is complete; and receiving a second specified thickness of the one or more second metal oxide layers to be formed on the second conductive substrate when a second conversion of the one or more second metal precursors to the one or more second metal oxides is complete, wherein applying the first solution to the first conductive substrate includes applying a first amount of the first solution that is sufficient to form the one or more first metal oxide layers of the first specified thickness, and applying the second solution to the second conductive substrate includes applying a second amount of the second solution that is sufficient to form the one or more second metal oxide layers of the second specified thickness.

20. The process of claim 17 wherein the one or more first metal oxide layers are one or more cathodic electrochromic layers, the one or more first metal oxides include one or more of WOx, WNbOx, TiWOx, and LiWOx, the one or more second metal oxide layers are one or more anodic electrochromic layers, and the one or more second metal oxides include one or more of NiOx, LiNiOx, NiNbOx, NiNbLiOx, NiAILiOx, NiCeOx, NiCeLiOx, and VOx.

21. The process of claim 17 wherein at least one of the one or more first metal oxide layers and the one or more second metal oxide layers is one or more doped metal oxide layers that are doped using a dopant atom that is one or more of niobium, aluminum, lithium, tantalum, molybdenum, cerium, cobalt and titanium.

22. The process of claim 17 wherein at least one of the one or more first metal precursors and the one or more second metal precursors include one or more of tungsten (VI) chloride, tungsten (VI) isopropoxide, vanadium (III) chloride, nickel (II) nitrate hexahydrate, tantalum (V) ethoxide, niobium (IV) 2-ethylhexanoate, niobium (V) ethoxide, nickel (II) 2-ethylhexanoate, lithium methoxide, lithium ethoxide, lithium 2-ethylhexanoate, lithium trimethylsilanolate, and molybdenum (IV) 2-ethylhexanoate.

23. The process of claim 17 wherein both the first conductive substrate and the second conductive substrate are non-rigid.

24. An electrochromic device manufactured according to the process of any of claims 17 to 23.

25. A process comprising: applying a first solution to a first substrate, the first solution including one or more first metal precursors that may be converted into one or more first metal oxides upon exposure to plasma; exposing the one or more first metal precursors to first plasma to form one or more first metal oxide layers on the first substrate, the one or more first metal oxide layers including the one or more first metal oxides; applying a second solution to a second substrate, the second solution including one or more second metal precursors that may be converted into one or more second metal oxides upon exposure to plasma; exposing the one or more second metal precursors to second plasma to form one or more second metal oxide layers on the second substrate, the one or more second metal oxide layers including the one or more second metal oxides; positioning an ion-conducting interlayer between the one or more first metal oxide layers and the one or more second metal oxide layers to form an assembly; and laminating the assembly.

26. The process of claim 25, further comprising: annealing the one or more first metal oxide layers; and annealing the one or more second metal oxide layers.

27. The process of claim 25 wherein the one or more first metal oxide layers are not subjected to annealing after the one or more first metal oxide layers are formed and prior to laminating the assembly, and the one or more second metal oxide layers are not subjected to annealing after the one or more second metal oxide layers are formed and prior to laminating the assembly.

28. An electrochemical device manufactured according to the process of any of claims 25 to 27.

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