CN114096913A - Electrochromic cathode material - Google Patents

Abstract

Various embodiments herein relate to electrochromic devices and electrochromic device precursors, and methods and apparatus for making such electrochromic devices and electrochromic device precursors. In certain embodiments, the electrochromic device or precursor may comprise one or more specific materials, such as a specific electrochromic material and/or a specific counter electrode material. In various embodiments, the electrochromic material comprises tungsten molybdenum oxide. In these or other embodiments, the counter electrode material may include nickel tungsten oxide, nickel tungsten tantalum oxide, nickel tungsten niobium oxide, nickel tungsten tin oxide, or another material.

Description

Electrochromic cathode material

Is incorporated by reference

The present application is a continuation-in-part application of U.S. patent application No. 16/384,822 filed on 15/4/2019; and this application claims the benefit of U.S. provisional patent application No. 62/858,943 filed on 7.6.2019. Both of these applications are incorporated by reference herein in their entirety and for all purposes.

The application data sheet is filed concurrently with this specification as part of this application. Each application for which this application claims a benefit or priority identified in a concurrently filed application data sheet is incorporated by reference herein in its entirety and for all purposes.

Background

Electrochromism is a phenomenon that exhibits a reversible electrochemically-mediated change in optical properties when the material is placed in different electronic states, typically by being subjected to a change in voltage. The optical characteristic is typically one or more of color, transmittance, absorbance, and reflectance. One well-known electrochromic material is tungsten oxide (WO)₃). Tungsten oxide is a cathodic electrochromic material in which a colored transition from transparent to blue occurs by electrochemical reduction.

Electrochromic materials may be incorporated into windows for residential, commercial, and other uses, for example. The color, transmission, absorption and/or reflectance of such windows can be changed by changing the characteristics of the electrochromic material, i.e., an electrochromic window is a window that can be darkened or lightened electronically. A small voltage applied to the electrochromic device of the window will darken the window; reversing the voltage brightens the window. This capability allows control of the amount of light passing through the window and provides the electrochromic window with the opportunity to act as an energy saving device.

Despite the discovery of electrochromism in the 60's of the 20 th century, electrochromic devices, and electrochromic windows in particular, have unfortunately suffered from various problems, and have not yet begun to realize their full commercial potential despite recent advances in electrochromic technology, equipment, and related methods of manufacturing and/or using electrochromic devices.

The background description provided herein is for the purpose of generally presenting the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure.

Disclosure of Invention

Certain embodiments herein relate to electrochromic devices and electrochromic device precursors, and methods and apparatus for forming such electrochromic devices and electrochromic device precursors. In various embodiments, an electrochromic device or electrochromic device precursor includes an electrochromic layer including an electrochromic material including tungsten, molybdenum, and oxygen. This material is commonly referred to as tungsten molybdenum oxide. In some cases, the tungsten molybdenum oxide electrochromic material may be paired with a specific counter electrode material, for example to provide the desired color quality when the device is in a colored state. In some cases, the tungsten molybdenum oxide electrochromic material may be paired with a specific counter electrode material, wherein the intrinsic ionically conductive and electrically insulating layer is formed after the tungsten molybdenum oxide electrochromic material and the counter electrode material in question are layered in direct contact with each other. In some cases, alone or in combination with the above, the tungsten molybdenum oxide electrochromic material is part of a layered stack of electrochromic materials. In some cases, a layered stack of electrochromic materials may be combined with a layered stack of counter electrode materials, with a conventional ion conductor layer or an intrinsic ion conductor layer formed in situ as described above. In certain embodiments, the layered stack of electrochromic material, counter electrode material, or both may be replaced with a single layer having a graded composition, i.e., the composition of the stack varies over the thickness of the stack.

In one aspect of the disclosed embodiments, there is provided an electrochromic device or an electrochromic device precursor comprising: a first conductive layer having a thickness between about 10-500 nm; an electrochromic layer comprising an electrochromic material comprising a polymer having a formula W_1-xMo_xO_yWherein x is between about 0.05-0.30 and y is between about 2.5-4.5. The electrochromic layer may have a thickness of between about 100 and 500 nm; pair comprising counter electrode materialAn electrode layer, the pair of electrode materials including nickel tungsten oxide, the thickness of the pair of electrode layers being between about 100nm and 500 nm; and a second conductive layer having a thickness between about 100-400nm, wherein the electrochromic layer and the counter electrode layer are positioned between the first conductive layer and the second conductive layer, and wherein the electrochromic device is all solid state and inorganic.

In some embodiments, the electrochromic layer may be crystalline (e.g., nanocrystalline, microcrystalline, or a combination thereof). In some embodiments, the electrochromic layer may be amorphous. Heating the device during fabrication can impart particular characteristics to the electrochromic layer, including durability, faster switching, and improved adhesion. In these or other embodiments, the counter electrode material may be crystalline (e.g., nanocrystals, microcrystals, or combinations thereof). In some embodiments, the counter electrode layer may be amorphous. In certain embodiments, the counter electrode material comprises nickel tungsten tantalum oxide. In certain embodiments, the counter electrode material comprises nickel tungsten niobium oxide. In certain embodiments, the counter electrode material comprises nickel tungsten tin oxide.

One or more layers of the electrochromic device or electrochromic device precursor may be formed by sputtering. In some cases, the electrochromic layer, the counter electrode layer, and the second conductive layer are all formed by sputtering.

In various embodiments, the electrochromic device or electrochromic device precursor does not comprise a homogenous layer of ion conducting electrically insulating material between the electrochromic layer and the counter electrode layer. In some cases, the electrochromic material is in physical contact with the counter electrode material. In these or other cases, at least one of the electrochromic layer and the counter electrode layer may include two or more layers or portions, one of which is superstoichiometric with respect to oxygen. In one embodiment, (a) the electrochromic layer comprises two or more layers, with the layer being superstoichiometric with respect to oxygen in contact with the counter electrode layer, or (b) the counter electrode layer comprises two or more layers, with the layer being superstoichiometric with respect to oxygen in contact with the electrochromic layer. In another embodiment, (a) the electrochromic layer comprises two or more portions that together form the electrochromic layer as a graded layer, a portion of the electrochromic layer that is superstoichiometric with respect to oxygen being in contact with the counter electrode layer, or (b) the counter electrode layer comprises two or more portions that together form the counter electrode layer as a graded layer, a portion of the counter electrode layer that is superstoichiometric with respect to oxygen being in contact with the electrochromic layer. In some embodiments, the electrochromic device or electrochromic device precursor further comprises an ionically conductive and substantially electrically insulating material formed in situ at the interface between the electrochromic layer and the counter electrode layer.

In certain embodiments, the electrochromic device or electrochromic device precursor further comprises an ion conducting layer comprising a material selected from the group consisting of: lithium silicate, lithium aluminum silicate, lithium oxide, lithium tungstate, lithium aluminum borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium oxynitride, lithium aluminum fluoride, lithium phosphorus oxynitride (LiPON), Lanthanum Lithium Titanate (LLT), lithium tantalate, lithium zirconium oxide, lithium silicon oxycarbonitride (LiSiCON), lithium phosphate, lithium titanium phosphate, lithium germanium vanadium oxide, lithium zinc germanium oxide, and combinations thereof. In some such cases, the thickness of the ion conducting layer can be between about 5-100 nm. In some embodiments, the ion conducting layer comprises a material selected from the group consisting of: lithium silicate, lithium aluminum silicate, lithium zirconium silicate, lithium borosilicate, lithium phosphosilicate, lithium phosphorus oxynitride (LiPON), lithium silicon oxycarbonitride (LiSiCON), and combinations thereof.

In another aspect of the disclosed embodiments, there is provided a method of manufacturing an electrochromic device or an electrochromic device precursor, the method comprising: receiving a substrate, wherein the substrate is provided with a first conducting layer; forming an electrochromic layer comprising an electrochromic material comprising a material having a formula W according to_1-xMo_xO_yWherein x is between about 0.05-0.20 and y is between about 2.5-4.5; forming a counter electrode layer including a counter electrode material including nickel tungsten oxide; and forming a second conductive layer, wherein the electrochromic layer and the counter electrode layer are positioned between the first conductive layer and the second conductive layerAnd wherein the electrochromic device is all solid state and inorganic.

In some embodiments, the electrochromic layer may be crystalline (e.g., nanocrystalline, microcrystalline, or a combination thereof). In some embodiments, the electrochromic layer may be amorphous. In these or other embodiments, the counter electrode layer may be crystalline (e.g., nanocrystals, microcrystals, or combinations thereof). In some embodiments, the counter electrode layer is amorphous. In certain embodiments, the counter electrode material comprises nickel tungsten tantalum oxide. In certain embodiments, the counter electrode material comprises nickel tungsten niobium oxide. In some embodiments, the counter electrode material comprises nickel tungsten tin oxide.

One or more of these layers may be formed by sputtering. For example, in some cases, the electrochromic layer, the counter electrode layer, and the second conductive layer are all formed by sputtering.

In some cases, the electrochromic device or electrochromic device precursor does not include a homogenous layer of ion conducting electrically insulating material between the electrochromic layer and the counter electrode layer. In some such cases, the electrochromic material may be in physical contact with the counter electrode material. In these or other cases, at least one of the electrochromic layer and the counter electrode layer may include two or more layers or portions, one of which is superstoichiometric with respect to oxygen. For example, in one example, either: (a) the electrochromic layer comprises two or more layers, the oxygen-superstoichiometric layer being in contact with the counter electrode layer, or (b) the counter electrode layer comprises two or more layers, the oxygen-superstoichiometric layer being in contact with the electrochromic layer. In another example, either: (a) the electrochromic layer comprises two or more portions, the portion of the electrochromic layer that is superstoichiometric with respect to oxygen being in contact with the counter electrode layer, or (b) the counter electrode layer comprises two or more portions, the portion of the counter electrode layer that is superstoichiometric with respect to oxygen being in contact with the electrochromic layer.

In some embodiments, the method may further comprise forming in situ an ion conducting layer comprising an ion conducting and substantially electrically insulating material, the ion conducting layer being positioned at an interface between the electrochromic layer and the counter electrode layer. In some embodiments, the method may further comprise forming an ion conducting layer comprising a material selected from the group consisting of: lithium silicate, lithium aluminum silicate, lithium oxide, lithium tungstate, lithium aluminum borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium oxynitride, lithium aluminum fluoride, lithium phosphorus oxynitride (LiPON), Lanthanum Lithium Titanate (LLT), lithium tantalate, lithium zirconium oxide, lithium silicon oxycarbonitride (LiSiCON), lithium phosphate, lithium titanium phosphate, lithium germanium vanadium oxide, lithium zinc germanium oxide, and combinations thereof, wherein the ion conducting layer is formed prior to forming at least one of the electrochromic layer and the counter electrode layer. In these or other cases, the thickness of the ion conducting layer may be between about 5-100 nm. In some cases, the ion conducting layer may comprise a material selected from the group consisting of: lithium silicate, lithium aluminum silicate, lithium zirconium silicate, lithium borosilicate, lithium phosphosilicate, lithium phosphorus oxynitride (LiPON), lithium silicon oxycarbonitride (LiSiCON), and combinations thereof.

In certain embodiments, one or more metal-containing targets and comprising between about 40-80% O can be used₂And between about 20-60% Ar, wherein the substrate is at least intermittently heated to between about 150-450 ℃ during the formation of the electrochromic layer, the thickness of the electrochromic layer is between about 200-700nm, and using one or more metal-containing targets and an atmosphere comprising between about 30-100% O₂And between about 0-30% Ar, the counter electrode layer having a thickness between about 100-400 nm. The method may include, after forming the counter electrode layer: heating the substrate in an inert atmosphere at a temperature between about 150-450 ℃ for a duration of between about 10-30 minutes; heating the substrate in an inert atmosphere at a temperature of about 150 ℃ - & lt 450 ℃ for a duration of between about 1-15 minutes in an oxygen atmosphere; and heating the substrate in air at a temperature between about 250-350 ℃ for a duration of between about 20-40 minutes after heating the substrate in an oxygen atmosphere. In various embodiments, the electrochromic layer is formed, and the counter electrode is chargedThe substrate may be maintained in a vertical orientation during the pole layer and the second conductive layer.

These and other features will be described below with reference to the associated drawings.

Drawings

Fig. 1 depicts a view of an electrochromic device according to some embodiments.

Fig. 2A is a flow diagram of a process flow describing aspects of a method of fabricating an electrochromic device according to an embodiment.

Fig. 2B is a top view depicting a step in the process flow described with respect to fig. 2A.

Fig. 2C depicts a cross-section of the electrochromic lite described with respect to fig. 2B.

Figure 2D is a flow chart describing a method of depositing an electrochromic stack on a substrate.

Fig. 3A depicts an integrated deposition system according to some embodiments.

Fig. 3B depicts the integrated deposition system in a perspective view.

Fig. 3C depicts a modular integrated deposition system.

Fig. 3D depicts an integrated deposition system with two lithium deposition stations.

Fig. 3E depicts an integrated deposition system with one lithium deposition station.

Fig. 4 depicts an example of an electrochromic stack with a cathodic electrochromic layer comprising two sub-layers

Fig. 5 depicts an additional example of an electrochromic stack having an anodic electrochromic layer comprising a plurality of sub-layers.

Detailed Description

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well known process operations have not been described in detail in order not to unnecessarily obscure the disclosed embodiments. Although the disclosed embodiments will be described in conjunction with specific details, it will be understood that it is not intended to limit the disclosed embodiments.

Various embodiments herein relate to electrochromic devices, electrochromic device precursors, and methods and apparatus for forming such electrochromic devices and electrochromic device precursors. In many embodiments, an electrochromic device includes an electrochromic material having a particular composition including at least tungsten, molybdenum, and oxygen. The amount of oxygen in the material will vary depending on the stoichiometry of the metals in the composition, but may be defined more specifically as follows.

I. Overview of electrochromic devices

A schematic cross section of an electrochromic device 100 according to some embodiments is shown in fig. 1. The electrochromic device includes a substrate 102, a first electrically Conductive Layer (CL)104, an electrochromic layer (EC)106, an ion conductive layer (IC)108, a counter electrode layer (CE)110, and a second electrically Conductive Layer (CL) 114. Elements 104, 106, 108, 110, and 114 are collectively referred to as an electrochromic stack 120. In some cases, the ion conductor layer 108 may be omitted, as discussed further below. A voltage source 116 operable to apply a potential across the electrochromic stack 120 effects a transition of the electrochromic device from, for example, a clear state to a colored state. In other embodiments, the order of the layers is reversed relative to the substrate. That is, the order of layers is as follows: the electrode comprises a substrate, a conducting layer, a counter electrode layer, an ion conducting layer, an electrochromic material layer and a conducting layer.

The electrochromic layer 106 is cathodically colored, while the counter electrode layer 110 may be anodically colored or optically passivated (sometimes referred to as an "ion storage layer" because ions are left there when the device is not colored). For example, while tungsten oxide cathodes are colored dark blue, nickel oxide anodes are colored brown. When colored in tandem, a more neutral blue color will be created. Nevertheless, improvements are still needed. The inventors have found that when coloured in series with certain nickel oxide based anode materials, certain materials become tungsten oxide cathode materials, making the colour tone of the electrochromic window more aesthetic.

It is to be understood that the reference to a transition between a bleached state and a colored state is non-limiting and only presents one example of the many possible electrochromic transitions that can be implemented. Unless otherwise specified herein, whenever a bleached-coloring transition is mentioned, the corresponding device or process includes other optical state transitions, such as non-reflective to reflective, transparent to opaque, and the like. Furthermore, the term "bleached" refers to an optically neutral state, such as colorless, transparent, or translucent. Still further, unless otherwise specified herein, the "color" of the electrochromic transition is not limited to any particular wavelength or range of wavelengths. As will be appreciated by those skilled in the art, the selection of suitable electrochromic and counter electrode materials determines the relevant optical transition.

In embodiments described herein, the electrochromic device reversibly cycles between a bleached state and a colored state. In the bleached state, an electrical potential is applied to the electrochromic stack 120 such that the available ions in the stack that can place the electrochromic material 106 in the colored state are primarily present in the counter electrode 110. When the potential on the electrochromic stack is reversed, ions are transported across ion conducting layer 108 to electrochromic material 106 and bring the material into a colored state.

In certain embodiments, all of the materials comprising electrochromic stack 120 are inorganic, solid (i.e., in the solid state), or both inorganic and solid. Since organic materials tend to degrade over time, inorganic materials offer the advantage of reliable electrochromic stacks that can operate for long periods of time. Materials in the solid state also offer the advantage of not having containment and leakage problems, as materials in the liquid state often present containment and leakage problems. Each of the layers in the electrochromic device is discussed in detail below. It is to be understood that any one or more of the layers in the stack may contain a certain amount of organic material, but in many embodiments, one or more of these layers contains little or no organic material. This can also be said for liquids that may be present in small amounts in one or more layers. It should also be understood that the solid material may be deposited or otherwise formed by processes employing liquid components, such as certain processes employing sol-gel or chemical vapor deposition.

Referring again to fig. 1, the voltage source 116 is typically a low voltage power supply (on the order of between about 1V and about 20V depending on the electrochromic device used) and may be configured to operate with radiation sensors and other environmental sensors. The voltage source 116 may also be configured to interface with an energy management system, such as a computer system that controls the electrochromic device according to factors such as time of year, time of day, and measured environmental conditions. Such energy management systems in combination with large area electrochromic devices (i.e., electrochromic apertures) can significantly reduce the energy consumption of a building.

A. Substrate

Any material having suitable optical, electrical, thermal and mechanical properties may be used as the substrate 102 in fig. 1. Such substrates include, for example, glass, plastic, and mirror materials.

In some embodiments, the substrate comprises glass, such as soda lime glass. The substrate may include one or more optional optical tuning and/or ion diffusion barriers. Examples of these include silica, titania and undoped tin oxide. The thickness of each of the optical tuning and/or ion diffusion barriers may be about 1-100 nm. In one embodiment, the thickness of the optical tuning and/or ion diffusion barrier layer may be about 5-50nm or 5-30 nm. One or more such layers may be employed. In some embodiments, such layers include at least a silicon dioxide layer and an undoped tin oxide layer. In some embodiments, such layers include at least two separate silica layers. Further examples of such layers are provided in U.S. patent No. 5,168,003, which is incorporated herein by reference in its entirety.

The substrate may have any thickness as long as it has suitable mechanical properties to support the electrochromic stack 120. Although substrate 102 may be any thickness or transparent material, in some embodiments it is glass or plastic and is between about 0.01mm and about 10mm thick. In certain embodiments, the substrate is glass, has a thickness between about 3mm and 9mm, and may be strengthened. In other embodiments, the glass may be very thin, between about 0.01mm and 1mm thick, or between about 0.1mm and 1mm thick, and sodium free or have a very high glass transition temperatureLow sodium or other base content, e.g., such as those of Corning, N.Y.)

Or other similar glass substrates from commercial sources, such as substrates from the asahi glass company (AGC from tokyo, japan).

In some embodiments of the invention, the substrate is architectural glass. Architectural glass is glass used as a building material. Architectural glass is typically used in commercial buildings, but may also be used in residential buildings, and typically, but not necessarily, separates an indoor environment from an outdoor environment. In certain embodiments, the architectural glass is at least 20 inches by 20 inches, and may be larger, for example up to about 72 inches by 120 inches. The architectural glass typically has a thickness of at least about 2 mm.

B. Conductive layer

Returning to fig. 1, on top of the substrate 102 is a conductive layer 104. In certain embodiments, one or both of the conductive layers 104 and 114 are inorganic and/or solid. The conductive layers 104 and 114 can be made of many different materials, including conductive oxides, thin metal coatings, conductive metal nitrides, and composite conductors of metal oxides and metals. In some embodiments, the first conductive layer closest to the substrate is a metal layer and the second conductive layer is a transparent metal oxide. Such a configuration is useful for an electrochromic mirror, where incident light is reflected from the first conductive layer and must pass through the electrochromic material, and thus a dimming mirror is realized. Typically, the conductive layers 104 and 114 are transparent at least in the wavelength range in which the electrochromic layer exhibits electrochromism and/or substantially in the visible spectral range. 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, fluorinated tin oxide, zinc oxide, aluminum zinc oxide, doped zinc oxide, ruthenium oxide, doped ruthenium oxide, and the like. Since oxides are commonly used for these layers, they are sometimes referred to as "transparent conductive oxide" (TCO) layers. A substantially transparent thin metal coating may also be used. Examples of metals for such thin metal coatings include transition metals, including gold, platinum, silver, aluminum, nickel alloys, and the like. Thin silver-based metal coatings, well known in the glass industry, are also used. Examples of the conductive nitride include titanium nitride, tantalum nitride, titanium oxynitride, and tantalum oxynitride. The conductive layers 104 and 114 may also be composite conductors. Such composite conductors can be fabricated by placing a pattern of highly conductive ceramic and metal wires or conductive layers on one surface of a substrate and then coating with a transparent conductive material such as doped tin oxide or indium tin oxide. Ideally, such wires should be thin enough to be invisible to the naked eye (e.g., about 100 μm or less). Other composite conductors include metal oxide-metal oxide sandwich materials, such as indium tin oxide-metal-indium tin oxide layers, sometimes collectively referred to as "IMIs," where the metal is, for example, silver, gold, copper, aluminum, or alloys thereof.

In some embodiments, commercially available substrates (such as glass substrates) contain a transparent conductive layer coating. Such products may be used for both the substrate 102 and the conductive layer 104. Examples of such Glass substrates include those sold under the trademark TEC Glass by Pilkington, Toledo, Ohio^TMSold and sold under the trademark SUNGATE by PPG Industries of pittsburgh, pennsylvania ^TM300 and SUNGATE^TM500, which is coated with a conductive layer. TEC Glass^TMIs glass coated with a fluorinated tin oxide conductive layer.

In some embodiments of the present invention, the same conductive layer is used for both conductive layers (i.e., conductive layers 104 and 114). In some embodiments, a different conductive material is used for each conductive layer 104 and 114. For example, in some embodiments, TEC Glass^TMFor the substrate 102 (float glass) and conductive layer 104 (fluorinated tin oxide), and indium tin oxide for the conductive layer 114. As mentioned above, some use TEC Glass^TMIn an embodiment of (a), a sodium diffusion barrier layer is present between the glass substrate 102 and the TEC conductive layer 104. In some embodiments, the conductive layer 104 has a titanium dioxide layer thereon, adjacent to one side of the substrateAnd (4) oppositely. In certain embodiments, the thickness of the titanium dioxide layer is about 50nm or less. An optional titanium dioxide layer may be employed for its optical and/or insulating properties. An example of a stack employing titanium dioxide layers is provided in U.S. patent application publication No. 2014/0022621, published 2014, 1-23, which is incorporated herein by reference in its entirety.

The function of the conductive layer is to spread the potential provided by the voltage source 116 over the surface of the electrochromic stack 120 to the interior regions of the stack with a relatively small ohmic potential drop. The electrical potential is transferred to the conductive layer through an electrical connection to the conductive layer. In some embodiments, bus bars (one in contact with conductive layer 104 and one in contact with conductive layer 114) provide electrical connections between voltage source 116 and conductive layers 104 and 114. The conductive layers 104 and 114 may also be connected to a voltage source 116 using other conventional methods.

The two conductive layers may be resistance matched even if they are composed of different materials. Resistance matching can avoid the situation where one conductive layer becomes a tinting bottleneck, since a conductive layer with a higher resistance can limit the tinting time. Furthermore, in such cases, uneven coloring fronts can be a problem.

In some embodiments, the thickness of conductive layers 104 and 114 is between about 5nm to about 10,000 nm. In some embodiments, the thickness of conductive layers 104 and 114 is between about 10nm to about 1,000 nm. In other embodiments, the thickness of the conductive layers 104 and 114 is between about 10nm and about 500 nm. In the use of TEC Glass^TMIn some embodiments for the substrate 102 and the conductive layer 104, the conductive layer has a thickness of about 300 to 400 nm. In some embodiments using indium tin oxide for the conductive layer 114, the thickness of the conductive layer is about 100nm to 500nm (280 nm in one embodiment). More generally, thicker layers of conductive material may be used, so long as they provide the necessary electrical (e.g., conductivity) and optical (e.g., transmittance) properties. Typically, the conductive layers 104 and 114 are as thin as possible to increase transparency and reduce cost. In some embodiments, one or both conductive layers are crystalline or substantially crystalline. In some embodiments, the conductive layer is of a high proportionLarge equiaxed grains.

Sheet resistance (R) of the conductive layer_s) It is also important because in large electrochromic windows the area covered by these layers is relatively large. In some embodiments, the sheet resistance of conductive layers 104 and 114 is about 5 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 sheet resistances of both layers are about 10-15 ohms per square. In one embodiment, the sheet resistance of the two layers is less than 10 ohms per square or less than 5 ohms per square or less than 3 ohms per square, respectively.

C. Electrochromic layer

Returning to fig. 1, overlying conductive layer 104 is an electrochromic layer 106. In an embodiment of the present invention, the electrochromic layer 106 is inorganic and/or solid, in an exemplary embodiment. A variety of different materials may be used for the electrochromic layer 106. In conventional electrochromic devices, the electrochromic layer may contain, for example, tungsten oxide. The inventors have found that electrochromic devices using tungsten molybdenum oxide in the electrochromic layer have superior characteristics over conventional devices, as described herein. The electrochromic metal oxide may further include protons, lithium, sodium, potassium, or other ions. The electrochromic layer 106 as described herein is capable of receiving such ions transferred from the counter electrode layer 110.

Tungsten oxide has long been used as an electrochromic material. Over time, various materials have been added to tungsten oxide to adjust its characteristics. In various embodiments herein, the electrochromic layer 106 comprises an electrochromic material comprising tungsten, molybdenum, and oxygen. Such materials may be referred to as tungsten molybdenum oxides. Tungsten molybdenum oxide exhibits both a high degree of durability and improved color characteristics compared to conventional devices, particularly when used with certain nickel oxide-based counter electrode materials, such as nickel oxide containing one or more of tungsten oxide, tantalum oxide, niobium oxide, tin oxide, and mixtures thereof.

Molybdenum included in the electrochromic material changes the color characteristics of the electrochromic layer, resulting in a more neutral color of the electrochromic device. For example, tungsten oxide has an intense blue appearance, which may be undesirable. The inclusion of molybdenum makes the blue color more neutral.

The tungsten molybdenum oxide materials used in the electrochromic devices described herein may be represented by the formula: w_1-xMo_xO_yWherein the total amount of tungsten and molybdenum in the material is expressed in relative atomic percent, wherein x represents the atomic percent of molybdenum, and 1-x represents the atomic percent of tungsten. For example, from W_0.90Mo_0.10O_yThe compounds represented have a metal content of 90 atomic% for tungsten and a metal content of 10 atomic% for molybdenum.

Of course, the actual material contains both oxygen and two metals. For materials, y represents the stoichiometric ratio of oxygen to metal in the compound. In certain embodiments, y is between about 2.5 and about 4.5. In one embodiment, y is between about 3.0 and about 3.5. In one embodiment, y is between about 3.0 and about 3.2. The value of y may have a large influence on the properties of the material. Such characteristics may include whether the material exhibits electrochromism, and whether the material can act as a precursor to an ion-conducting material. That is, as described by WO_yThe electrochromic tungsten oxides represented may have an oxygen content (where y is 3 or less, typically between about 2.5 and 3), and are made by WO_yThe superstoichiometric tungsten oxide (which is superstoichiometric with respect to oxygen and can be used as a precursor for the ion-conducting material) represented has an oxygen content (where y is greater than 3, for example between 3.1 and 4.5); tungsten and molybdenum in the compounds described herein may have the same associated amount of oxygen. For example, for tungsten molybdenum oxide that exhibits electrochromism, each metal atom of the material may have 3 or fewer oxygen atoms, or each metal atom of tungsten molybdenum oxide that is superstoichiometric with respect to oxygen may have more than 3 oxygen atoms (and may function as a precursor for ion-conducting materials). Thus, when y is 3 or less, it represents the stoichiometry or of the two metals combined in the materialAt sub-stoichiometric oxygen levels, the material is cathodically colored. Notably, electrochromic tungsten molybdenum oxides are more color neutral than, for example, electrochromic tungsten oxides, which have a deep blue color when colored (e.g., via insertion of positive ions, such as protons or lithium ions, and electrons). In certain embodiments, when y is 3 or greater, the material is superstoichiometric oxidized, for example, when used in a fabrication process for fabricating an electrochromic device (and can be so stable in the electrochromic device precursors used in the foregoing fabrication process), described in more detail herein.

For tungsten molybdenum oxide W_1-xMo_xO_yIn certain embodiments, subscripts x and y fall within a specified range. For example, in some embodiments, x may be at least about 0.05, or at least about 0.10, or at least about 0.15. In these or other cases, x may be about 0.30 or less, or about 0.25 or less, or about 0.2 or less. In some embodiments, x is between about 0.05 and 0.30, or between about 0.10 and 0.25, or between about 0.15 and 0.2. In these or other embodiments, y may be between about 2.5 and 4.5, or between about 2.5 and 3.0, or between about 2.5 and 2.9, or between about 3.0 and 3.5, or between about 3.5 and 4.5. In these or other embodiments, y may be at least about 2.5, such as at least about 2.7, or at least about 2.9, or at least about 3.0, or at least about 3.5, or at least about 4.0. In these or other cases, y can be about 4.5 or less, for example about 4.0 or less, or about 3.5 or less, or about 3.3 or less, or about 3.1 or less, or about 3.0 or less, or about 2.9 or less. In certain embodiments, y is about 2.5 to 3.5, about 2.7 to 3.3, about 2.8 to 3.2, or about 2.8 to 3.1.

In some embodiments, the electrochromic material may further comprise titanium. For example, the electrochromic material may include tungsten, titanium, molybdenum, and oxygen. This material may be referred to as tungsten titanium molybdenum oxide. The inclusion of titanium in the electrochromic material may improve the stability/durability of the electrochromic layer, which means that the resulting electrochromic device is less likely to crack over time with repeated insertion/extraction of ions and electrons.

In various embodiments, the electrochromic layer may include two or more materials (e.g., deposited as a bilayer, graded layer, or other combination of layers) having different compositions, one or both of which may include tungsten molybdenum oxide. In various embodiments where the electrochromic layer includes two or more materials, one material may provide electrochromic properties, while the other material may serve as a precursor for the ion-conducting and substantially electrically insulating material.

In certain embodiments, the tungsten oxide portion of the electrochromic stack is deposited in at least two different compositions having different amounts of oxygen. In one example, the tungsten molybdenum electrochromic layer is deposited as a bilayer, where y is between about 2.5 and about 3.5 in a first layer of the bilayer and is greater than 3 in a second layer of the bilayer. In another embodiment, the tungsten molybdenum electrochromic layer is deposited as a single graded layer fabricated such that the value of y varies according to the depth of the layer. For example, tungsten molybdenum oxide is sputtered onto a substrate with a first oxygen concentration in an initial portion of the deposition, and then the oxygen concentration is increased as additional tungsten molybdenum oxide material is deposited. For example, such varying oxygen concentrations between multiple layers or in a graded layer may be used to fabricate the ion conductor material in situ after deposition of the counter electrode material and at the interface between the tungsten molybdenum material and the counter electrode material, as described in more detail below. This fabrication scheme presents the electrochromic layer being formed before the counter electrode layer. In the case where the counter electrode layer is formed before the electrochromic layer, the first and second layers of the electrochromic layer may be interchanged (e.g., such that the electrochromic material, which acts as a precursor for the ion-conducting and substantially electrically insulating material, is deposited before the electrochromic material exhibits electrochromic).

In some cases, the electrochromic layer is deposited in at least two different compositions having different metals or combinations of metals in the compositions. In one example, the electrochromic layer is deposited as a bilayer, wherein a first layer of the bilayer includes at least one metal that is not present in a second layer of the bilayer. In these or other embodiments, the second layer of the bilayer may include at least one metal that is not present in the first layer of the bilayer.

In one example, the first layer of the bilayer is tungsten molybdenum oxide (e.g., W)_1-xMo_xO_yWhere y is about 3.5 or less), and the second layer of the bilayer is tungsten oxide (e.g., WO)_yWherein y is greater than 3). In another example, the first layer of the bilayer is tungsten molybdenum oxide (e.g., W)_1-xMo_xO_yWhere y is about 3.5 or less), and the second layer of the bilayer is tungsten molybdenum oxide (e.g., W)_1-xMo_xO_yWherein x is between about 0.05 and 0.20, or between about 0.05 and 0.08; and y is greater than 3). In some other examples, the first and second layers of the bilayer may be switched, e.g., such that the second layer of the bilayer is W_1-xMo_xO_y(wherein y is greater than 3) and the first layer of the bilayer is WO_yOr W_1-xMo_xO_y(wherein x is as above for W_1-xMo_xO_yDescribed, and wherein y is about 3.5 or less). For W discussed in this paragraph_1-xMo_xO_yThe materials, values for x and y may be within the ranges described elsewhere herein.

In embodiments using a bilayer electrode as described above, each layer of the bilayer may have a different morphology. In some embodiments, each of the first and second layers of the bilayer has a morphology comprising a microcrystalline, a nanocrystalline, or an amorphous phase, wherein each of the morphologies of the first and second layers is different. For example, the first layer of the bilayer is tungsten molybdenum oxide (e.g., W)_1-xMo_xO_yWhere y is about 3.5 or less), which is amorphous, and the second layer of the bilayer is tungsten oxide (e.g., WO)_yWhere y is greater than 3), which is a nanocrystal. In certain embodiments, the first layer of the bilayer is crystalline tungsten molybdenum oxide (e.g., W)_1-xMo_xO_yWherein y is about 3.5 or less), and the second layer of the bilayer is amorphous tungsten oxide (e.g., WO)_yWherein y is greater than 3). The different morphologies of the layers may be selected for specific purposes, or may be based on the particular used for each layerThe process conditions and/or materials are selected to be different morphologies.

The counter electrode layer, which may be discussed further below, is similarly deposited as a bi-layer or graded layer comprising two or more materials, which may have different compositions in terms of oxygen content, metal content, etc.

In various embodiments, the molybdenum content of the tungsten molybdenum oxide can be at least about 5% (atomic), at least about 6% (atomic), at least about 8% (atomic), or at least about 9% (atomic), or at least about 10% (atomic), or at least about 12% (atomic), or at least about 15% (atomic). In these or other cases, the molybdenum content of the tungsten molybdenum oxide can be about 30% (atomic) or less molybdenum content, such as about 25% (atomic) or less molybdenum content, or about 20% (atomic) or less molybdenum content, or about 18% (atomic) or less. In one particular example, the tungsten molybdenum oxide is about 5-30 atomic percent, or about 10-25 atomic percent, or about 15-20 atomic percent molybdenum.

In certain embodiments, the tungsten molybdenum oxide electrochromic material is crystalline, nanocrystalline, or amorphous. In some embodiments, the electrochromic material is substantially nanocrystalline with an average grain size of about 5nm to 50nm (or about 5nm to 20nm), as characterized by Transmission Electron Microscopy (TEM). The morphology of electrochromic materials can also be characterized as nanocrystals using X-ray diffraction (XRD); XRD. For example, nanocrystalline electrochromic materials can be characterized by the following XRD characteristics: a crystal size of about 10 to 100nm (e.g., about 55 nm). Furthermore, nanocrystalline electrochromic materials may exhibit limited long-range order, for example, over the order of several (about 5 to 20) electrochromic material unit cells. In some embodiments, the tungsten molybdenum oxide electrochromic material may be amorphous. Many factors can affect the morphology of the electrochromic material, including, for example, the composition of the material and the conditions used to deposit and process the material. In some embodiments, the electrochromic material is not subjected to heating above a particular temperature (e.g., any process involving heating the substrate during or after deposition of the electrochromic material may be maintained at less than about 300 ℃, less than about 250 ℃, less than about 200 ℃, less than about 150 ℃, less than about 100 ℃, less than about 75 ℃, or less than about 50 ℃). Without wishing to be bound by theory or mechanism of action, this lack of heating may result in an amorphous morphology of the tungsten molybdenum oxide. In some other embodiments, heating the substrate may cause the morphology of the tungsten molybdenum oxide to change to crystalline/nanocrystalline. While not wishing to be bound by theory, it is believed that the content of tungsten molybdenum oxide inhibits crystallization, but more crystalline morphology may be formed under the processing conditions described herein, e.g., higher temperatures and a combination of heating under an inert atmosphere and then heating in air.

In embodiments where the electrochromic layer is deposited to include two or more different materials, the different materials may each independently include a microcrystalline phase, a nanocrystalline phase, and/or an amorphous phase. In one example, a first or lower portion of the electrochromic layer is microcrystalline or nanocrystalline, while a second or upper portion of the electrochromic layer is amorphous. In another example, a first or lower portion of the electrochromic layer is amorphous, while a second or upper portion of the electrochromic layer is microcrystalline or nanocrystalline. In another example, both the first/lower and second/upper layers of the electrochromic layer are microcrystalline or nanocrystalline. In another example, both the first/lower and second/upper layers of the electrochromic layer are amorphous.

The thickness of the electrochromic layer 106 depends on the electrochromic material selected for the electrochromic layer. In some embodiments, the electrochromic layer 106 is about 50nm to 2,000nm, or about 200nm to 700 nm. In some embodiments, the electrochromic layer is about 300nm to about 500 nm. In the use of an additional tungsten oxide layer (e.g. with WO)_yWherein y is greater than 3), the additional layer has a thickness of about 50 to 100 nm. In certain embodiments, the additional layer is amorphous.

Typically, in electrochromic materials, the coloration (or any change in optical properties-e.g., absorbance, reflectance, and transmittance) of the electrochromic material is caused by reversible ion insertion (e.g., intercalation) into the material and corresponding charge-balancing electron injection. Typically, a portion of the ions responsible for the optical transition are irreversible in the electrochromic materialAnd (4) combining the ground. Some or all of the irreversibly bound ions are used to compensate for "blind charges" in the material. In most electrochromic materials, suitable ions include lithium ions (Li)⁺) And hydrogen ion (H)⁺) (i.e., protons). However, in some cases, other ions will be suitable. These include, for example, deuterium ions (D)⁺) Sodium ion (Na)⁺) Potassium ion (K)⁺) Calcium ion (Ca)⁺⁺) Barium ion (Ba)⁺⁺) Strontium ion (Sr)⁺⁺) And magnesium ion (Mg)⁺⁺). In various embodiments described herein, lithium ions are used to create the electrochromic phenomenon.

D. Counter electrode layer

Referring again to fig. 1, in electrochromic stack 120, ion conducting layer 108 overlies electrochromic layer 106. On top of ion conducting layer 108 is counter electrode layer 110. In some embodiments, the counter electrode layer 110 is inorganic and/or solid. The counter electrode layer may comprise one or more of a number of different materials that act as ion reservoirs when the electrochromic device is in a bleached state. During the electrochromic transition, which is initiated by, for example, applying an appropriate potential, the counter electrode layer transfers some or all of the ions it holds to the electrochromic layer, changing the electrochromic layer to a colored state. Meanwhile, for example, in the case of a nickel oxide-based material having electrochromic activity, the counter electrode layer is colored due to loss with ions.

In some embodiments, suitable materials for the counter electrode include nickel oxide (NiO), nickel tungsten oxide (NiWO), nickel tungsten tantalum oxide (NiWTaO), nickel vanadium oxide, nickel chromium oxide, nickel aluminum oxide, nickel manganese oxide, nickel magnesium oxide, chromium oxide (Cr)₂O₃) Manganese oxide (MnO)₂) Prussian blue, cerium titanium oxide (CeO)₂-TiO₂) Cerium zirconium oxide (CeO)₂-ZrO₂) Vanadium oxide (V)₂O₅) And mixtures of oxides (e.g. Ni)₂O₃And WO₃Mixtures of (a) and (b). Doping formulations of oxides may also be used, including dopants such as tantalum and tungsten. Specific examples of counter electrode materialsIncluding nickel tungsten tantalum oxide, nickel tungsten niobium oxide, and nickel tungsten tin oxide. Since the counter electrode layer 110 contains ions for generating an electrochromic phenomenon in the electrochromic material when the electrochromic material is in a bleached state, the counter electrode preferably has high transmittance and a neutral color when the counter electrode holds a large amount of these ions.

In some embodiments, nickel tungsten oxide (NiWO) is used as the counter electrode material in the counter electrode layer. In certain embodiments, the amount of nickel present in the nickel tungsten oxide may be up to about 90% by weight of the nickel tungsten oxide. In a particular embodiment, the mass ratio of nickel to tungsten in the nickel-tungsten oxide is between about 4:6 and 6:4 (e.g., about 1: 1). In one embodiment, NiWO contains from about 15 atomic percent Ni to about 60 atomic percent Ni; from about 10 atomic% W to about 40 atomic% W; and from about 30 atomic percent O to about 75 atomic percent O. In another embodiment, NiWO contains about 30 atomic percent Ni and about 45 atomic percent Ni; from about 10 atomic% W to about 25 atomic% W; and from about 35 atomic percent O to about 50 atomic percent O. In one embodiment, NiWO contains about 42% (atomic) Ni, about 14% (atomic) W, and about 44% (atomic) O.

In some embodiments, nickel tungsten tantalum oxide (NiWTaO) is used as or for the counter electrode material in the counter electrode layer. When used as or in a counter electrode material, the nickel tungsten tantalum oxide can have various compositions. In certain embodiments, a particular balance may be made between the various constituents of the NiWTaO. For example, the atomic ratio of Ni (W + Ta) in the material may fall between about 1.5:1 and 3:1, such as between about 1.5:1 and 2.5:1, or between about 2:1 and 2.5: 1. In one particular example, the atomic ratio of Ni (W + Ta) is between about 2:1 and 3: 1. The atomic ratio of Ni (W + Ta) is related to the ratio of the number of nickel atoms in (i) the material to the sum of the number of tungsten and tantalum atoms in (ii) the material. The nickel tungsten tantalum oxide material may also have a particular atomic ratio of W to Ta. In certain embodiments, the atomic ratio of W: Ta is between about 0.1:1 and 6:1, such as 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 to Ta 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 embodiments, specific atomic ratios of Ni (W + Ta) and W: Ta are used. Although all combinations of the disclosed Ni (W + Ta) compositions and the disclosed W: Ta compositions are contemplated, only certain combinations are explicitly listed herein. For example, the atomic ratio of Ni (W + Ta) may be between about 1.5:1 and 3:1, with the atomic ratio of W: Ta being between about 1.5:1 and 3: 1. In another example, the atomic ratio of Ni (W + Ta) may be between about 1.5:1 and 2.5:1, where the atomic ratio of W to Ta is between about 1.5:1 and 2.5: 1. In another example, the atomic ratio of Ni (W + Ta) may be between about 2:1 and 2.5:1, where the atomic ratio of W to Ta 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.

In some embodiments, nickel tungsten niobium oxide (NiWNbO) is used as the counter electrode material in the counter electrode layer. The nickel tungsten niobium oxide may have various compositions when used as an anode coloring material. In certain embodiments, a particular balance may be made between the various components of NiWNbO. For example, the atomic ratio of Ni (W + Nb) in the material may fall between about 1.5:1 and 3:1, such as between about 1.5:1 and 2.5:1, or between about 2:1 and 2.5: 1. In one particular example, the atomic ratio of Ni (W + Nb) is between about 2:1 and 3: 1. The atomic ratio of Ni (W + Nb) is related to the ratio of the number of nickel atoms in (i) the material to the sum of the number of tungsten and niobium atoms in (ii) the material. The nickel tungsten niobium oxide material may also have a specific atomic ratio of W to Nb. In certain embodiments, the atomic ratio of W to Nb is between about 0.1:1 and 6:1, such as 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 to 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 embodiments, specific atomic ratios of Ni (W + Nb) and W: Nb are used. Although all combinations of the disclosed Ni (W + Nb) compositions and the disclosed W: Nb compositions are contemplated, only certain combinations are specifically listed herein. For example, the atomic ratio of Ni (W + Nb) may be between about 1.5:1 and 3:1, with the atomic ratio of W to Nb being 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, with the atomic ratio of W to Nb being between about 1.5:1 and 2.5: 1. In further examples, the atomic ratio of Ni (W + Nb) may be between about 2:1 and 2.5:1, where the atomic ratio of W to 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.

In some embodiments, nickel tungsten tin oxide (NiWSnO) is used in the counter electrode layer. The nickel tungsten tin oxide may have various compositions when used as an anodic coloring material. In certain embodiments, a particular balance may be made between the constituents of NiWSnO. For example, the atomic ratio of Ni (W + Sn) in the material may fall between about 1:1 and 4:1, such as between about 1:1 and 3:1, or between about 1.5:1 and 2.5:1, or between about 2:1 and 2.5: 1. In one particular example, the atomic ratio of Ni (W + Sn) is between about 2:1 and 3: 1. The atomic ratio of Ni (W + Sn) is related to the ratio of the number of nickel atoms in (i) the material to the sum of the number of tungsten and tin atoms in (ii) the material. The nickel tungsten tin oxide material may also have a specific atomic ratio of W to Sn. In certain embodiments, the atomic ratio of W: Sn is between about 1:9 and 9:1, such as 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 embodiments, a particular atomic ratio of Ni (W + Sn) and W: Sn is used. For example, the atomic ratio of Ni (W + Sn) may be between about 1:1 and 3:1, with the atomic ratio of W: Sn being between about 1:1 and 3: 1. In another example, the atomic ratio of Ni (W + Sn) may be between about 1.5:1 and 2.5:1, where the atomic ratio of W to Sn is between about 1.5:1 and 2.5: 1. In another example, the atomic ratio of Ni (W + Sn) may be between about 2:1 and 2.5:1, where the atomic ratio of W to Sn is between about 1.5:1 and 2: 1.

When charge is removed from the counter electrode 110 made of nickel tungsten oxide (i.e., ions are transported from the counter electrode 110 to the electrochromic layer 106), the counter electrode layer will transition from the transparent state to the brown colored state. Other electrochromic active counter electrode materials may exhibit similar or other colors after removal of ions.

As discussed above with respect to the electrochromic layer, the counter electrode layer may be deposited to include two or more materials having different compositions (e.g., as a bilayer, graded layer, or other combination of layers). In many of these embodiments, one of the pair of electrode materials may provide electrochromic properties, while the other pair of electrode materials may serve as precursors to the ionically conductive and substantially electrically insulating material. Typically, the material used as a precursor for the ion conducting and substantially electrically insulating material (if present) is formed so that it is in contact with the electrochromic material. In the case where the electrochromic layer is formed prior to the counter electrode layer, the counter electrode material, which serves as a precursor for the ion-conducting and substantially electrically insulating material, may be deposited as a first or lower portion of the counter electrode layer. Then, a counter electrode material exhibiting electrochromism may be provided as a second layer or an upper portion of the counter electrode layer. In the case where the counter electrode layer is deposited prior to the electrochromic layer, a first or lower portion of the counter electrode may be formed from a counter electrode material exhibiting electrochromic properties, and a second or upper portion of the counter electrode may be formed from the counter electrode material, which serves as a precursor for the ionically conductive and substantially electrically insulating material.

In one example, the counter electrode is deposited to include two materials with different oxygen contents. For example, the counter electrode layer may comprise two different forms of nickel oxide, or two different forms of nickel tungsten tantalum oxide, or two different forms of nickel tungsten niobium oxide, or two different forms of nickel tungsten tin oxide, etc., wherein the two different forms of counter electrode material have different oxygen concentrations. One form of the counter electrode material may exhibit electrochromism and may have relatively little oxygen. Another form of the counter electrode material may or may not exhibit electrochromic phenomena, may be used as a precursor for ion conducting and substantially electrically insulating materials, and may have relatively more oxygen. The counter electrode material, which has relatively more oxygen and serves as a precursor for the ion-conducting and substantially electrically insulating material, may be super-stoichiometric with respect to oxygen. The details provided herein regarding the oxygen content differences between different layers or portions of the electrochromic or counter electrode layer may apply regardless of whether other compositional differences (e.g., different metals) exist between the two layers or portions discussed.

In certain embodiments, the counter electrode may be deposited to include two or more materials having different metal compositions, optionally in different layers disposed closer to and further from the electrochromic layer. For example, the first pair of electrode materials (in a layer proximate to the electrochromic layer) may include one or more metals that are not present in the second pair of electrode materials. Likewise, the second pair of electrode materials may include one or more metals not present in the first pair of electrode materials. Exemplary first pair electrode materials include, but are not limited to, nickel oxide, nickel tungsten tantalum oxide, nickel tungsten tin oxide, and nickel tungsten niobium oxide. Exemplary second pair electrode materials also include, but are not limited to, nickel oxide, nickel tungsten tantalum oxide, nickel tungsten tin oxide, and nickel tungsten niobium oxide. Some example combinations are provided, but are not intended to be limiting. In one example, the first pair of electrode materials (in the layer proximate to the electrochromic layer) is nickel tungsten oxide, while the second pair of electrode materials is nickel oxide. In another example, the first pair of electrode materials is nickel tungsten tantalum oxide and the second pair of electrode materials is nickel tungsten oxide. In another example, the first pair of electrode materials is nickel tungsten tin oxide and the second pair of electrode materials is nickel tungsten oxide. In another example, the first pair of electrode materials is nickel tungsten niobium oxide and the second pair of electrode materials is nickel tungsten oxide. In another example, the first pair of electrode materials (in the layer proximate to the electrochromic layer) is nickel tungsten oxide and the second pair of electrode materials is nickel tungsten tantalum oxide. Any of these examples may be modified to include different first/second pairs of electrode materials.

The counter electrode morphology may be crystalline, amorphous or some mixture thereof. The crystalline phase may be nanocrystalline. In some embodiments, the counter electrode material is amorphous or substantially amorphous. It has been found that various substantially amorphous counter electrodes perform better than their crystalline counterparts under certain conditions. The amorphous state of the counter electrode oxide material may be obtained by using certain processing conditions as described below. While not wishing to be bound by any theory or mechanism, it is believed that certain amorphous counter electrode oxides are generated from relatively low energy atoms in the sputtering process. For example, low energy atoms are obtained in a sputtering process with lower target power, higher chamber pressure (i.e., lower vacuum), and/or greater source-to-substrate distance. Amorphous films are also more likely to form where the fraction/concentration of heavy atoms (e.g., W) is relatively high. Under the process conditions described, films with better stability under UV/thermal exposure are produced. The substantially amorphous material may have some crystals, typically but not necessarily nanocrystals, dispersed in an amorphous matrix.

In embodiments where the counter electrode is deposited to include two or more different materials, the different materials may each independently include a microcrystalline phase, a nanocrystalline phase, and/or an amorphous phase. In one example, a first or lower portion of the counter electrode layer is microcrystalline or nanocrystalline, while a second or upper portion of the counter electrode layer is amorphous. In another example, a first or lower portion of the counter electrode layer is amorphous, while a second or upper portion of the counter electrode layer is microcrystalline or nanocrystalline. In another example, both the first/lower and second/upper layers of the counter electrode layer are microcrystalline or nanocrystalline. In another example, both the first/lower and second/upper layers of the counter electrode layer are amorphous.

In some embodiments, the counter electrode morphology may include a microcrystalline phase, a nanocrystalline phase, and/or an amorphous phase. For example, the counter electrode may be a material, for example, having an amorphous matrix with nanocrystals distributed throughout. In certain embodiments, the nanocrystals comprise 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 volume, depending on the embodiment). In certain embodiments, the nanocrystals have a maximum diameter of less than about 50nm, in certain cases less than about 25nm, less than about 10nm, or less than about 5 nm. In some cases, the average diameter of the nanocrystals is about 50nm or less, or about 10nm or less, or about 5nm or less (e.g., about 1-10 nm).

In certain embodiments, it is desirable to have a distribution of nanocrystal sizes wherein at least about 50% of the nanocrystals have diameters within 1 standard deviation of the mean nanocrystal diameter, for example, wherein at least about 75% of the nanocrystals have diameters within 1 standard deviation of the mean nanocrystal diameter, or wherein at least about 90% of the nanocrystals have diameters within 1 standard deviation of the mean nanocrystal diameter.

It has been found that a counter electrode comprising an amorphous matrix can operate more efficiently than a counter electrode that is relatively more crystalline. In certain embodiments, the additive may form a host matrix in which regions of the underlying anodic coloring material may be found. In each case, the host matrix is substantially amorphous. In certain embodiments, the only crystalline structure in the counter electrode is formed by the basic anodically coloring electrochromic material, for example in the form of an oxide. One example of a basic anodically coloring electrochromic material in oxide form is nickel tungsten oxide. The additives can help form an amorphous host matrix that is not substantially crystalline, but incorporates domains (e.g., in some cases, nanocrystals) of the underlying anodically coloring electrochromic material. Exemplary additives include, but are not limited to, tin, tantalum, and niobium. In other embodiments, the additive and the anodically coloring base material together form a compound having covalent and/or ionic bonds. The compound may be crystalline, amorphous, or a combination thereof. In other embodiments, the anodically coloring base material forms a host matrix in which the regions of the additive are present as discrete phases or pockets. For example, certain embodiments include an amorphous counter electrode having an amorphous matrix of a first material and a second material that is also amorphous distributed throughout the first material in pockets, e.g., pockets of a diameter as described herein for crystalline material distributed throughout the amorphous matrix.

In some embodiments, the counter electrode is between about 50nm and about 650nm thick. In some embodiments, the counter electrode has a thickness of about 100nm to about 400nm, preferably in the range of about 200nm to 300 nm.

The number of ions that remain in the counter electrode layer during the bleached state (and correspondingly in the electrochromic layer during the colored state) and that can drive the electrochromic transition depends on the composition of these layers as well as on the thickness and manufacturing method of these layers. Both the electrochromic layer and the counter electrode layer are capable of supporting the available charge (in the form of lithium ions and electrons) in the vicinity of tens of nanoamperes per square centimeter of layer surface area. The charge capacity of an electrochromic film is the amount of charge that can be reversibly loaded and unloaded per unit area and per unit thickness of the film by applying an external voltage or potential. In one embodiment, the electrochromic layer has about 30 and about 150mC/cm²Charge capacity between/micron. In another embodiment, the electrochromic layer has between about 50 and about 100mC/cm²Charge capacity between/micron. In one embodiment, the counter electrode layer has about 75 and about 200mC/cm²Charge capacity per micron. In another embodiment, the counter electrode layer has about 100 to about 150mC/cm²Charge capacity per micron.

E. Ion conducting layer

In various embodiments, such as shown in fig. 1, an ion conductor layer 108 is provided between the electrochromic layer 106 and the counter electrode layer 110. In such cases, the ion conductor material is deposited over the electrochromic layer in the conventional sense, e.g., via sputtering, evaporation, sol-gel techniques, etc., followed by deposition of the counter electrode material. In other embodiments, the conventional ion conductor layer may be omitted. In such cases, the electrochromic layer and the counter electrode layer may be deposited in direct contact with each other, and the ion-conducting material formed in situ at the interface between the two layers may serve the purpose of a conventional ion-conductor layer. The electrochromic device precursor may comprise a stack of the aforementioned layers prior to the in situ formation of the ionic conductor material. Each of these embodiments will be discussed in turn.

i. Embodiments utilizing separately deposited ion conducting layers

As shown in fig. 1, between the electrochromic layer 106 and the counter electrode layer 110, there is an ion conducting layer 108. When the electrochromic device is floatingIn transitioning between the white and colored states, ion-conducting layer 108 serves as a medium through which ions are transported (in the manner of an electrolyte). Preferably, ion conducting layer 108 has a high conductivity for the relevant ions of the electrochromic layer and the counter electrode layer, but a sufficiently low electronic conductivity such that negligible electron transfer occurs during normal operation. Thin ion conducting layers with high ion conductivity allow fast ion conduction and thus fast switching for achieving high performance electrochromic devices. In certain embodiments, ion conducting layer 108 is inorganic and/or solid. When fabricated from a single material and in a manner that produces relatively few defects, the ion conductor layer can be made very thin to produce a high performance device. In various embodiments, the ionic conductor material has a thickness of about 10⁸Siemens per centimeter (Siemens/cm) or ohms^-1Centimeter^-1(ohm^-1cm^-1) And about 10⁹Siemens/cm or ohm^-1cm^-1Ion conductivity and about 10¹¹Ohm-centimeter (ohms-cm) electronic resistance.

Examples of suitable materials for the lithium ion conductor layer include lithium silicate, lithium aluminum silicate, lithium oxide, lithium tungstate, lithium aluminum borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium oxynitride, lithium aluminum fluoride, lithium phosphorus oxynitride (LiPON), lanthanum titanate (LLT), lithium tantalate, lithium zirconium oxide, lithium silicon oxycarbonitride (LiSiCON), lithium titanium phosphate, lithium germanium vanadium oxide, lithium zinc germanium oxide, to allow lithium ions to pass through them while having a high resistance (preventing electrons from moving therethrough). However, any material may be used for the ion conducting layer 108 as long as it can be fabricated with a low defect rate and allows ions to pass between the counter electrode layer 110 and the electrochromic layer 106 while substantially preventing electrons from passing.

In certain embodiments, the ion conducting layer is crystalline, nanocrystalline, or amorphous. Typically, the ion conducting layer is amorphous. In another embodiment, the ion conducting layer is a nanocrystal. In yet another embodiment, the ion conducting layer is crystalline.

In some embodiments, silicon-aluminum-oxide (SiAlO) is used for the ion conductive layer 108. In particular embodiments, the silicon/aluminum target used to fabricate the ion conductor layer via sputtering contains about 6 and about 20 atomic percent aluminum. This defines the ratio of silicon to aluminum in the ion conductive layer. In some embodiments, silicon aluminum oxide ion conducting layer 108 is amorphous.

The thickness of ion conducting layer 108 may vary depending on the material. In some embodiments, ion conducting layer 108 has a thickness of about 5nm to 100nm, preferably about 10nm to 60 nm. In some embodiments, the thickness of the ion conducting layer is about 15nm to 40nm, or about 25nm to 30 nm.

The ions transported across the ion conducting layer between the electrochromic layer and the counter electrode layer are used to effect a color change of the electrochromic layer (i.e., change the electrochromic device from a bleached state to a colored state). These ions include lithium ions (Li), depending on the choice of materials used for the electrochromic device stack⁺) And hydrogen ion (H)⁺) (i.e., protons). As noted above, other ions may be employed in certain embodiments. These include deuterium ions (D)⁺) Sodium ion (Na)⁺) Potassium ion (K)⁺) Calcium ion (Ca)⁺⁺) Barium ion (Ba)⁺⁺) Strontium ion (Sr)⁺⁺) And magnesium ion (magnesium)⁺⁺)。

Embodiments omitting separately deposited ion conducting layer

In most conventional electrochromic devices, the ion conducting layer is deposited as a different material in different deposition steps to provide separation between the electrochromic layer and the counter electrode layer. However, in certain embodiments herein, the ion conducting layer may be omitted. In such cases, the electrochromic material of the electrochromic layer may be deposited in direct physical contact with the counter electrode material of the counter electrode layer. The interfacial region between the electrochromic layer and the counter electrode layer can be formed and function as an ion conductor layer (e.g., allowing ions to pass through, but not electrons to pass between the electrochromic layer and the counter electrode layer) without the need to deposit this layer as a distinct material. This simplifies the formation of the electrochromic device, as there is no need to provide a separate deposition step for forming the ion conductor layer.

In such embodiments, one or both of the electrochromic layer and the counter electrode layer may be deposited to include a portion that is oxygen-rich compared to the remainder of the layer. The oxygen-rich portion may be super-stoichiometric with respect to oxygen. Typically, the oxygen-rich portion is in contact with another type of layer. For example, the electrochromic stack can include a counter electrode material in contact with the electrochromic material, wherein the electrochromic material includes an oxygen-rich portion in direct physical contact with the counter electrode material. In another example, the electrochromic stack includes a counter electrode material in contact with the electrochromic material, wherein the counter electrode material includes an oxygen-rich portion in direct physical contact with the electrochromic material. In yet another example, both the electrochromic material and the counter electrode material include an oxygen-rich portion, wherein the oxygen-rich portion of the electrochromic material is in direct physical contact with the oxygen-rich portion of the counter electrode material.

The oxygen-rich portions of these materials may be provided as distinct layers. For example, the electrochromic and/or counter electrode material may comprise a first layer that is oxygen-rich and a second layer that is not oxygen-rich (or has relatively less oxygen than the first layer). The term "oxygen-rich" as used herein, unless otherwise specified, refers to a material that is superstoichiometric with respect to oxygen. Furthermore, a material that is "oxygen-rich" compared to the second material has a higher stoichiometric ratio of oxygen compared to the second material. In some examples, the electrochromic layer comprises two layers of tungsten molybdenum oxide, wherein a second layer of tungsten molybdenum oxide is oxygen-rich compared to a first layer of tungsten molybdenum oxide. The second layer of tungsten molybdenum oxide may be superstoichiometric with respect to oxygen. The second layer of tungsten molybdenum oxide may be in direct physical contact with the counter electrode layer and in direct physical contact with the first layer of tungsten molybdenum oxide. As mentioned above, the counter electrode layer may be homogeneous or may also comprise an oxygen-rich part.

The oxygen-rich portions of these layers may also be disposed in graded layers. For example, the electrochromic and/or counter electrode material may include a gradual change in oxygen concentration in a direction normal to the surfaces of the layers. In some examples, the electrochromic layer is a graded layer of tungsten molybdenum oxide having a graded oxygen concentration in a direction normal to a surface of the layer. For example, the highest oxygen concentration in the graded tungsten molybdenum oxide layer may be near the counter electrode layer. As mentioned above, the counter electrode layer may be homogeneous or may also comprise an oxygen-rich part.

Embodiments that omit the ion conductor layer deposition step and deposit the counter electrode material in direct contact with the electrochromic material are further discussed in the following U.S. patents, which are hereby incorporated by reference in their entirety: U.S. patent No. 8,300,298, U.S. patent No. 8,764,950, and U.S. patent No. 9,261,751.

F. Additional layer

Electrochromic device 100 may include one or more additional layers (not shown in fig. 1), such as one or more passivation layers. A passivation layer for improving certain optical characteristics may be included in the electrochromic device 100. A passivation layer for providing moisture or scratch resistance may also be included in the electrochromic device 100. For example, the conductive layer may be treated with an antireflective or protective oxide or nitride layer. Other passivation layers may be used to hermetically seal electrochromic device 100.

In various embodiments, one or more Defect Mitigating Insulating Layers (DMILs) may be provided. Such DMILs can be provided between or within the layers depicted in fig. 1. In some particular embodiments, the DMIL may be provided between sub-layers of the counter electrode layer, but may also be provided at alternative or additional locations. DMIL helps to minimize the risk of manufacturing defective devices. In certain embodiments, the resistivity of the insulating layer is between about 1 and 5x10¹⁰Between Ohm-cm. In certain embodiments, the insulating layer contains one or more of the following metal oxides: cerium oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, silicon aluminum oxide, tungsten oxide, nickel tungsten oxide, tantalum oxide, and indium tin oxide. In certain embodiments, the insulating layer contains a nitride, carbide, oxynitride or oxycarbide, such as the nitrides, carbides, oxynitrides or oxycarbides of the listed oxides and the like. As an example, the insulating layer comprises one or more of the following metal nitrides: nitridingTitanium, aluminum nitride, silicon nitride, and tungsten nitride. The insulating layer may also contain a mixture or other combination of oxide and nitride materials (e.g., silicon oxynitride). DMIL is described in more detail in U.S. patent No. 9,007,674, which is incorporated herein by reference in its entirety.

G. Electrochromic device stack examples with cathodic electrochromic sublayers

Fig. 4 shows an example of an electrochromic stack with a cathodic electrochromic layer comprising two sublayers. As shown, the stack in fig. 4 includes transparent conductive oxide layers 404 and 414, a cathodically coloring electrochromic layer 406, and an anodically coloring counter electrode layer 410. Here, the cathodically coloring electrochromic layer 406 includes two sublayers 406a and 406 b. The first sub-layer 406a may comprise a known electrochromic cathodically coloring material, such as tungsten oxide or tungsten molybdenum oxide. The second sub-layer 406b may include one or more different elements, such as where the sub-layer 406a contains tungsten, molybdenum, and oxygen and the sub-layer 406b contains only tungsten and oxygen, or vice versa. In another embodiment, sublayers 406a and 406b comprise the same elements, but have different relative concentrations. For example, both sublayers may contain tungsten, molybdenum, and oxygen, but the oxygen of sublayer 406a is stoichiometric or sub-stoichiometric, while the oxygen of sublayer 406b is super-stoichiometric. As described above, in various embodiments, the second sublayer (e.g., sublayer 406b) may be superstoichiometric in oxygen. By way of example, sublayer 406b may be denoted as WO_yWherein y is greater than 3 or represented by W_{1- x}Mo_xO_yWherein y is greater than 3. A counter electrode layer 410. In some embodiments, an IC layer (not shown in fig. 4) is disposed between electrochromic layer 406 and counter electrode layer 410. In some embodiments, the second sub-layer 406b is at least partially converted for use as an IC layer.

Fig. 5 shows an additional example of an electrochromic stack, which includes transparent conductive oxide layers 504 and 514, a cathodically coloring electrochromic layer 606, and an anodically coloring counter electrode layer 511. Here, the counter electrode layer 511 comprises three sub-layers 511 a-c. The first sublayer 511a may be a flash layer. Each of the sublayers 511a-c may have a different composition. Or any two or three of them may have the same composition. In some embodiments, second sublayer 511b and third sublayer 511c may include the same elements in different relative concentrations. In another embodiment, all of the sublayers 511a-c include the same elements in different relative concentrations. There may be an IC layer (not shown in fig. 5) between the electrochromic layer 506 and the counter electrode layer 511.

The first sublayer 511a may be a first anodically coloring counter electrode material, and the second and third sublayers 511b, 511c may be a second anodically coloring counter electrode material (each deposited with a different composition). The composition of the second sublayer 511b and the third sublayer 511c may be homogeneous within each sublayer.

In this embodiment, as in the embodiment of fig. 4, the cathodically coloring electrochromic layer 506 includes two sub-layers 506a and 506 b. The first sub-layer 506a may comprise a known electrochromic cathodically coloring material, such as tungsten oxide or tungsten molybdenum oxide. The second sub-layer 506b may include one or more different elements, such as where sub-layer 506a contains tungsten, molybdenum, and oxygen and sub-layer 506b contains only tungsten and oxygen. In another embodiment, sublayers 506a and 506b include the same elements, but have different relative concentrations. For example, both sublayers may contain tungsten, molybdenum, and oxygen, but the oxygen of sublayer 506a is stoichiometric or sub-stoichiometric, while the oxygen of sublayer 506b is super-stoichiometric.

Various examples of multilayer counter electrodes are described in U.S. patent application publication No. 20170003564 filed on 7.7.2016, the entire contents of which are incorporated herein by reference. As explained therein, in some embodiments, the first pair of electrode sublayers is a scintillation layer, which is typically characterized as a thin and generally rapidly deposited layer, typically no greater than about 100nm in thickness, in each case no greater than about 80 nm. The flash layer may be between about 5nm thick to about 100nm thick, about 10nm thick to about 80nm thick, or about 10nm thick to about 50nm thick, or about 10nm to about 30nm thick. In some other cases, a separate flash layer (which may be an anodically colored counter electrode material) may be provided between the electrochromic layer and the first sublayer of the counter electrode. In some embodiments, it may be in the second sub-layer and transparentA flash layer is provided between the conductor layers. 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 the remaining electrochromic/counter electrode layer (although this layer may have a very similar composition to other layers such as the anodically coloring layer). In some embodiments, the first sublayer, whether a flash layer or thicker than a flash layer, has a relatively high resistivity, e.g., between about 1 and 5x10¹⁰Between Ohm-cm.

In some examples, the third pair of electrodes is a defect mitigating insulating layer as described elsewhere herein.

In certain embodiments, the electrochromic stack has an optional cap layer, which may be disposed between the counter electrode layer (or electrochromic layer if it is separated from the substrate by the counter electrode layer) and the second transparent conductive layer. In some embodiments, the cap layer has a composition that matches or is similar to the counter electrode layer or a sub-layer therein. In some embodiments, the cap layer comprises nickel tungsten oxide, such as NiWO. In certain embodiments, the cap layer is about 0 to 50nm thick. In some embodiments, the capping layer serves as a defect mitigating insulating layer.

In certain embodiments, the electrochromic stack includes a sealing layer over the second conductive layer. By way of example, the hermetic layer can comprise silicon oxide, silicon oxynitride, silicon nitride, silicon aluminum oxide, aluminum nitride, aluminum zinc oxide, tin oxide, carbon (e.g., graphene, graphite, diamond-like carbon, and/or fluorinated diamond-like carbon), titanium oxide, titanium nitride, tantalum nitride, tin oxide, zinc oxide, chromium, organic polymers (e.g., parylene polymers), and mixtures thereof. In general, any of these materials may have any of a variety of morphologies or degrees of crystallinity, including amorphous, crystalline, or mixed amorphous-crystalline. In certain embodiments, the sealing layer has a thickness of about 50nm to 5 microns, or about 100nm to 3 microns, or about 100nm to 1 micron.

Table 1 below presents information for electrochromic device stacks according to certain embodiments.

Methods of making electrochromic devices and precursors

The formation of electrochromic devices and electrochromic device precursors involves the deposition of many different layers on a substrate. Each of these layers is discussed above. For example, as depicted in fig. 2A, many other steps may also be taken in the fabrication of an electrochromic device or precursor.

As used herein, an electrochromic device precursor is a partially fabricated electrochromic device that is not yet suitable for use as a final electrochromic device. Typically, the electrochromic device precursor comprises at least a first conductive layer, an electrochromic layer, a counter electrode layer and a second conductive layer. In some cases, additional layers may be present. In some embodiments, the electrochromic device precursor has a material within its structure that, while not suitable for use as a final device, is configured or suitable for physical and/or chemical transformation to a functional device. Such device precursors may be desirable, for example, where the substrate is coated with the precursor material, stored, or transported to another facility for later and/or downstream processing.

For example, a separate ion conducting layer may not be present in certain embodiments. In the case where the ion conducting layer is omitted, the electrochromic device precursor may lack any layer or region that can be used for ion conducting purposes (e.g., allowing ions to pass but not electrons to pass between the electrochromic layer and the counter electrode layer). The electrochromic device precursor can be further processed to form an electrochromic device. In case the ion conducting layer is omitted, the further processing may form a material that is ion conducting and substantially electrically insulating in the interface region between the electrochromic layer and the counter electrode layer. In various embodiments, this further processing may involve thermal conditioning, as described further below. In certain embodiments, one or both of the electrochromic and counter electrode materials are superstoichiometrically oxygenated at the interface of the layers, or otherwise, there is an excess of oxygen or other reactive species between the layers. The superstoichiometrically oxygenated material can then be converted to an ionically conductive and substantially electrically insulating material. In these or other embodiments, further processing may include lithiation of one or more layers in the electrochromic device by direct lithium deposition or by diffusion. For example, the added lithium reacts or otherwise combines with oxygen or other reactive species at the interface, forming an ion conducting and electrically insulating material at the interface between the electrochromic material layer and the counter electrode material layer. In these or other embodiments, the further processing may involve flowing an electric current between the electrochromic layer and the counter electrode layer. In certain embodiments, any one or more of these further processing steps may involve forming an electrochromic device from an electrochromic device precursor.

Fig. 2A is a process flow 200 that describes aspects of a method of manufacturing an electrochromic device or other optical device having opposing bus bars, each applied to one of the electrically conductive layers of the optical device. The dotted line represents an optional step in the process flow. As described with respect to fig. 2B-2C, the exemplary device 240 is used to illustrate a process flow. Fig. 2B provides a top view depicting the fabrication of a device 240 that includes numerical indicators of the process flow 200 described with respect to fig. 2A. Fig. 2C shows a cross-section of a sheet including the device 240 described with respect to fig. 2B. Device 240 is a rectangular device, but process flow 200 is applicable to any shape of optical device having opposing bus bars, each bus bar on one of the conductive layers.

Referring to fig. 2A and 2B, after receiving a substrate having a first conductive layer thereon, process flow 200 begins with optional polishing of the first conductive layer, see 201. If performed, polishing can be performed prior to edge removal in the process flow (see 205) and/or after edge removal.

Referring again to fig. 2A, if polishing 201 is not performed, the process 200 begins by removing a first width at the edge around a portion of the perimeter of the substrate, see 205. The edge removal may remove only the first conductive layer or may also remove the diffusion barrier layer (if present). In one embodiment, the substrate is glass and includes a sodium diffusion barrier layer and a transparent conductive layer thereon, for example, a tin oxide-based transparent metal oxide conductive layer. The dashed area in fig. 2B represents the first conductive layer. Thus, after edge removal according to process 205, width a is removed from three sides of the perimeter of substrate 230. The width is typically, but not necessarily, a uniform width. The second width B is described below. In the case where the width a and/or the width B are not uniform, then their relative sizes with respect to each other are in terms of their average width.

As a result of removing the first width a at 205, there is a newly exposed edge of the lower conductive layer. In certain embodiments, at least a portion of the edge of the first conductive layer may optionally be tapered, see 207 and 209. The underlying diffusion barrier layer may also be tapered. Tapering the edges of one or more device layers before fabrication of subsequent layers thereon has unexpected advantages in device structure and performance. The edge tapering process is described in more detail in U.S. patent No. 9,454,053, which is incorporated herein by reference in its entirety. Although edge tapering is shown at both 207 and 209 in fig. 2A, edge tapering, if performed, would typically be performed once (e.g., at 207 or 209).

In certain embodiments, the lower conductive layer is optionally polished before or after edge tapering, see 208.

After removal of the first width a and optional polishing and/or optional edge tapering as described above, the EC device is deposited on the surface of the substrate 230, see 210. The EC stack deposition is further described with respect to fig. 2D. The deposition includes one or more material layers of the optical device and a second conductive layer, for example a transparent conductive layer, such as Indium Tin Oxide (ITO). The coverage depicted is the entire substrate, but there may be some shadowing due to the carrier that must hold the glass in place. In one embodiment, the entire area of the remaining portion of the first conductive layer is covered, including overlapping the first conductor around the previously removed first width a. This allows overlapping areas in the final device architecture.

In a particular embodiment, electromagnetic radiation is used to perform edge removal and provide a peripheral region of the substrate, for example to remove a transparent conductive layer or layers (up to and including the top conductive layer and any vapor barrier layer applied thereto), depending on the process steps. In one embodiment, at least edge removal is performed to remove material comprising the transparent conductive layer on the substrate, and optionally also to remove the diffusion barrier layer (if present). In certain embodiments, edge removal is used to remove surface portions of a substrate (e.g., float glass) and may reach a depth that does not exceed the thickness of the compression zone. Edge removal is performed, for example, to form a good surface for sealing by at least a portion of the primary and secondary seals of the IGU. For example, transparent conductive layers sometimes lose adhesion when the conductive layer spans the entire area of the substrate and thus has exposed edges, despite the presence of a secondary seal. Also, it is believed that when metal oxides and other functional layers have such exposed edges, they can act as a path for moisture to enter the overall device, thereby compromising the primary and secondary seals.

Edge removal is described herein as being performed on a substrate that has been cut to size. However, in other disclosed embodiments, the edge removal may be performed prior to cutting the substrate from the unitary glass sheet. For example, untempered float glass can be cut into individual sheets after the EC device is patterned thereon. The methods described herein may be performed on an integral block, which is then cut into individual EC sheets. In some embodiments, edge removal may be performed in some edge regions before cutting the EC lite sheets, and again after cutting them from the monolithic block. In certain embodiments, all edge removal is performed before the sheet is cut from the unitary piece. In embodiments employing "edge deletion" prior to cutting the pane, it is contemplated that the cut (and edge) of the newly formed EC sheet will be located to remove a portion of the coating on the glass sheet. In other words, there is no actual substrate edge, but only a defined area that will be cut to produce an edge. Thus, "edge removal" is meant to include the removal of one or more layers of material in areas where an edge of the substrate is expected to be present. Methods of making EC lamellae by cutting from monolithic blocks after Fabrication of EC devices thereon are described in U.S. patent application No. 12/941,882 (now U.S. patent No. 8,164,818), filed on 8/2010, and U.S. patent application No. 13/456,056, filed on 25/4/2012, each of which is entitled "Electrochromic Window Fabrication Methods," and each of which is incorporated herein by reference in its entirety. One of ordinary skill in the art will appreciate that if the methods described herein are to be performed on a unitary glass sheet and then individual sheets are cut therefrom, in certain embodiments, it may be necessary to use a mask, which is optional when performed on a sheet having the desired final dimensions.

Exemplary electromagnetic radiation includes UV, laser, and the like. For example, material may be removed using directed and focused energy at one or more of wavelengths 248nm, 355nm (UV), 1030nm (IR, e.g., a disk laser), 1064nm (e.g., Nd: YAG laser), and 532nm (e.g., green laser). The laser radiation is delivered to the substrate using, for example, an optical fiber or an open beam path. Depending on the selection and configuration parameters of the substrate processing equipment, ablation may be performed from the substrate side or the EC film side. The energy density required to ablate the film thickness is achieved by passing a laser beam through an optical lens. The lens focuses the laser beam to a desired shape and size. In one embodiment, a "flat-top" beam configuration is used, e.g., with a focal region of about 0.005mm²To about 2mm²In the meantime. In one embodiment, the level of focus of the beam is used to achieve the energy density required to ablate the EC film stack. In one embodiment, the energy density used in ablation is about 2J/cm²And about 6J/cm²In the meantime.

During the laser edge removal process, the laser spot is scanned peripherally over the surface of the EC device. In one embodiment, a scanning F θ lens is used to scan the laser spot. For example, homogeneous removal of EC film is achieved by overlapping areas of spots during scanning. In one embodiment, the overlap is between about 5% and about 100%, in another embodiment between about 10% and about 90%, and in yet another embodiment between about 10% and about 80%. Various scanning patterns may be used, for example, scanning in a straight line, a curved line, and various patterns may be scanned, for example, scanning a rectangular or other shaped portion, collectively creating a peripheral edge removal region. In one embodiment, scan lines (or "pens," i.e., lines formed by adjacent or overlapping laser spots (e.g., squares, circles, etc.)) are overlapped at the level described above for spot overlap. That is, the region of ablated material defined by the path of a previously scanned line overlaps with a later scanned line, so that there is overlap. I.e. the area of the pattern ablated by overlapping or adjacent laser spots overlaps with the area of the subsequent ablation pattern. For embodiments using overlap, spots, lines, or patterns, e.g., higher frequency lasers in the range between about 11KHz and about 500KHz, may be used. To minimize damage to the thermally related EC device at the exposed edge (the heat affected zone or "HAZ"), shorter pulse duration lasers are used. In one example, the pulse duration is between about 100fs (femtoseconds) and about 100ns (nanoseconds), in another embodiment the pulse duration is between about 1ps (picoseconds) and about 50ns, and in yet another embodiment the pulse duration is between about 20ps and about 30 ns. In other embodiments, other ranges of pulse durations may be used.

Referring again to fig. 2A and 2B, the process flow 200 continues with removing a second width B, which is narrower than the first width a, around substantially the entire perimeter of the substrate, see 215. This may include removing material down to the glass or diffusion barrier (if present). After completing process flows 200 through 215, for example, on a rectangular substrate as shown in fig. 2B, there is a perimeter region of width B where there is no first transparent conductor, one or more material layers of the device, or second conductive layer-removing width B has exposed the diffusion barrier layer or substrate. Within the peripheral region is a device stack comprising a first transparent conductor surrounded on three sides by overlapping one or more material layers and a second conductive layer. On the remaining side (e.g., the bottom side in fig. 2B), there is no overlap of the one or more material layers and the second conductive layer. Next to the remaining side (e.g., the bottom side in fig. 2B), one or more material layers and the second conductive layer are removed so as to expose a portion of the first conductive layer (bus bar pad exposure, or "BPE") 235, see 220. The BPE235 need not run the entire length of the side, it need only be long enough to accommodate the bus bar and leave some space between the bus bar and the second conductive layer so that it does not short circuit the second conductive layer. In one embodiment, the BPE235 spans the length of the first conductive layer on that side.

In various embodiments, the BPE is a removal of a portion of a layer of material down to a lower electrode or other conductive layer (e.g., a transparent conductive oxide layer) in order to create a surface for the bus bar to be applied, thereby making electrical contact with the electrode. The bus bars applied may be soldered bus bars, ink bus bars, and the like. BPEs typically have rectangular areas, but this is not required; the BPE may be any geometric or irregular shape. For example, the BPEs may be circular, triangular, elliptical, trapezoidal, and other polygonal shapes, as desired. The shape may depend on the configuration of the EC device, the substrate on which it is carried (e.g., an irregularly shaped window), or even the more efficient laser ablation pattern used to create it (e.g., in terms of material removal, time, etc.). In one embodiment, the BPE spans at least about 50% of the length of one side of the EC device. In one embodiment, the BPE spans at least about 80% of the length of one side of the EC device. Typically, but not necessarily, the BPE is wide enough to accommodate the bus bars, but should leave at least some space between the active EC device stack and the bus bars. In one embodiment, the BPE is generally rectangular, has a length approximating one side of the EC device, and a width between about 5mm and about 15mm, in another embodiment between about 5mm and about 10mm, and in yet another embodiment between about 7mm and about 9 mm. As mentioned, the width of the bus bar may be between about 1mm and about 5mm, typically about 3 mm.

As mentioned, the manufactured width of the BPE is sufficient to accommodate the width of the bus bar, and there is still space left between the bus bar and the EC device (since the bus bar should only contact the lower conductive layer). As long as there is space between the bus bar and the EC device (in embodiments with L3 isolation scratches, the bus bar may contact the deactivated portion), the bus bar width may exceed the width of the BPE (thus, the bus bar material contacts the lower conductor and glass (and/or diffusion barrier) of the region 241). In embodiments where the BPE fully accommodates the width of the bus bar, that is, the bus bar is fully on top of the lower conductor, the outer edge of the bus bar may be aligned with the outer edge of the BPE along the length of the bus bar, or inserted about 1mm to about 3 mm. Likewise, the space between the bus bar and the EC device is between about 1mm and about 3mm, in another embodiment between about 1mm and 2mm, and in another embodiment about 1.5 mm. The formation of the BPE is described in more detail below with respect to an EC device having a lower electrode as a TCO. This is for convenience only and the electrodes may be any suitable electrodes for an optical device, transparent or opaque.

To fabricate the BPE, a region of the bottom TCO (e.g., the first TCO) is cleaned of deposited material so that bus bars can be fabricated on the TCO. In one embodiment, this is achieved by a laser process that selectively removes the deposited film layer while exposing the bottom TCO in defined areas at defined locations. In one embodiment, the absorption properties of the bottom electrode and the deposited layer are exploited in order to achieve selectivity during laser ablation, i.e., so that the EC material on the TCO is selectively removed while the TCO material remains intact. In certain embodiments, the upper portion (depth) of the TCO layer is also removed to ensure good electrical contact of the bus bars, for example, by removing any mixture of TCO and EC materials that may occur during deposition. In some embodiments, when laser machining the BPE edges to minimize damage at these edges, the use of L3 isolation scribes to limit leakage current can be avoided-this eliminates process steps while achieving desired device performance results.

In some embodiments, the electromagnetic radiation used to fabricate the BPE is the same as the electromagnetic radiation used to perform edge deletion described aboveThe shots are the same. The (laser) radiation is transmitted to the substrate using an optical fiber or an open beam path. Depending on the choice of the wavelength of the electromagnetic radiation, ablation may be performed from the glass side or the membrane side. The energy density required to ablate the film thickness is achieved by passing a laser beam through an optical lens. In one embodiment, the lens focuses the laser beam to a desired shape and size, such as a "flat top" having the dimensions described above, with an energy density of about 0.5J/cm²And about 4J/cm²In the meantime. In one embodiment, the laser scan overlap is performed for BPE, as described above for laser edge ablation. In certain embodiments, variable depth ablation is used for BPE fabrication.

In certain embodiments, laser processing at the focal plane results in an amount (between about 10nm and about 100 nm) of residue (e.g., tungsten oxide) remaining on the exposed areas of the lower conductor, for example, due to the selective nature of absorption in the EC film. Since many EC materials are less conductive than the underlying conductive layer, the bus bar fabricated on this residue cannot make full contact with the underlying conductor, resulting in a voltage drop across the bus bar to the lower conductor interface. The voltage drop affects the color of the device and the adhesion of the bus bar to the lower conductor. One way to solve this problem is to increase the energy used for film removal, however, this approach results in trenches being formed where the spots overlap, thereby depleting the lower conductor, which is unacceptable. To overcome this problem, laser ablation is performed above the focal plane, i.e., the laser beam is defocused. In one embodiment, the defocused profile of the laser beam is a modified flat top or "flat top-like". By using a defocused laser profile, the effect transferred to the surface can be increased without damaging the underlying TCO at the spot overlap region. The method minimizes the amount of residue remaining on the exposed lower conductive layer, thereby allowing the bus bar to better contact the lower conductive layer.

Referring again to fig. 2A and 2B, after the BPE is formed, bus bars are applied to the device, one on the exposed region 235 of the first conductive layer (e.g., the first TCO) and one on the opposite side of the device, on the second conductive layer (e.g., the second TCO), on the portion of the second conductive layer not above the first conductive layer, see 225. This arrangement of the bus bar 1 on the second conductive layer avoids discoloration under the bus bar and other related problems with having a functional device under the bus bar. In this example, laser isolation scratches are not required in the device fabrication process-this is in stark contrast to conventional fabrication methods where one or more isolation scratches leave non-functional device portions in the final configuration.

FIG. 2B indicates cross-sections Z-Z 'and W-W' of device 240. A cross-sectional view of device 240 at Z-Z 'and W-W' is shown in fig. 2C. The depicted layers and dimensions are not drawn to scale but are intended to functionally represent configurations. In this example, the diffusion barrier layer is removed when fabricating width a and width B. Specifically, the peripheral region 241 is free of the first conductive layer and the diffusion barrier layer; although in one embodiment the diffusion barrier layer is left intact at the edge of the substrate around the perimeter of one or more sides. In another embodiment, the diffusion barrier layer is coextensive with the one or more material layers and the second conductive layer (thus, width a is fabricated at the depth of the diffusion barrier layer and width B is fabricated to a depth sufficient to remove the diffusion barrier layer). In this example, there are overlapping portions 245 of one or more layers of material around three sides of the functional device. On one of these overlapping parts, on the second TCO, a bus bar 1 is manufactured. In one embodiment, the vapor barrier layer is fabricated coextensive with the second electrically conductive layer. The vapor barrier layer is typically highly transparent, such as alumina, zinc oxide, tin oxide, silicon dioxide, and mixtures thereof, amorphous, crystalline, or mixed amorphous-crystalline. In this embodiment, a portion of the vapor barrier layer is removed to expose the second conductive layer for the bus bar 1. This exposed portion is similar to the BPE for bus bar 2 in region 235. In certain embodiments, the vapor barrier is also electrically conductive and no exposure of the second electrically conductive layer is required, i.e., a bus bar can be fabricated on the vapor barrier. The vapor barrier layer may be, for example, ITO, such as amorphous ITO, and thus be sufficiently conductive for this purpose. The amorphous form of the vapor barrier layer may provide greater hermeticity than the crystalline form. In some cases, the vapor barrier layer may be deposited using Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD), and may comprise a conductive metal nitride, silicon oxide, or mixtures thereof.

Fig. 2D provides another flow chart depicting a method of fabricating an electrochromic device or precursor, in accordance with certain embodiments. The method depicted in fig. 2D focuses on the deposition step. The method 260 begins by (a) receiving a substrate having a first conductive layer thereon or (b) depositing a first conductive layer on the substrate, see 261. As described above, in various embodiments, the substrate includes the first conductive layer thereon, and the first conductive layer need not be separately deposited. In other embodiments, the conductive layer may be deposited before the deposition of the remaining layers. The deposition of the second conductive layer is discussed further below. In some embodiments, these details may also be applied to the deposition of the first conductive layer.

The method continues with the deposition of an electrochromic layer, see 263. In many cases, the electrochromic layer is formed by sputtering. In certain embodiments where the electrochromic layer is homogeneous, the following conditions may be used to deposit the electrochromic layer. One or more metal-containing targets and comprising between about 40% and about 80% O can be used₂And between about 20% and about 60% Ar by sputtering to form the electrochromic layer. Each target may comprise one or more metals such as tungsten and molybdenum. The substrate on which the electrochromic layer is deposited may be heated, at least intermittently, to between about 150 ℃ and about 450 ℃ (in some cases, between about 250 ℃ and 350 ℃) during the formation of the electrochromic layer. The electrochromic layer may be deposited to a thickness of between about 500 and 600 nm.

In some embodiments where the ion conductor layer is omitted, the electrochromic layer may be deposited as two or more layers or graded layers. One of these layers or a portion of the graded layer may be enriched with oxygen compared to the other layer or the remainder of the graded layer. The oxygen-rich portion may be super-stoichiometric with respect to oxygen. Typically, the oxygen-rich layer or oxygen-rich portion is in contact with the counter electrode layer. In other embodiments, the oxygen-rich material at the interface may be provided in the form of a counter electrode material instead of or in addition to the electrochromic material.

In the case where the electrochromic layer is deposited as two or more layers (one of the layers is oxygen-rich), the following conditions may be used. In some such cases, the first layer of the electrochromic layer may have a thickness between about 350nm and about 450 nm. One or more targets and including between about 40% and about 80% O may be used₂And between about 20% Ar and about 60% Ar. The target may comprise one or more metals, such as tungsten and molybdenum. The second layer may have a thickness between about 100nm and about 200 nm. One or more targets and between about 70% and 100% O can be used₂And between 0% Ar and about 30% Ar to form the second layer by sputtering. In this embodiment, the heat may be applied, for example, by heating the substrate to between about 150 ℃ and about 450 ℃ at least intermittently during the deposition of the first electrochromic layer, while no (or substantially no) heating occurs during the deposition of the second electrochromic layer. In a more specific embodiment, the first electrochromic layer is about 400nm thick; the first sputtering gas comprises between about 50% and about 60% O₂And between about 40% and about 50% Ar; the second electrochromic layer is about 150nm thick; and the second sputtering gas is substantially pure O₂. In this embodiment, heat is applied to between about 200 ℃ and about 350 ℃ at least intermittently during formation of the first electrochromic layer, while no (or substantially no) heat is applied during formation of the second electrochromic layer.

In the case of depositing the electrochromic layer as a graded layer having a graded oxygen composition, the following conditions may be used to deposit the electrochromic layer. The electrochromic layer may be formed by sputtering using one or more metal-containing targets and a sputtering gas, wherein the sputtering gas includes between about 40% and about 80% O at the beginning of sputtering the electrochromic layer₂And between about 20% and about 60% Ar, while at the end of sputtering the electrochromic layer, the sputtering gas comprises between about 70% and 100% O₂And between 0% and about 30% Ar. At the beginning of the formation of the electrochromic layer, the substrate may be heated, at least intermittently, to about 200 ℃ and aboutBetween 350 c but no heating is applied during at least the final part of the deposition of the electrochromic layer. The description presents the electrochromic layer being deposited prior to the counter electrode layer, as shown in fig. 2D. In the case where the electrochromic layer is deposited as a graded layer after the counter electrode layer is formed, the details regarding the "initial"/"start" and "final"/"end" portions of sputtering may be reversed. In either case, the electrochromic material with the higher oxygen concentration may be in contact with the counter electrode layer.

Regardless of the structure of the electrochromic layer, the pressure in the deposition station or chamber during formation of the electrochromic layer may be between about 1 and about 75 millitorr (mTorr), or between about 5 and about 50mTorr, or between about 10 to about 20 mTorr. In one embodiment, the power density used to sputter the one or more targets may be about 2 watts per square centimeter (W/cm)²) And about 50W/cm²Based on the applied power divided by the surface area of the target; in another embodiment, at about 10W/cm²And about 20W/cm²To (c) to (d); and in yet another embodiment, at about 15W/cm²And about 20W/cm²In the meantime. In some embodiments, the power delivered to achieve 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 20kHz and about 400kHz, in another embodiment between about 20kHz and about 50kHz, in yet another embodiment between about 40kHz and about 50kHz, and in another embodiment about 40 kHz. The above conditions may be used in combination with each other to achieve deposition of a high quality electrochromic layer. In one embodiment, the distance between the target (cathode or source) to the substrate surface is between about 35mm and about 150 mm; between about 45mm and about 130mm in another embodiment; and in another embodiment, between about 70mm and about 100 mm. These same distances may be applicable to other targets used to deposit other layers of the device.

Next, the process continues with optional deposition of an ion conducting layer, see 263. When present, the ion-conducting layer can be provided in a number of different ways. For example, the ion conductor layer may be formed by sputtering, a vapor-based technique, a sol-gel technique, or the like. In many cases, the ion conducting layer is omitted.

The method then continues with the deposition of an electrode layer, see 267. Much like the electrochromic layer, the counter electrode layer may be deposited as a homogeneous layer, two or more layers, or a graded layer. In the case where the counter electrode is deposited as two or more layers or graded layers, a portion of one of the layers or graded layers may be enriched in oxygen compared to the remainder of the other layer or graded layer. The oxygen-rich layer or oxygen-rich portion can be positioned in direct physical contact with the electrochromic material in the electrochromic layer. In such cases, the deposition conditions may be varied between depositing the first and second layers, or between depositing an initial portion of the graded layer and a final portion of the graded layer. In various embodiments, the oxygen concentrations and substrate temperatures listed above with respect to the deposition of the electrochromic layer may also be applied to the deposition of the counter electrode layer. Generally, a sputtering gas having a higher oxygen concentration and a lower inert gas concentration can be used to form an oxygen-rich layer or a portion of a graded layer as compared to the sputtering gas used to deposit the remainder of another layer or graded layer.

In some embodiments, the sputtering gas used to form the counter electrode may include 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, and in another embodiment about 100% oxygen. In one embodiment, the power density used to sputter the CE target is about 2W/cm²And about 50W/cm²Based on the applied power divided by the surface area of the target; in another embodiment at about 5W/cm²And about 20W/cm²To (c) to (d); and in yet another embodiment at about 8W/cm²And about 10W/cm²And in another embodiment about 8W/cm². In some embodiments, the power delivered to achieve sputtering is provided via Direct Current (DC). In other embodiments, pulsed DC/AC reactive sputtering is used. In one embodiment, pulsed DC/AC reactive sputtering is usedThe frequency is between about 20kHz and about 400kHz, in another embodiment between about 20kHz and about 50kHz, in yet another embodiment between about 40kHz and about 50kHz, and in another embodiment about 40 kHz. The pressure in the deposition station or chamber is between about 1 and about 50mTorr in one embodiment, between about 20 and about 40mTorr in another embodiment, between about 25 to about 35mTorr in another embodiment, and about 30mTorr in another embodiment. In some embodiments, the counter electrode layer is deposited to a thickness of between about 150 and 350 nm; in yet another embodiment, between about 200 and about 250nm thick.

Next, the method continues with the deposition of a second conductive layer, see 269. The stated conditions can be employed to form a thin low-defect layer of indium tin oxide by, for example, sputtering a target containing indium oxide in tin oxide with or without an argon sputtering gas of oxygen. This is merely an example, and other materials and conditions may be used in other cases. In one embodiment, the thickness of the TCO layer is between about 5nm and about 10,000nm, in another embodiment, between about 10nm and about 1,000 nm; in yet another embodiment, between about 10nm and about 500 nm. In one embodiment, the substrate temperature during deposition of the second conductive layer is between about 20 ℃ and about 300 ℃, in another embodiment between about 20 ℃ and about 250 ℃, and in another embodiment between about 80 ℃ and about 225 ℃. In one embodiment, depositing the TCO layer includes sputtering from about 80% (by weight) to about 99% In using an inert gas, optionally with oxygen₂O₃And between about 1% and about 20% SnO₂The target of (1). In more specific embodiments, the target is between about 85% (by weight) to about 97% In₂O₃And between about 3% and about 15% SnO₂. In another embodiment, the target is at about 90% In₂O₃And between about 10% SnO₂. In one embodiment, the gas composition contains between about 0.1% and about 3% oxygen, in another embodiment between about 0.5% and about 2% oxygen, in yet another embodiment between about 1% and about 1.5% oxygen, and in another embodiment about 1.2% oxygen. At one isIn an embodiment, the power density for sputtering the TCO target is about 0.5W/cm²And about 10W/cm²Based on the applied power divided by the surface area of the target; in another embodiment at about 0.5W/cm²And about 2W/cm²To (c) to (d); and in yet another embodiment at about 0.5W/cm²And about 1W/cm²And in another embodiment about 0.7W/cm². In some embodiments, the power delivered to achieve 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 20kHz and about 400kHz, in another embodiment between about 50kHz and about 100kHz, in yet another embodiment between about 60kHz and about 90kHz, and in another embodiment about 80 kHz. In one embodiment, the pressure in the deposition station or chamber is between about 1 and about 10mTorr in one embodiment, between about 2 and about 5mTorr in another embodiment, between about 3 and about 4mTorr in another embodiment, and about 3.5mTorr in another embodiment. In one embodiment, the indium tin oxide layer is between about 20% (atomic) In and about 40% In; between about 2.5% Sn and about 12.5% Sn; and between about 50% O and about 70% O; in another embodiment, between about 25% In and about 35% In; between about 5.5% Sn and about 8.5% Sn; and between about 55% O and about 65% O; and In another embodiment, about 30% In, about 8% Sn, and about 62% O. The above conditions can be used in combination with each other to achieve deposition of a high quality indium tin oxide layer.

When practicing the method of fig. 2D, one or more of the deposited layers may be lithiated prior to depositing the next layer. For example, one or more of the electrochromic layer, the optional ion conducting layer, and the counter electrode layer may be lithiated. In one example, the electrochromic layer is lithiated. In another example, the counter electrode layer is lithiated. In another example, the ion conductor layer is lithiated. In another example, both the electrochromic layer and the counter electrode layer are lithiated. In another example, the electrochromic layer, the counter electrode layer, and the ion conducting layer are all lithiated. In another example, the electrochromic layer and the ion conductor layer are lithiated. In another example, the counter electrode layer and the ion conducting layer are lithiated. Furthermore, any of these layers may be lithiated during deposition of that layer. In some cases, a portion of one layer may be deposited, then lithiated, and then the remainder of the layer may be deposited. In one example, a first portion of the electrochromic layer is deposited, then lithiated, and then a second portion of the electrochromic layer is deposited. In another example, a first portion of the counter electrode layer is deposited, then lithiated, and then a second portion of the counter electrode layer is deposited. These first and second portions of the relevant layer may be deposited according to the same conditions or different conditions. In some cases, the first and second portions of the relevant layer may have different compositions.

In the case where the ion conducting layer is omitted, the electrochromic and/or lithiation of the counter electrode layer may facilitate the formation of an interfacial region between the electrochromic layer and the counter electrode layer, where the interfacial region comprises an ion conducting and substantially electrically insulating material. For example, in some such embodiments, when the electrochromic and counter electrode materials are contiguous and one or both of the materials contain excess oxygen (e.g., above a stoichiometric level), the intercalation of lithium and subsequent heating allows a chemical change to occur at the interface between the two electrode materials (e.g., between the electrochromic and counter electrode materials), thereby forming an ionically conductive and electrically insulating material at the interface region between the electrochromic and counter electrode layers. For example, the multi-step, abrupt thermal conditioning described herein can facilitate the formation of ionically conductive and electrically insulating materials.

In various embodiments, the operations shown in fig. 2D may be used to form an electrochromic device precursor. To form an electrochromic device from electrochromic device precursors, one or more steps may be performed as described above. As described above, one technique that may be used to form an electrochromic device from electrochromic device precursors is multi-step shock thermal conditioning. Conditioning may include a series of heating operations including heating the substrate under an inert atmosphere, heating the substrate under an oxygen atmosphere, and heating the substrate in air.

In one embodiment, the stack formed as described in fig. 2D is heated between about 150 ℃ and about 450 ℃ (before or after depositing the second conductive layer at 269) under Ar for between about 10 minutes and about 30 minutes, and then at O₂Between about 1 minute and about 15 minutes. After this treatment, the stack is further treated by heating the stack in air at between about 250 ℃ and about 350 ℃ for between about 20 minutes and about 40 minutes. In one particular example, the stack is heated at about 250 ℃ for about 15 minutes under an inert atmosphere, then O₂The stack was treated by heating under an atmosphere for 5 minutes and then heating the stack in air at about 300 ℃ for about 30 minutes. Flowing current between the electrochromic layer and the counter electrode layer may also be performed as part of an initial activation cycle of the electrochromic device.

Although fig. 2D shows the electrochromic layer being deposited prior to the counter electrode layer, this is not always the case. In some embodiments, operations 263 and 267 may be reversed such that the counter electrode layer is deposited prior to the electrochromic layer.

Apparatus for manufacturing electrochromic devices and precursors

An integrated deposition system can be employed to fabricate electrochromic devices on, for example, architectural glass or other substrates. Electrochromic devices can be used to fabricate Insulated Glass Units (IGUs), which in turn can be used to fabricate electrochromic windows. The term "integrated deposition system" refers to an apparatus for fabricating electrochromic devices on optically transparent and translucent substrates. The apparatus has a plurality of stations, each dedicated to a particular unit operation, such as depositing a particular component (or portion of a component) of an electrochromic device, and cleaning, etching, and temperature control of the device or portion thereof. The multiple stations are fully integrated together so that the substrate on which the electrochromic device is fabricated can be transferred from one station to the next without exposure to the external environment. The integrated deposition system operates in a controlled ambient environment inside the system in which the process stations are located. A fully integrated system allows for better control of the quality of the interface between the deposited layers. Interface quality refers to, among other factors, the quality of adhesion between these layers and the lack of contaminants in the interface region. The term "controlled ambient environment" refers to a sealed environment that is separate from the external environment (such as an open atmospheric environment or a clean room). In the controlled ambient environment, at least one of the pressure and the gas composition is controlled independently of conditions in the external environment. Typically, although not necessarily, the controlled ambient environment is at a pressure below atmospheric pressure, such as at least a partial vacuum. The conditions in the controlled ambient environment may remain constant during the processing operation or may change over time. For example, the electrochromic device layer may be deposited in a controlled ambient environment and under vacuum at the end of the deposition operation, the environment may be backfilled with a purge gas or a reactant gas, and the pressure increased to, for example, atmospheric pressure for processing at another station, and then the vacuum is re-established for the next operation, and so on.

In one embodiment, the system includes a plurality of deposition stations aligned in series and interconnected and operable to transfer a substrate from one station to the next without exposing the substrate to an external environment. The plurality of deposition stations includes: (i) a first deposition station comprising one or more targets for depositing a cathodically coloring electrochromic layer; (ii) a second optional deposition station containing one or more targets for depositing an ion conducting layer; (iii) a third deposition station containing one or more targets for depositing a counter electrode layer. In some cases, the second deposition station may be omitted. For example, the apparatus may not include any targets for depositing separate ion conductor layers. The system also includes a controller containing program instructions for passing the substrate through the plurality of stations in the following manner: sequentially depositing (i) an electrochromic layer, (ii) (optional) an ion conducting layer, and (iii) a counter electrode layer on a substrate to form a stack. In the case where the electrochromic layer or the counter electrode layer includes two or more layers, these layers may be formed at different positions or at the same position depending on the desired composition of each layer and other factors. In one example, a first station may be used to deposit the electrochromic layer, a second station may be used to deposit the first layer of the counter electrode layer, and a third station may be used to deposit the second layer of the counter electrode layer.

In one embodiment, multiple deposition stations may be operated to transfer substrates from one station to the next without breaking the 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 the architectural glass substrate. In another embodiment, an integrated deposition system includes a substrate holder and a transport mechanism operable to hold an architectural glass substrate in a vertical orientation while in a plurality of deposition stations. In yet another embodiment, the integrated deposition system includes one or more load locks for passing substrates between an external environment and the integrated deposition system. In another embodiment, the plurality of deposition stations comprises at least two stations for depositing a layer selected from the group consisting of an electrochromic layer, an ion conducting layer, and a 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 the individual processing stations from each other during operation. In one embodiment, one or more of the lithium deposition stations have an isolation valve. In this context, the term "isolation valve" refers to a device that isolates a deposition or other process performed at one station from processes at other stations in an integrated deposition system. In one example, the isolation valve is a physical (solid) isolation valve within the integrated deposition system that participates in depositing lithium. The actual physical solid valve may participate in completely or partially isolating (or shielding) the lithium deposition in the integrated deposition system from other processes or stations. In another embodiment, the isolation valve may be a gas knife or shield, for example, where a partial pressure of argon or other inert gas is passed over the area between the lithium deposition station and the other stations to prevent ions from flowing to the other stations. In another example, the isolation valve may be an evacuated region between the lithium deposition station and other process stations, such that lithium ions or ions entering the evacuated region from other stations are removed, for example, to a waste stream, rather than contaminating an adjacent process. This is achieved, for example, by dynamic flow in a controlled ambient environment via a pressure differential in a lithiation station of the integrated deposition system, such that lithium deposition in the integrated deposition system is substantially isolated from other processes. Also, the isolation valve is not limited to the lithium deposition station.

In some embodiments, the integrated deposition system includes one or more stations for depositing a conductive layer (e.g., a transparent conductive oxide layer, sometimes referred to as a TCO). In case both the first and the second electrically conductive layer are deposited on the substrate, two stations may be provided, each dedicated to depositing one of the electrically conductive layers. In other embodiments, a single station may be used to deposit both conductive layers. In the case where only a single conductive layer is deposited, only a single conductive layer deposition station is required. For example, in many cases, the substrate is received with a first conductive layer disposed thereon, and only a second conductive layer is deposited during the manufacture of the electrochromic device.

Fig. 3A schematically depicts an integrated deposition system 300 according to some embodiments. In this example, the system 300 includes an entry load lock 302 for introducing substrates into the system, and an exit load lock 304 for removing substrates from the system. The load lock allows substrates to be introduced into or removed from the system without disturbing the controlled ambient environment of the system. The integrated deposition system 300 has a module 306 with a plurality of deposition stations: an EC layer deposition station, an IC layer deposition station, and a CE layer deposition station. In the broadest sense, the integrated deposition system need not have load lock functionality, e.g., module 306 can be used alone as an integrated deposition system. For example, the substrate may be loaded into the module 306, a controlled ambient environment established, and then the substrate processed through various stations within the system. Each station within the integrated deposition system may contain heaters, coolers, various sputtering targets and instruments that move them, RF and/or DC power supplies and power delivery mechanisms, etching tools (e.g., plasma etching), gas sources, vacuum sources, glow discharge sources, process parameter monitors and sensors, robots, power supplies, and the like.

Fig. 3B depicts a portion (or simplified version) of the integrated deposition system 300 in perspective view, and with more detail (including a cross-sectional view of the interior). In this example, the system 300 is modular, with the entry load lock 302 and the exit load lock 304 connected to a deposition module 306. There is an entry port 310 for loading, for example, an architectural glass substrate 325 (the load lock 304 has a corresponding exit port). The substrate 325 is supported by the tray 320 traveling along the rail 315. In this example, the pallet 320 is supported by the track 315 via suspension, but the pallet 320 may also be supported on a track located near the bottom of the device 300, or for example, midway between the top and bottom of the device 300. The tray 320 may be translated forward and/or backward (as indicated by the double arrow) by the system 300. For example, during lithium deposition, the substrate may be moved forward and backward in front of the lithium target 330, making multiple passes to achieve the desired lithiation. Tray 320 and base 325 are in a substantially vertical orientation. The substantially vertical orientation is not limiting, but may help prevent defects because particulate matter that may be generated, for example, due to sputtered atomic agglomeration, will tend to yield to gravity and thus not deposit on the substrate 325. Also, because architectural glass substrates tend to grow larger, the vertical direction as the substrate traverses the stations of the integrated deposition system enables thinner glass substrates to be coated because there is less concern for sagging to occur for thicker hot glass.

The target 330, in this case a cylindrical target, is oriented substantially parallel to and in front of the substrate surface on which deposition is to occur (for convenience, other sputtering equipment is not shown here). The substrate 325 can be translated past the target 330 during deposition, and/or the target 330 can be moved in front of the substrate 325. The path of motion of the target 330 is not limited to translation along the path of the substrate 325. The target 330 may rotate along an axis through its length, translate along a 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 the substrate 325, and so forth. The target 330 need not be cylindrical, but can be planar or any shape required to deposit a desired layer having desired properties. Also, there may be more than one target in each deposition station, and/or the targets may be moved from station to station depending on the desired process.

The integrated deposition system 300 also has various vacuum pumps, gas inlets, pressure sensors, etc., which establish and maintain a controlled ambient environment within the system. These components are not shown, but will be understood by those of ordinary skill in the art. The system 300 is controlled, for example, via a computer system or other controller (represented in fig. 3B by the LCD and keyboard 335). One of ordinary skill in the art will appreciate that embodiments herein can employ various processes involving data stored in or transmitted across one or more computer systems. Embodiments are also related to devices, such as computers and microcontrollers, for performing these operations. These devices and processes can be used to deposit the electrochromic materials of the methods herein as well as devices designed to implement them. The control device may be specially constructed for the required purposes, or it may be a general-purpose computer selectively activated or reconfigured by a computer program and/or data structure stored in the computer. The processes presented herein are not inherently related to any particular computer or other apparatus. In particular, various general-purpose machines may be used with programs written in accordance with the teachings herein, or it may be more convenient to construct a more specialized apparatus to perform and/or control the desired methods and processes.

As mentioned, the various stations of the integrated deposition system may be modular, but once connected form a continuous system where a controlled ambient environment is established and maintained for processing substrates at the various stations within the system. FIG. 3C depicts an integrated deposition system 300a similar to system 300, but in this example each station is modular, specifically an EC landing 304a, an IC landing 304b, and a CE landing 306C. In a similar embodiment, the IC landing 304b is omitted. The modular form is not required, but it is convenient because the integrated deposition system can be assembled as needed according to custom requirements and emerging process advances. For example, fig. 3D depicts an integrated deposition system 300b having two lithium deposition stations 307a and 307 b. The system 300b is, for example, equipped to perform methods herein as described above, such as a dual lithiation method. The system 300b may also be used to perform a single lithiation process, such as by utilizing only the lithium station 307b during processing of the substrate. But in a modular format, for example, if a single lithiation is desired, one of the lithiation stations is redundant and a system 300c as shown in fig. 3E can be used. The system 300c has only one lithium deposition station 307.

The systems 300b and 300c also have one or more TCO landing 308 for depositing a TCO layer on the EC stack. TCO refers to a transparent conductive oxide. Referring to fig. 1, the conductive layers 104 and 114 may be TCO layers. Although fig. 3D and 3E only show a single TCO station 308, it is understood that where a first conductive layer is deposited on the substrate (e.g., rather than providing the first conductive layer on the substrate), an additional TCO station may be provided, for example, between the entry load lock 302 and the EC station 306a (or between the entry load lock 302 and the CE station 306c where the counter electrode layer is deposited prior to the electrochromic layer). Additional stations may be added to the integrated deposition system, such as stations for cleaning processes, laser scribing, capping layers, etc., depending on process requirements.

The sputtering process used to form the layer (e.g., electrochromic layer or counter electrode layer) may utilize one or more sputtering targets. In the case where one sputtering target is used, the target may include all the metals needed to deposit the layers (e.g., nickel and tungsten for a NiWO layer; nickel, tungsten and tantalum for a NiWTaO layer; nickel, tungsten and niobium for a NiWNbO layer; nickel, tungsten and tin for a NiWSnO layer; tungsten and molybdenum for a WMoO layer; etc.). In such cases, the target may be in the form of a metal alloy, an intermetallic mixture, a metal oxide material, or a combination thereof. In the case of a metal alloy or intermetallic mixture, the composition of the target reflects the metal ratio described herein using the variables x and y, without oxygen (y is 0). For example, a metallic sputtering target may have a composition of 94% (atomic) tungsten and 6% (atomic) molybdenum (x ═ 0.06). It is understood that in sputtered tungsten molybdenum oxide, the atomic ratio of the metal target may not be directly converted to a metal ratio, as the metal may react with oxygen at different rates, be sputtered off the target at different rates, and so forth. Where more than one target is used, the targets may have the same composition or different compositions (e.g., different metals or combinations of metals on each target).

The sputtering target can include a grid or other overlapping shape in which different portions of the grid include different relevant materials (e.g., certain portions of the grid can include elemental metals or metal alloys that together form a desired composition). For example, where two targets are used to form a tungsten molybdenum oxide electrochromic layer, each target may comprise one or more of tungsten and molybdenum. In one example, the first target comprises tungsten and the second target comprises molybdenum. In certain embodiments, two targets are used to form a nickel tungsten tantalum oxide counter electrode. In such cases, the first target can include nickel and the second target can include tungsten and tantalum; or the first target may comprise nickel and tungsten and the second target may comprise tantalum; or the first target may comprise nickel and tantalum and the second target may comprise tungsten. Similar examples are possible for other materials, including but not limited to nickel tungsten tin oxide and nickel tungsten niobium oxide, each of which may be used as a counter electrode material in certain embodiments. In any case where two or more metals are provided together on the same target, the metals may be provided separately (e.g., elemental metals provided together in a grid or otherwise), as alloys, or combinations thereof.

In some cases, a sputtering target can include an alloy of related materials (e.g., tungsten and molybdenum for forming a tungsten molybdenum oxide layer; two or more of nickel, tungsten, and tantalum for forming a nickel tungsten tantalum oxide layer; two or more of nickel, tungsten, and tin for forming a nickel tungsten tin oxide layer; two or more of nickel, tungsten, and niobium for forming a nickel tungsten niobium oxide layer). Where two or more sputtering targets are used, each sputtering target can include at least one of the relevant materials (e.g., elemental and/or alloy forms of the relevant metal, either can be provided in oxide form). In some cases, the sputtering targets may overlap. In some embodiments, the sputtering target can also be rotated. As noted, the electrochromic and counter electrode layers are typically each an oxide material. Oxygen may be provided as part of the sputtering target and/or sputtering gas. In some cases, the sputtering target is a substantially pure metal or alloy (e.g., lacking oxygen), and sputtering is performed in the presence of oxygen to form an oxide.

In one embodiment, to regulate the deposition rate of the electrochromic or counter electrode layers, multiple targets are used, thereby eliminating the need for unduly high power (or other undue adjustment of desired process conditions) to increase the deposition rate.

Table 2 provides various examples of target sets that may be used together to form tungsten molybdenum oxide according to certain embodiments. Any of these materials may be provided in oxide form. When the two metals are provided together, they may be provided as elemental metals (e.g., in a grid or other pattern), or may be provided as an alloy.

TABLE 2

Composition of the first target	Composition of the second target
		Tungsten	Molybdenum (Mo)
Tungsten and molybdenum	-

Table 3 provides various examples of target sets that may be used together to form nickel tungsten tantalum oxide according to certain embodiments. Any of these materials may be provided in oxide form. When the two metals are provided together, they may be provided as elemental metals (e.g., in a grid or other pattern), or may be provided as an alloy.

TABLE 3

Composition of the first target	Composition of the second target	Composition of third target
			Nickel and tungsten	Tantalum	-
Nickel and tantalum	Tungsten	-
			Nickel (II)	Tantalum	Tungsten

Table 4 provides various examples of target sets that may be used together to form nickel tungsten niobium oxide in accordance with certain embodiments. Any of these materials may be provided in oxide form. When the two metals are provided together, they may be provided as elemental metals (e.g., in a grid or other pattern), or may be provided as an alloy.

TABLE 4

Composition of the first target	Composition of the second target	Composition of third target
			Nickel and tungsten	Niobium (Nb)	-
Nickel and niobium	Tungsten	-
			Nickel (II)	Niobium (Nb)	Tungsten

Table 5 provides various examples of target sets that may be used together to form nickel tungsten tin oxide according to certain embodiments. Any of these materials may be provided in oxide form. When the two metals are provided together, they may be provided as elemental metals (e.g., in a grid or other pattern), or may be provided as an alloy.

TABLE 5

Composition of the first target	Composition of the second target	Composition of third target
			Nickel and tungsten	Tin (Sn)	-
Nickel and tin	Tungsten	-
			Nickel (II)	Tin (Sn)	Tungsten

Tables 2-5 describe various examples relating to the formation of tungsten molybdenum oxide, nickel tungsten tantalum oxide, nickel tungsten niobium oxide, and nickel tungsten tin oxide. These values are merely examples and are not intended to be limiting. In other examples, different electrochromic and/or counter electrode materials may be used.

Various sputtering target designs, orientations, and embodiments are further discussed in U.S. patent No. 9,261,751, which is incorporated by reference herein in its entirety.

The density and orientation/shape of the material sputtered from the sputter target depends on various factors including, for example, the shape and strength of the magnetic field, the pressure, and the power density used to generate the sputtering plasma. The distance between adjacent targets and the distance between each target and the substrate also affect how the sputtering plasma mixes and the resulting material is deposited on the substrate.

In certain embodiments, two different types of sputtering targets are provided to deposit a monolayer in the electrochromic stack: (a) a primary sputtering target that sputters material onto a substrate; and (b) a secondary sputtering target that sputters material onto the primary sputtering target. The primary and secondary sputtering targets can include any combination of metals, metal alloys, and metal oxides (including but not limited to any of the combinations described in tables 2-5, where the "first target" listed in these tables corresponds to either the primary or secondary target) that achieve the desired composition in the deposited layer. In one particular example where the target is used to form tungsten molybdenum oxide, the primary sputtering target comprises tungsten and the secondary sputtering target comprises molybdenum. These sputtering targets can be used to deposit electrochromic layers comprising tungsten molybdenum oxide. Other combinations of elemental metals and alloys may also be used, as desired.

In the case where both the primary and secondary sputtering targets are used, the secondary sputtering target can be operated at a potential that is the cathode (which is already the cathode) compared to the potential of the primary sputtering target. Alternatively, the targets may be operated independently. Further, neutral species ejected from the secondary target will deposit on the primary target regardless of the relative target potential. Neutral atoms will be part of the flux and, regardless of the relative potential, these atoms will be deposited on the cathode primary target.

It is to be understood that the configurations and/or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, various acts illustrated may be performed in the sequence illustrated, in other sequences, in parallel, or in some cases omitted. Likewise, the order of the above-described processes may be changed. Certain references have been incorporated herein by reference. It should be understood that any disclaimer or disclaimer made in such references is not necessarily applicable to the embodiments described herein. Similarly, any features described as essential in these references may be omitted in the embodiments herein.

Claims (47)

1. An electrochromic device or electrochromic device precursor comprising:

a first conductive layer having a thickness between about 10-500 nm;

an electrochromic layer comprising an electrochromic material comprising a polymer having formula W_1-xMo_xO_yWherein x is between about 0.05-0.30 and y is between about 2.5-4.5, the electrochromic layer has a thickness of between about 100-500 nm;

a counter electrode layer comprising a counter electrode material comprising nickel tungsten oxide, the counter electrode layer having a thickness of between about 100 and 500 nm; and

a second conductive layer having a thickness of between about 100 and 400nm,

wherein the electrochromic layer and the counter electrode layer are positioned between the first conductive layer and the second conductive layer, and wherein the electrochromic device is all solid state and inorganic.

2. The electrochromic device or electrochromic device precursor of claim 1, wherein the electrochromic layer is a nanocrystal.

3. The electrochromic device or electrochromic device precursor of claim 1, wherein the electrochromic layer is amorphous.

4. The electrochromic device or electrochromic device precursor of claim 1, wherein the counter electrode layer is a nanocrystal.

5. The electrochromic device or electrochromic device precursor of claim 1, wherein the counter electrode layer is amorphous.

6. The electrochromic device or electrochromic device precursor of claim 1, wherein the counter electrode material comprises nickel tungsten tantalum oxide.

7. The electrochromic device or electrochromic device precursor of claim 1, wherein the counter electrode material comprises nickel tungsten niobium oxide.

8. The electrochromic device or electrochromic device precursor of claim 1, wherein the counter electrode material comprises nickel tungsten tin oxide.

9. The electrochromic device or electrochromic device precursor of claim 1, wherein the electrochromic layer, the counter electrode layer, and the second conductive layer are all formed by sputtering.

10. The electrochromic device or electrochromic device precursor of claim 1, wherein the electrochromic device or electrochromic device precursor does not comprise a homogenous layer of ion-conducting electrically insulating material between the electrochromic layer and the counter electrode layer.

11. The electrochromic device or electrochromic device precursor of claim 1, wherein the electrochromic material is in physical contact with the counter electrode material.

12. The electrochromic device or electrochromic device precursor of claim 1, wherein at least one of the electrochromic layer and the counter electrode layer comprises two or more layers or portions, one of the layers or portions being superstoichiometric with respect to oxygen.

13. The electrochromic device or electrochromic device precursor of claim 12, wherein:

(a) the electrochromic layer comprises the two or more layers, and a layer superstoichiometric with respect to oxygen is in contact with the counter electrode layer, or

(b) The counter electrode layer comprises the two or more layers, and a layer that is superstoichiometric with respect to oxygen is in contact with the electrochromic layer.

14. The electrochromic device or electrochromic device precursor of claim 12, wherein:

(a) the electrochromic layer comprises the two or more portions which together form the electrochromic layer as a layer of graded composition and the portion of the electrochromic layer that is superstoichiometric with respect to oxygen is in contact with the counter electrode layer, or

(b) The counter electrode layer comprises the two or more portions which together form the counter electrode layer as a graded composition layer and the portion of the counter electrode layer that is superstoichiometric with respect to oxygen is in contact with the electrochromic layer.

15. The electrochromic device or electrochromic device precursor of claim 1, further comprising an ionically conductive and substantially electrically insulating material formed in situ at an interface between the electrochromic layer and the counter electrode layer.

16. The electrochromic device or electrochromic device precursor of claim 1, further comprising an ion-conducting layer comprising a material selected from the group consisting of: lithium silicate, lithium aluminum silicate, lithium oxide, lithium tungstate, lithium aluminum borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium oxynitride, lithium aluminum fluoride, lithium phosphorus oxynitride (LiPON), Lanthanum Lithium Titanate (LLT), lithium tantalate, lithium zirconium oxide, lithium silicon oxycarbonitride (LiSiCON), lithium phosphate, lithium titanium phosphate, lithium germanium vanadium oxide, lithium zinc germanium oxide, and combinations thereof.

17. The electrochromic device or electrochromic device precursor of claim 16, wherein the thickness of said ion-conducting layer is between about 5-100 nm.

18. The electrochromic device or electrochromic device precursor of claim 16, wherein said ion-conducting layer comprises a material selected from the group consisting of: lithium silicate, lithium aluminum silicate, lithium zirconium silicate, lithium borosilicate, lithium phosphosilicate, lithium phosphorus oxynitride (LiPON), lithium silicon oxycarbonitride (LiSiCON), and combinations thereof.

19. The electrochromic device or electrochromic device precursor of claim 1, wherein x is between about 0.1 and 0.25.

20. The electrochromic device or electrochromic device precursor of claim 1, wherein x is between about 0.15 and 0.2.

21. The electrochromic device or electrochromic device precursor of claim 12, wherein said layer or portion that is superstoichiometric with respect to oxygen has an excess of oxygen.

22. The electrochromic device or electrochromic device precursor of claim 1, further comprising an intermediate layer located between the electrochromic layer and the counter electrode layer, wherein the intermediate layer comprises tungsten oxide that is superstoichiometric with respect to oxygen.

23. The electrochromic device or electrochromic device precursor of claim 22, wherein said tungsten oxide is free of molybdenum.

24. The electrochromic device or electrochromic device precursor of claim 22, wherein said tungsten oxide comprises molybdenum.

25. The electrochromic device or electrochromic device precursor of claim 22, wherein said tungsten oxide does not comprise molybdenum and is amorphous.

26. The electrochromic device or electrochromic device precursor of claim 1, wherein the counter electrode layer comprises a first sublayer and a second sublayer, wherein the first sublayer comprises a first composition of nickel tungsten oxide and the second sublayer comprises a second composition of nickel tungsten oxide, wherein the first and second compositions are different from each other.

27. A method of making an electrochromic device or electrochromic device precursor, the method comprising:

receiving a substrate having a first conductive layer thereon;

forming an electrochromic layer comprising an electrochromic material comprising a polymer having formula W_1-xMo_xO_yTungsten molybdenum of compositionAn oxide, wherein x is between about 0.05-0.30 and y is between about 2.5-4.5;

forming a counter electrode layer comprising a counter electrode material comprising nickel tungsten oxide; and

a second conductive layer is formed on the first conductive layer,

wherein the electrochromic layer and the counter electrode layer are positioned between the first conductive layer and the second conductive layer, and wherein the electrochromic device is all solid state and inorganic.

28. The method of claim 27, wherein the electrochromic layer is a nanocrystal.

29. The method of claim 27, wherein the electrochromic layer is amorphous.

30. The method of claim 27, wherein the counter electrode layer is a nanocrystal.

31. The method of claim 27, wherein the counter electrode layer is amorphous.

32. The method of claim 27, wherein the counter electrode material comprises nickel tungsten tantalum oxide.

33. The method of claim 27, wherein the counter electrode material comprises nickel tungsten niobium oxide.

34. The method of claim 27, wherein the counter electrode material comprises nickel tungsten tin oxide.

35. The method of claim 27, wherein the electrochromic layer, the counter electrode layer, and the second conductive layer are all formed by sputtering.

36. The method of claim 27, wherein the electrochromic device or electrochromic device precursor does not comprise a homogenous layer of ion-conducting electrically insulating material between the electrochromic layer and the counter electrode layer.

37. The method of claim 27, wherein the electrochromic material is in physical contact with the counter electrode material.

38. The method of claim 27, wherein at least one of the electrochromic layer and the counter electrode layer is deposited to include two or more layers, one of the layers being superstoichiometric with respect to oxygen.

39. The method of claim 38, wherein:

(a) the electrochromic layer comprises the two or more layers, and a layer superstoichiometric with respect to oxygen is in contact with the counter electrode layer, or

(b) The counter electrode layer comprises the two or more layers, and a layer that is superstoichiometric with respect to oxygen is in contact with the electrochromic layer.

40. The method of claim 38, wherein:

(a) the electrochromic layer comprises an electrochromic graded layer comprising a portion that is superstoichiometric with respect to oxygen and is in contact with the counter electrode layer, or

(b) The counter electrode layer includes a counter electrode graded layer including a portion that is super-stoichiometric with respect to oxygen and in contact with the electrochromic layer.

41. The method of claim 27, further comprising: forming in situ an ion conducting layer comprising an ion conducting and substantially electrically insulating material, the ion conducting layer being located at an interface between the electrochromic layer and the counter electrode layer.

42. The method of claim 27, further comprising: forming an ion conducting layer comprising a material selected from the group consisting of: lithium silicate, lithium aluminum silicate, lithium oxide, lithium tungstate, lithium aluminum borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium oxynitride, lithium aluminum fluoride, lithium phosphorus oxynitride (LiPON), Lanthanum Lithium Titanate (LLT), lithium tantalate, lithium zirconium oxide, lithium silicon oxycarbonitride (LiSiCON), lithium phosphate, lithium titanium phosphate, lithium germanium vanadium oxide, lithium zinc germanium oxide, and combinations thereof, wherein the ion conducting layer is formed prior to forming at least one of the electrochromic layer and the counter electrode layer.

43. The method of claim 42, wherein the ion conducting layer is between about 5-100nm thick.

44. The method of claim 42, wherein the ion conducting layer comprises a material selected from the group consisting of: lithium silicate, lithium aluminum silicate, lithium zirconium silicate, lithium borosilicate, lithium phosphosilicate, lithium phosphorus oxynitride (LiPON), lithium silicon oxycarbonitride (LiSiCON), and combinations thereof.

45. The method of claim 27, wherein:

using one or more metal-containing targets and including between about 40-80% O₂And between about 20-60% Ar, wherein during the formation of the electrochromic layer, the substrate is at least intermittently heated to between about 150-450 ℃, the thickness of the electrochromic layer is between about 200-700nm, and

using one or more metal-containing targets and including between about 30-100% O₂And between about 0-30% Ar, the counter electrode layer having a thickness between about 100-500 nm.

46. The method of claim 27, further comprising: after forming the counter electrode layer:

heating the substrate in an inert atmosphere at a temperature between about 150-450 ℃ for a duration of between about 10-30 minutes;

heating the substrate in an oxygen atmosphere at a temperature between about 150-450 ℃ for a duration of between about 1-15 minutes after heating the substrate in the inert atmosphere; and

after heating the substrate in the oxygen atmosphere, heating the substrate in air at a temperature between about 250-350 ℃ for a duration of between about 20-40 minutes.

47. The method of claim 27, wherein the substrate is maintained in a vertical orientation during the forming of the electrochromic layer, the counter electrode layer, and the second conductive layer.

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