Patent Grant
11960188
An Application Data Sheet is filed concurrently with this specification as part of the present application. Each application that the present application claims benefit of or priority to as identified in the concurrently filed Application Data Sheet is incorporated by reference herein in their entireties and for all purposes.
Electrochromism is a phenomenon in which a material exhibits a reversible electrochemically-mediated change in an optical property when placed in a different electronic state, typically by being subjected to a voltage change. The optical property is typically one or more of color, transmittance, absorbance, and reflectance. One well known electrochromic material, for example, is tungsten oxide (WO3). Tungsten oxide is a cathodic electrochromic material in which a coloration transition, transparent to blue, occurs by electrochemical reduction. Anodic electrochromic materials are also known, e.g., nickel oxide (e.g. NiO).
Electrochromic materials may be incorporated into, for example, windows and mirrors. The color, transmittance, absorbance, and/or reflectance of such windows and mirrors may be changed by inducing a change in the electrochromic material. One well known application of electrochromic materials, for example, is electrochromic windows for buildings.
While electrochromism was discovered in the 1960's, electrochromic devices have historically suffered from various problems that have prevented the technology from realizing its full commercial potential. For example, electrochromic windows may use tungsten oxide and/or nickel oxide materials, but there is much room for improvement. Certain areas that can be improved include material stability over time, switching speed, and optical properties, e.g., tinted states are often too blue and transparent states are often too yellow.
The embodiments herein relate to electrochromic materials, electrochromic stacks, electrochromic devices, as well as methods and apparatus for making such materials, stacks, and devices. In various embodiments, a counter electrode material includes a novel composition of materials including nickel, tungsten, niobium, and oxygen.
In one aspect of the disclosed embodiments, a method of fabricating an electrochromic stack is provided, the method including: forming a cathodically coloring layer including a cathodically coloring electrochromic material; and forming an anodically coloring layer including nickel tungsten niobium oxide (NiWNbO). The NiWNbO material may meet have a particular composition. For example, in some cases, the NiWNbO has an atomic ratio of Ni:(W+Nb) that is between about 1.5:1 and 3:1, or between about 1.5:1 and 2.5:1, or between about 1.8:1 and 2.5:1, or between about 2:1 and 2.5:1, or between about 2:1 and 3:1. In these or other cases, the NiWNbO may have an atomic ratio of W:Nb that is between about 0.1:1 and 6:1, or between about 0.2:1 and 5:1, or between about 0.2:1 and 1:1, or between about 1:1 and 2:1.
The anodically coloring layer may be formed by sputtering one or more sputter targets to form the NiWNbO. At least one of the one or more of the sputter targets may include an elemental metal selected from the group consisting of: nickel, tungsten, and niobium. In some cases, at least one of the one or more of the sputter targets may include an alloy including two or more metals selected from the group consisting of: nickel, tungsten, and niobium. At least one of the one or more sputter targets may include an oxide in some cases. In various embodiments, the anodically coloring layer may be substantially amorphous.
The cathodically coloring layer and the anodically coloring layer may be formed in direct physical contact with one another, without a separately deposited ion conductor layer between them. In some implementations, the anodically coloring layer includes two or more sub-layers that have different compositions and/or morphologies. In certain embodiments the cathodically coloring electrochromic material includes tungsten oxide (WOx). In some such cases, x may be less than 3.0. In these or other cases, x may be at least about 2.7. In various implementations, the cathodically coloring layer may include a bilayer or a graded layer, and a portion of the cathodically coloring layer may be superstoichiometric with respect to oxygen.
In another aspect of the disclosed embodiments, an electrochromic stack is provided, the electrochromic stack including: a cathodically coloring layer including a cathodically coloring material; and an anodically coloring layer including nickel tungsten niobium oxide (NiWNbO).
The NiWNbO may have a particular composition in some cases. For instance, the NiWNbO may an atomic ratio of Ni:(W+Nb) that is between about 1.5:1 and 3:1, or between about 1.5:1 and 2.5:1, or between about 1.8:1 and 2.5:1, or between about 2:1 and 2.5:1, or between about 2:1 and 3:1. In these or other cases, the NiWNbO may have an atomic ratio of W:Nb that is between about 0.1:1 and 6:1, or between about 0.2:1 and 5:1, or between about 0.2:1 and 1:1, or between about 1:1 and 2:1. The anodically coloring layer may be substantially amorphous. In some cases, the anodically coloring layer may include an amorphous matrix of a first material having domains of a second material scattered throughout the amorphous matrix.
The cathodically coloring layer may be in direct physical contact with the anodically coloring layer in some cases. In a number of embodiments, the anodically coloring layer may include two or more sub-layers having different compositions and/or morphologies. In certain embodiments the cathodically coloring material includes tungsten oxide (WOx). In some such cases, x may be less than 3.0. In these or other cases, x may be at least about 2.7. In various implementations, the cathodically coloring layer may include a bilayer or a graded layer, and a portion of the cathodically coloring layer may be superstoichiometric with respect to oxygen.
In a further aspect of the disclosed embodiments, an integrated deposition system for fabricating an electrochromic stack is provided, the system including: a plurality of deposition stations aligned in series and interconnected and operable to pass a substrate from one station to the next without exposing the substrate to an external environment, where the plurality of deposition stations include (i) a first deposition station containing one or more material sources for depositing a cathodically coloring layer; (ii) a second deposition station containing one or more material sources for depositing an anodically coloring layer including nickel tungsten niobium oxide (NiWNbO); and a controller containing program instructions for passing the substrate through the plurality of stations in a manner that deposits on the substrate (i) the cathodically coloring layer, and (ii) the anodically coloring layer to form a stack including at least the cathodically coloring layer and the anodically coloring layer.
The NiWNbO may be deposited to include a particular composition in some cases. For example, the NiWNbO may haves an atomic ratio of Ni:(W+Nb) that is between about 1.5:1 and 3:1, or between about 1.5:1 and 2.5:1, or between about 1.8:1 and 2.5:1, or between about 2:1 and 2.5:1, or between about 2:1 and 3:1. In these or other cases, the NiWNbO may have an atomic ratio of W:Nb that is between about 0.1:1 and 6:1, or between about 0.2:1 and 5:1, or between about 0.2:1 and 1:1, or between about 1:1 and 2:1.
In certain implementations, at least one of the one or more material sources for depositing the anodically coloring layer include an elemental metal selected from the group consisting of: nickel, tungsten, and niobium. In these or other implementations, at least one of the one or more material sources for depositing the anodically coloring layer include an alloy including two or more metals selected from the group consisting of: nickel, tungsten, and niobium. In some embodiments, at least one of the one or more material sources for depositing the anodically coloring layer include an oxide. The anodically coloring layer may be deposited to include a particular morphology in some cases. For instance, the deposition system may be configured to deposit the anodically coloring layer as a substantially amorphous material.
In these or other cases, the integrated deposition system may be configured to deposit the cathodically coloring layer and the anodically coloring layer in direct physical contact with one another. Further, the anodically coloring layer may be deposited to include a particular structure. In some embodiments, for instance, the controller may contain program instructions for depositing the anodically coloring layer as two or more sub-layers having different compositions and/or morphologies. The sub-layers of the anodically coloring layer may all be deposited in the second deposition station, though in some cases one or more sub-layers of the anodically coloring layer may be deposited in a third deposition station. In certain embodiments the cathodically coloring layer includes tungsten oxide (WOx). In some such cases, x may be less than 3.0. In these or other cases, x may be at least about 2.7. In various implementations, the cathodically coloring layer may include a bilayer or a graded layer, and a portion of the cathodically coloring layer may be superstoichiometric with respect to oxygen.
In a further aspect of the disclosed embodiments, a composition of matter is provided, including: (a) nickel; (b) tungsten; (c) niobium; and (d) oxygen, where the composition includes an atomic ratio of Ni:(W+Nb) that is between about 1.5:1 and 3:1, and an atomic ratio of W:Nb that is between about 0.1:1 and 6:1.
In certain embodiments, the atomic ratio of Ni:(W+Nb) may be between about 1.5:1 and 3:1, or between about 1.5:1 and 2.5:1, or between about 1.8:1 and 2.5:1, or between about 2:1 and 2.5:1, or between about 2:1 and 3:1. In these or other embodiments, the atomic ratio of W:Nb may be between about 0.1:1 and 6:1, or between about 0.2:1 and 5:1, or between about 0.2:1 and 1:1, or between about 1:1 and 2:1. The composition may be provided in a layer having a thickness between about 50-650 nm. The composition may be formed through sputtering one or more sputter targets. In various embodiments, the composition becomes tinted in response to an applied anodic potential.
In some implementations, the composition is amorphous. In some cases, the composition is provided as an amorphous matrix with nanocrystals distributed throughout. The nanocrystals may have a mean diameter of about 50 nm or less, in some cases a mean diameter between about 1-10.
These and other features and advantages of the disclosed embodiments will be described in further detail below, with reference to the associated drawings.
The following detailed description can be more fully understood when considered in conjunction with the drawings in which:
Electrochromic Devices
A schematic cross-section of an electrochromic device 100 in accordance with some embodiments is shown in
A voltage source 116 operable to apply an electric potential across the electrochromic stack 120 effects the transition of the electrochromic device from, e.g., a clear state to a tinted state. In other embodiments, the order of layers is reversed with respect to the substrate. That is, the layers are in the following order: substrate, conductive layer, counter electrode layer, ion conducting layer, electrochromic material layer, conductive layer.
It should be understood that the reference to a transition between a clear state and tinted state is non-limiting and suggests only one example, among many, of an electrochromic transition that may be implemented. Unless otherwise specified herein, whenever reference is made to a clear-tinted transition, the corresponding device or process encompasses other optical state transitions such as non-reflective-reflective, transparent-opaque, etc. Further the terms “clear” and “bleached” refer to an optically neutral state, e.g., untinted, transparent or translucent. Still further, unless specified otherwise herein, the “color” or “tint” of an electrochromic transition is not limited to any particular wavelength or range of wavelengths. As understood by those of skill in the art, the choice of appropriate electrochromic and counter electrode materials governs the relevant optical transition. In various embodiments herein, a counter electrode is fabricated to include nickel, tungsten, niobium, and oxygen, sometimes referred to as nickel tungsten niobium oxide or NiWNbO. The individual elements may be present at varying levels/concentrations. In certain embodiments, for instance, a NiWNbO counter electrode may have a composition that falls within the various composition ranges disclosed herein.
In certain embodiments, the electrochromic device reversibly cycles between a clear state and a tinted state. In the clear state, a potential is applied to the electrochromic stack 120 such that available ions in the stack that can cause the electrochromic material 106 to be in the tinted state reside primarily in the counter electrode 110. When the potential on the electrochromic stack is reversed, the ions are transported across the ion conducting layer 108 to the electrochromic material 106 and cause the material to enter the tinted state.
In certain embodiments, all of the materials making up electrochromic stack 120 are inorganic, solid (i.e., in the solid state), or both inorganic and solid. Because organic materials tend to degrade over time, inorganic materials offer the advantage of a reliable electrochromic stack that can function for extended periods of time. Materials in the solid state also offer the advantage of not having containment and leakage issues, as materials in the liquid state often do. Each of the layers in the electrochromic device is discussed in detail, below. It should be understood that any one or more of the layers in the stack may contain some amount of organic material, but in many implementations one or more of the layers contains little or no organic matter. The same can be said for liquids that may be present in one or more layers in small amounts. It should also be understood that solid state material may be deposited or otherwise formed by processes employing liquid components such as certain processes employing sol-gels or chemical vapor deposition.
Referring again to
Any material having suitable optical, electrical, thermal, and mechanical properties may be used as substrate 102. Such substrates include, for example, glass, plastic, and mirror materials. Suitable plastic substrates include, for example acrylic, polystyrene, polycarbonate, allyl diglycol carbonate, SAN (styrene acrylonitrile copolymer), poly(4-methyl-1-pentene), polyester, polyamide, etc. If a plastic substrate is used, it is preferably barrier protected and abrasion protected using a hard coat of, for example, a diamond-like protection coating, a silica/silicone anti-abrasion coating, or the like, such as is well known in the plastic glazing art. Suitable glasses include either clear or tinted soda lime glass, including soda lime float glass. The glass may be tempered or untempered. In some embodiments of electrochromic device 100 with glass, e.g. soda lime glass, used as substrate 102, there is a sodium diffusion barrier layer (not shown) between substrate 102 and conductive layer 104 to prevent the diffusion of sodium ions from the glass into conductive layer 104.
In some embodiments, the optical transmittance (i.e., the ratio of transmitted radiation or spectrum to incident radiation or spectrum) of substrate 102 is about 40 to 95%, e.g., about 90-92%. The substrate may be of any thickness, as long as it has suitable mechanical properties to support the electrochromic stack 120. While the substrate 102 may be of any size, in some embodiments, it is about 0.01 mm to 10 mm thick, preferably about 3 mm to 9 mm thick.
In some embodiments, the substrate is architectural glass. Architectural glass is glass that is used as a building material. Architectural glass is typically used in commercial buildings, but may also be used in residential buildings, and typically, though not necessarily, separates an indoor environment from an outdoor environment. In certain embodiments, architectural glass is at least 20 inches by 20 inches, and can be much larger, e.g., as large as about 72 inches by 120 inches. Architectural glass is typically at least about 2 mm thick. Architectural glass that is less than about 3.2 mm thick cannot be tempered. In some embodiments with architectural glass as the substrate, the substrate may still be tempered even after the electrochromic stack has been fabricated on the substrate. In some embodiments with architectural glass as the substrate, the substrate is a soda lime glass from a tin float line.
On top of substrate 102 is conductive layer 104. In certain embodiments, one or both of the conductive layers 104 and 114 is inorganic and/or solid. Conductive layers 104 and 114 may be made from a number of different materials, including conductive oxides, thin metallic coatings, conductive metal nitrides, and composite conductors. Typically, conductive layers 104 and 114 are transparent at least in the range of wavelengths where electrochromism is exhibited by the electrochromic layer. Transparent conductive oxides include metal oxides and metal oxides doped with one or more metals. Examples of such metal oxides and doped metal oxides include indium oxide, indium tin oxide, doped indium oxide, tin oxide, doped tin oxide, zinc oxide, aluminum zinc oxide, doped zinc oxide, ruthenium oxide, doped ruthenium oxide and the like.
Since oxides are often used for these layers, they are sometimes referred to as “transparent conductive oxide” (TCO) layers. Thin metallic coatings that are substantially transparent may also be used. Examples of metals used for such thin metallic coatings include transition metals including gold, platinum, silver, aluminum, nickel alloy, and the like. Thin metallic coatings based on silver, well known in the glazing industry, are also used. Examples of conductive nitrides include titanium nitrides, tantalum nitrides, titanium oxynitrides, and tantalum oxynitrides. The conductive layers 104 and 114 may also be composite conductors. Such composite conductors may be fabricated by placing highly conductive ceramic and metal wires or conductive layer patterns on one of the faces of the substrate and then over-coating with transparent conductive materials such as doped tin oxides or indium tin oxide. Ideally, such wires should be thin enough as to be invisible to the naked eye (e.g., about 100 μm or thinner).
In some embodiments, commercially available substrates such as glass substrates contain a transparent conductive layer coating. Such products may be used for both substrate 102 and conductive layer 104. Examples of such glasses include conductive layer coated glasses sold under the trademark TEC Glass™ by Pilkington, of Toledo, Ohio and SUNGATE™ 300 and SUNGATE™ 500 by PPG Industries of Pittsburgh, Pennsylvania TEC Glass™ is a glass coated with a fluorinated tin oxide conductive layer. In other embodiments the substrate may be annealed glass, e.g. thin glass made by Corning, Inc. of Corning NY, such as Gorilla Glass™, Willow Glass™ Eagle Glass™ and the like.
In some embodiments, the same conductive layer is used for both conductive layers (i.e., conductive layers 104 and 114). In some embodiments, different conductive materials are used for each conductive layer 104 and 114. For example, in some embodiments, TEC Glass™ is used for substrate 102 (float glass) and conductive layer 104 (fluorinated tin oxide) and indium tin oxide is used for conductive layer 114. As noted above, in some embodiments employing TEC Glass™ there is a sodium diffusion barrier between the glass substrate 102 and TEC conductive layer 104. Some glasses are low sodium and do not require a sodium diffusion barrier.
The function of the conductive layers is to spread an electric potential provided by voltage source 116 over surfaces of the electrochromic stack 120 to interior regions of the stack, with very little ohmic potential drop. The electric potential is transferred to the conductive layers though electrical connections to the conductive layers. In some embodiments, bus bars, one in contact with conductive layer 104 and one in contact with conductive layer 114, provide the electric connection between the voltage source 116 and the conductive layers 104 and 114. The conductive layers 104 and 114 may also be connected to the voltage source 116 with other conventional means.
In some embodiments, the thickness of conductive layers 104 and 114 is between about 5 nm and about 10,000 nm. In some embodiments, the thickness of conductive layers 104 and 114 are between about 10 nm and about 1,000 nm. In other embodiments, the thickness of conductive layers 104 and 114 are between about 10 nm and about 500 nm.
The thickness of the each conductive layer 104 and 114 is also substantially uniform. Smooth layers (i.e., low roughness, Ra) of the conductive layer 104 are desirable so that other layers of the electrochromic stack 120 are more compliant. The sheet resistance (Rs) of the conductive layers is also important because of the relatively large area spanned by the layers. In some embodiments, the sheet resistance of conductive layers 104 and 114 is about 1 to 30 Ohms per square. In some embodiments, the sheet resistance of conductive layers 104 and 114 is about 15 Ohms per square. In general, it is desirable that the sheet resistance of each of the two conductive layers be about the same. In one embodiment, the two layers each have a sheet resistance of about 10-15 Ohms per square. In certain embodiments conductive layers may be themselves stack structures, e.g., a stack of transparent conductive oxide/metal/transparent conductive oxide, e.g., ITO/Ag/ITO and similar transparent conductive layers known to skilled artisans. In such layers, e.g., the metal inner layer is typically thin enough so as to be transparent, e.g., between about 0.5 nm and about 20 nm thick, or between about 1 nm and about 10 nm thick, or between about 1 nm and about 5 nm thick. The metal interlayer, e.g., silver, may be doped with other metals to increase its flexibility and/or ductility, e.g., silver interlayers may be doped with bismuth, beryllium and/or other metals. Such dopants may be, e.g., between about 1% to 25% by weight of the metal interlayer, e.g., between about 1% and about 20%, e.g., between about 1% and about 10%, e.g., between about 1% and about 5%.
Overlaying conductive layer 104 is cathodically coloring layer 106 (also referred to as electrochromic layer 106). In certain embodiments, electrochromic layer 106 is inorganic and/or solid, in typical embodiments inorganic and solid. The electrochromic layer may contain any one or more of a number of different cathodically coloring electrochromic materials, including metal oxides. Such metal oxides include, e.g., tungsten oxide (WO3), molybdenum oxide (MoO3), niobium oxide (Nb2O5), titanium oxide (TiO2), vanadium oxide (V2O5) and tantalum oxide (Ta2O5). In some embodiments, the cathodically coloring metal oxide is doped with one or more dopants such as lithium, sodium, potassium, molybdenum, vanadium, titanium, and/or other suitable metals or compounds containing metals. Such dopants can be cathodically coloring, anodically coloring, or non-electrochromic, so long as the bulk material is cathodically coloring. For example, mixed oxides (e.g., W—Mo oxide, W—V oxide) are also used in certain embodiments. An electrochromic layer 106 comprising a metal oxide is capable of receiving ions transferred from counter electrode layer 110.
In some embodiments, tungsten oxide or doped tungsten oxide is used for electrochromic layer 106. In one embodiment, the electrochromic layer is made substantially of WOx, where “x” refers to an atomic ratio of oxygen to tungsten in the electrochromic layer, and x is between about 2.7 and 3.5. It has been suggested that only sub-stoichiometric tungsten oxide exhibits electrochromism; i.e., stoichiometric tungsten oxide, WO3, does not exhibit electrochromism. In a more specific embodiment, WOx, where x is less than 3.0 and at least about 2.7 is used for the electrochromic layer. In another embodiment, the electrochromic layer is WOx, where x is between about 2.7 and about 2.9. Techniques such as Rutherford Backscattering Spectroscopy (RBS) can identify the total number of oxygen atoms which include those bonded to tungsten and those not bonded to tungsten. In some instances, tungsten oxide layers where x is 3 or greater exhibit electrochromism, presumably due to unbound excess oxygen along with sub-stoichiometric tungsten oxide. In another embodiment, the tungsten oxide layer has stoichiometric or greater oxygen, where x is 3.0 to about 3.5.
In certain embodiments, the tungsten oxide is crystalline, nanocrystalline, or amorphous. In some embodiments, the tungsten oxide is substantially nanocrystalline, with grain sizes, on average, from about 5 nm to 50 nm (or from about 5 nm to 20 nm), as characterized by transmission electron microscopy (TEM). The tungsten oxide morphology may also be characterized as nanocrystalline using x-ray diffraction (XRD). For example, nanocrystalline electrochromic tungsten oxide may be characterized by the following XRD features: a crystal size of about 10 to 100 nm (e.g., about 55 nm. Further, nanocrystalline tungsten oxide may exhibit limited long range order, e.g., on the order of several (about 5 to 20) tungsten oxide unit cells.
The thickness of the electrochromic layer 106 depends on the cathodically coloring material selected for the electrochromic layer. In some embodiments, the electrochromic layer 106 is about 50 nm to 2,000 nm, or about 200 nm to 700 nm. In some embodiments, the electrochromic layer is about 300 nm to about 500 nm. The thickness of the electrochromic layer 106 is also substantially uniform. In one embodiment, a substantially uniform electrochromic layer varies only about ±10% in each of the aforementioned thickness ranges. In another embodiment, a substantially uniform electrochromic layer varies only about +5% in each of the aforementioned thickness ranges. In another embodiment, a substantially uniform electrochromic layer varies only about ±3% in each of the aforementioned thickness ranges.
Generally, in cathodically coloring electrochromic materials, the colorization/tinting (or change in any optical property—e.g., absorbance, reflectance, and transmittance) of the electrochromic material is caused by reversible ion insertion into the material (e.g., intercalation) and a corresponding injection of a charge balancing electron. Typically some fraction of the ion responsible for the optical transition is irreversibly bound up in the electrochromic material. As explained below, some or all of the irreversibly bound ions are used to compensate “blind charge” in the material. In most electrochromic materials, suitable ions include lithium ions (Li+) and hydrogen ions (H+) (i.e., protons). In some cases, however, other ions will be suitable. These include, for example, deuterium ions (D+), sodium ions (Na+), potassium ions (K+), calcium ions (Ca++), barium ions (Ba++), strontium ions (Sr++), and magnesium ions (Mg++). In various embodiments described herein, lithium ions are used to produce the electrochromic phenomena. Intercalation of lithium ions into tungsten oxide (WO3-y (0<y≤˜0.3)) causes the tungsten oxide to change from transparent (clear state) to blue (tinted state).
Referring again to
In various embodiments, the anodically coloring counter electrode material includes nickel, tungsten, niobium, and oxygen. The materials may be provided together as NiWNbO, at any appropriate composition. The NiWNbO material is especially beneficial as an anodically coloring material because it is particularly clear or color neutral in the clear state. Many counter electrode materials are slightly tinted (colored) even in their clear states. For instance, NiO is brown and NiWO generally has a slight yellow tint in the clear state. For aesthetic reasons, it is preferable that both the cathodically coloring and anodically coloring materials in an electrochromic device are very clear (transparent) and colorless when the device is in the clear state.
Further, some counter electrode materials exhibit good color qualities (i.e., are very clear in their clear state), but are unsuitable for commercial use because the materials' ability to undergo rapid optical transitions fades over time. In other words, for these materials the duration of an optical transition increases with the age/use of the device. In this case, a newly fabricated window would exhibit higher switching speeds than an identical window that has been in use for e.g., six months. One example of an anodically coloring counter electrode material that shows good color quality but decreasing transition speed over time is nickel tantalum oxide (NiTaO). By contrast, NiWNbO is a valuable candidate for the anodically coloring counter electrode material because it exhibits good color qualities and maintains good switching speeds over long periods of use.
The NiWNbO may have various compositions when used as an anodically coloring material. In certain embodiments, particular balances may be made between the various components of the NiWNbO. For instance, an atomic ratio of Ni:(W+Nb) in the material may fall between about 1.5:1 and 3:1, for example between about 1.5:1 and 2.5:1, or between about 2:1 and 2.5:1. In a particular example the atomic ratio of Ni:(W+Nb) is between about 2:1 and 3:1. The atomic ratio of Ni:(W+Nb) relates to the ratio of (i) nickel atoms in the material to (ii) the sum of the number of tungsten and niobium atoms in the material.
The NiWNbO material may also have a particular atomic ratio of W:Nb. In certain embodiments, the atomic ratio of W:Nb is between about 0.1:1 and 6:1, for example between about 0.2:1 and 5:1, or between about 1:1 and 3:1, or between about 1.5:1 and 2.5:1, or between about 1.5:1 and 2:1. In some cases the atomic ratio of W:Nb is between about 0.2:1 and 1:1, or between about 1:1 and 2:1, or between about 2:1 and 3:1, or between about 3:1 and 4:1, or between about 4:1 and 5:1. In some implementations, particular atomic ratios of Ni:(W+Nb) and W:Nb are used. All combinations of disclosed Ni:(W+Nb) compositions and disclosed W:Nb compositions are contemplated, though only certain combinations are explicitly listed herein. For instance, the atomic ratio of Ni:(W+Nb) may be between about 1.5:1 and 3:1, where the atomic ratio of W:Nb is between about 1.5:1 and 3:1. In another example, the atomic ratio of Ni:(W+Nb) may be between about 1.5:1 and 2.5:1, where the atomic ratio of W:Nb is between about 1.5:1 and 2.5:1. In a further example, the atomic ratio of Ni:(W+Nb) may be between about 2:1 and 2.5:1, where the atomic ratio of W:Nb is between about 1.5:1 and 2:1, or between about 0.2:1 and 1:1, or between about 1:1 and 2:1, or between about 4:1 and 5:1.
Other example materials for the counter electrode include, but are not limited to, nickel oxide, nickel tungsten oxide, nickel vanadium oxide, nickel chromium oxide, nickel aluminum oxide, nickel manganese oxide, nickel magnesium oxide, chromium oxide, iron oxide, cobalt oxide, rhodium oxide, iridium oxide, manganese oxide, Prussian blue. The materials (e.g., metal and oxygen) may be provided at different stoichiometric ratios as appropriate for a given application. Optically passive counter electrodes may be used in some cases. In certain embodiments, the counter electrode material may comprise cerium titanium oxide, cerium zirconium oxide, nickel oxide, nickel-tungsten oxide, vanadium oxide, and mixtures of oxides (e.g., a mixture of NiO and/or Ni2O3 with WO3). Doped formulations of these oxides may also be used, with dopants including, e.g., tantalum, niobium, tungsten, etc.
Because anodically coloring counter electrode layer 110 contains the ions used to produce the electrochromic phenomenon in the cathodically coloring electrochromic material when the cathodically coloring electrochromic material is in the clear state, the anodically coloring counter electrode preferably has high transmittance and a neutral color when it holds significant quantities of these ions.
When charge is removed from an anodically coloring counter electrode 110, e.g., made of conventional nickel tungsten oxide (i.e., ions are transported from the counter electrode 110 to the electrochromic layer 106), the counter electrode layer will turn from a (more or less) transparent state to a brown tinted state. Similarly, when charge is removed from an anodically coloring counter electrode 110 made of NiWNbO, the counter electrode layer will turn from a transparent state to a brown tinted state. However, the transparent state of a NiWNbO counter electrode layer may be clearer, having less color (particularly less yellow color, for example) than the transparent state of a NiWO counter electrode layer.
The counter electrode morphology may be crystalline, amorphous, or some mixture thereof. Crystalline phases may be nanocrystalline. In some embodiments, the nickel-tungsten-niobium-oxide (NiWNbO) counter electrode material is amorphous or substantially amorphous. Various substantially amorphous counter electrodes have been found to perform better, under some conditions, in comparison to their crystalline counterparts. The amorphous state of the counter electrode oxide material may be obtained through the use of certain processing conditions, described below. While not wishing to be bound to any theory or mechanism, it is believed that amorphous nickel-tungsten oxide or nickel-tungsten-niobium oxide is produced by relatively low energy atoms in the sputtering process. Low energy atoms are obtained, for example, in a sputtering process with lower target powers, higher chamber pressures (i.e., lower vacuum), and/or larger source to substrate distances. Amorphous films are also more likely to form where there is a relatively higher fraction/concentration of heavy atoms (e.g., W). Under the described process conditions films with better stability under UV/heat exposure are produced. Substantially amorphous materials may have some crystalline, typically but not necessarily nanocrystalline, material dispersed in the amorphous matrix. The grain size and amounts of such crystalline materials are described in more detail below.
In some embodiments, the counter electrode morphology may include microcrystalline, nanocrystalline and/or amorphous phases. For example, the counter electrode may be, e.g., a material with an amorphous matrix having nanocrystals distributed throughout. In certain embodiments, the nanocrystals constitute about 50% or less of the counter electrode material, about 40% or less of the counter electrode material, about 30% or less of the counter electrode material, about 20% or less of the counter electrode material or about 10% or less of the counter electrode material (by weight or by volume depending on the embodiment). In certain embodiments, the nanocrystals have a maximum diameter of less than about 50 nm, in some cases less than about 25 nm, less than about 10 nm, or less than about 5 nm. In some cases, the nanocrystals have a mean diameter of about 50 nm or less, or about 10 nm or less, or about 5 nm or less (e.g., about 1-10 nm).
In certain embodiments, it is desirable to have a nanocrystal size distribution where at least about 50% of the nanocrystals have a diameter within 1 standard deviation of the mean nanocrystal diameter, for example where at least about 75% of the nanocrystals have a diameter within 1 standard deviation of the mean nanocrystal diameter or where at least about 90% of the nanocrystals have a diameter within 1 standard deviation of the mean nanocrystal diameter.
It has been found that counter electrodes that include an amorphous matrix tend to operate more efficiently compared to counter electrodes that are relatively more crystalline. In certain embodiments, the additive may form a host matrix in which domains of the base anodically coloring material may be found. In various cases, the host matrix is substantially amorphous. In certain embodiments, the only crystalline structures in the counter electrode are formed from a base anodically coloring electrochromic material in, e.g., oxide form. One example of a base anodically coloring electrochromic material in oxide form is nickel tungsten oxide. Additives may contribute to forming an amorphous host matrix that is not substantially crystalline, but which incorporates domains (e.g., nanocrystals in some cases) of the base anodically coloring electrochromic material. One example additive is niobium. In other embodiments, the additive and the anodically coloring base material together form a chemical compound with covalent and/or ionic bonding. The compound may be crystalline, amorphous, or a combination thereof. In other embodiments, the anodically coloring base material forms a host matrix in which domains of the additive exist as discrete phases or pockets. For example certain embodiments include an amorphous counter electrode having an amorphous matrix of a first material, with a second material, also amorphous, distributed throughout the first material in pockets, for example, pockets of the diameters described herein for crystalline materials distributed throughout an amorphous matrix.
In some embodiments, the thickness of the counter electrode is about 50 nm about 650 nm. In some embodiments, the thickness of the counter electrode is about 100 nm to about 400 nm, sometimes in the range of about 150 nm to 300 nm, or between about 200 nm to 300 nm. The thickness of the counter electrode layer 110 is also substantially uniform. In one embodiment, a substantially uniform counter electrode layer varies only about ±10% in each of the aforementioned thickness ranges. In another embodiment, a substantially uniform counter electrode layer varies only about ±5% in each of the aforementioned thickness ranges. In another embodiment, a substantially uniform counter electrode layer varies only about ±3% in each of the aforementioned thickness ranges.
The amount of ions held in the counter electrode layer during the clear state (and correspondingly in the electrochromic layer during the tinted state) and available to drive the electrochromic transition depends on the composition of the layers as well as the thickness of the layers and the fabrication method. Both the electrochromic layer and the counter electrode layer are capable of supporting available charge (in the form of lithium ions and electrons) in the neighborhood of several tens of millicoulombs per square centimeter of layer surface area. The charge capacity of an electrochromic film is the amount of charge that can be loaded and unloaded reversibly per unit area and unit thickness of the film by applying an external voltage or potential. In one embodiment, the WO3 layer has a charge capacity of between about 30 and about 150 mC/cm2/micron. In another embodiment, the WO3 layer has a charge capacity of between about 50 and about 100 mC/cm2/micron. In one embodiment, the NiWNbO layer has a charge capacity of between about 75 and about 200 mC/cm2/micron. In another embodiment, the NiWNbO layer has a charge capacity of between about 100 and about 150 mC/cm2/micron.
Returning to
In other embodiments, the ion conductor layer may be omitted. In such embodiments, no separate ion conductor material is deposited when forming an electrochromic stack for an electrochromic device. Instead, in these embodiments the cathodically coloring electrochromic material may be deposited in direct physical contact with the anodically coloring counter electrode material. One or both of the anodically coloring and cathodically coloring materials may be deposited to include a portion that is oxygen rich compared to the remaining portion of the material. Typically, the oxygen rich portion is in contact with the other type of layer. For instance, an electrochromic stack may include an anodically coloring material in contact with a cathodically coloring material, where the cathodically coloring material includes an oxygen-rich portion in direct physical contact with the anodically coloring material. In another example, an electrochromic stack includes an anodically coloring material in contact with a cathodically coloring material, where the anodically coloring material includes an oxygen-rich portion in direct physical contact with the cathodically coloring material. In a further example, both the anodically coloring material and the cathodically coloring material include an oxygen-rich portion, where the oxygen-rich portion of the cathodically coloring material is in direct physical contact with the oxygen-rich portion of the anodically coloring material. The oxygen-rich portions of these layers may be provided as distinct sub-layers (e.g., a cathodically or anodically coloring material includes an oxygen-rich sublayer and a less-oxygen-rich sublayer). The oxygen-rich portion of the layers may also be provided in a graded layer (e.g., the cathodically or anodically coloring material may include a gradient in oxygen concentration, the gradient being in a direction normal to the surface of the layers. Embodiments where the ion conductor layer is omitted and the anodically coloring counter electrode material is in direct contact with the cathodically coloring electrochromic material are further discussed in the following U.S. patents, each of which is herein incorporated by reference in its entirety: U.S. Pat. Nos. 8,300,298, and 8,764,950.
Returning to the embodiment of
In certain embodiments, the ion conducting layer is crystalline, amorphous, or a mixture thereof. Typically, the ion conducting layer is amorphous. In another embodiment, the ion conducting layer is nanocrystalline. In another embodiment, the ion conducting layer is a mixed amorphous and crystalline phase, where the crystalline phase is nanocrystalline.
The thickness of the ion conducting layer 108 may vary depending on the material. In some embodiments, the ion conducting layer 108 is about 5 nm to 100 nm thick, preferably about 10 nm to 60 nm thick. In some embodiments, the ion conducting layer is about 15 nm to 40 nm thick or about 25 nm to 30 nm thick. The thickness of the ion conducting layer is also substantially uniform.
Ions transported across the ion conducting layer between the electrochromic layer and the counter electrode layer serve to effect a color change in the electrochromic layer (i.e., change the electrochromic device from the clear state to the tinted state) when they reside in the electrochromic layer. For devices having anodically coloring counter electrode layers, the absence of these ions induces color in the counter electrode layer. Depending on the choice of materials for the electrochromic device stack, such ions include lithium ions (Li+) and hydrogen ions (H+) (i.e., protons). As mentioned above, other ions may be employed in certain embodiments. These include deuterium ions (D+), sodium ions (Na+), potassium ions (K+), calcium ions (Ca++), barium ions (Ba++), strontium ions (Sr++), and magnesium ions (Mg++). In certain embodiments, hydrogen ions are not used because side reactions during operation of the device cause recombination to hydrogen gas which may escape the device and degrade performance. Thus, ions that do not have this issue, for example lithium ions, may be used.
The electrochromic devices in embodiments herein are also scalable to substrates smaller or larger than architectural glass. An electrochromic stack can be deposited onto substrates that are a wide range of sizes, up to about 12 inches by 12 inches, or even 80 inches by 120 inches.
In some embodiments, electrochromic glass is integrated into an insulating glass unit (IGU). An insulating glass unit consists of multiple glass panes assembled into a unit, generally with the intention of maximizing the thermal insulating properties of a gas contained in the space formed by the unit while at the same time providing clear vision through the unit. Insulating glass units incorporating electrochromic glass would be similar to insulating glass units currently known in the art, except for electrical leads for connecting the electrochromic glass to voltage source. Due to the higher temperatures (due to absorption of radiant energy by an electrochromic glass) that electrochromic insulating glass units may experience, more robust sealants than those used in conventional insulating glass units may be necessary. For example, stainless steel spacer bars, high temperature polyisobutylene (PIB), new secondary sealants, foil coated PIB tape for spacer bar seams, and the like.
Heterogeneous Counter Electrode
As shown in
In certain embodiments, the counter electrode layer includes two or more sublayers, where the sublayers have different compositions and/or morphologies. One or more of such sublayers may also have a graded composition. The composition and/or morphology gradient may have any form of transition including a linear transition, a sigmoidal transition, a Gaussian transition, etc. A number of advantages can be realized by providing the counter electrode as two or more sublayers. For instance, the sublayers may be different materials that have complimentary properties. One material may promote better color quality while another material promotes high quality, long lifetime switching behavior. The combination of materials may promote a high degree of film quality and uniformity while at the same time achieving a high rate of deposition (and therefore throughput). Some of the approaches outlined herein may also promote better control of the lithium distribution throughout the electrochromic device, and in some cases may lead to improvements in morphology in the counter electrode (e.g., higher transmission) and the overall reduction of defects in the electrochromic device. Another benefit that may result from various embodiments herein is the availability of one or more intermediate states. Differences in electrical potentials between various sublayers may allow for lithium to reside in discrete locations (e.g., within particular sublayers to particular degrees), thereby enabling the electrochromic device to achieve intermediate tint states between e.g., a fully tinted device and a fully clear device. In some cases, intermediate states can be achieved by applying different voltages to the device. The inclusion of multiple sub-layers within the counter electrode layer may reduce or eliminate the need to apply different voltages to achieve different intermediate tint states. These and other benefits of the disclosed embodiments are further described below.
In some cases, a counter electrode includes a first sublayer of a first anodically coloring counter electrode material and one or more additional sublayers of a second anodically coloring counter electrode material. In various cases, the first sublayer of the CE layer may be situated closer to the cathodically coloring electrochromic material than the second (and optional additional) sublayer(s) of the CE layer. In some implementations, the first sublayer is a flash layer, which is generally characterized as a thin and often quickly deposited layer typically having a thickness of not greater than about 50 nm. The flash layer, if present, may or may not exhibit electrochromic properties. In certain embodiments, the flash layer is made of a counter electrode material that does not change color with remaining electrochromic/counter electrode layers (though this layer may have a composition that is very similar to other layers such as an anodically coloring layer). In some embodiments, the first sublayer/flash layer has a relatively high electronic resistivity, for example between about 1 and 5×1010 Ohm-cm.
Generally speaking, the first and second anodically coloring counter electrode materials may each, independently, be any anodically coloring counter electrode material. The first and/or second counter electrode materials may be binary metal oxides (e.g., oxides that include two metals in addition to lithium or other transported ion, NiWO being one example), ternary metal oxides (e.g., oxides that include three metals, NiWNbO being one example), or even more complex materials. In many cases the materials also include lithium, which to a certain extent may be mobile within the device.
In a particular example, the first anodically coloring material is NiWO. In these or other examples, the second anodically coloring material may be NiWO that is doped with or otherwise includes an additional metal (e.g., a non-alkali metal, a transition metal, a post-transition metal, or a metalloid in certain cases), with one example material being NiWNbO.
In some embodiments, the first and second anodically coloring materials contain the same elements, but in different proportions. For example, both materials may contain Ni, W, and Nb, but two or three of the elements may be present in different mass or atomic ratios. In some other embodiments, the first and second sublayers may be more significantly different from one another compositionally. For instance, the first and second sublayers (and any additional sublayers) may each be any anodically coloring material, regardless of the composition of the other sublayers.
The two or more sublayers may have different physical properties. In various cases, a material used in one or more of the sublayers is a material that would not perform well (e.g., would exhibit poor color quality, poor lifetime performance, slow switching speed, slow deposition rate, etc.) as a counter electrode material if provided without the accompanying sublayer(s).
The first and second sublayers 210a and 210b of the anodically coloring counter electrode layer 210 may have different compositions and/or morphologies. In various examples, the second sublayer 210b includes at least one metal and/or metal oxide that is not present in the first sublayer 210a. In a particular example, the first sublayer 210a is NiWO and the second sublayer 210b is NiWO doped or otherwise combined with another metal (e.g., NiWTaO, NiWSnO, NiWNbO, NiWZrO, etc.). In another embodiment, the first and second sublayers 210a and 210b include the same elements at different relative concentrations.
In some embodiments, the first sublayer 210a is a flash layer. Flash layers are typically thin layers (and as such they are typically, but not necessarily, deposited relatively quickly). In some embodiments, a first sublayer of an anodically coloring counter electrode is a flash layer that is between about 10-100 nm thick, for example between about 20-50 nm thick. In a number of embodiments, the first sublayer/flash layer may be a material that deposits at a higher deposition rate than the material of the remaining sublayers. Similarly, the flash layer may be deposited at a lower power than the remaining sublayers. The remaining sublayer(s) may be thicker than the first sublayer 210a in many embodiments. In certain embodiments where the counter electrode layer 210 includes two sublayers such as 210a and 210b, the second sublayer 210b may be between about 20-300 nm thick, for example between about 150-250 nm thick.
In certain embodiments, the second sublayer 210b is homogeneous with respect to composition.
In other embodiments, the second sublayer 210b may include a graded composition. The composition may be graded with respect to the relative concentration of a metal therein. For instance, in some cases the second sublayer 210b has a graded composition with respect to a metal that is not present in the first sublayer. In one particular example, the first sublayer is NiWO and the second sublayer is NiWNbO, where the concentration of niobium is graded throughout the second sublayer. The relative concentrations of the remaining elements (excluding the niobium) may be uniform throughout the second sublayer, or they may also change throughout this sublayer. In a particular example, the concentration of oxygen may also be graded within the second sublayer 210b (and/or within the first sublayer 210a).
In certain embodiments, the first and second sublayers may have compositions that are more different from one another.
In some embodiments, additional sublayers may be provided. The additional sublayers may be homogeneous with respect to composition, or they may be graded as described above. The trends described with relation to the first, second, and third sublayers of
In still another embodiment, the counter electrode may be provided as a single layer, but the composition of the counter electrode layer may be graded. The composition may be graded with respect to one or more elements present in the material. In some embodiments, the counter electrode has a graded composition with respect to one or more metals in the material. In these or other embodiments, the counter electrode may have a graded composition with respect to one or more non-metals, for example oxygen.
Without wishing to be bound by theory or mechanism of action, it is believed that the disclosed first sublayer may help protect the ion conducting layer and/or electrochromic layer from damage arising from excessive heating or other harsh condition during deposition of the counter electrode layer. The first sublayer may be deposited under conditions that are milder than those used to deposit the remaining sublayers. For instance, in some embodiments, the first sublayer may be deposited at a sputter power between about 5-20 kW/m2, and the second sublayer may be deposited at a sputter power between about 20-45 kW/m2. In one particular example where the first sublayer is NiWO and the second sublayer is NiWNbO, the NiWNbO may be deposited using higher sputtering power than the NiWO. This high power process, if performed to deposit directly on the ion conducting and/or electrochromic layer, might in some implementations degrade the ion conducting and/or electrochromic layer, for example due to excessive heating and premature crystallization of the relevant materials, and/or due to loss of oxygen in the ion conducting and/or electrochromic layer. However, where a thin flash layer of NiWO is provided as a first sublayer, this NiWO layer can be deposited under more gentle conditions. The NiWO sublayer may then protect the underlying ion conducting and/or electrochromic layer during deposition of subsequent NiWNbO sublayer(s). This protection may lead to a more reliable, better functioning electrochromic device.
The disclosed embodiments may also exhibit improved performance arising from higher quality morphology and improved morphology control within the anodically coloring materials. For example, by providing the counter electrode as two or more sublayers, one or more additional interfaces are introduced within the counter electrode (e.g., interfaces where the sublayers contact one another). These interfaces can disrupt the formation of crystals, for example due to renucleation and related grain growth effects. Such effects may act to prevent the crystals from growing larger and limit the size of any crystals that form. This effect on morphology may lead to fabrication of devices with fewer voids or other defects.
Without wishing to be bound by theory or mechanism of action, it is also believed that the disclosed methods may be used to achieve improved control over the distribution of lithium within an electrochromic device. Different counter electrode materials exhibit different affinities for lithium, and therefore the choice of counter electrode material(s) affects how the lithium ions are distributed in an electrochromic device. By selecting particular materials and combinations of materials, the distribution of lithium within the device can be controlled. In certain embodiments, the sublayers of the counter electrode include materials having different affinities for lithium. For instance, the material of the first sublayer may have a higher or lower affinity for lithium compared to the material of the second (or additional) sublayer(s) of the counter electrode.
Relatedly, the disclosed methods may be used to achieve improved control over the total amount of lithium used to fabricate an electrochromic device. In various cases, lithium may be added during deposition of the counter electrode layer. In some embodiments, lithium may be added during deposition of one or more sublayers of the counter electrode. In these or other embodiments, lithium may be added between depositions of subsequent sublayers of the counter electrode. By controlling the distribution of lithium and the total amount of lithium within the electrochromic device, device uniformity and appearance may be improved.
Another benefit that may arise with the disclosed techniques is improved color and switching performance. As mentioned above, certain counter electrode materials exhibit better performance in terms of color (e.g., clearer clear states, more attractive tinted states, etc.), switching speed, lifetime, and other properties. However, certain materials that promote high quality results with respect to one property may have drawbacks with respect to other properties. For instance, a material that is desirable because it exhibits a very transparent and uncolored clear state may suffer problems related to slow switching speed and/or short lifetime. By combining this material with another counter electrode material (which may have its own problems such as a relatively more yellow clear state), it is possible in various implementations to achieve a counter electrode with improved properties. The drawbacks related to one counter electrode material may be mitigated by properties of another counter electrode material.
Method of Fabricating Electrochromic Windows
Deposition of the Electrochromic Stack
As mentioned above, one aspect of the embodiments is a method of fabricating an electrochromic window. In a broad sense, the method includes sequentially depositing on a substrate (i) a cathodically coloring electrochromic layer, (ii) an optional ion conducting layer, and (iii) an anodically coloring counter electrode layer to form a stack in which the ion conducting layer separates the cathodically coloring electrochromic layer and the anodically coloring counter electrode layer. The sequential deposition employs a single integrated deposition system having a controlled ambient environment in which the pressure, temperature, and/or gas composition are controlled independently of an external environment outside of the integrated deposition system, and the substrate does not leave the integrated deposition system at any time during the sequential deposition of the electrochromic layer, the ion conducting layer, and the counter electrode layer. (Examples of integrated deposition systems which maintain controlled ambient environments are described in more detail below in relation to
Typically, but not necessarily, this method of fabrication is integrated into a multistep process for making an electrochromic window using architectural glass as the substrate. For convenience, the following description contemplates the method and its various embodiments in the context of a multistep process for fabricating an electrochromic window, but methods are not so limited. Electrochromic mirrors and other devices may be fabricated using some or all of the operations and approaches described herein.
Method 700 begins with a cleaning process, 705, where the substrate is cleaned to prepare it for subsequent processing. As mentioned above, it is important to remove contaminants from the substrate because they can cause defects in the device fabricated on the substrate. One critical defect is a particle or other contaminant that creates a conductive pathway across the IC layer and thus shorts the device locally causing visually discernable anomalies in the electrochromic window. One example of a cleaning process and apparatus suitable for the fabrication methods herein is Lisec™ (a trade name for a glass washing apparatus and process available from (LISEC Maschinenbau Gmbh of Seitenstetten, Austria).
Cleaning the substrate may include mechanical scrubbing as well as sonication conditioning to remove unwanted particulates. As mentioned, particulates may lead to cosmetic flaws as well as local shorting within the device.
Once the substrate is cleaned, a first laser scribe process, 710, is performed in order to remove a line of the first TCO layer on the substrate. In one embodiment, the resulting trench ablates through both the TCO and the diffusion barrier (although in some cases the diffusion barrier is not substantially penetrated).
The laser trench is dug along a side of the substrate from end to end to isolate a portion of the first TCO layer; the depth and width dimensions of trench 620 made via first laser scribe 710 should be sufficient to isolate the first TCO layer from the bulk TCO once the device is subsequently deposited. The depth and width of the trench should be sufficient to prevent any remaining particulates to short across the trench. In one embodiment, the trench is between about 300 nm and 900 nm deep (e.g., between about 300 nm and 500 nm) and between about 20 μm and 50 μm wide. In another embodiment, the trench is between about 350 nm and 450 nm deep and between about 30 μm and 45 μm wide. In another embodiment, the trench is about 400 nm deep and about 40 μm wide.
After the first laser scribe 710, the substrate is cleaned again (operation 715), typically but not necessarily, using cleaning methods described above. This second cleaning process is performed to remove any debris caused by the first laser scribe. Once cleaning operation 715 is complete, the substrate is ready for deposition of EC stack 625. This is depicted in process flow 700 as process 720. As mentioned above, the method includes sequentially depositing on a substrate (i) a cathodically coloring EC layer, (ii) an optional IC layer, and (iii) an anodically coloring CE layer (e.g., NiWNbO in various embodiments) to form a stack in which the IC layer separates the EC layer and the CE layer using a single integrated deposition system having a controlled ambient environment in which the pressure and/or gas composition are controlled independently of an external environment outside of the integrated deposition system, and the substrate does not leave the integrated deposition system at any time during the sequential deposition of the EC layer, the IC layer, and the CE layer. In one embodiment, each of the sequentially deposited layers is physical vapor deposited. In general the layers of the electrochromic device may be deposited by various techniques including physical vapor deposition, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition, to name a few. The term physical vapor deposition as used herein includes the full range of art understood PVD techniques including sputtering, evaporation, ablation, and the like.
It should be understood that while certain embodiments are described in terms of a counter electrode layer, an ion conductor layer, and an electrochromic layer, any one or more of these layers may be composed of one or more sub-layers, which may have distinct compositions, sizes, morphologies, charge densities, optical properties, etc. Further any one or more of the device layers may have a graded composition or a graded morphology in which the composition or morphology, respectively, changes over at least a portion of the thickness of the layer. In one example, the concentration of oxygen, a dopant, or charge carrier varies within a given layer, at least as the layer is fabricated. In another example, the morphology of a layer varies from crystalline to amorphous. Such graded composition or morphology may be chosen to impact the functional properties of the device. In some cases, additional layers may be added to the stack. In one example a heat spreader layer is interposed between one or both TCO layers and the EC stack.
Also, as described above, the electrochromic devices of certain embodiments utilize ion movement between the electrochromic layer and the counter electrode layer via an ion conducting layer. In some embodiments these ions (or neutral precursors thereof) are introduced to the stack as one or more layers (as described below in more detail in relation to
Referring again to process 722 in
It should be understood that while deposition of the EC layer is described in terms of sputtering from a target, other deposition techniques are employed in some embodiments. For example, chemical vapor deposition, atomic layer deposition, and the like may be employed. Each of these techniques, along with PVD, has its own form of material source as is known to those of skill in the art.
Referring again to
Referring again to
In certain embodiments where the anodically coloring counter electrode layer includes NiWNbO, many deposition targets or combinations of targets may be used. For instance, individual metal targets of nickel, tungsten, and niobium can be used. In other cases at least one of the targets includes an alloy. For instance, an alloy target of nickel-tungsten can be used together with a metal niobium target. In another case, an alloy target of nickel-niobium can be used together with a metal tungsten target. In a further case, an alloy of tungsten-niobium can be used together with a metal nickel target. In yet a further case, an alloy target containing a nickel-tungsten-niobium material may be used. Moreover, any of the listed targets can be provided as an oxide. Oftentimes, sputtering occurs in the presence of oxygen, and such oxygen is incorporated into the material. Sputter targets containing oxygen may be used alternatively or in addition to an oxygen-containing sputtering atmosphere.
The sputtering target(s) for forming the anodically coloring counter electrode material may have compositions that permit the counter electrode to be formed at any of the compositions described herein. In one example where a single sputter target is used, the sputter target may have a composition that matches the composition of any of the NiWNbO materials disclosed herein. In other examples a combination of sputter targets are used, and the composition of the combined targets allows for deposition at any of the NiWNbO materials disclosed herein. Further, the sputter targets may be arranged in any way that permits the material to be deposited as desired, as discussed further below.
In one embodiment, the gas composition used when forming the CE contains between about 30% and about 100% oxygen, in another embodiment between about 80% and about 100% oxygen, in yet another embodiment between about 95% and about 100% oxygen, in another embodiment about 100% oxygen. In one embodiment, the power density used to sputter the CE target is between about 2 Watts/cm2 and about 50 Watts/cm2 (determined based on the power applied divided by the surface area of the target); in another embodiment between about 5 Watts/cm2 and about 20 Watts/cm2; and in yet another embodiment between about 8 Watts/cm2 and about 10 Watts/cm2, in another embodiment about 8 Watts/cm2. In some embodiments, the power delivered to effect sputtering is provided via direct current (DC). In other embodiments, pulsed DC/AC reactive sputtering is used. In one embodiment, where pulsed DC/AC reactive sputtering is used, the frequency is between about 20 kHz and about 400 kHz, in another embodiment between about 20 kHz and about 50 kHz, in yet another embodiment between about 40 kHz and about 50 kHz, in another embodiment about 40 kHz.
The pressure in the deposition station or chamber, in one embodiment, is between about 1 and about 50 mTorr, in another embodiment between about 20 and about 40 mTorr, in another embodiment between about 25 and about 35 mTorr, in another embodiment about 30 mTorr. In some cases, a nickel tungsten oxide NiWO ceramic target is sputtered with, e.g., argon and oxygen. In one embodiment, the NiWO is between about 15% (atomic) Ni and about 60% Ni; between about 10% W and about 40% W; and between about 30% O and about 75% O. In another embodiment, the NiWO is between about 30% (atomic) Ni and about 45% Ni; between about 10% W and about 25% W; and between about 35% O and about 50% O. In one embodiment, the NiWO is about 42% (atomic) Ni, about 14% W, and about 44% O. In another embodiment, depositing the counter electrode layer includes depositing the counter electrode layer to a thickness of between about 150 and 350 nm; in yet another embodiment between about 200 and about 250 nm thick. The above conditions may be used in any combination with one another to effect deposition of a high quality NiWNbO layer.
The sputtering process for forming the CE layer may utilize one or more sputter targets. In one example where one sputter target is used, the target may include nickel, tungsten, and niobium. In some cases the sputter target also includes oxygen. The sputter target may include a grid or other overlapping shape where different portions of the grid include the different relevant materials (e.g., certain portions of the grid may include elemental nickel, elemental tungsten, elemental niobium, a nickel-tungsten alloy, a nickel-niobium alloy, and/or a tungsten-niobium alloy). In some cases, a sputter target may be an alloy of the relevant materials (e.g., two or more of nickel, tungsten, and niobium). Where two or more sputter targets are used, each sputter target may include at least one of the relevant materials (e.g., elemental and/or alloy forms of nickel, tungsten, and/or niobium, any of which can be provided in oxide form). The sputter targets may overlap in some cases. The sputter targets may also rotate in some embodiments. As noted, the counter electrode layer is typically an oxide material. Oxygen may be provided as a part of the sputter target and/or sputter gas. In certain cases, the sputter targets are substantially pure metals, and sputtering is done in the presence of oxygen to form the oxide.
In one embodiment, in order to normalize the rate of deposition of the CE layer, multiple targets are used so as to obviate the need for inappropriately high power (or other inappropriate adjustment to desired process conditions) to increase deposition rate. In one embodiment, the distance between the CE target (cathode or source) to the substrate surface is between about 35 mm and about 150 mm; in another embodiment between about 45 mm and about 130 mm; and in another embodiment between about 70 mm and about 100 mm.
As noted, one or more rotating targets may be used in some cases. In various cases, a rotating target may include an interior magnet.
In one example, two rotating targets are used to deposit a NiWNbO anodically coloring EC layer: a first target including nickel and tungsten, and a second target including niobium (either or both optionally in oxide form).
In a similar embodiment to the one shown in
Various sputter target designs, orientations, and implementations are further discussed in U.S. patent application Ser. No. 13/462,725, filed May 2, 2012, and titled “ELECTROCHROMIC DEVICES,” which is herein incorporated by reference in its entirety.
The density and orientation/shape of material that sputters off of a sputter target depends on various factors including, for example, the magnetic field shape and strength, pressure, and power density used to generate the sputter plasma. The distance between adjacent targets, as well as the distance between each target and substrate, can also affect how the sputter plasmas will mix and how the resulting material is deposited on the substrate.
In certain embodiments, two different types of sputter targets are provided to deposit a single layer in an electrochromic stack: (a) primary sputter targets, which sputter material onto a substrate, and (b) secondary sputter targets, which sputter material onto the primary sputter targets. The primary and secondary sputter targets may include any combination of metal, metal alloys, and metal oxides that achieve a desired composition in a deposited layer. In one particular example, a primary sputter target includes an alloy of nickel and tungsten, and a secondary sputter target includes niobium. In another example a primary sputter target includes niobium and a secondary sputter target includes an alloy of nickel and tungsten. These sputter targets may be used together to deposit an anodically coloring layer of NiWNbO. Other combinations of alloys (e.g., nickel-niobium, tungsten-niobium) and metals (e.g., nickel, tungsten) can also be used. Any sputter target may be provided as an oxide.
A number of different setups are possible when using both primary and secondary sputter targets.
When material is sputtered off of the primary sputter target 1001 and deposited onto the substrate 1004, the deposited material includes material that originated from both the primary and secondary sputter targets 1001 and 1002, respectively. In effect, this method involves in-situ formation of an intermixed sputter target surface on the primary sputter target 1001. One advantage of this method is that a fresh coating of material from the secondary sputter target 1002 (e.g., in some cases this material is niobium, tungsten, nickel, or combinations and/or alloys thereof) is periodically deposited on the surface of the primary sputter target 1001. The intermixed materials are then delivered together to the substrate 1004.
In a related embodiment shown in
In similar embodiments, the secondary sputter target (e.g., the secondary target in
Where both a primary and a secondary sputter target are used, the secondary sputter target may be operated at a potential that is cathodic compared to the potential of the primary sputter target (which is already cathodic). Alternatively, the targets may be operated independently. Still further, regardless of relative target potentials, neutral species ejected from the secondary target will deposit on the primary target. Neutral atoms will be part of the flux, and they will deposit on a cathodic primary target regardless of relative potentials.
In various embodiments, reactive sputtering may be used to deposit one or more materials in the electrochromic stack.
In certain embodiments where two or more sputter targets are used to deposit a material in the electrochromic stack, one target may be operated in the metal deposition regime and another target may be operated in the metal oxide deposition regime. By controlling the target power density, magnetic strength of the internal magnet 1003, and the atmosphere to which each target is exposed/operated under over time, it is possible to operate at both of these regimes simultaneously. In one example, a first nickel tungsten target is exposed to a relatively low concentration of oxygen and then brought to a mid-level concentration of oxygen such that it operates in the metal deposition regime. A second niobium target is exposed to a relatively high concentration of oxygen and then brought to a mid-level concentration of oxygen such that it operates in the metal oxide deposition regime. The two targets can then be brought together, still exposed to the mid-level oxygen concentration, where they are used to deposit material onto a substrate under both regimes (the first target continuing to operate under the metal deposition regime and the second target continuing to operate under the metal oxide deposition regime).
The different atmosphere exposures for each target may not be needed in many cases. Other factors besides different historical oxygen exposure can result in the targets operating under the different deposition regimes. For instance, the targets may have different hysteresis curves due to the different material in the targets. As such, the targets may be able to operate under different regimes even if they are historically exposed to and operated under the same atmospheric oxygen conditions. Further, the amount of power applied to each target can significantly affect the deposition regime experienced by each target. In one example, therefore, one target is operated under a metal deposition regime and another target is operated under a metal oxide deposition regime due to the different powers applied to each target. This approach may be easier because it does not require separating the targets from one another such that they can be exposed to different oxygen concentrations. One advantage to operating the targets at different points in the hysteresis curves is that the composition of a deposited material can be closely controlled.
It should be understood that while the order of deposition operations is depicted in
Since the amount of charge each of the EC and the CE layers can safely hold varies, depending on the material used, the relative thickness of each of the layers may be controlled to match capacity as appropriate. In one embodiment, the electrochromic layer includes tungsten oxide and the counter electrode includes nickel tungsten niobium oxide, and the ratio of thicknesses of the electrochromic layer to the counter electrode layer is between about 1.7:1 and 2.3:1, or between about 1.9:1 and 2.1:1 (with about 2:1 being a specific example).
Referring again to
As mentioned, the EC stack is fabricated in an integrated deposition system where the substrate does not leave the integrated deposition system at any time during fabrication of the stack. In one embodiment, the second TCO layer is also formed using the integrated deposition system where the substrate does not leave the integrated deposition system during deposition of the EC stack and the TCO layer. In one embodiment, all of the layers are deposited in the integrated deposition system where the substrate does not leave the integrated deposition system during deposition; that is, in one embodiment the substrate is a glass sheet and a stack including the EC layer, the IC layer and the CE layer, sandwiched between a first and a second TCO layer, is fabricated on the glass where the glass does not leave the integrated deposition system during deposition. In another implementation of this embodiment, the substrate is glass with a diffusion barrier deposited prior to entry in the integrated deposition system. In another implementation the substrate is glass and the diffusion barrier, a stack including the EC layer, the IC layer and the CE layer, sandwiched between a first and a second TCO layer, are all deposited on the glass where the glass does not leave the integrated deposition system during deposition.
While not wishing to be bound by theory, it is believed that prior art electrochromic devices suffered from high defectivity for various reasons, one of which is the integration of unacceptably high numbers of particles into the IC layer during fabrication. Care was not taken to ensure that each of the EC layer, IC layer, and CE layer were deposited in a single integrated deposition apparatus under a controlled ambient environment. In one process, the IC layer is deposited by a sol gel process, which is necessarily performed apart from other vacuum integrated processes. In such process, even if the EC layer and/or the CE layer are deposited in a controlled ambient environment, thereby promoting high quality layers, the substrate would have to be removed from the controlled ambient environment to deposit the IC layer. This would normally involve passing the substrate through a load lock (from vacuum or other controlled ambient environment to an external environment) prior to formation of the IC layer. Passage through a load lock typically introduces numerous particles onto the substrate. Introducing such particles immediately before the IC layer is deposited greatly increases the likelihood that defects will form in the critical IC layer. Such defects lead to bright spots or constellations as discussed above.
As mentioned above, lithium may be provided with the EC, CE and/or IC layers as they are formed on the substrate. This may involve, for example, co-sputtering of lithium together with the other materials of a given layer (e.g., tungsten and oxygen). In certain embodiments described below the lithium is delivered via a separate process and allowed to diffuse or otherwise incorporate into the EC, CE and/or IC layers. In some embodiments, only a single layer in the electrochromic stack is lithiated. For example, only the anodically coloring CE layer is lithiated in some examples. In other cases, only the cathodically coloring EC layer is lithiated. In still other cases, only the IC layer is lithiated.
In some embodiments, the electrochromic stack includes a counter electrode layer in direct physical contact with an electrochromic layer, without an ion conducting layer in between. The electrochromic and/or counter electrode layer may include an oxygen-rich portion in contact with the other of these layers. The oxygen-rich portion includes the electrochromic material or counter electrode material, with a higher concentration of oxygen than in the remaining portion of the electrochromic layer and/or counter electrode layer. Electrochromic devices fabricated according to such a design are further discussed and described in U.S. Pat. No. 8,300,298, filed Apr. 30, 2010, which is incorporated by reference above.
In certain embodiments, fabrication of the electrochromic stack occurs in an integrated deposition system. Such an integrated system may allow for deposition of the various layers in the stack without breaking vacuum. In other cases, one or more layers in the stack may be deposited by a process that requires removal from a protected vacuum environment. For example, in some cases one or more layers (e.g., a cathodically coloring EC layer) is deposited on a substrate under vacuum using physical vapor deposition, then the substrate is removed from vacuum and an ion conductor layer is deposited using a sol-gel (or other non-vacuum) process, and then the substrate is returned to a vacuum environment for deposition of the anodically coloring counter electrode layer. Sol-gel processes involve producing solid materials from small molecules. Monomers are converted into a colloidal solution that acts as the precursor for an integrated network of discrete particles or network polymers. Examples of ion conductor materials that may be deposited include, for example, silicate-based structures, lithium silicate, lithium aluminum silicate, lithium aluminum borate, lithium borate, lithium Zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium aluminum fluoride, and other such lithium-based ceramic materials, silicas, or silicon oxides, silicon dioxide, and tantalum oxide.
Direct Lithiation of the Electrochromic Stack
In some embodiments, as mentioned above, intercalation of lithium ions is responsible for switching the optical state of an electrochromic device stack. It should be understood that the needed lithium may be introduced to the stack by various means. For example, lithium may be provided to one or more of these layers concurrently with the deposition of the material of the layer (e.g., concurrent deposition of lithium and tungsten oxide during formation of the EC layer). In some cases, however, the process of
In one embodiment of the dual lithiation method, as explained above, the EC layer is treated with sufficient lithium to satisfy the requirements of the EC material irreversibly bound lithium (to, e.g., compensate “blind charge”). The lithium needed for reversible cycling is added to the CE layer (which also may have a blind charge). In certain embodiments, the lithium needed to compensate the blind charge can be titrated by monitoring optical density of the EC layer as lithium is added since the EC layer will not substantially change color until sufficient lithium has been added to fully compensate the blind charge.
One of ordinary skill in the art would appreciate that because metallic lithium is pyrophoric, i.e., highly reactive with moisture and oxygen, that lithiation methods described herein where lithium might be exposed to oxygen or moisture are performed either under vacuum, inert atmosphere or both. The controlled ambient environment of apparatus and methods of the disclosed embodiments provides flexibility in lithium depositions, particularly where there are multiple lithiation steps. For example, where lithiation is performed in a titration process and/or among multiple steps in a stack layering, the lithium can be protected from exposure to oxygen or moisture.
In certain embodiments, the lithiation is performed at a rate sufficient to prevent formation of a substantial thickness of free lithium on the EC layer surface. In one embodiment, during lithiation of the EC layer, lithium targets are spaced sufficiently to give time for lithium to diffuse into the EC layer. Optionally, the substrate (and hence the EC layer) is heated to between about 100° C. and about 150° C. to enhance diffusion of lithium into the EC layer. Heating may be done separately or in combination with target spacing and substrate translation past the target(s). In some cases, the substrate is moved back and forth in front of a sputtered lithium target in order to slow the delivery of lithium to the substrate and prevent accumulation of free metallic lithium on the stack surface. Isolation protocols may be used for performing lithiation. Such protocols are further discussed in U.S. patent application Ser. No. 12/645,111, which is incorporated by reference above.
Multistep Thermochemical Conditioning
Referring again to
Referring to
As mentioned above, additional layers may be needed for improved optical performance (e.g. anti-reflectives), durability (due to physical handling), hermeticity, and the like. Addition of one or more of these layers is meant to be included in additional embodiments to those described above.
The lithiation and high temperature processing operations described herein can affect the composition and structure of various materials in the electrochromic stack. As one example, where an electrochromic stack includes a cathodically coloring EC layer in direct contact with an anodically coloring CE layer (with no separate ion conducting layer deposited in between them), the thermal processing operations can change the composition and/or structure of the cathodically coloring EC and anodically coloring CE layers at an interfacial region between these layers, to thereby form a region that has ion conducting, electronically insulating properties. Similarly, lithiation and thermal processing operations can affect the composition and structure of an anodically coloring counter electrode layer. In various cases an anodically coloring counter electrode layer is improved through such operations.
Fabrication Process for Completion of the Device
Again referring to
Next, a third laser scribe, 745, is performed along the perimeter of the stack near the edge of the substrate opposite the first laser scribe and parallel to the first laser scribe. This third laser scribe is only deep enough to isolate the second TCO layer and the EC stack, but not cut through the first TCO layer. Referring to
Referring again to process 700, in
Referring again to
In addition to the process steps described in relation to the methods above, an edge deletion step or steps may be added to the process flow. Edge deletion is part of a manufacturing process for integrating the electrochromic device into, e.g. a window, where the roll off (as described in relation to
In certain embodiments, a different process flow may be used to fabricate an electrochromic device. Alternative process flows are further discussed in U.S. patent application Ser. No. 14/362,863, filed Jun. 4, 2014, and titled “THIN-FILM DEVICES AND FABRICATION,” and in U.S. patent application Ser. No. 13/763,505, filed Feb. 8, 2013, and titled “DEFECT-MITIGATION LAYERS IN ELECTROCHROMIC DEVICES,” which are each herein incorporated by reference in their entireties.
Integrated Deposition System
As explained above, an integrated deposition system may be employed to fabricate electrochromic devices on, for example, architectural glass. As described above, the electrochromic devices are used to make IGUs which in turn are used to make electrochromic windows. The term “integrated deposition system” means an apparatus for fabricating electrochromic devices on optically transparent and translucent substrates. The apparatus has multiple stations, each devoted to a particular unit operation such as depositing a particular component (or portion of a component) of an electrochromic device, as well as cleaning, etching, and temperature control of such device or portion thereof. The multiple stations are fully integrated such that a substrate on which an electrochromic device is being fabricated can pass from one station to the next without being exposed to an external environment. Integrated deposition systems operate with a controlled ambient environment inside the system where the process stations are located. A fully integrated system allows for better control of interfacial quality between the layers deposited. Interfacial quality refers to, among other factors, the quality of the adhesion between layers and the lack of contaminants in the interfacial region. The term “controlled ambient environment” means a sealed environment separate from an external environment such as an open atmospheric environment or a clean room. In a controlled ambient environment at least one of pressure and gas composition is controlled independently of the conditions in the external environment. Generally, though not necessarily, a controlled ambient environment has a pressure below atmospheric pressure; e.g., at least a partial vacuum. The conditions in a controlled ambient environment may remain constant during a processing operation or may vary over time. For example, a layer of an electrochromic device may be deposited under vacuum in a controlled ambient environment and at the conclusion of the deposition operation, the environment may be backfilled with purge or reagent gas and the pressure increased to, e.g., atmospheric pressure for processing at another station, and then a vacuum reestablished for the next operation and so forth.
In one embodiment, the system includes a plurality of deposition stations aligned in series and interconnected and operable to pass a substrate from one station to the next without exposing the substrate to an external environment. The plurality of deposition stations comprise (i) a first deposition station containing one or more targets for depositing a cathodically coloring electrochromic layer; (ii) a second deposition station containing one or more targets for depositing an ion conducting layer; and (iii) a third deposition station containing one or more targets for depositing a counter electrode layer. The second deposition station may be omitted in certain cases. For instance, the apparatus may not include any target for depositing a separate ion conductor layer. The system also includes a controller containing program instructions for passing the substrate through the plurality of stations in a manner that sequentially deposits on the substrate (i) an electrochromic layer, (ii) an (optional) ion conducting layer, and (iii) a counter electrode layer to form a stack. In cases where the counter electrode layer includes two or more sub-layers, the sub-layers may be formed in different stations or in the same station, depending on the desired composition of each sub-layer, among other factors. In one example, a first station may be used to deposit the cathodically coloring electrochromic layer, a second station may be used to deposit a first sub-layer of an anodically coloring counter electrode layer, and a third station may be used to deposit a second sub-layer of the anodically coloring counter electrode layer.
In one embodiment, the plurality of deposition stations are operable to pass a substrate from one station to the next without breaking vacuum. In another embodiment, the plurality of deposition stations are configured to deposit the electrochromic layer, the optional ion conducting layer, and the counter electrode layer on an architectural glass substrate. In another embodiment, the integrated deposition system includes a substrate holder and transport mechanism operable to hold the architectural glass substrate in a vertical orientation while in the plurality of deposition stations. In yet another embodiment, the integrated deposition system includes one or more load locks for passing the substrate between an external environment and the integrated deposition system. In another embodiment, the plurality of deposition stations include at least two stations for depositing a layer selected from the group consisting of the cathodically coloring electrochromic layer, the ion conducting layer, and the anodically coloring counter electrode layer.
In some embodiments, the integrated deposition system includes one or more lithium deposition stations, each including a lithium containing target. In one embodiment, the integrated deposition system contains two or more lithium deposition stations. In one embodiment, the integrated deposition system has one or more isolation valves for isolating individual process stations from each other during operation. In one embodiment, the one or more lithium deposition stations have isolation valves. In this document, the term “isolation valves” means devices to isolate depositions or other processes being carried out one station from processes at other stations in the integrated deposition system. In one example, isolation valves are physical (solid) isolation valves within the integrated deposition system that engage while the lithium is deposited. Actual physical solid valves may engage to totally or partially isolate (or shield) the lithium deposition from other processes or stations in the integrated deposition system. In another embodiment, the isolation valves may be gas knifes or shields, e.g., a partial pressure of argon or other inert gas is passed over areas between the lithium deposition station and other stations to block ion flow to the other stations. In another example, isolation valves may be an evacuated regions between the lithium deposition station and other process stations, so that lithium ions or ions from other stations entering the evacuated region are removed to, e.g., a waste stream rather than contaminating adjoining processes. This is achieved, e.g., via a flow dynamic in the controlled ambient environment via differential pressures in a lithiation station of the integrated deposition system such that the lithium deposition is sufficiently isolated from other processes in the integrated deposition system. Again, isolation valves are not limited to lithium deposition stations.
Target 830, in this case a cylindrical target, is oriented substantially parallel to and in front of the substrate surface where deposition is to take place (for convenience, other sputter means are not depicted here). Substrate 825 can translate past target 830 during deposition and/or target 830 can move in front of substrate 825. The movement path of target 830 is not limited to translation along the path of substrate 825. Target 830 may rotate along an axis through its length, translate along the path of the substrate (forward and/or backward), translate along a path perpendicular to the path of the substrate, move in a circular path in a plane parallel to substrate 825, etc. Target 830 need not be cylindrical, it can be planar or any shape necessary for deposition of the desired layer with the desired properties. Also, there may be more than one target in each deposition station and/or targets may move from station to station depending on the desired process.
Integrated deposition system 800 also has various vacuum pumps, gas inlets, pressure sensors and the like that establish and maintain a controlled ambient environment within the system. These components are not shown, but rather would be appreciated by one of ordinary skill in the art. System 800 is controlled, e.g., via a computer system or other controller, represented in
As mentioned, the various stations of an integrated deposition system may be modular, but once connected, form a continuous system where a controlled ambient environment is established and maintained in order to process substrates at the various stations within the system.
Systems 800b and 800c also have a TCO layer station, 808, for depositing the TCO layer on the EC stack. Depending on the process demands, additional stations can be added to the integrated deposition system, e.g., stations for cleaning processes, laser scribes, capping layers, MTC, etc.
Although the foregoing embodiments have been described in some detail to facilitate understanding, the described embodiments are to be considered illustrative and not limiting. It will be apparent to one of ordinary skill in the art that certain changes and modifications can be practiced within the scope of the appended claims.
Experimental Results
Experimental results show that the disclosed NiWNbO materials exhibit very high quality coloring characteristics. In particular, the NiWNbO materials are very clear (transparent) in their untinted state, having less color (particularly yellow color) as compared to other materials that are somewhat colored in their untinted states. Further, the NiWNbO materials show good switching characteristics over time. In other words, the switching speed does not significantly decrease over the life of the counter electrode, as compared to certain other materials that exhibit increasingly slow switching speeds.
NiWNbO Deposition
Mixed nickel tungsten niobium oxide, NiWNbO, may be deposited using repeated deposition of very thin layers of sputtered material as the substrate is rastered back-and-forth in a deposition chamber. Reactive sputtering of NiW alloy and niobium metal targets in a mixture of argon and molecular oxygen with a chamber pressure of approximately 10 mTorr may be used. The NiW alloy target may be produced using a Hot Isostatic Press (HIP) method using Ni and W powders. The power to each target can be independently controlled using two synchronized pulsed DC power supplies. The ratio of Nb to Ni+W can be adjusted by varying the power ratio between the two targets. The thickness of the NiWNbO for a given set of power conditions may be changed by increasing or decreasing the speed of the substrate as it moves through the deposition chamber. In order to achieve the desired thickness of the entire counter-electrode, the number of passes in front of the targets is increased or decreased as needed. The degree of oxidation of the film can be controlled by adjusting the partial pressures of Ar and O2 in the sputtering gas, as well as the total pressure. Through the manipulation of these process parameters, the ratio of NiW:Nb:O can be controlled. Heaters may be used for temperature variation, but the highest-performance films and devices are typically deposited without additional heating. The substrate temperature is typically less than 100° C.
As an example, a high performance counter electrode may be achieved by sputtering in a pure oxygen environment with power and substrate speed settings chosen to achieve a thickness of less than 5 nm per pass. More than 150 passes through the deposition system can be performed in some cases to build film thickness. The power supplies for the two sputter targets may be chosen such that the NiW power (e.g., about 6 kW) is greater than (e.g., about 12× greater) the Nb power (e.g., about 0.5 kW). The resulting Ni:(W+Nb) ratio may be approximately 2.
Although the foregoing embodiments have been described in some detail to facilitate understanding, the described embodiments are to be considered illustrative and not limiting. It will be apparent to one of ordinary skill in the art that certain changes and modifications can be practiced within the scope of the appended claims.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3840286 | Kiss | Oct 1974 | A |
| 3971624 | Bruesch et al. | Jul 1976 | A |
| 4009935 | Faughnan et al. | Mar 1977 | A |
| 4193670 | Giglia et al. | Mar 1980 | A |
| 4264150 | Yano et al. | Apr 1981 | A |
| 4293194 | Takahashi | Oct 1981 | A |
| 4297006 | Bissar | Oct 1981 | A |
| 4365870 | Morita et al. | Dec 1982 | A |
| 4396253 | Kuwagaki et al. | Aug 1983 | A |
| 4482216 | Hashimoto et al. | Nov 1984 | A |
| 4561729 | Heinz et al. | Dec 1985 | A |
| 4832463 | Goldner et al. | May 1989 | A |
| 4851095 | Scobey et al. | Jul 1989 | A |
| 4923289 | Demiryont | May 1990 | A |
| 4938571 | Cogan et al. | Jul 1990 | A |
| 5019420 | Rauh | May 1991 | A |
| 5124832 | Greenberg et al. | Jun 1992 | A |
| 5130841 | Demiryont | Jul 1992 | A |
| 5138481 | Demiryont | Aug 1992 | A |
| 5142406 | Lampert et al. | Aug 1992 | A |
| 5168003 | Proscia | Dec 1992 | A |
| 5209980 | Spindler | May 1993 | A |
| 5216536 | Agrawal et al. | Jun 1993 | A |
| 5657150 | Kallman et al. | Aug 1997 | A |
| 5659417 | Van Dine et al. | Aug 1997 | A |
| 5666771 | Macquart et al. | Sep 1997 | A |
| 5668663 | Varaprasad et al. | Sep 1997 | A |
| 5699192 | Van Dine et al. | Dec 1997 | A |
| 5724175 | Hichwa et al. | Mar 1998 | A |
| 5724177 | Ellis, Jr. et al. | Mar 1998 | A |
| 5754329 | Coleman | May 1998 | A |
| 5757537 | Ellis, Jr. et al. | May 1998 | A |
| 5814195 | Lehan et al. | Sep 1998 | A |
| 5831760 | Hashimoto et al. | Nov 1998 | A |
| 5847858 | Krings et al. | Dec 1998 | A |
| 5859723 | Jodicke et al. | Jan 1999 | A |
| 5910854 | Varaprasad et al. | Jun 1999 | A |
| 6020987 | Baumann et al. | Feb 2000 | A |
| 6178034 | Allemand et al. | Jan 2001 | B1 |
| 6185034 | Nakamura et al. | Feb 2001 | B1 |
| 6211995 | Azens | Apr 2001 | B1 |
| 6266177 | Allemand et al. | Jul 2001 | B1 |
| 6277523 | Giron | Aug 2001 | B1 |
| 6337758 | Beteille et al. | Jan 2002 | B1 |
| 6515787 | Westfall et al. | Feb 2003 | B1 |
| 6529308 | Beteille et al. | Mar 2003 | B2 |
| 6559411 | Borgeson et al. | May 2003 | B2 |
| 6791737 | Giron | Sep 2004 | B2 |
| 6791738 | Reynolds et al. | Sep 2004 | B2 |
| 6822778 | Westfall et al. | Nov 2004 | B2 |
| 6856444 | Ingalls et al. | Feb 2005 | B2 |
| 6859297 | Lee et al. | Feb 2005 | B2 |
| 6919530 | Borgeson et al. | Jul 2005 | B2 |
| 6940628 | Giron | Sep 2005 | B2 |
| 7099062 | Azens et al. | Aug 2006 | B2 |
| 7193763 | Beteille et al. | Mar 2007 | B2 |
| 7230748 | Giron et al. | Jun 2007 | B2 |
| 7265891 | Demiryont | Sep 2007 | B1 |
| 7277215 | Greer | Oct 2007 | B2 |
| 7372610 | Burdis et al. | May 2008 | B2 |
| 7531101 | Beteille | May 2009 | B2 |
| 7564611 | Jang et al. | Jul 2009 | B2 |
| 7593154 | Burdis et al. | Sep 2009 | B2 |
| 7604717 | Beteille et al. | Oct 2009 | B2 |
| 7646526 | Wang et al. | Jan 2010 | B1 |
| 7679810 | Fuss et al. | Mar 2010 | B2 |
| 7704555 | Demiryont | Apr 2010 | B2 |
| 7830585 | Widjaja et al. | Nov 2010 | B2 |
| 7869114 | Valentin et al. | Jan 2011 | B2 |
| 7894120 | Valentin et al. | Feb 2011 | B2 |
| 8004744 | Burdis et al. | Aug 2011 | B2 |
| 8031389 | Wang et al. | Oct 2011 | B2 |
| 8168265 | Kwak et al. | May 2012 | B2 |
| 8228592 | Wang et al. | Jul 2012 | B2 |
| 8300298 | Wang et al. | Oct 2012 | B2 |
| 8432603 | Wang et al. | Apr 2013 | B2 |
| 8582193 | Wang et al. | Nov 2013 | B2 |
| 8638487 | Veerasamy | Jan 2014 | B2 |
| 8687261 | Gillaspie et al. | Apr 2014 | B2 |
| 8749868 | Wang et al. | Jun 2014 | B2 |
| 8758575 | Wang et al. | Jun 2014 | B2 |
| 8764950 | Wang et al. | Jul 2014 | B2 |
| 8764951 | Wang et al. | Jul 2014 | B2 |
| 8773747 | Ferreira et al. | Jul 2014 | B2 |
| 8995041 | Weir et al. | Mar 2015 | B2 |
| 9007674 | Kailasam et al. | Apr 2015 | B2 |
| 9116409 | Sun et al. | Aug 2015 | B1 |
| 9140951 | Wang et al. | Sep 2015 | B2 |
| 9164346 | Wang et al. | Oct 2015 | B2 |
| 9261751 | Pradhan et al. | Feb 2016 | B2 |
| 9334557 | Neudecker et al. | May 2016 | B2 |
| 9429809 | Kailasam et al. | Aug 2016 | B2 |
| 9454053 | Strong et al. | Sep 2016 | B2 |
| 9477129 | Kozlowski et al. | Oct 2016 | B2 |
| 9581875 | Burdis et al. | Feb 2017 | B2 |
| 9664974 | Kozlowski et al. | May 2017 | B2 |
| 9671664 | Pradhan et al. | Jun 2017 | B2 |
| 9720298 | Wang et al. | Aug 2017 | B2 |
| 9759975 | Wang et al. | Sep 2017 | B2 |
| 9904138 | Kailasam et al. | Feb 2018 | B2 |
| 10054833 | Kailasam et al. | Aug 2018 | B2 |
| 10088729 | Wang et al. | Oct 2018 | B2 |
| 10152762 | Wu et al. | Dec 2018 | B2 |
| 10156762 | Gillaspie et al. | Dec 2018 | B2 |
| 10162240 | Rozbicki | Dec 2018 | B2 |
| 10185197 | Pradhan et al. | Jan 2019 | B2 |
| 10228601 | Gillaspie et al. | Mar 2019 | B2 |
| 10254615 | Kailasam et al. | Apr 2019 | B2 |
| 10261381 | Pradhan et al. | Apr 2019 | B2 |
| 10288969 | Kailasam et al. | May 2019 | B2 |
| 10345671 | Gillaspie et al. | Jul 2019 | B2 |
| 10585321 | Gillaspie et al. | Mar 2020 | B2 |
| 10591765 | Nakano et al. | Mar 2020 | B2 |
| 10591795 | Gillaspie et al. | Mar 2020 | B2 |
| 10591797 | Wang et al. | Mar 2020 | B2 |
| 10599001 | Wang et al. | Mar 2020 | B2 |
| 10663830 | Pradhan et al. | May 2020 | B2 |
| 10684523 | Gillaspie et al. | Jun 2020 | B2 |
| 10690987 | Gillaspie et al. | Jun 2020 | B2 |
| 10852613 | Pradhan et al. | Dec 2020 | B2 |
| 10877348 | Kang et al. | Dec 2020 | B2 |
| 10996533 | Pradhan et al. | May 2021 | B2 |
| 11187954 | Rozbicki et al. | Nov 2021 | B2 |
| 11189954 | Kwon et al. | Nov 2021 | B2 |
| 11327382 | Gillaspie et al. | May 2022 | B2 |
| 11370699 | Gillaspie et al. | Jun 2022 | B2 |
| 11409177 | Gillaspie et al. | Aug 2022 | B2 |
| 11422426 | Gillaspie et al. | Aug 2022 | B2 |
| 11440838 | Pradhan et al. | Sep 2022 | B2 |
| 11525181 | Wang et al. | Dec 2022 | B2 |
| 11592722 | Wang et al. | Feb 2023 | B2 |
| 11635665 | Pradhan et al. | Apr 2023 | B2 |
| 20020041443 | Varaprasad et al. | Apr 2002 | A1 |
| 20030010957 | Haering et al. | Jan 2003 | A1 |
| 20030031928 | Beteille et al. | Feb 2003 | A1 |
| 20030156313 | Serra et al. | Aug 2003 | A1 |
| 20040150867 | Lee et al. | Aug 2004 | A1 |
| 20050002081 | Beteille | Jan 2005 | A1 |
| 20050007645 | Tonar et al. | Jan 2005 | A1 |
| 20050147825 | Arnaud et al. | Jul 2005 | A1 |
| 20050259310 | Giri et al. | Nov 2005 | A1 |
| 20060105103 | Hartig | May 2006 | A1 |
| 20060209383 | Burdis et al. | Sep 2006 | A1 |
| 20070008603 | Sotzing et al. | Jan 2007 | A1 |
| 20070008605 | Garg et al. | Jan 2007 | A1 |
| 20070097481 | Burdis et al. | May 2007 | A1 |
| 20070292606 | Demiryont | Dec 2007 | A1 |
| 20080213477 | Zindel et al. | Sep 2008 | A1 |
| 20080304130 | Nguyen | Dec 2008 | A1 |
| 20080304131 | Nguyen | Dec 2008 | A1 |
| 20090057137 | Pitts et al. | Mar 2009 | A1 |
| 20090285978 | Burdis et al. | Nov 2009 | A1 |
| 20090304912 | Kwak et al. | Dec 2009 | A1 |
| 20090323156 | Shin et al. | Dec 2009 | A1 |
| 20090323158 | Wang et al. | Dec 2009 | A1 |
| 20100007937 | Widjaja et al. | Jan 2010 | A1 |
| 20100079844 | Kurman et al. | Apr 2010 | A1 |
| 20100103496 | Schwendeman et al. | Apr 2010 | A1 |
| 20100165440 | Nguyen et al. | Jul 2010 | A1 |
| 20100243427 | Kozlowski et al. | Sep 2010 | A1 |
| 20100245973 | Wang et al. | Sep 2010 | A1 |
| 20110013254 | Widjaja et al. | Jan 2011 | A1 |
| 20110043885 | Lamine et al. | Feb 2011 | A1 |
| 20110043886 | Jeon et al. | Feb 2011 | A1 |
| 20110051220 | Lee | Mar 2011 | A1 |
| 20110051221 | Veerasamy | Mar 2011 | A1 |
| 20110151283 | Gillaspie et al. | Jun 2011 | A1 |
| 20110211247 | Kozlowski et al. | Sep 2011 | A1 |
| 20110249314 | Wang et al. | Oct 2011 | A1 |
| 20110266137 | Wang et al. | Nov 2011 | A1 |
| 20110266138 | Wang et al. | Nov 2011 | A1 |
| 20110267674 | Wang et al. | Nov 2011 | A1 |
| 20110267675 | Wang et al. | Nov 2011 | A1 |
| 20110297535 | Higdon et al. | Dec 2011 | A1 |
| 20110299149 | Park et al. | Dec 2011 | A1 |
| 20120181167 | Jiang et al. | Jul 2012 | A1 |
| 20120200908 | Bergh et al. | Aug 2012 | A1 |
| 20120218621 | Kwak et al. | Aug 2012 | A1 |
| 20120275008 | Pradhan et al. | Nov 2012 | A1 |
| 20120276734 | Van Mol et al. | Nov 2012 | A1 |
| 20130003157 | Wang et al. | Jan 2013 | A1 |
| 20130016417 | Veerasamy | Jan 2013 | A1 |
| 20130101751 | Berland et al. | Apr 2013 | A1 |
| 20130182307 | Gillaspie et al. | Jul 2013 | A1 |
| 20130201545 | Frey | Aug 2013 | A1 |
| 20130270105 | Wang et al. | Oct 2013 | A1 |
| 20130286459 | Burdis et al. | Oct 2013 | A1 |
| 20140022621 | Kailasam et al. | Jan 2014 | A1 |
| 20140177027 | Wang et al. | Jun 2014 | A1 |
| 20140204444 | Choi et al. | Jul 2014 | A1 |
| 20140204445 | Choi et al. | Jul 2014 | A1 |
| 20140204446 | Choi et al. | Jul 2014 | A1 |
| 20140204447 | Choi et al. | Jul 2014 | A1 |
| 20140204448 | Bergh et al. | Jul 2014 | A1 |
| 20140205746 | Choi et al. | Jul 2014 | A1 |
| 20140205748 | Choi et al. | Jul 2014 | A1 |
| 20140313561 | Wang et al. | Oct 2014 | A1 |
| 20140329006 | Bhatnagar et al. | Nov 2014 | A1 |
| 20150131140 | Kailasam et al. | May 2015 | A1 |
| 20150362763 | Wheeler et al. | Dec 2015 | A1 |
| 20150370139 | Wang et al. | Dec 2015 | A1 |
| 20160011480 | Pradhan et al. | Jan 2016 | A1 |
| 20160026055 | Choi et al. | Jan 2016 | A1 |
| 20160209722 | Wang et al. | Jul 2016 | A1 |
| 20170003564 | Gillaspie et al. | Jan 2017 | A1 |
| 20170097552 | Pradhan et al. | Apr 2017 | A1 |
| 20170176832 | Pradhan et al. | Jun 2017 | A1 |
| 20170184937 | Wang et al. | Jun 2017 | A1 |
| 20170255076 | Gillaspie et al. | Sep 2017 | A1 |
| 20170299933 | Kailasam et al. | Oct 2017 | A1 |
| 20170329200 | Wang et al. | Nov 2017 | A1 |
| 20170357135 | Gillaspie et al. | Dec 2017 | A1 |
| 20170371221 | Gillaspie et al. | Dec 2017 | A1 |
| 20180052374 | Wang et al. | Feb 2018 | A1 |
| 20180173071 | Mathew et al. | Jun 2018 | A1 |
| 20180203320 | Kailasam et al. | Jul 2018 | A1 |
| 20180231858 | Kailasam et al. | Aug 2018 | A1 |
| 20190064623 | Gillaspie et al. | Feb 2019 | A1 |
| 20190107763 | Gillaspie et al. | Apr 2019 | A1 |
| 20190113819 | Pradhan et al. | Apr 2019 | A1 |
| 20190171078 | Pradhan et al. | Jun 2019 | A1 |
| 20190171079 | Gillaspie et al. | Jun 2019 | A1 |
| 20190187531 | Pradhan et al. | Jun 2019 | A1 |
| 20190302561 | Rozbicki et al. | Oct 2019 | A1 |
| 20200050072 | Kozlowski et al. | Feb 2020 | A1 |
| 20200096830 | Sarrach et al. | Mar 2020 | A1 |
| 20200124933 | Kozlowski et al. | Apr 2020 | A1 |
| 20200133088 | Gillaspie et al. | Apr 2020 | A1 |
| 20200166817 | Wang et al. | May 2020 | A1 |
| 20200174332 | Gillaspie et al. | Jun 2020 | A1 |
| 20200174335 | Wang et al. | Jun 2020 | A1 |
| 20200257178 | Pradhan et al. | Aug 2020 | A1 |
| 20200272014 | Gillaspie et al. | Aug 2020 | A1 |
| 20200278588 | Gillaspie et al. | Sep 2020 | A1 |
| 20210055618 | Pradhan et al. | Feb 2021 | A1 |
| 20210191215 | Pradhan et al. | Jun 2021 | A1 |
| 20210247654 | Mogensen et al. | Aug 2021 | A1 |
| 20210269706 | Meshcheryakov et al. | Sep 2021 | A1 |
| 20210373401 | Wang et al. | Dec 2021 | A1 |
| 20220055943 | Kozlowski et al. | Feb 2022 | A1 |
| 20220066274 | Rozbicki | Mar 2022 | A1 |
| 20220204398 | Gillaspie et al. | Jun 2022 | A1 |
| 20220308416 | Rozbicki et al. | Sep 2022 | A1 |
| 20220334442 | Gillaspie et al. | Oct 2022 | A1 |
| 20220350217 | Gillaspie et al. | Nov 2022 | A1 |
| 20220388900 | Pradhan et al. | Dec 2022 | A1 |
| 20230008603 | Gillaspie et al. | Jan 2023 | A1 |
| 20230074776 | Wang et al. | Mar 2023 | A1 |
| 20230099188 | Kozlowski et al. | Mar 2023 | A1 |
| 20230144179 | Wang et al. | May 2023 | A1 |
| 20230205032 | Pradhan et al. | Jun 2023 | A1 |
| 20230296953 | Rozbicki et al. | Sep 2023 | A1 |
| Number | Date | Country |
|---|---|---|
| 2014210572 | Jan 2017 | AU |
| 2019229399 | Dec 2020 | AU |
| 2015353823 | Feb 2021 | AU |
| 1207182 | Feb 1999 | CN |
| 1245540 | Feb 2000 | CN |
| 1350048 | May 2002 | CN |
| 1476548 | Feb 2004 | CN |
| 1492274 | Apr 2004 | CN |
| 1541420 | Oct 2004 | CN |
| 1688923 | Oct 2005 | CN |
| 1710481 | Dec 2005 | CN |
| 1738885 | Feb 2006 | CN |
| 1739057 | Feb 2006 | CN |
| 1928685 | Mar 2007 | CN |
| 101188886 | May 2008 | CN |
| 101310217 | Nov 2008 | CN |
| 101322069 | Dec 2008 | CN |
| 100462830 | Feb 2009 | CN |
| 101377599 | Mar 2009 | CN |
| 101419374 | Apr 2009 | CN |
| 101634790 | Jan 2010 | CN |
| 101833932 | Sep 2010 | CN |
| 101930142 | Dec 2010 | CN |
| 102099736 | Jun 2011 | CN |
| 102230172 | Nov 2011 | CN |
| 102376379 | Mar 2012 | CN |
| 102388340 | Mar 2012 | CN |
| 102388341 | Mar 2012 | CN |
| 102414610 | Apr 2012 | CN |
| 102455560 | May 2012 | CN |
| 102478739 | May 2012 | CN |
| 102540612 | Jul 2012 | CN |
| 102576818 | Jul 2012 | CN |
| 102666778 | Sep 2012 | CN |
| 102934009 | Feb 2013 | CN |
| 102998870 | Mar 2013 | CN |
| 103080825 | May 2013 | CN |
| 103135306 | Jun 2013 | CN |
| 103168269 | Jun 2013 | CN |
| 103339560 | Oct 2013 | CN |
| 103838050 | Jun 2014 | CN |
| 103930954 | Jul 2014 | CN |
| 104040417 | Sep 2014 | CN |
| 104321497 | Jan 2015 | CN |
| 104364707 | Feb 2015 | CN |
| 104730796 | Jun 2015 | CN |
| 106773436 | May 2017 | CN |
| 107111197 | Aug 2017 | CN |
| 0497616 | Aug 1992 | EP |
| 0497616 | Jul 1999 | EP |
| 1918412 | May 2008 | EP |
| S4834547 | May 1973 | JP |
| S5050892 | May 1975 | JP |
| S55124440 | Sep 1980 | JP |
| S5781242 | May 1982 | JP |
| S5833223 | Feb 1983 | JP |
| S58139128 | Aug 1983 | JP |
| S58163921 | Sep 1983 | JP |
| S5940625 | Mar 1984 | JP |
| S6066238 | Apr 1985 | JP |
| S6078423 | May 1985 | JP |
| S6078424 | May 1985 | JP |
| S60202429 | Oct 1985 | JP |
| H03500096 | Jan 1991 | JP |
| H04211227 | Aug 1992 | JP |
| H05182512 | Jul 1993 | JP |
| H09152634 | Jun 1997 | JP |
| H10501847 | Feb 1998 | JP |
| H1193827 | Apr 1999 | JP |
| 2004205628 | Jul 2004 | JP |
| 2004309926 | Nov 2004 | JP |
| 2005091788 | Apr 2005 | JP |
| 2006235632 | Sep 2006 | JP |
| 2007108750 | Apr 2007 | JP |
| 2008026605 | Feb 2008 | JP |
| 2008197679 | Aug 2008 | JP |
| 2008216744 | Sep 2008 | JP |
| 2009009145 | Jan 2009 | JP |
| 2010509720 | Mar 2010 | JP |
| 2012078774 | Apr 2012 | JP |
| 2012523018 | Sep 2012 | JP |
| 2012523019 | Sep 2012 | JP |
| 2013525860 | Jun 2013 | JP |
| 2014052510 | Mar 2014 | JP |
| 2015128055 | Jul 2015 | JP |
| 5868726 | Feb 2016 | JP |
| 2016062696 | Apr 2016 | JP |
| 5955414 | Jul 2016 | JP |
| 2017538965 | Dec 2017 | JP |
| 20060092362 | Aug 2006 | KR |
| 100824302 | Apr 2008 | KR |
| 20080051280 | Jun 2008 | KR |
| 20110100457 | Sep 2011 | KR |
| 20130112693 | Oct 2013 | KR |
| 20140068026 | Jun 2014 | KR |
| 101535100 | Jul 2015 | KR |
| 20170112183 | Oct 2017 | KR |
| 102010733 | Aug 2019 | KR |
| 102010755 | Aug 2019 | KR |
| 2117972 | Aug 1998 | RU |
| 490391 | Jun 2002 | TW |
| 200417280 | Sep 2004 | TW |
| M338359 | Aug 2008 | TW |
| 200839402 | Oct 2008 | TW |
| 201003270 | Jan 2010 | TW |
| 201211664 | Mar 2012 | TW |
| 201222119 | Jun 2012 | TW |
| 201435464 | Sep 2014 | TW |
| 201439371 | Oct 2014 | TW |
| WO-9519588 | Jul 1995 | WO |
| WO-9847613 | Oct 1998 | WO |
| WO-0201287 | Jan 2002 | WO |
| WO-03017387 | Feb 2003 | WO |
| WO-2004087985 | Oct 2004 | WO |
| WO-2008017777 | Feb 2008 | WO |
| WO-2008055824 | May 2008 | WO |
| WO-2008154517 | Dec 2008 | WO |
| WO-2009000547 | Dec 2008 | WO |
| WO-2009029111 | Mar 2009 | WO |
| WO-2009108184 | Sep 2009 | WO |
| WO-2009115424 | Sep 2009 | WO |
| WO-2009148861 | Dec 2009 | WO |
| WO-2010120537 | Oct 2010 | WO |
| WO-2010147494 | Dec 2010 | WO |
| WO-2011137080 | Nov 2011 | WO |
| WO-2011137104 | Nov 2011 | WO |
| WO-2012138281 | Oct 2012 | WO |
| WO-2013054367 | Apr 2013 | WO |
| WO-2014025876 | Feb 2014 | WO |
| WO-2014025900 | Feb 2014 | WO |
| WO-2014113795 | Jul 2014 | WO |
| WO-2014113796 | Jul 2014 | WO |
| WO-2014113801 | Jul 2014 | WO |
| WO-2014201287 | Dec 2014 | WO |
| WO-2015168166 | Nov 2015 | WO |
| WO-2016039157 | Mar 2016 | WO |
| WO-2017011272 | Jan 2017 | WO |
| WO-2020247831 | Dec 2020 | WO |
| Entry |
|---|
| Arvizu, M.A. et al., “Electrochromic W1-x-yTixMoyO3 thin films made by sputter deposition: Large optical modulation, good cycling durability, and approximate color neutrality,” Chemistry of Materials [online, just accepted manuscript], Feb. 23, 2017, [retrieved on Feb. 24, 2017]. Retrieved from the internet: http://pubs.acs.org DOI: 10.1021/acs.chemmater.6b05198. |
| AU Examination report dated Feb. 21, 2022, in Application No. AU2020294239. |
| Australian Examination Report dated Apr. 19, 2016 in AU Application No. 2014210572. |
| Australian Examination Report dated Dec. 17, 2018 in AU Application No. 2017202249. |
| Australian Examination Report dated Jan. 6, 2014 in AU Application No. 2011245431. |
| Australian Examination Report dated Jun. 7, 2018 in AU Application No. 2017202249. |
| Australian Examination Report dated Mar. 18, 2019 in AU Application No. 2017202249. |
| Australian Examination Report dated May 15, 2020 in AU Application No. 2019229399. |
| Australian Examination Report dated Sep. 17, 2020 in AU Application No. 2019229399. |
| Australian Office Action dated Dec. 8, 2020 in AU Application No. 2016294343. |
| Australian Office Action dated Feb. 19, 2021 in AU Application No. 2016294343. |
| Australian Office Action dated Oct. 28, 2020 in AU Application No. 2015353823. |
| Avendano, E. et al., “Electrochromic Nickel-Oxide-Based Films with Minimized Bleached-State Absorptance,” I 203rd Meeting of the Electrochemical Society, Electrochemical Society Proceedings vol. 2003-17, 2003, pp. 80-90. |
| Brazilian Office Action dated Sep. 24, 2019 in BR Application No. 1120120278916. |
| Burdis, et al., “Technology Advancements to Lower Costs of Electrochromic Window Glazings”, SAGE Electronics, Inc., DE-PS26-06NT42764, Final Report, Apr. 2, 2010. |
| CA Office Action dated Nov. 10, 2021, in Application No. CA2968832. |
| Chinese Allowance with Search Report dated May 8, 2021 in CN Application No. 201610832436.6—No Translation. |
| Chinese Decision of Rejection dated Jun. 2, 2021 in CN Application No. 201580072326.8. |
| Chinese Notice of Allowance with Search Report dated Mar. 17, 2021 in CN Application No. 201680047325.2. |
| Chinese Office Action dated Apr. 1, 2020 in CN Application No. CN201610832436.6. |
| Chinese Office Action dated Apr. 7, 2021 in CN Application No. 201810154035.9. |
| Chinese Office Action dated Aug. 24, 2020 in CN Application No. 201810154035.9. |
| Chinese Office Action dated Dec. 21, 2020 in CN Application No. 201680047325.2. |
| Chinese Office Action dated Dec. 26, 2018 in CN Application No. 201580032579.2. |
| Chinese Office Action dated Dec. 27, 2018 in CN Application No. 201580029451.0. |
| Chinese Office Action dated Dec. 3, 2020 in CN Application No. CN201610832436.6. |
| Chinese Office Action dated Feb. 10, 2021 in CN Application No. 201580072326.8. |
| Chinese Office Action dated Feb. 19, 2021 in CN Application No. 201580069923.5. |
| Chinese Office Action dated Jan. 2, 2020 in CN Application No. 201580069923.5. |
| Chinese Office Action dated Jan. 2, 2020 in CN Application No. 201580072326.8. |
| Chinese Office Action dated Jan. 22, 2020 in CN Application No. 201580053092.2. |
| Chinese Office Action dated Jul. 17, 2019 in CN Application No. 201580029451.0. |
| Chinese Office Action dated Jul. 2, 2019 in CN Application No. 201580032579.2. |
| Chinese Office Action dated Jun. 2, 2020 in CN Application No. 201680047325.2. |
| Chinese Office Action dated Mar. 17, 2021 in CN Application No. 201680047325.2. |
| Chinese Office Action dated Mar. 5, 2020 in CN Application No. 201580029451.0. |
| Chinese Office Action dated Mar. 5, 2020 in CN Application No. 201580032579.2. |
| Chinese Office Action dated Nov. 4, 2020 in CN Application No. 201580029451.0. |
| Chinese Office Action dated Sep. 27, 2020 in CN Application No. 201580069923.5. |
| Chinese Office Action dated Sep. 27, 2020 in CN Application No. 201580072326.8. |
| Chinese Office Action dated Aug. 28, 2018 in CN Application No. CN201610412630.9. |
| Chinese Office Action dated Aug. 31, 2015 in CN Application No. CN201180027892.9. |
| Chinese Office Action dated Jan. 8, 2015 in CN Application No. CN201180027892.9. |
| Chinese Office Action dated Jun. 15, 2017 in CN Application No. 201380031908.2. |
| Chinese Office Action dated Mar. 22, 2019 in CN Application No. CN201610412630.9. |
| Chinese Office Action dated Mar. 31, 2016 in CN Application No. CN201180027892.9. |
| Chinese Office Action dated Sep. 28, 2016 in CN Application No. 201380031908.2. |
| Chinese Reexamination dated May 21, 2021 in CN Application No. 201580032579.2. |
| CN Office Action dated Aug. 3, 2021, in CN Application No. 201810154035.9. |
| CN Office Action dated Aug. 30, 2021, in CN Application No. 201580032579.2 with English translation. |
| Co-pending U.S. Appl. No. 17/596,266, filed Dec. 6, 2021. |
| EP Office Action dated Feb. 11, 2022, in Application No. EP15863517.7. |
| EP Office Action dated Mar. 16, 2022, in Application No. EP15862207.6. |
| EP Summons to Attend Oral Proceedings dated Apr. 28, 2020 in EP Application No. 13785049.1. |
| EP Summons to attend Oral Proceedings dated Oct. 18, 2021 in Application No. 15785891.1. |
| European Extended Search Report dated Aug. 2, 2021 in EP Application No. 3872563. |
| European Office Action dated Feb. 10, 2017 in EP Application No. 11775488.7. |
| European Office Action dated Mar. 12, 2020 in EP Application No. 15862207.6. |
| European Office Action dated Mar. 13, 2020 in EP Application No. 15863517.7. |
| European Office Action dated May 11, 2021 in EP Application No. 20153706.5. |
| European Office Action dated May 3, 2021 in EP Application No. 16824923.3. |
| European Office Action dated May 7, 2019 in EP Application No. 13785049.1. |
| European Office Action dated Oct. 10, 2019 in EP Application No. 15785891.1. |
| European Office Action dated Oct. 16, 2017 in EP Application No. 11775488.7. |
| European Office Action dated Oct. 23, 2018 in EP Application No. 15785437.3. |
| European Search Report dated May 13, 2014 in EP Application No. 11775488.7. |
| European Search Report (Extended) dated Apr. 17, 2020 in EP Application No. 20156430.9. |
| European Search Report (Extended) dated Apr. 6, 2016 in EP Application No. 13785049.1. |
| European Search Report (Extended) dated Dec. 1, 2017 in EP Application No. 15785891.1. |
| European Search Report (Extended) dated Dec. 14, 2018 in EP Application No. 16824923.3. |
| European Search Report (Extended) dated Jan. 29, 2018 in EP Application No. 15837472.8. |
| European Search Report (Extended) dated Mar. 30, 2020 in EP Application No. 20153706.5. |
| European Search Report (Extended) dated May 2, 2018 in EP Application No. 15862207.6. |
| European Search Report (Extended) dated May 24, 2018 in EP Application No. 15863517.7. |
| European Search Report (Extended) dated May 26, 2020 in EP Application No. 19206961.5. |
| European Search Report (Extended) dated Nov. 28, 2017 in EP Application No. 15785437.3. |
| European Search Report (Partial Supplementary) dated Jan. 8, 2016 in EP Application No. 13785049.1. |
| Extended European Search Report dated Aug. 2, 2021 for EP Application No. 21169812.1. |
| Green, Sara, “Electrochromic nickel-tungsten oxides: optical, electrochemical and structural characterization of sputter-deposited thin films in the whole composition range,” Dissertation, Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 963, Uppsala University, Sweden, 2012. |
| Hersh, H.N., “Mechanism of Electrochromism in WO3,” Applied Physics Letters, vol. 27, No. 12, Dec. 15, 1975, pp. 646-648. |
| Hutchins, M.G. et al., “The electrochromic behavior of tin-nickel oxide,” Solar Energy Materials and Solar Cells, vol. 54, 1998, pp. 75-84. |
| IN Examination Report dated Oct. 12, 2021, in application No. IN201838043541. |
| IN First Examination report dated on Aug. 26, 2021, in application No. IN201717044876. |
| Indian Hearing Notice dated Oct. 20, 2020 in IN Application No. 3663/KOLNP/2012. |
| Indian Office Action dated Jun. 19, 2018 in IN Application No. 3663/KOLNP/2012. |
| Indian Office Action dated Jun. 30, 2021 in IN Application No. 201737018863. |
| International Preliminary Report on Patentability dated Dec. 16, 2021, in application No. PCT/US2020/036440. |
| International Preliminary Report on Patentability dated Jan. 25, 2018 in PCT/US16/41375. |
| International Preliminary Report on Patentability dated Jun. 8, 2017 in PCT/US15/61668. |
| International Preliminary Report on Patentability dated Jun. 8, 2017 in PCT/US15/61995. |
| International Preliminary Report on Patentability dated Mar. 16, 2017 in PCT/US15/47891. |
| International Preliminary Report on Patentability dated Nov. 13, 2014 in PCT/US2013/038481. |
| International Preliminary Report on Patentability, dated Nov. 15, 2012 in PCT/US2011/033822. |
| International Preliminary Report on Patentability dated Nov. 15, 2012 in PCT/US2011/033906. |
| International Preliminary Report on Patentability dated Nov. 17, 2016 in PCT/US15/028899. |
| International Preliminary Report on Patentability dated Nov. 17, 2016 in PCT/US15/28067. |
| International Preliminary Report on Patentability dated Nov. 5, 2020 in PCT/US19/027931. |
| International Preliminary Report on Patentability dated Oct. 4, 2018 in PCT/US17/24120. |
| International Search Report and Written Opinion, dated Aug. 14, 2013 in PCT/US2013/038481. |
| International Search Report and Written Opinion dated Aug. 26, 2015 in PCT/US15/28067. |
| International Search Report and Written Opinion dated Feb. 29, 2016 in PCT/US15/61668. |
| International Search Report and Written Opinion dated Jul. 16, 2015 in PCT/US15/028899. |
| International Search Report and Written Opinion, dated Jul. 7, 2011, issued in PCT/US2011/033822. |
| International Search Report and Written Opinion dated Jul. 9, 2019 in PCT/US19/027931. |
| International Search Report and Written Opinion dated Mar. 18, 2016 in PCT/US15/47891. |
| International Search Report and Written Opinion dated Mar. 7, 2016 in PCT/US15/61995. |
| International Search Report and Written Opinion dated Oct. 18, 2016 in PCT/US16/41375. |
| International Search Report and Written Opinion, dated Sep. 14, 2011, issued in PCT/US2011/033906. |
| International Search Report and Written Opinion dated Sep. 21, 2020 in PCT/US2020/036440. |
| International Search Report and Written Opinion (ISA/KR) dated Jul. 7, 2017 in PCT/US17/24120. |
| Japanese Decision to Grant dated Mar. 16, 2021 in JP Application No. 2020-067107. |
| Japanese Office Action dated Apr. 21, 2021 in JP Application No. 2017-527761. |
| Japanese Office Action dated Mar. 5, 2019 in JP Application No. JP2018-028971. |
| Japanese Office Action dated May 7, 2020 in JP Application No. 2017-564044. |
| Japanese Office Action dated Sep. 23, 2020 in JP Application No. 2017-527761. |
| Japanese Office Action dated Sep. 24, 2019 in JP Application No. 2017-527761. |
| Japanese Office Action dated Mar. 8, 2016 in JP Application No. JP2015-118553. |
| Japanese Office Action dated Nov. 21, 2017 in JP Application No. JP2016-215029. |
| JP Office Action dated Aug. 3, 2021, in Application No. JP2017527761. |
| JP Office Action dated Dec. 7, 2021, in Application No. JP20200207808. |
| JP Office Action dated Mar. 1, 2022, in Application No. JP2021-013861. |
| Kondrachova, L. et al., “Cathodic Electrodeposition of Mixed Molybdenum Tungsten Oxides From Peroxo-polymolybdotungstate Solutions”, Langmuir 2006, vol. 22, No. 25, Aug. 31, 2006, pp. 10490-10498. |
| Korean Notice of Allowance & Search Reported dated May 26, 2021 in KR Application No. 10- 2021-7006423. |
| Korean Office Action dated Sep. 28, 2020 in KR Application No. 10-2019-7024032. |
| Korean Office Action dated Feb. 28, 2017 in KR Application No. 10-2012-7031407. |
| Korean Office Action dated Feb. 8, 2018 in KR Application No. 10-2018-7002491. |
| Korean Office Action dated Mar. 24, 2021 in KR Application No. 10-2021-7006423. |
| Korean Office Action dated Oct. 30, 2018 in KR Application No. 10-2018-7030647. |
| KR Office Action dated Jan. 14, 2022, in Application No. KR1020217042357 with English translation. |
| KR Office Action dated Nov. 25, 2021, in Application No. KR1020177017239 with English translation. |
| Mexican Office Action dated Jun. 6, 2013 in MX Application No. MX/a/2012/012573. |
| Pennisi, A. et al., “Electrochromic Properties of Tungsten-molybdenum Oxide Electrodes”, Solar Energy Materials and Solar Cells, vol. 28, No. 3, Dec. 1, 1992, pp. 233-247, XP000328508. |
| Preliminary Amendment filed Aug. 3, 2018 in U.S. Appl. No. 15/916,142. |
| Preliminary Amendment filed Feb. 27, 2020 for U.S. Appl. No. 16/785,547. |
| Preliminary Amendment filed Jul. 13, 2020 for U.S. Appl. No. 15/931,359. |
| Preliminary Amendment filed Jul. 29, 2020 for U.S. Appl. No. 16/879,255. |
| Preliminary Amendment filed Jul. 6, 2020 for U.S. Appl. No. 16/859,856. |
| Russian Office Action dated Apr. 11, 2019 in RU Application No. 2017120233. |
| Russian Office Action dated Feb. 25, 2015 in RU Application No. 2012151304. |
| Russian Office Action dated Mar. 12, 2019 in RU Application No. 2015148673. |
| Russian Search Report dated Nov. 1, 2019 in RU Application No. 2018105193. |
| Singapore Examination Report dated Nov. 5, 2013 in SG Application No. 201208018-0. |
| Taiwanese Allowance with Search Report dated Mar. 12, 2021 in TW Application No. 109123760—No Translation. |
| Taiwanese Decision of Rejection dated Jul. 7, 2020 in TW Application No. 104139219. |
| Taiwanese Decision of Rejection dated Nov. 29, 2016 in TW Application No. 104144317. |
| Taiwanese Decision of Rejection dated Feb. 24, 2017 in TW Application No. 100115201. |
| Taiwanese Office Action dated Aug. 26, 2019 in TW Application No. 108106923. |
| Taiwanese Office Action dated Dec. 7, 2018 in TW Application No. 106128807. |
| Taiwanese Office Action dated Feb. 18, 2020 in TW Application No. 105122100. |
| Taiwanese Office Action dated Mar. 12, 2021 in TW Application No. 108135570. |
| Taiwanese Office Action dated Mar. 25, 2019 in TW Application No. 106128807. |
| Taiwanese Office Action dated Oct. 12, 2018 in TW Application No. 104144317. |
| Taiwanese Office Action dated Oct. 15, 2020 in TW Application No. 105122100. |
| Taiwanese Office Action dated Sep. 20, 2019 in TW Application No. 104139219, with summary translation. |
| Taiwanese Office Action dated Jul. 22, 2015 in TW Application No. 100115190. |
| Taiwanese Office Action dated Jun. 1, 2016 in TW Application No. 104144317. |
| Taiwanese Office Action dated May 26, 2016 in TW Application No. 100115201. |
| Taiwanese Search Report dated Oct. 11, 2018 in TW Application No. 106118525. |
| TW Office Action dated Mar. 29, 2022, in Application No. TW110125561 with English translation. |
| TW Office Action dated Mar. 29, 2022, in Application No. TW110134875 with English translation. |
| TW Office Action dated Nov. 24, 2021, in Application No. TW105122100 with English translation. |
| TW Office Action dated Nov. 24, 2021 in Application No. TW110121767 with English translation. |
| U.S. Corrected Notice of Allowability dated Jan. 25, 2022, in U.S. Appl. No. 16/785,547. |
| U.S. Final Office Action dated Dec. 14, 2020 in U.S. Appl. No. 15/916,142. |
| U.S. Final Office Action dated Jan. 31, 2020 in U.S. Appl. No. 15/916,142. |
| U.S. Final Office Action dated Jan. 6, 2020 in U.S. Appl. No. 16/088,024. |
| U.S. Final Office Action dated Jul. 23, 2015 in U.S. Appl. No. 13/462,725. |
| U.S. Final Office Action dated Jun. 27, 2013 in U.S. Appl. No. 12/814,277. |
| U.S. Final Office Action dated Jun. 27, 2013 in U.S. Appl. No. 12/814,279. |
| U.S. Final Office Action dated Mar. 7, 2022, in U.S. Appl. No. 15/916,142. |
| U.S. Non Final Office Action dated Jan. 13, 2022 in U.S. Appl. No. 16/879,255. |
| U.S. Non-Final Office action dated Oct. 4, 2021, in U.S. Appl. No. 16/721,655. |
| U.S. Non-Final Office action dated Oct. 4, 2021, in U.S. Appl. No. 16/859,856. |
| U.S. Non-Final Office Action dated Oct. 15, 2021 in U.S. Appl. No. 15/931,359. |
| U.S. Notice of Allowability (corrected) dated Jan. 8, 2020 in U.S. Appl. No. 16/250,738. |
| U.S. Notice of Allowance (corrected) dated Feb. 27, 2017 in U.S. Appl. No. 14/683,541. |
| U.S. Notice of Allowance (Corrected) dated Nov. 28, 2018 for U.S. Appl. No. 15/526,969. |
| U.S. Notice of Allowance dated Apr. 11, 2022 in U.S. Appl. No. 16/785,547. |
| U.S. Notice of Allowance dated Apr. 12, 2017 in U.S. Appl. No. 15/004,794. |
| U.S. Notice of Allowance dated Apr. 15, 2022 in U.S. Appl. No. 16/879,255. |
| U.S. Notice of Allowance dated Apr. 5, 2022, in U.S. Appl. No. 15/931,359. |
| U.S. Notice of Allowance dated Aug. 19, 2020 U.S. Appl. No. 16/088,024. |
| U.S. Notice of Allowance dated Aug. 4, 2015 in U.S. Appl. No. 14/209,993. |
| U.S. Notice of Allowance dated Aug. 9, 2017 in U.S. Appl. No. 15/004,794. |
| U.S. Notice of Allowance dated Dec. 10, 2020 in U.S. Appl. No. 16/205,084. |
| U.S. Notice of Allowance dated Dec. 19, 2019 in U.S. Appl. No. 15/612,928. |
| U.S. Notice of Allowance dated Dec. 24, 2021 in U.S. Appl. No. 16/785,547. |
| U.S. Notice of Allowance dated Dec. 3, 2019 in U.S. Appl. No. 15/795,843. |
| U.S. Notice of Allowance dated Dec. 4, 2017 for U.S. Appl. No. 15/587,114. |
| U.S. Notice of Allowance dated Feb. 12, 2020 in U.S. Appl. No. 16/168,587. |
| U.S. Notice of Allowance dated Feb. 14, 2014 for U.S. Appl. No. 13/627,798. |
| U.S. Notice of Allowance dated Feb. 23, 2022, in U.S. Appl. No. 16/721,655. |
| U.S. Notice of Allowance dated Feb. 5, 2020 in U.S. Appl. No. 16/204,540. |
| U.S. Notice of Allowance dated Jan. 11, 2017 in U.S. Appl. No. 14/841,511. |
| U.S. Notice of Allowance dated Jan. 21, 2014 in U.S. Appl. No. 13/610,684. |
| U.S. Notice of Allowance dated Jan. 22, 2015 in U.S. Appl. No. 14/052,455. |
| U.S. Notice of Allowance dated Jan. 23, 2020 for U.S. Appl. No. 16/284,876. |
| U.S. Notice of Allowance dated Jan. 26, 2022, in U.S. Appl. No. 16/859,856. |
| U.S. Notice of Allowance dated Jan. 27, 2017 in U.S. Appl. No. 14/683,541. |
| U.S. Notice of Allowance dated Jan. 3, 2019 for U.S. Appl. No. 15/340,853. |
| U.S. Notice of Allowance dated Jul. 10, 2013 in U.S. Appl. No. 12/772,075. |
| U.S. Notice of Allowance dated Jul. 17, 2019 in U.S. Appl. No. 15/795,843. |
| U.S. Notice of Allowance dated Jul. 22, 2021 in U.S. Appl. No. 16/384,822. |
| U.S. Notice of Allowance dated Jul. 26, 2019 in U.S. Appl. No. 15/612,928. |
| U.S. Notice of Allowance dated Mar. 11, 2019 for U.S. Appl. No. 15/507,734. |
| U.S. Notice of Allowance dated Mar. 12, 2014 in U.S. Appl. No. 12/814,277. |
| U.S. Notice of Allowance dated Mar. 17, 2014 in U.S. Appl. No. 12/814,279. |
| U.S. Notice of Allowance dated Mar. 26, 2018 for U.S. Appl. No. 15/587,114. |
| U.S. Notice of Allowance dated May 11, 2015 in U.S. Appl. No. 14/052,455. |
| U.S. Notice of Allowance dated May 22, 2018 in U.S. Appl. No. 15/457,609. |
| U.S. Notice of Allowance dated May 28, 2015 in U.S. Appl. No. 14/209,993. |
| U.S. Notice of Allowance dated May 31, 2012 issued in U.S. Appl. No. 13/166,537. |
| U.S. Notice of Allowance dated Nov. 21, 2019 for U.S. Appl. No. 15/204,868. |
| U.S. Notice of Allowance dated Nov. 25, 2015 in U.S. Appl. No. 13/462,725. |
| U.S. Notice of Allowance dated Nov. 28, 2018 for U.S. Appl. No. 15/953,327. |
| U.S. Notice of Allowance dated Nov. 6, 2019 in U.S. Appl. No. 16/250,738. |
| U.S. Notice of Allowance dated Oct. 18, 2018 for U.S. Appl. No. 15/526,969. |
| U.S. Notice of Allowance dated Oct. 31, 2018 in U.S. Appl. No. 15/441,130. |
| U.S. Notice of Allowance, dated Sep. 18, 2012, issued in U.S. Appl. No. 12/772,055. |
| U.S. Notice of Allowance dated Sep. 24, 2018 for U.S. Appl. No. 15/527,194. |
| U.S. Notice of Allowance dated Sep. 25, 2018 for U.S. Appl. No. 15/507,734. |
| U.S. Office Action, dated Apr. 26, 2012, issued in U.S. Appl. No. 12/772,055. |
| U.S. Office Action dated Apr. 5, 2018 in U.S. Appl. No. 15/441,130. |
| U.S. Office Action dated Aug. 12, 2016 in U.S. Appl. No. 14/683,541. |
| U.S. Office Action dated Aug. 12, 2019 in U.S. Appl. No. 15/916,142. |
| U.S. Office Action dated Aug. 16, 2012 issued in U.S. Appl. No. 12/772,075. |
| U.S. Office Action dated Aug. 2, 2021 in U.S. Appl. No. 16/785,547. |
| U.S. Office Action dated Aug. 6, 2014 in U.S. Appl. No. 14/052,455. |
| U.S. Office Action dated Dec. 26, 2012 in U.S. Appl. No. 12/772,075. |
| U.S. Office Action dated Dec. 30, 2016 in U.S. Appl. No. 15/004,794. |
| U.S. Office Action dated Dec. 31, 2018 in U.S. Appl. No. 15/795,843. |
| U.S. Office Action dated Feb. 16, 2012 issued in U.S. Appl. No. 13/166,537. |
| U.S. Office Action dated Feb. 25, 2019 for U.S. Appl. No. 15/204,868. |
| U.S. Office Action dated Jan. 14, 2015 in U.S. Appl. No. 13/462,725. |
| U.S. Office Action dated Jan. 20, 2012 issued in U.S. Appl. No. 12/772,075. |
| U.S. Office Action dated Jan. 23, 2019 in U.S. Appl. No. 15/612,928. |
| U.S. Office Action dated Jul. 10, 2018 for U.S. Appl. No. 15/953,327. |
| U.S. Office Action dated Jul. 10, 2019 in U.S. Appl. No. 16/250,738. |
| U.S. Office Action dated Jul. 23, 2021 in U.S. Appl. No. 15/916,142. |
| U.S. Office Action dated Jul. 25, 2019 for U.S. Appl. No. 16/168,587. |
| U.S. Office Action dated Jul. 25, 2019 in U.S. Appl. No. 16/088,024. |
| U.S. Office Action dated Jul. 25, 2019 in U.S. Appl. No. 16/204,540. |
| U.S. Office Action dated Jul. 25, 2019 in U.S. Appl. No. 16/284,876. |
| U.S. Office Action dated Jul. 28, 2016 in U.S. Appl. No. 14/841,511. |
| U.S. Office Action dated Jun. 16, 2020 in U.S. Appl. No. 15/916,142. |
| U.S. Office Action dated Jun. 25, 2013 in U.S. Appl. No. 13/610,684. |
| U.S. Office Action dated Jun. 27, 2018 in U.S. Appl. No. 15/612,928. |
| U.S. Office Action dated Mar. 16, 2022, in U.S. Appl. No. 16/719,700. |
| U.S. Office Action dated May 15, 2018 for U.S. Appl. No. 15/507,734. |
| U.S. Office Action dated May 15, 2018 for U.S. Appl. No. 15/527,194. |
| U.S. Office Action dated May 25, 2018 for U.S. Appl. No. 15/526,969. |
| U.S. Office Action dated Nov. 20, 2012 in U.S. Appl. No. 12/814,277. |
| U.S. Office Action dated Nov. 20, 2012 in U.S. Appl. No. 12/814,279. |
| U.S. Office Action dated Oct. 25, 2011 issued in U.S. Appl. No. 13/166,537. |
| U.S. Office Action dated Sep. 11, 2017 for U.S. Appl. No. 15/587,114. |
| U.S. Office Action dated Sep. 20, 2018 for U.S. Appl. No. 15/340,853. |
| U.S. Appl. No. 17/696,783, filed Mar. 16, 2022. |
| U.S. Restriction Requirement dated Apr. 27, 2022 in U.S. Appl. No. 16/782,543. |
| U.S. Restriction Requirement dated Feb. 17, 2022 in U.S. Appl. No. 16/774,621. |
| Velux SageGlass Flyer, 2007, 4 pages. |
| Vink, et al., “Lithium Trapping at Excess Oxygen in Sputter-Deposited a-WO3 Films”, Japanese Journal of Applied Physics, vol. 8, No. 3, Feb. 1, 1999, pp. 1540-1544. |
| Wikipedia webpage “Doping (semiconductors)” (Year: 2008). |
| Wikipedia webpage “Non-stoichiometric compound” (Year: 2008). |
| Yoshimura, et al., “Electrochromism in a Thin-Film Device Using Li2WO4 as an Li-Electrolyte”, Japanese Journal of Applied Physics, vol. 22, No. 1, Jan. 1983, pp. 152-156. |
| AU Examination report dated Aug. 17, 2022, in Application No. AU2020294239. |
| AU Examination report dated Jul. 5, 2022, in Application No. AU2020294239. |
| AU Office Action dated Jun. 23, 2022 in Application No. AU20210202495. |
| AU Office Action dated Oct. 19, 2022, in application No. AU2021236496. |
| CA Office Action dated Jul. 14, 2023, in Application No. CA2968832. |
| CA Office Action dated Jun. 9, 2022, in Application No. CA2992423. |
| Chinese Allowance with Search Report dated May 8, 2021 in CN Application No. 201610832436.6 with English translation. |
| Chinese Notice of Allowance with Search Report dated Jul. 15, 2021 in CN Application No. 201680047325.2 with English translation. |
| CN Office Action dated Apr. 3, 2023, in application No. 20158069923.5 with English translation. |
| CN Office Action dated Aug. 23, 2023, in application No. CN202080050069.9 with English translation. |
| CN Office Action dated Dec. 1, 2022 in Application No. CN201580069923.5 with English translation. |
| CN Office Action dated Jul. 31, 2023, in application No. CN202210140306.1 with English translation. |
| CN Office Action dated Jun. 9, 2023, in CN Application No. 201810154035.9 with English Translation. |
| CN Office Action dated Sep. 1, 2023, in Application No. CN202110652522.X with English translation. |
| CN Office Action dated Sep. 20, 2023, in Application No. CN202111168365.1 with English translation. |
| CN Office Action dated Sep. 25, 2023, in Application No. CN202011285041.1 with English translation. |
| CN Office Action dated Sep. 27, 2023, in application No. CN201980038535.9 with English translation. |
| CN Office Action dated Sep. 27, 2023, in application No. CN202111411891.6 with English translation. |
| EP Extended European Search Report dated Aug. 31, 2023, in Application No. EP23158636.3. |
| EP Extended European Search Report dated Dec. 19, 2022 in Application No. EP22187492.8. |
| EP Extended European Search report dated Feb. 3, 2023 in Application No. EP22204822.5. |
| EP Search report dated Mar. 15, 2022, in Application No. EP21206721.9. |
| Extended European search report dated Oct. 31, 2022, in Application No. EP22190639.9. |
| IN Office Action dated Aug. 4, 2022, in Application No. IN202238017115. |
| IN Office Action dated Aug. 26, 2022, in Application No. IN202037048424. |
| JP Office Action dated Apr. 4, 2023 in Application No. JP2021-013861 with English translation. |
| JP Office Action dated Aug. 22, 2023, in Application No. JP2022-112947 with English translation. |
| JP Office Action dated Dec. 7, 2021, in Application No. JP20200207808 with English translation. |
| JP Office Action dated Feb. 7, 2023 in Application No. JP2022-112947 with English translation. |
| JP Office Action dated Jan. 4, 2023, in Application No. JP2020-559396 with English translation. |
| JP Office Action dated Jun. 27, 2023, in Application No. JP2020-559396 with English translation. |
| JP Office Action dated Mar. 1, 2022, in Application No. JP2021-013861 with English translation. |
| JP Office Action dated Sep. 13, 2022, in Application No. JP2021-013861 with English translation. |
| KR Office Action dated Dec. 15, 2022, in Application No. KR10-2018-7002665 with English translation. |
| KR Office Action dated Jul. 31, 2023, in Application No. KR10-2018-7002665 with English translation. |
| Lee, S. et al., Electrochromic coloration efficiency of a-WO3-y thin films as a function of oxygen deficiency, Applied Physics Letters, Sep. 13, 1999, vol. 75, No. 11, pp. 1541-1543. |
| Lee, S. et al., “Electrochromic mechanism in a-WO3-y thin films”, Applied Physics Letters, Jan. 11, 1999, vol. 74, No. 2, pp. 242-244. |
| Ozin, G.A et al., “Smart Zeolites: New Forms of Tungsten and Molybdenum Oxides” Accounts of Chemical Research, 1992, vol. 25, No. 12, pp. 553-560. |
| TW Office Action dated Aug. 29, 2022, in Application No. TW110134875 with English translation. |
| TW Office Action dated Aug. 2, 2023, in application No. TW20220119773 with English translation. |
| TW Office Action dated Aug. 4, 2023, in application No. TW111145963 with English translation. |
| TW Office Action dated Aug. 7, 2023 in Application No. TW108114133 with English translation. |
| TW Office Action dated Mar. 21, 2023, in Application No. TW108114133 with English translation. |
| U.S. Corrected Notice of Allowance dated Jan. 5, 2023 in U.S. Appl. No. 16/782,543. |
| U.S. Corrected Notice of Allowance dated Nov. 15, 2022 in U.S. Appl. No. 16/774,621. |
| U.S. Corrected Notice of Allowance dated Sep. 21, 2022 in U.S. Appl. No. 16/774,621. |
| U.S. Non-Final office Action dated Sep. 8, 2022 in U.S. Appl. No. 15/916,142. |
| U.S. Notice of Allowance dated Jul. 11, 2022 in U.S. Appl. No. 16/774,621. |
| U.S Advisory Action dated Apr. 5, 2023 in U.S. Appl. No. 16/719,700. |
| U.S Advisory Action dated Mar. 3, 2023 in U.S. Appl. No. 16/660,660. |
| U.S. Corrected Notice of Allowance dated Dec. 23, 2022 in U.S. Appl. No. 16/949,463. |
| U.S. Corrected Notice of Allowance dated May 11, 2022 in U.S. Appl. No. 16/879,255. |
| U.S. Corrected Notice of Allowance dated Oct. 12, 2023, in U.S. Appl. No. 17/445,245. |
| U.S. Corrected Notice of Allowance dated Sep. 7, 2023, in U.S. Appl. No. 15/916,142. |
| U.S. Final Office Action dated Dec. 23, 2022 in U.S. Appl. No. 16/660,660. |
| U.S. Final Office Action dated Dec. 27, 2022 in U.S. Appl. No. 16/719,700. |
| U.S. Final Office Action dated Jul. 17, 2023, in U.S. Appl. No. 16/660,660. |
| U.S. Final Office Action dated Mar. 10, 2023 in U.S. Appl. No. 15/916,142. |
| U.S. Final Office Action dated Nov. 13, 2023 in U.S. Appl. No. 16/719,700. |
| U.S. Final Office Action dated Oct. 2, 2023, in U.S. Appl. No. 17/517,510. |
| U.S. Non-Final office Action dated Jul. 22, 2022 in U.S. Appl. No. 16/782,543. |
| U.S. Non-Final Office Action dated Apr. 4, 2023 in U.S. Appl. No. 16/660,660. |
| U.S. Non-Final Office Action dated Jul. 25, 2023, in U.S. Appl. No. 17/812,734. |
| U.S Non-Final Office Action dated Jul. 28, 2022, in U.S. Appl. No. 16/949,463. |
| U.S. Non-Final Office Action dated Jul. 31, 2023, in U.S. Appl. No. 17/810,656. |
| U.S Non-Final Office Action dated Jun. 10, 2022, in U.S. Appl. No. 16/660,660. |
| U.S. Non-Final Office Action dated May 2, 2023, in U.S. Appl. No. 17/517,510. |
| U.S. Non-Final Office Action dated May 19, 2023 in U.S. Appl. No. 16/719,700. |
| U.S. Non-Final Office Action dated May 25, 2023 in U.S. Appl. No. 17/445,245. |
| U.S. Non-Final Office Action dated Oct. 20, 2022, in U.S. Appl. No. 17/452,387. |
| U.S. Non-Final Office Action dated Sep. 6, 2023, in U.S. Appl. No. 17/249,641. |
| U.S. Non-Final Office Action dated Sep. 19, 2023, in U.S. Appl. No. 17/452,387. |
| U.S. Non-Final Office Action dated Sep. 26, 2023, in U.S. Appl. No. 17/804,515. |
| U.S. Notice of Allowance dated Sep. 6, 2022 in U.S. Appl. No. 16/774,621. |
| U.S. Notice of Allowance dated Aug. 23, 2023 in U.S. Appl. No. 15/916,142. |
| U.S. Notice of Allowance dated Dec. 2, 2022 in U.S. Appl. No. 16/782,543. |
| U.S. Notice of Allowance dated Dec. 5, 2022 in U.S. Appl. No. 16/949,463. |
| U.S. Notice of Allowance dated Feb. 24, 2023 in U.S. Appl. No. 17/452,387. |
| U.S. Notice of Allowance dated Jan. 30, 2023 in U.S. Appl. No. 16/782,543. |
| U.S. Notice of Allowance dated Mar. 16, 2023 in U.S. Appl. No. 17/452,387. |
| U.S. Notice of Allowance dated May 13, 2022 in U.S. Appl. No. 16/859,856. |
| U.S. Notice of Allowance dated Sep. 20, 2023, in U.S. Appl. No. 17/816,364. |
| U.S. Notice of Allowance dated Sep. 27, 2023, in U.S. Appl. No. 17/445,245. |
| U.S. Appl. No. 18/055,825, inventors Kozlowski et al., filed Nov. 15, 2022. |
| U.S. Appl. No. 18/153,090, Wang et al., filed Jan. 11, 2023. |
| U.S. Appl. No. 18/323,307, inventors Robert Tad Rozbicki et al., filed May 24, 2023. |
| U.S. Restriction Requirement dated Feb. 17, 2023 in U.S. Appl. No. 17/517,510. |
| U.S Restriction requirement dated Nov. 6, 2023 in U.S. Appl. No. 18/050,918. |
| Number | Date | Country | |
|---|---|---|---|
| 20220260885 A1 | Aug 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62192443 | Jul 2015 | US | |
| 62085098 | Nov 2014 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16785547 | Feb 2020 | US |
| Child | 17656367 | US | |
| Parent | 16250738 | Jan 2019 | US |
| Child | 16785547 | US | |
| Parent | 15526969 | US | |
| Child | 16250738 | US |
