Electrochromic device comprising tungsten titanium molybdenum oxide as electrochromic cathode material

Abstract

The present disclosure relates to an electrochromic device including tungsten titanium molybdenum oxide as an electrochromic cathode material. Various embodiments herein relate to electrochromic devices, and methods and apparatus for making such electrochromic devices, wherein the material of an electrochromic layer (106) includes a cathodically colored tungsten titanium molybdenum oxide. In certain embodiments, the electrochromic device may include one or more particular counter electrode materials. The material of the counter electrode material may include an electrochromic nickel tungsten oxide, a nickel tungsten tantalum oxide, a nickel tungsten niobium oxide, a nickel tungsten tin oxide, or another nickel-based anode coloring material.

Description

[0001] Information about divisional applications

[0002] This case is a divisional application. The parent case of the divisional application is an invention patent application with an application date of April 17, 2019, application number 201980038535.9, and invention name "Electrochromic device including tungsten-titanium-molybdenum oxide as electrochromic cathode material".

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] This application claims priority to U.S. Patent Application No. 16 / 384,822, filed on April 15, 2019, and entitled “ELECTROCHROMIC CATHODEMATERIALS,” which claims priority to U.S. Provisional Patent Application No. 62 / 662,034, filed on April 24, 2018, and entitled “ELECTROCHROMIC CATHODE MATERIALS,” the entire contents of each of the above patent applications are incorporated herein by reference in their entirety.

[0005] In addition, this application incorporates by reference and for all purposes the entire contents of each of the following applications: U.S. Patent No. 9,664,974 [Attorney Docket No.: VIEWP001]; U.S. Patent No. 8,300,298 [Attorney Docket No. VIEWP004]; U.S. Patent No. 8,764,951 [Attorney Docket No.: VIEWP004X2]; U.S. Patent Application No. 15 / 507,734 filed on February 28, 2017 and entitled “COUNTER ELECTRODE FOR ELECTROCHROMIC DEVICES” [Attorney Docket No.: VIEWP066]; U.S. Patent Application No. 15 / 507,734 filed on May 16, 2017 and entitled “COUNTER ELECTRODE FOR ELECTROCHROMIC DEVICES U.S. Patent Application No. 15 / 527,194, entitled “COUNTER ELECTRODE FOR ELECTROCHROMIC DEVICES” [Attorney Docket No. VIEWP074], filed on May 15, 2017; U.S. Patent Application No. 15 / 526,969, entitled “COUNTER ELECTRODE FOR ELECTROCHROMIC DEVICES” [Attorney Docket No. VIEWP075]. Background Art

[0006] Electrochromism is the phenomenon in which a material exhibits reversible electrochemically mediated changes in its optical properties when placed in different electronic states (usually subjected to voltage changes). The optical properties are typically one or more of color, transmittance, absorbance, and reflectance. A well-known electrochromic material is tungsten oxide (WO 3 ). Tungsten oxide is a cathodic electrochromic material in which the color transition from transparent to blue occurs by electrochemical reduction.

[0007] Electrochromic materials can be incorporated into windows for home, commercial and other uses, for example. The color, transmittance, absorptivity and / or reflectivity of such windows can be changed by causing changes in the electrochromic material, i.e., electrochromic windows are windows that can be electronically darkened or lightened. A small voltage applied to the electrochromic device of the window will darken them; reversing the voltage will lighten them. This capability allows the amount of light passing through the window to be controlled and provides the opportunity for electrochromic windows to be used as energy-saving devices.

[0008] Despite the discovery of electrochromism in the 1960s, electrochromic devices (and, in particular, electrochromic windows) unfortunately continue to suffer from a variety of problems and, despite many recent advances in electrochromic technology, devices and related methods of manufacturing and / or using electrochromic devices, have not yet begun to realize their full commercial potential.

[0009] The background description provided herein is for the purpose of generally presenting the content of the present disclosure. The work of the presently named inventors within the scope described in this background section, and aspects that may not otherwise qualify as prior art to the present disclosure at the time of filing of the specification, is neither expressly nor implied to be prior art to the present disclosure. Summary of the invention

[0010] Certain embodiments herein relate to electrochromic devices and electrochromic device precursors, as well as methods and apparatus for forming such electrochromic devices and electrochromic device precursors. In various embodiments, the electrochromic device or electrochromic device precursor includes an electrochromic layer, which includes an electrochromic material, which includes tungsten, titanium, molybdenum, and oxygen. This material is generally referred to as tungsten titanium molybdenum oxide. In some cases, the tungsten titanium molybdenum oxide electrochromic material can be paired with a specific counter electrode material, for example to provide a desired color quality when the device is in a colored state.

[0011] In one aspect of the disclosed embodiment, an electrochromic device or an electrochromic device precursor is provided, comprising: a first conductive layer, the thickness of the first conductive layer is between about 10-500 nm; an electrochromic layer comprising an electrochromic material, the electrochromic material comprising a composition W 1-x-y Ti x Mo y Oz Tungsten titanium molybdenum oxide, wherein x is between about 0.05-0.25, y is between about 0.01-0.15, and z is between about 2.5-4.5, the thickness of the electrochromic layer is between about 200-700nm; a counter electrode layer including a counter electrode material, the counter electrode material includes nickel tungsten oxide, the thickness of the counter electrode layer is between about 100-400nm; and a second conductive layer, the thickness of the second conductive layer is 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.

[0012] In some embodiments, the electrochromic layer can be crystalline (e.g., nanocrystals, microcrystals, or a combination thereof). In some embodiments, the electrochromic layer can be amorphous. In these or other embodiments, the counter electrode material can be crystalline (e.g., nanocrystals, microcrystals, or a combination thereof). In some embodiments, the counter electrode layer can 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.

[0013] 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.

[0014] In various embodiments, the electrochromic device or electrochromic device precursor does not include a homogeneous 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 includes two or more layers, and the layer that is superstoichiometric with respect to oxygen is in contact with the counter electrode layer, or (b) the counter electrode layer includes two or more layers, and the layer that is superstoichiometric with respect to oxygen is in contact with the electrochromic layer. In another embodiment, (a) the electrochromic layer includes two or more parts, which together form the electrochromic layer as a graded layer, and the part 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 includes two or more parts, which together form the counter electrode layer as a graded layer, and the part of the counter electrode layer that is superstoichiometric with respect to oxygen is in contact with the electrochromic layer. In some embodiments, the electrochromic device or electrochromic device precursor further includes an ionically conductive and substantially electrically insulating material that is formed in situ at the interface between the electrochromic layer and the counter electrode layer.

[0015] 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 borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium oxynitride, lithium aluminum fluoride, lithium phosphorus oxynitride (LiPON), lithium lanthanum titanate (LLT), lithium tantalate, lithium zirconium oxide, lithium silicon carbon oxynitride (LiSiCON), 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 may 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 phosphorus oxynitride, lithium phosphorus oxynitride (LiPON), lithium silicon carbon oxynitride (LiSiCON), and combinations thereof.

[0016] In another aspect of the disclosed embodiment, a method for manufacturing an electrochromic device or an electrochromic device precursor is provided, the method comprising: receiving a substrate having a first conductive layer thereon; forming an electrochromic layer comprising an electrochromic material, the electrochromic material comprising a composition W 1-x-y Ti x Mo y O z Tungsten titanium molybdenum oxide, wherein x is between about 0.05-0.25, y is between about 0.01-0.15, and z is between about 2.5-4.5; forming a counter electrode layer including a counter electrode material, the counter electrode material comprising 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 layer, and wherein the electrochromic device is all solid-state and inorganic.

[0017] In some embodiments, the electrochromic layer can be crystalline (e.g., nanocrystals, microcrystals, or a combination thereof). In some embodiments, the electrochromic layer can be amorphous. In these or other embodiments, the counter electrode layer can be crystalline (e.g., nanocrystals, microcrystals, or a combination 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.

[0018] 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.

[0019] In some cases, the electrochromic device or electrochromic device precursor does not include a homogeneous 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 relative to oxygen. For example, in one example, either: (a) the electrochromic layer includes two or more layers, and the layer with superstoichiometric relative to oxygen is in contact with the counter electrode layer, or (b) the counter electrode layer includes two or more layers, and the layer with superstoichiometric relative to oxygen is in contact with the electrochromic layer. In another example, either: (a) the electrochromic layer includes two or more portions, and the portion of the electrochromic layer with superstoichiometric relative to oxygen is in contact with the counter electrode layer, or (b) the counter electrode layer is included in two or more portions, and the portion of the counter electrode layer with superstoichiometric relative to oxygen is in contact with the electrochromic layer.

[0020] In some embodiments, the method may further include in situ forming an ion-conducting layer comprising an ion-conducting and substantially electrically insulating material, the ion-conducting layer being positioned at the interface between the electrochromic layer and the counter electrode layer. In some embodiments, the method may further include 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 borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium oxynitride, lithium aluminum fluoride, lithium phosphorus oxynitride (LiPON), lithium lanthanum titanate (LLT), lithium tantalate, lithium zirconium oxide, lithium silicon carbon oxynitride (LiSiCON), 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 include 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 carbon oxynitride (LiSiCON), and combinations thereof.

[0021] In certain embodiments, one or more metal-containing targets and a target containing between about 40% and 80% O may be used. 2 The electrochromic layer is formed by sputtering a first sputtering gas of between about 20% and about 60% Ar, wherein the substrate is at least intermittently heated to between about 150° C. and about 450° C. during the formation of the electrochromic layer, the thickness of the electrochromic layer is between about 200 and 700 nm, and one or more metal-containing targets and a first sputtering gas containing between about 30% and 100% O 2and a second sputtering gas of between about 0-30% Ar to form a counter electrode layer by sputtering, the thickness of the counter electrode layer being between about 100-400nm. The method may include, after forming the counter electrode layer: heating the substrate at a temperature between about 150-450°C in an inert atmosphere for a duration of between about 10-30 minutes; after heating the substrate in the inert atmosphere, heating the substrate at a temperature of about 150-450°C in an oxygen atmosphere for a duration of between about 1-15 minutes; and after heating the substrate in the oxygen atmosphere, heating the substrate at a temperature of between about 250-350°C in air for a duration of between about 20-40 minutes. In various embodiments, the substrate may be maintained in a vertical orientation during the formation of the electrochromic layer, the counter electrode layer, and the second conductive layer.

[0022] These and other features will be described below with reference to the associated drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Depicted are views of electrochromic devices according to certain embodiments.

[0024] Figure 2A is a flow chart describing a process flow of aspects of a method of manufacturing an electrochromic device according to an embodiment.

[0025] Figure 2B is a description of Figure 2A Top view of steps in the described process flow.

[0026] Figure 2C Describes about Figure 2B A cross section of an electrochromic flake is depicted.

[0027] Figure 2D is a flow chart describing a method of depositing an electrochromic stack on a substrate.

[0028] Figure 3A An integrated deposition system according to certain embodiments is depicted.

[0029] Figure 3B The integrated deposition system is depicted in perspective view.

[0030] Figure 3C A modular integrated deposition system is depicted.

[0031] Figure 3D An integrated deposition system with two lithium deposition stations is depicted.

[0032] Figure 3E An integrated deposition system with one lithium deposition station is depicted.

[0033] Figure 4A A rotating sputtering target is shown in accordance with certain embodiments.

[0034] Figure 4B A top view of two rotating sputtering targets depositing material on a substrate is shown in accordance with certain embodiments.

[0035] FIG. 5A to FIG. 5C Embodiments are contemplated wherein a secondary sputtering target is used to deposit material onto a primary sputtering target, which is then deposited onto a substrate according to certain embodiments. DETAILED DESCRIPTION

[0036] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the embodiments presented. The disclosed embodiments may be practiced without some or all of these specific details. In other cases, well-known process operations are not described in detail so as not to unnecessarily obscure the disclosed embodiments. Although the disclosed embodiments will be described in conjunction with the specific details, it should be understood that this is not intended to limit the disclosed embodiments.

[0037] 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, the electrochromic device includes an electrochromic material having a specific composition, the composition including at least tungsten, titanium, molybdenum, and oxygen. The amount of oxygen in the material will vary depending on the stoichiometry of the metals in the composition, but can be more specifically defined as follows.

[0038] I. Overview of electrochromic devices

[0039] Figure 1 , a schematic cross-section of an electrochromic device 100 according to some embodiments is shown. The electrochromic device includes a substrate 102, a first conductive layer (CL) 104, an electrochromic layer (EC) 106, an ion conductive layer (IC) 108, a counter electrode layer (CE) 110, and a second 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 an electric potential across the electrochromic stack 120 enables the electrochromic device to transition 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 the layers is as follows: substrate, conductive layer, counter electrode layer, ion conductive layer, electrochromic material layer, conductive layer.

[0040] The electrochromic layer 106 is cathodically colored, while the counter electrode layer 110 can be anodically colored or optically passivated (sometimes called an "ion storage layer" because the ions remain there when the device is not colored). For example, while tungsten oxide cathode colors a dark blue, nickel oxide anodizes to brown. When colored in series, a more neutral blue will be created. Nevertheless, there is still a need for improvement. The inventors have found that when colored in series with certain nickel oxide-based anode materials, certain materials become tungsten oxide cathode materials, making the hue of the electrochromic window more beautiful.

[0041] It should be understood that the reference to the transition between the bleached state and the colored state is non-limiting and only provides one example of many that can implement electrochromic transitions. Unless otherwise specified herein, whenever a bleached coloration transition is mentioned, the corresponding device or process includes other optical state transitions, such as non-reflective to reflective, transparent to opaque, etc. In addition, the term "bleached" refers to an optically neutral state, such as colorless, transparent or translucent. Further, unless otherwise specified herein, the "color" of the electrochromic transition is not limited to any specific wavelength or wavelength range. As understood by those skilled in the art, the selection of appropriate electrochromic and counter electrode materials determines the relevant optical transitions.

[0042] In the embodiments described herein, the electrochromic device reversibly cycles between a bleached state and a colored state. In the bleached state, an electric potential is applied to the electrochromic stack 120 so that the available ions in the stack that can cause the electrochromic material 106 to be in the colored state are primarily present in the counter electrode 110. When the electric potential across the electrochromic stack is reversed, ions are transported across the ion-conducting layer 108 to the electrochromic material 106 and cause the material to enter the colored state.

[0043] In certain embodiments, all materials constituting the 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 provide the advantage of a reliable electrochromic stack that can operate for a long time. Materials in the solid state also provide the advantage of not having containment and leakage problems, because materials in the liquid state often have containment and leakage problems. Each of the layers in the electrochromic device is discussed in detail below. It should be understood that any one or more of the layers in the stack may contain a certain amount of organic material, but in many embodiments, one or more of these layers contain little or no organic matter. The same is true for liquids that may be present in one or more layers in small amounts. It should also be understood that solid materials can be deposited or otherwise formed by a process using a liquid component, such as certain processes using sol-gel or chemical vapor deposition.

[0044] Reference again Figure 1, voltage source 116 is typically a low voltage power source (on the order of between about 1V and about 20V, depending on the electrochromic device used), and can be configured to operate with radiation sensors and other environmental sensors. Voltage source 116 can also be configured to interface with an energy management system, such as a computer system that controls the electrochromic device based on factors such as time of year, time of day, and measured environmental conditions. Such an energy management system in conjunction with large area electrochromic devices (i.e., electrochromic windows) can significantly reduce energy consumption in buildings.

[0045] A.Substrate

[0046] Any material with suitable optical, electrical, thermal and mechanical properties can be used as Figure 1 The substrate 102 in the embodiment of the present invention is shown in FIG. Such substrates include, for example, glass, plastic, and mirror materials.

[0047] The substrate can be of any thickness as long as it has suitable mechanical properties to support the electrochromic stack 120. Although the substrate 102 can be of any thickness or transparent material, in some embodiments, it is glass or plastic and has a thickness between about 0.01 mm and about 10 mm. In certain embodiments, the substrate is glass, has a thickness between about 3 mm and 9 mm, and can be strengthened. In other embodiments, the glass can be very thin, between about 0.01 mm and 1 mm, or between about 0.1 mm and 1 mm, and is sodium-free or has a very low sodium or other alkali content, such as, for example, substrates such as Corning Incorporated (Corning, NY). Or other similar glass substrates commercially available, such as those from Asahi Glass Co. (AGC, Tokyo, Japan).

[0048] In some embodiments of the present invention, the substrate is architectural glass. Architectural glass is glass used as a building material. Architectural glass is commonly used in commercial buildings, but can also be used in residential buildings, and typically, but not necessarily, separates an indoor environment from an outdoor environment. In certain embodiments, architectural glass is at least 20 inches by 20 inches, and can be larger, such as up to about 72 inches by 120 inches. Architectural glass is typically at least about 2 mm thick.

[0049] B. Conductive layer

[0050] Return to Figure 1, on top of substrate 102 is a conductive layer 104. In some embodiments, one or both of conductive layers 104 and 114 are inorganic and / or solid. 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. Typically, conductive layers 104 and 114 are transparent at least in the wavelength range in which the electrochromic layer exhibits electrochromism. Transparent conductive oxides include metal oxides and metal oxides doped with one or more metals. Examples of these metal oxides and doped metal oxides include indium oxide, indium tin oxide, doped indium oxide, tin oxide, doped tin oxide, zinc oxide, aluminum zinc oxide, doped zinc oxide, ruthenium oxide, doped ruthenium oxide, and the like. Since oxides are commonly used in these layers, they are sometimes referred to as "transparent conductive oxide" (TCO) layers. Substantially transparent thin metal coatings can also be used. Examples of metals used for such thin metal coatings include transition metals, including gold, platinum, silver, aluminum, nickel alloys, and the like. Thin silver-based metal coatings that are well known in the glass industry are also used. Examples of conductive nitrides include titanium nitride, tantalum nitride, titanium oxynitride, and tantalum oxynitride. Conductive layers 104 and 114 can also be composite conductors. Such composite conductors can be made by placing highly conductive ceramic and metal wires or conductive layer patterns on one surface of a substrate and then coating them 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 thinner). Other composite conductors include metal oxide-metal-metal oxide interlayer materials, such as indium tin oxide-metal-indium tin oxide layers, sometimes collectively referred to as "IMI", where the metal is, for example, silver, gold, copper, aluminum, or an alloy thereof.

[0051] In some embodiments, a commercially available substrate, such as a glass substrate, contains a transparent conductive layer coating. Such a product can be used for both substrate 102 and conductive layer 104. Examples of such glass substrates include those manufactured by Pilkington Corporation of Toledo, Ohio under the trademark TEC Glass. TM Sold and marketed by PPG Industries of Pittsburgh, Pennsylvania under the trademark SUNGATE TM 300 and SUNGATE TM 500 Conductive coated glass for sale. TEC Glass TM It is glass coated with a conductive layer of tin oxide fluoride.

[0052] 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, different conductive materials are used for each conductive layer 104 and 114. For example, in some embodiments, TECGlassTM For substrate 102 (float glass) and conductive layer 104 (fluorinated tin oxide), and indium tin oxide for conductive layer 114. As described above, in some TEC Glass TM In the embodiment of the present invention, a sodium diffusion barrier layer is present between the glass substrate 102 and the TEC conductive layer 104 .

[0053] 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 inner area of ​​the stack with a relatively small ohmic potential drop. The potential is transferred to the conductive layer by electrical connection with the conductive layer. In some embodiments, bus bars (one in contact with the conductive layer 104 and one in contact with the conductive layer 114) provide electrical connection between the voltage source 116 and the conductive layers 104 and 114. The conductive layers 104 and 114 can also be connected to the voltage source 116 by other conventional methods.

[0054] In some embodiments, the thickness of conductive layers 104 and 114 is between about 5 nm and about 10,000 nm. In some embodiments, the thickness of conductive layers 104 and 114 is between about 10 nm and about 1,000 nm. In other embodiments, the thickness of conductive layers 104 and 114 is between about 10 nm and about 500 nm. TM In some embodiments for substrate 102 and conductive layer 104, the conductive layer is about 400 nm thick. In some embodiments using indium tin oxide for conductive layer 114, the thickness of the conductive layer is about 100 nm to 400 nm (280 nm in one embodiment). More generally, thicker layers of conductive materials can be used as long as they provide the necessary electrical properties (e.g., conductivity) and optical properties (e.g., transmittance). Typically, conductive layers 104 and 114 are as thin as possible to increase transparency and reduce cost. In some embodiments, the conductive layer is substantially crystalline. In some embodiments, the conductive layer is crystalline with a high proportion of large equiaxed grains.

[0055] The sheet resistance of the conductive layer (R s ) 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. Generally, it is desirable that the sheet resistance of each of the two conductive layers is about the same. In one embodiment, the sheet resistance of the two layers is about 10-15 ohms per square. In one embodiment, the sheet resistance of the two layers is less than 10 ohms per square, less than 5 ohms per square, or less than 3 ohms per square, respectively.

[0056] C. Electrochromic layer

[0057] Return to Figure 1 , covering the conductive layer 104 is an electrochromic layer 106. In an embodiment of the present invention, the electrochromic layer 106 is inorganic and / or solid, and in a typical embodiment is inorganic and solid. A variety of different materials can be used for the electrochromic layer 106. In conventional electrochromic devices, the electrochromic layer can include, for example, tungsten oxide. The inventors have found that, as described herein, an electrochromic device using tungsten titanium molybdenum oxide in the electrochromic layer has performance superior to conventional devices. The electrochromic metal oxide may further include protons, lithium, sodium, potassium or other ions to function. The electrochromic layer 106 as described herein is capable of receiving such ions transferred from the counter electrode layer 110.

[0058] Tungsten oxide has long been used as an electrochromic material. Over time, various materials have been added to tungsten oxide to adjust its properties. In various embodiments herein, the electrochromic layer 106 includes an electrochromic material that includes tungsten, titanium, molybdenum, and oxygen. This material may be referred to as tungsten titanium molybdenum oxide. Compared to conventional devices, tungsten titanium molybdenum oxide exhibits both high durability and improved color performance, particularly when used with certain nickel oxide-based counter electrode materials (e.g., nickel oxide containing one or more of tungsten oxide, tantalum oxide, niobium oxide, tin oxide, and mixtures thereof).

[0059] The inclusion of titanium in the electrochromic material can improve the stability / durability of the electrochromic layer, which means that the resulting electrochromic device is less likely to break over time under repeated insertion / extraction of ions and electrons. The molybdenum included in the electrochromic material changes the color properties of the electrochromic layer, resulting in an electrochromic device with a more neutral color. For example, tungsten oxide has a strong blue appearance, which may be undesirable. The inclusion of molybdenum makes the blue more neutral. These two improvements (e.g., including both titanium and molybdenum in a tungsten oxide-based material) can be combined to produce a tungsten titanium molybdenum oxide that exhibits both a high degree of durability and desired color characteristics.

[0060] The tungsten titanium molybdenum oxide material used in the electrochromic device described herein can be represented by the following formula: 1-x- y Ti x Mo y O z , where the total amount of the three metals in the material is expressed in relative atomic percentages, where x is the atomic percentage of titanium, y is the atomic percentage of molybdenum, and 1-xy represents the atomic percentage of tungsten. 0.80 Ti 0.10 Mo 0.10 O zThe compound represented has a metal content of 80 atomic % tungsten and 10 atomic % each of titanium and molybdenum. Thus, in this example, the total metal content 100% is 80% W, 10% Ti and 10% Mo.

[0061] Of course, the actual material contains oxygen as well as the three metals. For the material, z represents the stoichiometry of oxygen relative to all three metals in the compound. In certain embodiments, z is about 2.5 to 3.5. The value of z can have a large impact on the properties of the material. These properties can include whether the material exhibits electrochromism and whether the material can act as a precursor to an ion-conducting material. That is, as shown by WO z The electrochromic tungsten oxide represented by WO may have an oxygen content (where z is 3 or less, typically between about 2.5 and 3) and a z The superstoichiometric tungsten oxide represented by (which is superstoichiometric relative to oxygen and can be used as a precursor to an ion-conducting material) has an oxygen content (where z is greater than 3, such as between 3.1 and 4); the tungsten titanium and molybdenum in the compounds described herein may have the same associated amount of oxygen together. For example, for tungsten titanium molybdenum oxide that exhibits electrochromism, each metal atom of the material may have 3 or fewer oxygen atoms, or each metal atom of tungsten titanium molybdenum oxide that is superstoichiometric relative to oxygen may have 3 or more oxygen atoms (and can function as a precursor to an ion-conducting material). Therefore, when z is 3 or less, representing a stoichiometric or substoichiometric oxygen level of the three metals combined in the material, the material is cathodically colored. It is noteworthy that the electrochromic tungsten titanium molybdenum oxide is more color-neutral than, for example, electrochromic tungsten oxide, which has a deep blue color when colored (e.g., via the insertion of positive ions such as protons or lithium ions, and electrons). In certain embodiments, when z is 3 or greater, the material is superstoichiometrically oxidized, for example when used in a manufacturing method for making an electrochromic device (and can be stable in an electrochromic device precursor such as used in the above-mentioned manufacturing method), as described in more detail herein.

[0062] For tungsten titanium molybdenum oxide W 1-x-y Ti x Mo y O z, in some embodiments, the subscripts x, y, and z are within a specific range. For example, in some embodiments, x can be at least about 0.05, or at least about 0.10, or at least about 0.15. In these or other cases, x can be about 0.25 or less, or about 0.20 or less, or about 0.15 or less. In these or other embodiments, y can be at least about 0.01, at least about 0.02, at least about 0.05, at least about 0.10, or at least about 0.15. In these or other embodiments, y can be about 0.25 or less, such as about 0.20 or less, about 0.15 or less, about 0.1 or less, or about 0.08 or less. In these or other embodiments, z can 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, z may be about 4.5 or less, such as 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 some embodiments, x may be between about 0.05 and 0.25, or between about 0.05 and 0.15, or between about 0.10 and 0.15. In these or other embodiments, y may be between about 0.01 and 0.15, or between about 0.02 and 0.10, or between about 0.02 and 0.08. In these or other embodiments, z may be between about 2.5-4.5, or between about 2.5-3.0, or between about 2.5-2.9, or between about 3.0-3.5, or between about 3.5-4.5.

[0063] In various embodiments, the electrochromic layer may include two or more materials having different compositions (e.g., deposited as a bilayer, gradient layer, or other combination of layers), one or both of the compositions may include tungsten titanium 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 to an ionically conductive and substantially electrically insulating material.

[0064] In certain embodiments, tungsten titanium molybdenum oxide is deposited in at least two different compositions with different amounts of oxygen. In one example, the tungsten titanium molybdenum electrochromic layer is deposited as a bilayer, wherein in the first layer of the bilayer, z is between about 2.5 and about 3.0, and in the second layer of the bilayer, z is greater than 3. In another embodiment, the tungsten titanium molybdenum electrochromic layer is deposited as a manufactured gradient layer so that the value of z varies according to the depth of the layer. For example, tungsten titanium molybdenum oxide is sputtered onto a substrate with a first oxygen concentration in the initial portion of the deposition, and then the oxygen concentration is increased as additional tungsten titanium molybdenum oxide material is deposited. For example, after depositing the counter electrode material and at the interface between the tungsten titanium molybdenum material and the counter electrode material, the ion conductor material can be manufactured in situ using this varying oxygen concentration between the multiple layers or in the gradient layer, as described in more detail below. This manufacturing scheme presents that the electrochromic layer is 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 can be interchanged (e.g., such that an electrochromic material that acts as a precursor to an ionically conductive and substantially electrically insulating material is deposited before an electrochromic material that exhibits electrochromism).

[0065] In some cases, the electrochromic layer is deposited in at least two different compositions having different metals or metal combinations. In one example, the electrochromic layer is deposited as a bilayer, wherein the first layer of the bilayer includes at least one metal that is not present in the 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.

[0066] In one example, the first layer of the bilayer is tungsten titanium molybdenum oxide (e.g., W 1-x-y Ti x Mo y O z , where z is about 3 or less), and the second layer of the bilayer is tungsten oxide (e.g., WO z , where z is greater than 3). In another example, the first layer of the bilayer is tungsten titanium molybdenum oxide (e.g., W 1-x-y Ti x Mo y O z , where z is about 3 or less), and the second layer of the bilayer is tungsten titanium oxide (e.g. W 1-x Ti y O z , wherein x is between about 0.05 and 0.20, or between about 0.05 and 0.15; and z is greater than 3). In another example, the first layer of the bilayer is tungsten titanium molybdenum oxide (e.g., W 1-x-y Ti x Mo y O z, where z is about 3 or less), and the second layer of the bilayer is tungsten molybdenum oxide (e.g. W 1-x Mo x O z , wherein x is between about 0.05 and 0.10, or between about 0.05 and 0.08; and z is greater than 3). In certain other examples, the first layer and the second layer of the bilayer can be switched, for example, so that the second layer of the bilayer is W 1-x-y Ti x Mo y O z (where z is greater than 3), and the first layer of the bilayer is WO z , W 1-x Ti x O z or W 1-x Mo x O z (where x and y are as above for W 1-x Ti x O z or W 1-x Mo x O z , and wherein z is about 3 or less). For W discussed in this paragraph 1-x-y Ti x Mo y O z Materials, values ​​for x and y may be within the ranges described elsewhere herein.

[0067] In embodiments using a double-layer electrode as described above, each layer of the double layer may have a different morphology. In some embodiments, each of the first layer and the second layer of the double layer has a morphology including a microcrystalline phase, a nanocrystalline phase, or an amorphous phase, wherein each of the morphologies of the first layer and the second layer is different. For example, the first layer of the double layer is tungsten titanium molybdenum oxide (e.g., W 1-x-y Ti x Mo y O z , where z is about 3 or less), which is amorphous, and the second layer of the bilayer is tungsten oxide (e.g. WO z , where z is greater than 3), which is a nanocrystal. The different morphologies of these layers may be selected for specific purposes, or may be selected based on specific process conditions and / or materials for each layer.

[0068] The counter electrode layer, which may be discussed further below, is similarly deposited as a bilayer or graded layer comprising two or more materials that may have different compositions with respect to oxygen content, metal content, and the like.

[0069] In many embodiments, the tungsten titanium molybdenum oxide may have a titanium content of at least about 3% (atoms), or at least about 5% (atoms), or at least about 8% (atoms). In these or other cases, the titanium content of the tungsten titanium molybdenum oxide may be about 20% (atoms) or less, such as about 15% (atoms) or less, or about 12% (atoms) or less. In these or other cases, the molybdenum content of the tungsten titanium molybdenum oxide may be at least about 1% (atoms), at least about 2% (atoms), at least about 3% (atoms), or at least about 4% (atoms). In these or other cases, the molybdenum content of the tungsten titanium molybdenum oxide may be about 8% (atoms) or less, such as about 6% (atoms) or less, or about 5% (atoms) or less. In a specific example, the tungsten titanium molybdenum oxide has titanium between about 8-12% (atoms), and molybdenum between about 2-8% (atoms).

[0070] In certain embodiments, the tungsten titanium molybdenum oxide electrochromic material is crystalline, nanocrystalline or amorphous. In some embodiments, the electrochromic material is substantially nanocrystalline, with a grain size of about 5nm to 50nm (or about 5nm to 20nm) on average, as characterized by transmission electron microscopy (TEM). The morphology of the electrochromic material can also be characterized as nanocrystalline by X-ray diffraction (XRD); XRD. For example, a nanocrystalline electrochromic material can be characterized by the following XRD features: a crystal size of about 10 to 100nm (e.g., about 55nm). In addition, the nanocrystalline electrochromic material can exhibit limited long-range order, for example, on the order of several (about 5 to 20) electrochromic material unit cells. In some embodiments, the tungsten titanium molybdenum oxide electrochromic material can be amorphous. Many factors can affect the morphology of the electrochromic material, including, for example, the composition of the material and the conditions for depositing and processing the material. In some embodiments, the electrochromic material is not heated above a particular temperature (e.g., any treatment involving heating the substrate during or after deposition of the electrochromic material may be maintained below about 300°C, below about 250°C, below about 200°C, below about 150°C, below about 100°C, below about 75°C, or below about 50°C). Without wishing to be bound by theory or mechanism of action, this lack of heating may result in an amorphous morphology of the tungsten titanium molybdenum oxide. In some other embodiments, heating the substrate may result in the morphology of the tungsten titanium molybdenum oxide being changed to crystalline / nanocrystalline. Although not wishing to be bound by theory, it is believed that the titanium content in the tungsten titanium molybdenum oxide inhibits crystallization, but under the processing conditions described herein, for example, a combination of higher temperatures and heating in an inert atmosphere followed by heating in air, a more crystalline morphology may be formed.

[0071] In an embodiment where an 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, the first layer or lower portion of the electrochromic layer is microcrystalline or nanocrystalline, and the second layer or upper portion of the electrochromic layer is amorphous. In another example, the first layer or lower portion of the electrochromic layer is amorphous, and the second layer or upper portion of the electrochromic layer is microcrystalline or nanocrystalline. In another example, the first layer / lower portion and the second layer / upper portion of the electrochromic layer are both microcrystalline or nanocrystalline. In another example, the first layer / lower portion and the second layer / upper portion of the electrochromic layer are both amorphous.

[0072] The thickness of electrochromic layer 106 depends on the electrochromic material selected for the electrochromic layer. In some embodiments, electrochromic layer 106 is about 50nm to 2,000nm, or about 200nm to 700nm. In some embodiments, the electrochromic layer is about 300nm to about 500nm.

[0073] Typically, in electrochromic materials, the coloration (or change in any optical property - e.g., absorbance, reflectivity, and transmittance) of the electrochromic material is caused by reversible ion insertion (e.g., embedding) into the material and the corresponding charge-balancing electron injection. Typically, a portion of the ions responsible for the optical transition are irreversibly bound in the electrochromic material. Some or all of the irreversibly bound ions serve to compensate for "blind charges" in the material. In most electrochromic materials, suitable ions include lithium ions (Li + ) and hydrogen ions (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 ions (Ca ++ ), barium ions (Ba ++ ), strontium ion (Sr ++ ), and magnesium ions (Mg ++ ). In various embodiments described herein, lithium ions are used to produce the electrochromic phenomenon.

[0074] D. Counter electrode layer

[0075] Reference again Figure 1, in the electrochromic stack 120, the ion conducting layer 108 covers the electrochromic layer 106. On top of the ion conducting layer 108 is the counter electrode layer 110. In some embodiments, the counter electrode layer 110 is inorganic and / or solid. The counter electrode layer may include one or more of a variety of different materials, which act as an ion reservoir when the electrochromic device is in a bleached state. During the electrochromic transition 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. At the same time, for example, in the case of a nickel oxide-based material with electrochromic activity, the counter electrode layer is colored due to the loss of ions.

[0076] In some embodiments, suitable materials for the counter electrode include nickel oxide (NiO), nickel tungsten oxide (NiWO), nickel vanadium oxide, nickel chromium oxide, nickel aluminum oxide, nickel manganese oxide, nickel magnesium oxide, chromium oxide (Cr 2 O 3 ), manganese oxide (MnO 2 ), Prussian blue, cerium titanium oxide (CeO 2 -TiO 2 ), cerium zirconium oxide (CeO 2 -ZrO 2 ), vanadium oxide (V 2 O 5 ) and a mixture of oxides (e.g., Ni 2 O 3 and WO 3 A mixture of tantalum and tungsten). Doping formulations of oxides may also be used, with dopants including, for example, tantalum and tungsten. Specific examples of counter electrode materials include nickel tungsten tantalum oxide, nickel tungsten niobium oxide, and nickel tungsten tin oxide. Because the counter electrode layer 110 contains ions for producing an electrochromic phenomenon in the electrochromic material when the electrochromic material is in a bleached state, the counter electrode preferably has a high transmittance and a neutral color when the counter electrode retains a large amount of these ions.

[0077] 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 specific 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 is between about 15% (atomic) Ni and about 60% Ni; between about 10% W and about 40% W; and between about 30% O and 75% O. In another embodiment, NiWO is between about 30% (atomic) Ni and about 45% Ni; between about 10% W and about 25% W; and between about 35% O and about 50% O. In one embodiment, NiWO is about 42% (atomic) Ni, about 14% W, and about 44% O.

[0078] In some embodiments, nickel tungsten tantalum oxide (NiWTaO) is used as a counter electrode material in the counter electrode layer. Nickel tungsten tantalum oxide can have various compositions when used as a counter electrode material. In certain embodiments, a specific balance can be made between the various components of NiWTaO. For example, the atomic ratio of Ni:(W+Ta) in the material can fall between about 1.5:1 and 3:1, for example, between about 1.5:1 and 2.5:1, or between about 2:1 and 2.5:1. In a specific 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 (i) nickel atoms in the material to (ii) the sum of the number of tungsten and tantalum atoms in the material. The nickel tungsten tantalum oxide material may also have a specific W:Ta atomic ratio. In certain embodiments, the atomic ratio of W:Ta is between about 0.1:1 and 6:1, for example, between about 0.2:1 and 5:1, or between about 1:1 to 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: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 to 4:1, or between about 4:1 and 5:1. In some embodiments, a specific atomic ratio of Ni:(W+Ta) and W:Ta is 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) can be between about 1.5:1 and 3:1, wherein the atomic ratio of W:Ta is between about 1.5:1 and 3:1. In another example, the atomic ratio of Ni:(W+Ta) can be between about 1.5:1 and 2.5:1, wherein the atomic ratio of W:Ta is between about 1.5:1 and 2.5:1. In another example, the atomic ratio of Ni:(W+Ta) can be between about 2:1 and 2.5:1, wherein the atomic ratio of W: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.

[0079] In some embodiments, nickel tungsten niobium oxide (NiWNbO) is used as the counter electrode material in the counter electrode layer. Nickel tungsten niobium oxide can have various compositions when used as an anode coloring material. In some embodiments, a specific balance can be made between the various components of NiWNbO. For example, the atomic ratio of Ni:(W+Nb) in the material can fall between about 1.5:1 and 3:1, for example, between about 1.5:1 and 2.5:1, or between about 2:1 and 2.5:1. In a specific 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 sum of the number of tungsten and niobium atoms in (i) the material and (ii) the material. The nickel tungsten niobium oxide material can also have a specific atomic ratio of W:Nb. In certain embodiments, the atomic ratio of W: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: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 explicitly listed herein. For example, the atomic ratio of Ni:(W+Nb) can be between about 1.5:1 and 3:1, wherein the atomic ratio of W:Nb is between about 1.5:1 and 3:1. In another example, the atomic ratio of Ni:(W+Nb) can be between about 1.5:1 and 2.5:1, wherein the atomic ratio of W:Nb is between about 1.5:1 and 2.5:1. In a further example, the atomic ratio of Ni:(W+Nb) can be between about 2:1 and 2.5:1, wherein the atomic ratio of W:Nb is between about 1.5:1 and 2:1, or between about 0.2:1 and 1:1, or between about 1:1 and 2:1, or between about 4:1 and 5:1.

[0080] In some embodiments, nickel tungsten tin oxide (NiWSnO) is used in the counter electrode layer. Nickel tungsten tin oxide can have various compositions when used as an anode coloring material. In some embodiments, a specific balance can be made between the components of NiWSnO. For example, the atomic ratio of Ni: (W + Sn) in the material can fall between about 1: 1 and 4: 1, for example, between about 1: 1 and 3: 1, or between about 1.5: 1 and 3: 1, or between about 1.5: 1 and 2.5: 1, or between about 2: 1 and 2.5: 1. In a specific 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 sum of the number of tungsten and tin atoms in (i) the material and (ii) the material. The nickel tungsten tin oxide material can also have a specific atomic ratio of W: Sn. In certain embodiments, the atomic ratio of W: Sn is between about 1:9 and 9:1, for example, 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 specific atomic ratio of Ni: (W + Sn) and W: Sn is used. For example, the atomic ratio of Ni: (W + Sn) can be between about 1:1 and 3:1, wherein the atomic ratio of W: Sn is between about 1:1 and 3:1. In another example, the atomic ratio of Ni: (W + Sn) can be between about 1.5:1 and 2.5:1, wherein the atomic ratio of W: Sn is between about 1.5:1 and 2.5:1. In another example, the atomic ratio of Ni: (W + Sn) can be between about 2:1 and 2.5:1, wherein the atomic ratio of W: Sn is between about 1.5:1 and 2:1.

[0081] When the charge is removed from the counter electrode 110 made of nickel tungsten oxide (i.e., ions are transferred from the counter electrode 110 to the electrochromic layer 106), the counter electrode layer will change from a transparent state to a brown colored state. Other electrochromic active counter electrode materials may exhibit similar or other colors after the ions are removed.

[0082] As discussed above about the electrochromic layer, the electrode layer can be deposited to include two or more materials with different compositions (for example, deposited as a double layer, a gradient layer or other layer combination). In many of these embodiments, one of the electrode materials can provide electrochromic properties, and the other electrode material can be used as a precursor of an ion-conducting and substantially electrically insulating material. Typically, the material used as a precursor of an 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 electrode layer, the electrode material used as a precursor of an ion-conducting and substantially electrically insulating material can be deposited as the first layer or lower portion of the electrode layer. Then, the electrode material showing electrochromism can be set to the second layer or upper portion of the electrode layer. In the case where the electrode layer is deposited prior to the electrochromic layer, the first layer or lower portion of the electrode can be formed by the electrode material showing electrochromism, and the second layer or upper portion of the electrode can be formed by the electrode material, which is used as a precursor of an ion-conducting and substantially electrically insulating material.

[0083] In one example, the counter electrode is deposited to include two materials with different oxygen contents. For example, the counter electrode layer may include two different forms of nickel oxide, or two different forms of nickel tungsten 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 materials have different oxygen concentrations. One form of the counter electrode material may exhibit electrochromism and may have relatively less oxygen. Another form of the counter electrode material may or may not exhibit electrochromism, may be used as a precursor of an ion-conducting and substantially electrically insulating material, and may have relatively more oxygen. The counter electrode material having relatively more oxygen and used as a precursor of an ion-conducting and substantially electrically insulating material may be superstoichiometric relative to oxygen. The details of the oxygen content difference between different layers or portions of the electrochromic or counter electrode layer provided herein may apply regardless of whether there are other composition differences (e.g., different metals) between the two layers or portions discussed.

[0084] In some embodiments, the electrode may be deposited to include two or more materials having different metal compositions. For example, the first electrode material may include one or more metals that are not present in the second electrode material. Similarly, the second electrode material may include one or more metals that are not present in the first electrode material. Exemplary first electrode materials include, but are not limited to, nickel oxide, nickel tungsten oxide, nickel tungsten tantalum oxide, nickel tungsten tin oxide, and nickel tungsten niobium oxide. Exemplary second electrode materials also include, but are not limited to, nickel oxide, nickel tungsten 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 electrode material is nickel tungsten oxide, and the second electrode material is nickel oxide. In another example, the first electrode material is nickel tungsten tantalum oxide, and the second electrode material is nickel tungsten oxide. In another example, the first electrode material is nickel tungsten tin oxide, and the second electrode material is nickel tungsten oxide. In another example, the first electrode material is nickel tungsten niobium oxide, and the second electrode material is nickel tungsten oxide. In another example, the first electrode material is nickel tungsten niobium oxide, and the second electrode material is nickel tungsten oxide. Any of these examples may be modified to include different first / second electrode materials.

[0085] The counter electrode morphology can be crystalline, amorphous or some mixture thereof. The crystalline phase can be nanocrystalline. In certain 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 can be obtained by using certain processing conditions as described below. Although it is not desired to be bound by any theory or mechanism, it is believed that some amorphous counter electrode oxides are produced by relatively low energy atoms in a 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 larger source to substrate distance. Where the fraction / concentration of heavy atoms (e.g., W) is relatively high, it is also more likely to form an amorphous film. Under the described process conditions, a film with better stability under UV / heat exposure is produced. Substantially amorphous materials can have some crystals dispersed in an amorphous matrix, usually but not necessarily nanocrystals.

[0086] In the embodiment where the electrode is deposited to include two or more different materials, the different materials can each independently include a microcrystalline phase, a nanocrystalline phase and / or an amorphous phase. In one example, the first layer or the bottom of the electrode layer is microcrystals or nanocrystals, and the second layer or the top of the electrode layer is amorphous. In another example, the first layer or the bottom of the electrode layer is amorphous, and the second layer or the top of the electrode layer is microcrystals or nanocrystals. In another example, the first layer / bottom and the second layer / top of the electrode layer are both microcrystals or nanocrystals. In another example, the first layer / bottom and the second layer / top of the electrode layer are both amorphous.

[0087] In some embodiments, the electrode morphology can include microcrystalline phase, nanocrystalline phase and / or amorphous phase. For example, the electrode can be, for example, a material with an amorphous matrix, which has nanocrystals distributed everywhere. In certain embodiments, nanocrystals constitute about 50% or less of the electrode material, about 40% or less of the electrode material, about 30% or less of the electrode material, about 20% or less of the electrode material, or about 10% or less of the electrode material (by weight or volume, depending on the embodiment). In certain embodiments, the maximum diameter of the nanocrystal is less than about 50nm, less than about 25nm, less than about 10nm, or less than about 5nm in some cases. In some cases, the average diameter of the nanocrystal is about 50nm or less, or about 10nm or less, or about 5nm or less (e.g., about 1-10nm).

[0088] In certain embodiments, it is desirable to have a nanocrystal size distribution wherein at least about 50% of the nanocrystals have diameters within 1 standard deviation of the average nanocrystal diameter, e.g., wherein at least about 75% of the nanocrystals have diameters within 1 standard deviation of the average nanocrystal diameter, or wherein at least about 90% of the nanocrystals have diameters within 1 standard deviation of the average nanocrystal diameter.

[0089] It has been found that, compared with the counter electrode with relatively more crystals, the counter electrode comprising an amorphous matrix tends to operate more effectively. In certain embodiments, additives can form a host matrix, in which the region of the basic anode coloring material can be found. In various cases, the host matrix is ​​substantially amorphous. In certain embodiments, the unique crystalline structure in the counter electrode is formed by, for example, a basic anode coloring electrochromic material in the form of an oxide. An example of a basic anode coloring electrochromic material in the form of an oxide is nickel tungsten oxide. Additives can contribute to the formation of an amorphous host matrix that is not substantially crystalline but combines the domain (for example, nanocrystal in some cases) of the basic anode coloring electrochromic material. Exemplary additives include but are not limited to tin, tantalum and niobium. In other embodiments, additives and anode coloring base materials form compounds with covalent and / or ionic bonds together. The compound can be crystalline, amorphous or a combination thereof. In other embodiments, the anode coloring base material forms a host matrix, in which the region of additives exists with discrete phases or bags. For example, certain embodiments include an amorphous counter electrode having an amorphous matrix of a first material and a second material, also amorphous, distributed throughout the first material in pockets, such as pockets of the diameter described herein for crystalline material distributed throughout the amorphous matrix.

[0090] In some embodiments, the thickness of the counter electrode is between about 50 nm and about 650 nm. In some embodiments, the thickness of the counter electrode is between about 100 nm and about 400 nm, preferably in the range of about 200 nm to 300 nm.

[0091] The number of ions that remain in the counter electrode layer in the bleached state (and correspondingly in the electrochromic layer during the colored state) and can drive the electrochromic transition depends on the composition of these layers as well as the thickness and manufacturing method of these layers. Both the electrochromic layer and the counter electrode layer are capable of supporting available charge (in the form of lithium ions and electrons) in the vicinity of tens of nanoliters per square centimeter of layer surface area. The charge capacity of the 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 a capacitance of about 30 to about 150 mC / cm 2 In another embodiment, the electrochromic layer has a charge capacity between about 50 and about 100 mC / cm 2 In one embodiment, the counter electrode layer has a charge capacity between about 75 and about 200 mC / cm 2 In another embodiment, the counter electrode layer has a charge capacity of about 100 to about 150 mC / cm 2 / micron charge capacity.

[0092] E. Ion Conducting Layer

[0093] In various embodiments, such as Figure 1 As shown in , an ion conductor layer 108 is provided between the electrochromic layer 106 and the counter electrode layer 110. In this case, the ion conductor material is deposited on the electrochromic layer in a conventional manner, such as via, for example, sputtering, evaporation, sol-gel techniques, etc., and then the counter electrode material is deposited. In other embodiments, the conventional ion conductor layer can be omitted. In this case, the electrochromic layer and the counter electrode layer can be deposited in direct contact with each other, and the ion conductive material formed in situ at the interface between the two layers can serve the purpose of the conventional ion conductor layer. The electrochromic device precursor can include a stack of the aforementioned layers prior to the in-situ formation of the ion conductor material. Each of these embodiments will be discussed in turn.

[0094] i. Embodiments Utilizing Separately Deposited Ion Conducting Layers

[0095] like Figure 1 As shown, between the electrochromic layer 106 and the counter electrode layer 110, there is an ion conducting layer 108. When the electrochromic device is transformed between the bleached state and the colored state, the ion conducting layer 108 acts as a medium through which ions (in the form of an electrolyte) are transported. Preferably, the ion conducting layer 108 has a high conductivity for the relevant ions of the electrochromic layer and the counter electrode layer, but has a sufficiently low electronic conductivity so that negligible electron transfer occurs during normal operation. Thin ion conducting layers with high ion conductivity allow for rapid ion conduction and therefore rapid switching for achieving high performance electrochromic devices. In certain embodiments, the ion conducting layer 108 is inorganic and / or solid. When made of a 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 ion conductor material has a thickness of about 10 8 Siemens / cm or Ohm -1 centimeter -1 (ohm -1 cm -1 ) and about 10 9 Siemens / cm or ohm -1 cm -1 The ionic conductivity and about 10 11 Electronic resistance in ohms-cm.

[0096] Examples of suitable materials for the lithium ion conductor layer include lithium silicate, lithium aluminum silicate, lithium oxide, lithium tungstate, lithium aluminum borate, lithium borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium oxynitride, lithium aluminum fluoride, lithium phosphorus oxynitride (LiPON), lithium lanthanum titanate (LLT), lithium tantalate, lithium zirconium oxide, lithium silicon carbon nitride oxide (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 (blocking electrons from moving therethrough). However, any material can be used for the ion conductive layer 108 as long as it can be manufactured 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 through.

[0097] 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 nanocrystalline. In yet another embodiment, the ion conducting layer is crystalline.

[0098] In some embodiments, silicon-aluminum-oxide (SiAlO) is used for ion conducting layer 108. In a specific embodiment, the silicon / aluminum target used to make the ion conductor layer via sputtering contains about 6 and about 20 atomic % aluminum. This defines the ratio of silicon to aluminum in the ion conducting layer. In some embodiments, silicon aluminum oxide ion conducting layer 108 is amorphous.

[0099] The thickness of ion conducting layer 108 may vary depending on the material. In some embodiments, the thickness of ion conducting layer 108 is about 5 nm to 100 nm, preferably about 10 nm to 60 nm. In some embodiments, the thickness of the ion conducting layer is about 15 nm to 40 nm, or about 25 nm to 30 nm.

[0100] Ions transported across the ion-conducting layer between the electrochromic layer and the counter electrode layer are used to effect a color change in the electrochromic layer (i.e., to change the electrochromic device from a bleached state to a colored state). Depending on the choice of materials used in the electrochromic device stack, these ions include lithium ions (Li + ) and hydrogen ions (H + ) (i.e., protons). As mentioned above, other ions may be employed in certain embodiments. These include deuterium ions (D + ), sodium ion (Na + ), potassium ion (K + ), calcium ions (Ca ++ ), barium ions (Ba ++ ), strontium ion (Sr ++ ) and magnesium ions (Mg ++ ).

[0101] ii. Embodiments in which a separately deposited ion-conducting layer is omitted

[0102] In most conventional electrochromic devices, the ion-conducting layer is deposited as a different material in different deposition steps to provide a separation between the electrochromic layer and the counter electrode layer. However, in certain embodiments herein, the ion-conducting layer can be omitted. In this case, the electrochromic material of the electrochromic layer can be deposited in direct physical contact with the counter electrode material of the counter electrode layer. The interface region between the electrochromic layer and the counter electrode layer can form and act as an ion conductor layer (e.g., allowing ions to pass through, but not allowing electrons to pass between the electrochromic layer and the counter electrode layer) without the need to deposit the layer as a unique material. Because there is no need to provide a separate deposition step for forming the ion conductor layer, this simplifies the formation of the electrochromic device.

[0103] In such an embodiment, one or both of the electrochromic layer and the counter electrode layer may be deposited to include an oxygen-rich portion compared to the rest of the layer. The oxygen-rich portion may be superstoichiometric relative to oxygen. Typically, the oxygen-rich portion is in contact with another type of layer. For example, the electrochromic stack may include a counter electrode material in contact with an 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, the electrochromic material and the counter electrode material both 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.

[0104] The oxygen-rich portions of these materials can be provided as different layers. For example, the electrochromic and / or counter electrode material may include an oxygen-rich first layer and a non-oxygen-rich second layer (or having relatively less oxygen than the first layer). Unless otherwise specified, the term "oxygen-rich" as used herein refers to a material that is superstoichiometric relative to oxygen. In addition, the "oxygen-rich" material compared to the second material has a higher stoichiometric ratio of oxygen compared to the second material. In some examples, the electrochromic layer includes two layers of tungsten titanium molybdenum oxide, wherein the second layer of tungsten titanium molybdenum oxide is oxygen-rich compared to the first layer of tungsten titanium molybdenum oxide. The second layer of tungsten titanium molybdenum oxide may be superstoichiometric relative to oxygen. The second layer of tungsten titanium molybdenum oxide may be in direct physical contact with the counter electrode layer and in direct physical contact with the first layer of tungsten titanium molybdenum oxide. As described above, the counter electrode layer may be homogeneous or may also include an oxygen-rich portion.

[0105] The oxygen-rich portions of these layers may also be disposed in a gradient layer. For example, the electrochromic and / or counter electrode materials may include a gradient of oxygen concentration in a direction orthogonal to the surfaces of the layers. In some examples, the electrochromic layer is a gradient layer of tungsten titanium molybdenum oxide having a gradient oxygen concentration in a direction orthogonal to the surface of the layer. For example, the highest oxygen concentration in the gradient tungsten titanium molybdenum oxide layer may be near the counter electrode layer. As described above, the counter electrode layer may be homogeneous or may also include an oxygen-rich portion.

[0106] Embodiments in which the ion conductor layer deposition step is omitted and the counter electrode material is deposited in direct contact with the electrochromic material are further discussed in the following U.S. Patents, which are hereby incorporated by reference in their entireties: U.S. Patent No. 8,300,298; U.S. Patent No. 8,764,950; and U.S. Patent No. 9,261,751.

[0107] F. Additional Layers

[0108] The electrochromic device 100 may include one or more additional layers (not shown). Figure 1 ), such as one or more passivation layers. A passivation layer for improving certain optical properties may be included in the electrochromic device 100. A passivation layer for providing moisture resistance or scratch resistance may also be included in the electrochromic device 100. For example, the conductive layer may be treated with an anti-reflective or protective oxide or nitride layer. Other passivation layers may be used to hermetically seal the electrochromic device 100. There may also be one or more insulating layers to mitigate defects to minimize the number of defects in the device, as discussed in U.S. Patent Application No. 13 / 763,505 filed on February 8, 2013 and entitled “DEFECT-MITIGATION LAYERS IN ELECTROCHROMIC DEVICES,” which is incorporated herein by reference in its entirety.

[0109] II. Methods of Making Electrochromic Devices and Precursors

[0110] 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, Figure 2A As described in , there are many other steps that can be taken when making an electrochromic device or precursor.

[0111] As used herein, an electrochromic device precursor is a partially manufactured electrochromic device that is not yet suitable for use as a final electrochromic device. Typically, an electrochromic device precursor includes 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, an electrochromic device precursor has materials within its structure that, although not suitable for use as a final device, are configured or suitable for physical and / or chemical conversion to become a functional device. Such a device precursor may be desirable, for example, where a substrate is coated with a precursor material, stored, or transported to another facility for later and / or downstream processing.

[0112] For example, in some embodiments, there may not be a separate ion-conducting layer. In the case of omitting the ion-conducting layer, the electrochromic device precursor may lack any layer or region that can be used for the purpose of the ion-conducting layer (for example, allowing ions to pass without allowing 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 the case of omitting the ion-conducting layer, the further processing can form an ion-conducting and substantially electrically insulating material in the interface region between the electrochromic layer and the counter electrode layer. In various embodiments, the further processing can involve thermal regulation, as further described below. In some embodiments, one or both of the electrochromic and counter electrode materials are superstoichiometrically oxygenated at the interface of these layers, or otherwise, there is an excess of oxygen or other active species between these layers. The superstoichiometrically oxygenated material can then be converted into an ion-conducting and substantially electrically insulating material. In these or other embodiments, further processing can include involving 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 active species at the interface to form 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 causing an electric current to flow 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.

[0113] Figure 2A 2 is a process flow 200 that describes aspects of a method of making an electrochromic device or other optical device having opposing bus bars, each of which is applied to one of the conductive layers of the optical device. Dashed lines represent optional steps in the process flow. Figure 2B-2C As described, an exemplary device 240 is used to illustrate the process flow. Figure 2B A top view is provided depicting the fabrication of device 240, including the fabrication of Figure 2ANumerical designators of process flow 200 are described. Figure 2C Shown includes about Figure 2B A cross section of a slice of device 240 is depicted. Device 240 is a rectangular device, but process flow 200 is applicable to any shape of optical device having opposing bus bars, each on one of the conductive layers.

[0114] Reference Figure 2A and Figure 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. Polishing, if performed, may be performed before edge removal (see 205) and / or after edge removal in the process flow.

[0115] Reference again Figure 2A , if polishing 201 is not performed, the process 200 begins with edge removal of a first width near 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, such as a transparent metal oxide conductive layer based on tin oxide. Figure 2B The dashed area in represents the first conductive layer. Therefore, after the edge removal according to process 205, a width A is removed from three sides of the periphery of substrate 230. This width is usually, but not necessarily, a uniform width. The second width B is described below. In the case where width A and / or width B are not uniform, their relative sizes relative to each other are in terms of their average width.

[0116] As a result of removing the first width A at 205, there is a newly exposed edge of the underlying conductive layer. In some embodiments, at least a portion of this 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 prior to fabricating 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 in Figure 2A Edge tapering is shown at both 207 and 209 in FIG, but if performed, edge tapering will typically be performed once (eg, at 207 or 209).

[0117] In some embodiments, the lower conductive layer is optionally polished before or after edge tapering, see 208 .

[0118] After removal of the first width A and optional polishing and / or optional edge tapering as described above, an EC device is deposited on the surface of substrate 230, see 210. Figure 2D The EC stack deposition is further described. 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 depicted coverage is the entire substrate, but there may be some obscuration due to the carrier that must hold the glass in place. In one embodiment, the entire area of ​​the remainder of the first conductive layer is covered, including overlapping the first conductor with the first width A previously removed. This allows overlapping areas in the final device architecture.

[0119] In certain embodiments, electromagnetic radiation is used to perform edge removal and provide a peripheral area of ​​the substrate, for example to remove a transparent conductive layer or more layers (up to and including the top conductive layer and any vapor barrier applied thereto), depending on the process steps. In one embodiment, at least edge removal is performed to remove the material including 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 a surface portion of a substrate (e.g., float glass), and can reach a depth not exceeding 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, despite the presence of a secondary seal, the transparent conductive layer sometimes loses adhesion when the conductive layer spans the entire area of ​​the substrate and therefore has an exposed edge. Similarly, it is believed that when metal oxides and other functional layers have such exposed edges, they can be used as a path for moisture to enter the overall device, thereby damaging the primary and secondary seals.

[0120] Edge removal is described herein as being performed on a substrate that has already been cut to size. However, in other disclosed embodiments, edge removal may be performed before the substrate is cut from the monolithic glass sheet. For example, untempered float glass may be cut into individual sheets after the EC device is patterned thereon. The methods described herein may be performed on a monolithic block, which is then cut into individual EC sheets. In certain embodiments, edge removal may be performed in some edge areas before the EC sheets are cut, and again after they are cut from the monolithic block. In certain embodiments, all edge removal is performed before the sheets are cut from the monolithic block. In embodiments where "edge removal" is employed before cutting the pane, a portion of the coating on the glass sheet may be removed in anticipation of where the cut (and edge) of the newly formed EC sheet will be located. In other words, there is no actual substrate edge yet, only a defined area where cutting will be performed to produce an edge. Therefore, "edge removal" refers to the removal of one or more material layers in an area where a substrate edge is expected to exist. Methods of making EC sheets by cutting from a monolithic block after fabricating EC devices on the monolithic block are described in U.S. Patent Application Serial No. 12 / 941,882 filed on November 8, 2010 (now U.S. Patent No. 8,164,818) and U.S. Patent Application Serial No. 13 / 456,056 filed on April 25, 2012, each of which is entitled "Electrochromic Window Fabrication Methods," and each 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 monolithic sheet of glass and then individual sheets are cut therefrom, then in certain embodiments, the use of a mask may be necessary, whereas when performed on sheets having the desired final dimensions, a mask is optional.

[0121] Exemplary electromagnetic radiation includes UV, laser, etc. For example, material can be removed using directed and focused energy at one or more of the wavelengths of 248 nm, 355 nm (UV), 1030 nm (IR, such as disk lasers), 1064 nm (such as Nd:YAG lasers), and 532 nm (such as green lasers). The laser irradiation is delivered to the substrate using, for example, optical fibers or open beam paths. Depending on the selection and configuration parameters of the substrate processing equipment, ablation can be performed from the substrate side or the EC film side. The energy density required to ablate the film thickness is achieved by passing the laser beam through an optical lens. The lens focuses the laser beam into the desired shape and size. In one embodiment, a "flat top" beam configuration is used, for example, with a focal area of ​​about 0.005 mm 2 To about 2mm 2In one embodiment, the focus level of the beam is used to achieve the energy density required to ablate the EC membrane stack. In one embodiment, the energy density used in ablation is about 2 J / cm 2 About 6J / cm 2 between.

[0122] In the laser edge removal process, a laser spot is scanned along the periphery on the surface of the EC device. In one embodiment, a scanning Fθ lens is used to scan the laser spot. For example, homogeneous removal of the EC film is achieved by overlapping the area of ​​the spot 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 can be used, for example, scanning in a straight line, a curve, and various patterns can be scanned, such as scanning a portion of a rectangle or other shape, to jointly create a peripheral edge removal area. In one embodiment, the scan line (or "pen", i.e., a line formed by adjacent or overlapping laser spots (e.g., a square, a circle, etc.)) is overlapped at the level described above for spot overlap. That is, the area of ​​ablated material defined by the path of the previously scanned line overlaps with the subsequent scan line, so that there is an overlap. That is, the pattern area ablated by overlapping or adjacent laser spots overlaps with the area of ​​the subsequent ablation pattern. For embodiments using overlap, higher frequency lasers, such as in the range of between about 11 KHz and about 500 KHz, may be used in spots, lines, or patterns. To minimize heat-related damage to EC devices at the exposed edges (heat affected zones or "HAZ"), shorter pulse duration lasers are used. In one example, the pulse duration is between about 100 fs (femtoseconds) and about 100 ns (nanoseconds), in another embodiment, the pulse duration is between about 1 ps (picoseconds) and about 50 ns, and in yet another embodiment, the pulse duration is between about 20 ps and about 30 ns. In other embodiments, other ranges of pulse durations may be used.

[0123] Reference again Figure 2A and Figure 2B , process flow 200 continues to remove a second width B that is narrower than the first width A substantially around the entire perimeter of the substrate, see 215. This may include removing material down to the glass or diffusion barrier layer (if present). After completing process flow 200 up to 215, for example, Figure 2B On the rectangular substrate shown, there is a peripheral region of width B in which there is no first transparent conductor, one or more material layers of the device, or the second conductive layer - removing width B has exposed the diffusion barrier layer or substrate. Within this peripheral region is the device stack, including the first transparent conductor surrounded on three sides by overlapping one or more material layers and the second conductive layer. On the remaining sides (e.g., Figure 2B There is no overlap between the one or more material layers and the second conductive layer. Figure 2B 220), removing one or more material layers and the second conductive layer to expose a portion of the first conductive layer (bus bar pad exposure, or "BPE") 235, see 220. The BPE 235 does not need to run the entire length of that side, it only needs to be long enough to accommodate the bus bar and leave some space between the bus bar and the second conductive layer so as not to short on the second conductive layer. In one embodiment, the BPE 235 spans the length of the first conductive layer on that side.

[0124] In various embodiments, the BPE is a portion of a material layer removed down to the lower electrode or other conductive layer (e.g., a transparent conductive oxide layer) to create a surface for the busbar to be applied, thereby making electrical contact with the electrode. The busbar applied can be a welded busbar, as well as an ink busbar, etc. The BPE typically has a rectangular area, but this is not required; the BPE can be any geometric or irregular shape. For example, the BPE can be circular, triangular, elliptical, trapezoidal, and other polygonal shapes as needed. The shape can depend on the configuration of the EC device, the substrate carrying the EC device (e.g., an irregularly shaped window), or even a more effective laser ablation pattern for creating 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 width of the BPE is sufficient to accommodate the busbar, but at least a certain amount of space should be left between the active EC device stack and the busbar. In one embodiment, the BPE is generally rectangular, with a length approximately equal to one side of the EC device, and a width between about 5 mm and about 15 mm, in another embodiment between about 5 mm and about 10 mm, and in yet another embodiment between about 7 mm and about 9 mm. As mentioned, the width of the busbar can be between about 1 mm and about 5 mm, typically about 3 mm.

[0125] As mentioned, the BPE is manufactured to a width sufficient to accommodate the width of the bus bar and also leave space between the bus bar and the EC device (because 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 an L3 isolation scratch, the bus bar may contact the deactivated portion), the bus bar width may exceed the width of the BPE (so that the bus bar material contacts the lower conductor and the glass (and / or diffusion barrier) in area 241). In embodiments where the BPE fully accommodates the width of the bus bar, that is, the bus bar is completely on top of the lower conductor, the outer edge of the bus bar can be aligned with the outer edge of the BPE along the length of the bus bar, or inset by about 1 mm to about 3 mm. Similarly, the space between the bus bar and the EC device is between about 1 mm and about 3 mm, between about 1 mm and 2 mm in another embodiment, and about 1.5 mm in another embodiment. 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 use in optical devices, transparent or opaque.

[0126] To fabricate the BPE, areas of the bottom TCO (e.g., the first TCO) are cleared of deposited material so that bus bars can be fabricated on the TCO. In one embodiment, this is achieved by laser processing that selectively removes the deposited film layers while exposing the bottom TCO in defined areas at defined locations. In one embodiment, the absorption properties of the bottom electrode and the deposited layers are utilized 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 some embodiments, the upper portion (depth) of the TCO layer is also removed to ensure good electrical contact for the bus bars, for example, by removing any mixture of TCO and EC material that may have occurred during deposition. In some embodiments, the use of L3 isolation lines to limit leakage current can be avoided when the BPE edges are laser machined to minimize damage at these edges - this saves a process step while achieving the desired device performance results.

[0127] In certain embodiments, the electromagnetic radiation used to make the BPE is the same as the electromagnetic radiation used to perform edge removal described above. The (laser) radiation is transmitted to the substrate using an optical fiber or an open beam path. Depending on the choice of electromagnetic radiation wavelength, ablation can be performed from the glass side or the film side. The energy density required to ablate the film thickness is achieved by passing the 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" with the dimensions described above, with an energy density of about 0.5 J / cm 2 About 4J / cm 2In one embodiment, laser scanning overlap is performed for BPE, as described above for laser edge removal. In certain embodiments, variable depth ablation is used for BPE fabrication.

[0128] In certain embodiments, laser processing at the focal plane results in a certain amount (between about 10 nm and about 100 nm) of residue (e.g., tungsten oxide) remaining on the exposed area of ​​the lower conductor, for example due to the selective nature of absorption in the EC film. Since many EC materials are not as conductive as the underlying conductive layer, the bus bar manufactured on this residue cannot fully contact the underlying conductor, resulting in a voltage drop on 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, but this method results in the formation of grooves at the spot overlap, thereby depleting the lower conductor, which is unacceptable. To overcome this problem, laser ablation is performed above the focal plane, that is, the laser beam is defocused. In one embodiment, the defocus profile of the laser beam is a modified flat top or "flat top-like". By using a defocused laser profile, the impact delivered to the surface can be increased without damaging the underlying TCO at the spot overlap area. This 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.

[0129] Reference again Figure 2A and Figure 2B , after forming the BPE, bus bars are applied to the device, one on the exposed area 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 that is 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 of having a functional device under the bus bar. In this example, no laser isolation scratches are required in the manufacturing process of the device - this is in stark contrast to traditional manufacturing methods, in which one or more isolation scratches retain non-functional device portions in the final construction.

[0130] Figure 2B The cross sections ZZ′ and WW′ of the indicator device 240 are shown. Figure 2C, a cross-sectional view of the device 240 at ZZ′ and WW′ is shown in FIG. The depicted layers and dimensions are not drawn to scale, but are intended to functionally represent the configuration. In this example, the diffusion barrier layer is removed when the width A and width B are manufactured. 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 periphery of one or more sides. In another embodiment, the diffusion barrier layer is coextensive with one or more material layers and the second conductive layer (thus, the width A is manufactured at the depth of the diffusion barrier layer, and the width B is manufactured to a depth sufficient to remove the diffusion barrier layer). In this example, there are overlapping portions 245 of one or more material layers near three sides of the functional device. On one of these overlapping portions, on the second TCO, the bus bar 1 is manufactured. In one embodiment, a vapor barrier layer is manufactured coextensively with the second conductive layer. The vapor barrier layer is typically highly transparent, such as aluminum oxide, 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 region 235, the BPE for bus bar 2. In some embodiments, the vapor barrier is also conductive and exposure of the second conductive layer is not required, i.e., the bus bar can be manufactured on the vapor barrier. For example, the vapor barrier can be ITO, such as amorphous ITO, and therefore has sufficient conductivity for this purpose. The amorphous form of the vapor barrier can provide greater airtightness than the crystalline form. In some cases, the vapor barrier can be deposited using chemical vapor deposition (CVD) or atomic layer deposition (ALD), and can include conductive metal nitrides, silicon nitrides, silicon oxides, or mixtures thereof.

[0131] Figure 2D Another flow chart is provided describing a method of making an electrochromic device or precursor according to certain embodiments. Figure 2D The method described in focuses on the deposition step. Method 260 begins by (a) receiving a substrate having a first conductive layer thereon or (b) depositing the 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 does not need to be deposited separately. In other embodiments, the conductive layer can be deposited before the remaining layers are deposited. The deposition of the second conductive layer is further discussed below. In some embodiments, these details can also be applied to the deposition of the first conductive layer.

[0132] The method continues with the deposition of the electrochromic layer, see 263. In many cases, the electrochromic layer is formed by sputtering. In certain embodiments where the electrochromic layer is homogeneous, the electrochromic layer may be deposited using the following conditions. One or more metal-containing targets and a substrate containing between about 40% and about 80% O2 The electrochromic layer may be formed by sputtering a sputtering gas of between about 20% and about 60% Ar. Each target may include one or more metals, such as tungsten, titanium, and molybdenum. The substrate on which the electrochromic layer is deposited may be heated to between about 150° C. and about 450° C. (in some cases, between about 250° C. and 350° C.) at least intermittently during the formation of the electrochromic layer. The electrochromic layer may be deposited to a thickness between about 500 and 600 nm.

[0133] In some embodiments where the ion conductor layer is omitted, the electrochromic layer may be deposited as two or more layers or gradient layers. A portion of one of the layers or gradient layers may be oxygen-enriched compared to the remainder of another layer or gradient layer. The oxygen-enriched portion may be superstoichiometric relative to oxygen. Typically, the oxygen-enriched layer or portion is in contact with the counter electrode layer. In other embodiments, the oxygen-enriched material at the interface may be provided in the form of a counter electrode material instead of or in addition to the electrochromic material.

[0134] In the case where the electrochromic layer is deposited as two or more layers, one of which is oxygen-rich, the following conditions may be used. In some such cases, the thickness of the first layer of the electrochromic layer may be between about 350 nm and about 450 nm. One or more targets and a catalyst layer including between about 40% and about 80% O 2 The first layer may be formed by sputtering using a first sputtering gas of between about 20% Ar and about 60% Ar. The target may include one or more metals, such as tungsten, titanium, and molybdenum. The thickness of the second layer may be between about 100 nm and about 200 nm. One or more targets and a first sputtering gas including between about 70% and 100% O 2 and a second sputtering gas of between 0% Ar and about 30% Ar to form the second layer by sputtering. In this embodiment, heat can be applied, for example, by heating the substrate to between about 150° C. and about 450° C. at least intermittently during deposition of the first electrochromic layer, while no (or substantially no) heating is applied during deposition of the second electrochromic layer. In a more specific embodiment, the first electrochromic layer is about 400 nm thick; the first sputtering gas comprises between about 50% and about 60% O 2 and between about 40% and about 50% Ar; the second electrochromic layer is about 150 nm thick; and the second sputtering gas is substantially pure O 2 In this embodiment, heat is at least intermittently applied to between about 200° C. and about 350° C. during formation of the first electrochromic layer, while no (or substantially no) heat is applied during formation of the second electrochromic layer.

[0135] In the case where the electrochromic layer is deposited 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 at the start of sputtering the electrochromic layer, the sputtering gas comprises between about 40% and about 80% O 2 and between about 20% and about 60% Ar, while at the end of sputtering the electrochromic layer, the sputtering gas contains between about 70% and 100% O 2 and between 0% and about 30% Ar. The substrate may be at least intermittently heated to between about 200° C. and about 350° C. at the beginning of formation of the electrochromic layer, but not during at least the last portion of deposition of the electrochromic layer. This description assumes that the electrochromic layer is deposited prior to the counter electrode layer, such as Figure 2D In the case where the electrochromic layer is deposited as a graded layer after forming the counter electrode layer, the details regarding the "initial" / "start" and "final" / "end" portions of the sputtering can be reversed. In either case, the electrochromic material with the higher oxygen concentration can be in contact with the counter electrode layer.

[0136] Regardless of the structure of the electrochromic layer, during the formation of the electrochromic layer, the pressure in the deposition station or deposition chamber can be between about 1 and about 75 mTorr, or between about 5 and about 50 mTorr, or between about 10 and about 20 mTorr. In one embodiment, the power density for sputtering one or more targets can be about 2 Watts / square centimeter (W / cm 2 ) and about 50W / cm 2 (determined based on the applied power divided by the surface area of ​​the target); in another embodiment, between about 10 W / cm 2 About 20W / cm 2 and in yet another embodiment, at about 15W / cm 2 About 20W / cm 2In some embodiments, the power delivered to achieve sputtering is provided via a direct current (DC). In other embodiments, pulsed DC / AC reactive sputtering is used. In one embodiment, when pulsed DC / AC reactive sputtering is used, the frequency is between about 20kHz and about 400kHz, between about 20kHz and about 50kHz in another embodiment, between about 40kHz and about 50kHz in yet another embodiment, and about 40kHz in another embodiment. The above conditions can be used in combination with each other to achieve the deposition of high-quality electrochromic layers. In one embodiment, the distance between the target (cathode or source) and the substrate surface is between about 35mm and about 150mm; in another embodiment, between about 45mm and about 130mm; and in another embodiment, between about 70mm and about 100mm. These same distances may be applicable to other targets used to deposit other layers of the device.

[0137] Next, the method continues with optional deposition of an ion conducting layer, see 263. When present, the ion conducting layer can be provided in a variety of different ways. For example, the ion conducting layer can be formed by sputtering, vapor based techniques, sol-gel techniques, etc. In many cases, the ion conducting layer is omitted.

[0138] Then, the method continues with the deposition of the electrode layer, see 267. Very similar to the electrochromic layer, the electrode layer can be deposited as a homogeneous layer, two or more layers or a gradient layer. In the case where the electrode is deposited as two or more layers or a gradient layer, one of these layers or a portion of the gradient layer can be oxygen-enriched compared to the rest of another layer or the gradient layer. The oxygen-enriched layer or oxygen-enriched portion can be positioned to be in direct physical contact with the electrochromic material in the electrochromic layer. In this case, the deposition conditions can be changed between the deposition of the first layer and the second layer, or between the initial portion of the deposition gradient layer and the final portion of the gradient layer. In various embodiments, the oxygen concentration and substrate temperature listed above for the deposition of the electrochromic layer can also be applied to the deposition of the electrode layer. Typically, a sputtering gas with a higher oxygen concentration and a lower inert gas concentration can be used to form a portion of an oxygen-enriched layer or a gradient layer compared to the sputtering gas used to deposit another layer or the rest of the gradient layer.

[0139] In certain embodiments, the sputtering gas used to form the counter electrode may include between about 30% and about 100% oxygen, between about 80% and about 100% oxygen in another embodiment, between about 95% and about 100% oxygen in yet another embodiment, and about 100% oxygen in another embodiment. In one embodiment, the power density used to sputter the CE target is about 2 W / cm 2 About 50W / cm 2(determined based on the applied power divided by the surface area of ​​the target); in another embodiment between about 5 W / cm 2 About 20W / cm 2 and in yet another embodiment at about 8W / cm 2 About 10W / cm 2 In another embodiment, it is about 8W / cm 2 . In some embodiments, the power delivered to achieve sputtering is provided via a 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, between about 20kHz and about 50kHz in another embodiment, between about 40kHz and about 50kHz in yet another embodiment, and about 40kHz in another embodiment. 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 certain embodiments, the counter electrode layer is deposited to a thickness between about 150 and 350nm; in yet another embodiment, to a thickness between about 200 and about 250nm.

[0140] Next, the method continues with the deposition of a second conductive layer, see 269. The conditions stated may be employed to form a thin, low-defect layer of indium tin oxide by, for example, sputtering a target comprising indium oxide in tin oxide in the presence of an argon sputtering gas with or without 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 5 nm and about 10,000 nm, in another embodiment, between about 10 nm and about 1,000 nm, and in yet another embodiment, between about 10 nm and about 500 nm. In one embodiment, the substrate temperature during deposition of the second conductive layer is between about 20° C. and about 300° C., in another embodiment, between about 20° C. and about 250° C., and in another embodiment, between about 80° C. and about 225° C. In one embodiment, depositing the TCO layer comprises sputtering a TCO layer comprising about 80% (by weight) to about 99% In using an inert gas, optionally with oxygen. 2 O 3 and between about 1% and about 20% SnO 2 In a more specific embodiment, the target is about 85% (by weight) to about 97% In 2 O 3 , and between about 3% and about 15% SnO 2In another embodiment, the target is about 90% In 2 O 3 With about 10% SnO 2 In one embodiment, the gas composition comprises 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. In one embodiment, the power density for sputtering the TCO target is about 0.5 W / cm 2 About 10W / cm 2 (determined based on the applied power divided by the surface area of ​​the target); in another embodiment between about 0.5 W / cm 2 About 2W / cm 2 and in yet another embodiment at about 0.5 W / cm 2 About 1W / cm 2 In another embodiment, it is about 0.7 W / cm 2 . 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 80kHz. 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.

[0141] When practice Figure 2DWhen the method is used, one or more of the deposited layers may be lithiated before the next layer is deposited. For example, one or more of the electrochromic layer, the optional ion conductive 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 conductive layer are all lithiated. In another example, the electrochromic layer and the ion conductive layer are lithiated. In another example, the counter electrode layer and the ion conductive layer are lithiated. In addition, any of these layers may be lithiated during the deposition of the layer. In some cases, a portion of a 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 associated layer may be deposited according to the same conditions or different conditions. In some cases, the first and second portions of the associated layer may have different compositions.

[0142] In the case of omitting the ion-conducting layer, the lithiation of the electrochromic and / or counter electrode layer can promote the formation of an interfacial region between the electrochromic layer and the counter electrode layer, wherein the interfacial region includes an ion-conducting and substantially electrically insulating material. For example, in some such embodiments, when the electrochromic and counter electrode materials are adjacent and one or both of the materials contain excess oxygen (e.g., above the stoichiometric level), the insertion of lithium and subsequent heating allow chemical changes to occur at the interface between the two electrode materials (e.g., between the electrochromic material and the counter electrode material), thereby forming an ion-conducting and electrically insulating material at the interfacial region between the electrochromic layer and the counter electrode layer. For example, the multi-step thermal conditioning described herein can promote the formation of ion-conducting and electrically insulating materials.

[0143] In various embodiments, Figure 2D The operations shown in can be used to form an electrochromic device precursor. In order to form an electrochromic device from an electrochromic device precursor, one or more steps can be performed as described above. As described above, one technique that can be used to form an electrochromic device from an electrochromic device precursor is multi-step thermal conditioning. Conditioning can 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.

[0144] In one embodiment, Figure 2DThe stack formed as described in the embodiment of the present invention is heated between about 150° C. and about 450° C. (before or after depositing the second conductive layer at 269) under Ar for between about 10 minutes and about 30 minutes, and then heated under O 2 After this treatment, the stack is further treated by heating the stack in air at between about 250° C. and about 350° C. for between about 20 minutes and about 40 minutes. In a specific example, the stack is further treated by heating the stack in air at about 250° C. for about 15 minutes and then in an inert atmosphere at about 0.5° C. for about 15 minutes. 2 The stack is treated by heating in an 80°C atmosphere for 5 minutes and then heating the stack in air at about 300°C 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.

[0145] although Figure 2D The electrochromic layer is shown to be deposited before the counter electrode layer, but this is not always the case. In some embodiments, operations 263 and 267 can be reversed so that the counter electrode layer is deposited before the electrochromic layer.

[0146] III. Apparatus for making electrochromic devices and precursors

[0147] An integrated deposition system can be used to manufacture electrochromic devices on, for example, architectural glass or other substrates. Electrochromic devices can be used to manufacture insulating glass units (IGUs), which in turn can be used to manufacture electrochromic windows. The term "integrated deposition system" refers to a device for manufacturing electrochromic devices on optically transparent and translucent substrates. The device has multiple stations, each station dedicated to specific unit operations, such as depositing a specific component (or part of a component) of an electrochromic device, and cleaning, etching and temperature control of the device or a part thereof. Multiple stations are fully integrated together so that the substrate on which the electrochromic device is manufactured can be transferred from one station to the next station without being exposed to the external environment. The integrated deposition system operates in a controlled ambient environment inside the system where the process station is located. A fully integrated system allows better control of the interface quality between the deposited layers. Interface quality refers to, among other factors, the bonding quality between these layers and the lack of contaminants in the interface region. The term "controlled ambient environment" refers to a sealed environment separated from the external environment (such as an open atmospheric environment or a clean room). In a controlled ambient environment, at least one of the pressure and gas composition is controlled independently of the conditions in the external environment. Typically, although not necessarily, the pressure of the controlled ambient environment is below atmospheric pressure, such as at least a partial vacuum. The conditions in the controlled ambient environment can remain constant during the processing operation, or can change over time. For example, an electrochromic device layer can be deposited under vacuum in a controlled ambient environment and at the end of a deposition operation, the environment can be backfilled with a purge gas or a reaction gas, and the pressure can be increased to, for example, atmospheric pressure for processing at another station, and then the vacuum can be reestablished for the next operation, and so on.

[0148] 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 include: (i) a first deposition station comprising one or more targets for depositing a cathode coloring electrochromic layer; (ii) a second optional deposition station comprising one or more targets for depositing an ion conducting layer; (iii) a third deposition station comprising one or more targets for depositing a counter electrode layer. In some cases, the second deposition station may be omitted. For example, the device may not include any targets for depositing a separate ion conductor layer. The system also includes a controller comprising program instructions for passing the substrate through the plurality of stations in the following manner: (i) an electrochromic layer, (ii) an (optional) ion conducting layer, and (iii) a counter electrode layer are sequentially deposited on the substrate to form a stack. In the case where the electrochromic layer or the counter electrode layer comprises two or more layers, the layers may be formed at different locations or at the same location, depending on the desired composition of each layer and other factors. In one example, a first station may be used to deposit an electrochromic layer, a second station may be used to deposit a first layer of a counter electrode layer, and a third station may be used to deposit a second layer of a counter electrode layer.

[0149] In one embodiment, the plurality of deposition stations are operable to transfer a substrate from one station to the next without breaking vacuum. In another embodiment, the plurality of deposition stations are configured to deposit an electrochromic layer, an optional ion conductive layer, and a counter electrode layer on an architectural glass substrate. In another embodiment, the integrated deposition system includes a substrate holder and a conveying mechanism operable to maintain the architectural glass substrate in a vertical orientation while in the plurality of deposition stations. In yet another embodiment, the integrated deposition system includes one or more load locks for passing a substrate between an external environment and the integrated deposition system. In another embodiment, the plurality of deposition stations include at least two stations for depositing a layer selected from the group consisting of an electrochromic layer, an ion conductive layer, and a counter electrode layer.

[0150] In some embodiments, the integrated deposition system includes one or more lithium deposition stations, each of which includes a lithium-containing target. In one embodiment, the integrated deposition system includes 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 lithium deposition stations have isolation valves. In this article, the term "isolation valve" refers to a device that isolates the deposition or other process performed by one station from the process at other stations in the integrated deposition system. In one example, the isolation valve is a physical (solid) isolation valve that participates in the deposition of lithium within the integrated deposition system. 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 can be an air knife or a protective shield, for example, a partial pressure of argon or other inert gas passes through the area between the lithium deposition station and other stations to prevent ions from flowing to other stations. In another example, the isolation valve can be an evacuation area between the lithium deposition station and other process stations, so that lithium ions or ions from other stations entering the evacuation area are removed to, for example, a waste stream, instead of contaminating adjacent processes. This is achieved, for example, by pressure differentials in the lithiation station of the integrated deposition system via dynamic flow in a controlled ambient environment, such that lithium deposition in the integrated deposition system is substantially isolated from other processes. Likewise, the isolation valve is not limited to lithium deposition stations.

[0151] 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 the case where both the first conductive layer and the second conductive layer are deposited on the substrate, two stations can be provided, each station being dedicated to depositing one of the conductive layers. In other embodiments, a single station can 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, a substrate is received with a first conductive layer disposed on the substrate, and only the second conductive layer is deposited during the manufacture of the electrochromic device.

[0152] Figure 3AAn integrated deposition system 300 according to certain embodiments is depicted in a schematic manner. In this example, the system 300 includes an entry load lock 302 for introducing a substrate into the system, and an exit load lock 304 for removing a substrate from the system. The load lock allows a substrate to be introduced into the system or removed from the system without disturbing the controlled ambient environment of the system. The integrated deposition system 300 has a module 306, which has multiple 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 does not need to have a load lock function, for example, the module 306 can be used alone as an integrated deposition system. For example, a substrate can be loaded into the module 306, a controlled ambient environment is established, and then the substrate is processed by each station in the system. Each station in the integrated deposition system can include a heater, a cooler, various sputtering targets and instruments that move them, RF and / or DC power supplies and power transmission mechanisms, etching tools (e.g., plasma etching), a gas source, a vacuum source, a glow discharge source, a process parameter monitor and sensor, a robot, a power supply, etc.

[0153] Figure 3B A portion (or simplified version) of the integrated deposition system 300 is depicted in perspective view, and with more details (including a cross-sectional view of the interior). In this example, the system 300 is modular, wherein the entry load lock 302 and the exit load lock 304 are connected to the 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 a tray 320 traveling along a track 315. In this example, the pallet 320 is supported by the track 315 via a suspension, but the pallet 320 can also be supported on a track near the bottom of the device 300, or, for example, on a track midway between the top and bottom of the device 300. The tray 320 can be translated forward and / or backward (as shown by the double arrows) by the system 300. For example, during lithium deposition, the substrate can be moved forward and backward in front of the lithium target 330, and multiple passes are made to achieve the desired lithiation. The tray 320 and the substrate 325 are in a substantially vertical orientation. The substantially vertical orientation is not limiting, but can help prevent defects because particulate matter that may be generated, for example, by agglomeration of sputtered atoms, will tend to succumb to gravity and therefore not be deposited on substrate 325. Also, because architectural glass substrates tend to get larger, the vertical orientation as the substrate traverses the stations of the integrated deposition system enables coating of thinner glass substrates because there is less concern about sagging with thicker hot glass.

[0154] Target 330 (in this case a cylindrical target) is oriented substantially parallel to and in front of the substrate surface where deposition is to occur (other sputtering equipment is not shown here for convenience). Substrate 325 may translate past target 330 during deposition, and / or target 330 may move in front of substrate 325. The path of motion of target 330 is not limited to translation along the path of substrate 325. Target 330 may rotate along an axis through its length, translate along the path of the substrate (forward and / or backward), translate along a path perpendicular to the path of the substrate, move in a circular path in a plane parallel to substrate 325, and the like. Target 330 need not be cylindrical, it may be planar or any shape required to deposit a desired layer having desired properties. Likewise, 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.

[0155] 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, by a computer system or other controller (in Figure 3B The control device may be specially constructed for the desired purpose, or may be a general-purpose computer selectively activated or reconfigured by a computer program and / or a data structure stored in the computer. The process proposed herein is not inherently related to any particular computer or other device. In particular, various general-purpose machines may be used in conjunction with programs written in accordance with the teachings of this article, or it may be more convenient to construct more specialized devices to perform and / or control the desired methods and processes.

[0156] As mentioned, the various stations of the integrated deposition system may be modular, but once connected form a continuous system in which a controlled ambient environment is established and maintained for processing substrates at the various stations within the system. Figure 3C An integrated deposition system 300a is depicted that is similar to system 300, but in this example, each station is modular, specifically EC level station 304a, IC level station 304b, and CE level station 306c. In a similar embodiment, IC level station 304b is omitted. The modular form is not required, but it is convenient because the integrated deposition system can be assembled according to customized requirements and emerging process advances as needed. For example, Figure 3DAn integrated deposition system 300b is depicted having two lithium deposition stations 307a and 307b. System 300b is, for example, equipped to perform the methods herein as described above, such as a dual lithiation method. System 300b can also be used to perform a single lithiation method, for example by utilizing only lithium station 307b during processing of a substrate. However, in a modular format, for example, if a single lithiation is desired, one of the lithiation stations is redundant and can be used as described above. Figure 3E The system 300c is shown. The system 300c has only one lithium deposition station 307.

[0157] Systems 300b and 300c also have one or more TCO layer stations 308 for depositing a TCO layer on the EC stack. TCO refers to transparent conductive oxide. Figure 1 , the conductive layers 104 and 114 may be TCO layers. Figure 3D and Figure 3E Only a single TCO layer station 308 is shown, but it should be understood that in the case where the first conductive layer is deposited on the substrate (e.g., rather than providing the first conductive layer on the substrate), additional TCO stations can be provided, for example, between the entry load lock 302 and the EC layer station 306a (or between the entry load lock 302 and the CE layer station 306c in the case where the counter electrode layer is deposited prior to the electrochromic layer). Depending on the process requirements, additional stations can be added to the integrated deposition system, such as stations for cleaning processes, laser scribing, capping layers, etc.

[0158] The sputtering process for forming a layer (e.g., an electrochromic layer or a counter electrode layer) can utilize one or more sputtering targets. In the case of using one sputtering target, the target can include all the metals required in the deposited layer (e.g., nickel and tungsten for NiWO layers; nickel, tungsten, and tantalum for NiWTaO layers; nickel, tungsten, and niobium for NiWNbO layers; nickel, tungsten, and tin for NiWSnO layers; tungsten, titanium, and molybdenum for WTiMoO layers; etc.). In this case, the target can 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 an intermetallic mixture, the composition of the target reflects the metal ratios described herein using variables x and y, without oxygen (z is 0). For example, the composition of a metal sputtering target can be 84% (atomic) tungsten, 10% (atomic) titanium, and 6% (atomic) molybdenum (x=0.10 and y=0.06, equivalent to 93.6% by weight tungsten, 2.9% by weight titanium, and 3.5% by weight molybdenum). It will be appreciated that the atomic ratios of the metal target may not translate directly to the ratios of the metals in the sputtered tungsten titanium molybdenum oxide because the three metals may react with oxygen at different rates, be sputtered from the target at different rates, etc. Where more than one target is used, the targets may be of the same composition or of different compositions (e.g., having a different metal or combination of metals on each target).

[0159] The sputtering target may include a grid or other overlapping shape, wherein different portions of the grid include different related materials (e.g., certain portions of the grid may include elemental metals or metal alloys that together form the desired composition). For example, in the case of using two targets to form a tungsten titanium molybdenum oxide electrochromic layer, each target may include one or more of tungsten, titanium, and molybdenum. In one example, the first target includes tungsten and titanium, and the second target includes molybdenum. In another example, the first target includes tungsten and molybdenum, and the second target includes titanium. In another example, the first target includes titanium and molybdenum, and the second target includes tungsten. In some embodiments, two targets are used to form a nickel tungsten tantalum oxide counter electrode. In this case, the first target may include nickel, and the second target may include tungsten and tantalum; or the first target may include nickel and tungsten, and the second target may include tungsten; or the first target may include nickel and tantalum, and the second target may include tungsten. Similar examples are also 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 some embodiments. In any case where two or more metals are provided together on the same target, the metals may be provided individually (eg, elemental metals provided together in a grid or otherwise), as an alloy, or a combination thereof.

[0160] In some cases, the sputtering target may include an alloy of the relevant materials (e.g., two or more of tungsten, titanium, and molybdenum for forming a tungsten-titanium-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). In the case of using two or more sputtering targets, each sputtering target may include at least one of the relevant materials (e.g., the element and / or alloy form of the relevant metal, any of which may be provided in the form of an oxide). In some cases, the sputtering targets may overlap. In some embodiments, the sputtering targets may also rotate. 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 the 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.

[0161] In one embodiment, to normalize the deposition rate of the electrochromic layer or the counter electrode layer, multiple targets are used, thereby eliminating the need for inappropriately high power (or other inappropriate adjustments to desired process conditions) to increase the deposition rate.

[0162] As noted, one or more rotating targets may be used in some cases. In various cases, the rotating target may include an internal magnet. Figure 4A A view of a rotating target 400 is shown. Inside the rotating target 400 are magnets 402 that (when appropriate power is provided to the target) cause material to be sputtered off of a target surface 404 in a sputter cone 406 (the sputter cone is sometimes also referred to as a sputter plasma). The magnets 402 can extend along the length of the sputter target 400. In various embodiments, the magnets 402 can be oriented to extend radially outward so that the resulting sputter cone 406 emanates from the sputter target 400 in a direction normal to the target's surface 404 (the direction measured along the central axis of the sputter cone 406, which generally corresponds to the average direction of the sputter cone 406). The sputter cone 406 can be V-shaped when viewed from above and can extend along the height of the target 400 (or along the height of the magnet 402 if not the same as the height of the target 400). The magnets 402 inside the rotating target 400 may be fixed (i.e., although the surface 404 of the target 400 rotates, the magnets 402 inside the target 400 do not rotate) so that the sputtering cone 406 is also fixed. The small circles / dots depicted in the sputtering cone 406 represent the sputtered material emanating from the sputtering target 400. The rotating target may be combined with other rotating targets and / or planar targets as desired.

[0163] In one example, two rotating targets are used to deposit a tungsten-titanium-molybdenum oxide electrochromic layer: a first target comprising tungsten and titanium, and a second target comprising molybdenum (optionally in either or both oxide forms). As described above, other combinations of these metals can be used to produce the same material. In another example, two rotating targets are used to deposit a nickel-tungsten-tantalum oxide counter electrode layer: a first target comprising nickel and tungsten, and a second target comprising tantalum (optionally in either or both oxide forms). As discussed above, other combinations of these metals can be used to produce the same material. Similarly, these examples can be applied to deposit other desired materials, including but not limited to nickel-tungsten oxide, nickel-tungsten-niobium oxide, and nickel-tungsten-tin oxide.

[0164] Figure 4B A top view of a deposition system for depositing layers of an electrochromic device in this manner is shown. This example is given in the context of forming a tungsten-titanium-molybdenum oxide electrochromic layer using a first target including tungsten and titanium and a second target including molybdenum. However, these techniques can be applied to form any mixed metal oxide described herein using any combination of targets that provide the desired composition (e.g., a combination of targets including all desired metals of the relevant layer). The first target 410 and the second target 412 both include an internal magnet 414. The magnets 414 are angled to each other so that the sputtering cones 416 and 418 from the first target 410 and the second target 412, respectively, overlap. In this way, the tungsten and titanium sputtered from the first target 410 are mixed with the molybdenum sputtered from the second target 412 to form the desired tungsten-titanium-molybdenum oxide. Figure 4B Also shown is a substrate 420 passing in front of targets 410 and 412. As shown, sputter cones 416 and 418 overlap closely where they strike substrate 420. In some embodiments, the sputter cones from various sputter targets may overlap closely with each other (e.g., when deposited on a substrate, the non-overlapping area reached by only a single sputter cone is less than about 10%, such as less than about 5%, of the total area reached by either sputter cone). In other embodiments, the sputter cones may diverge more from each other, such that one or both of the sputter cones have at least about 10%, such as at least about 20%, or at least about 30%, or at least about 50% of the total area reached by either sputter cone.

[0165] In with Figure 4BIn an embodiment similar to the illustrated embodiment, one sputtering target is tungsten and molybdenum (separately or as an alloy) and the other target is titanium (either one or both of the targets are optionally in the form of an oxide). Similarly, one sputtering target can be tungsten and the other sputtering target can be a combination of titanium and molybdenum (separately or as an alloy) (either one or both of the targets are optionally in the form of an oxide). In a related embodiment, three sputtering targets are used to form tungsten titanium molybdenum oxide: a tungsten target, a titanium target, and a nickel target (any one of which can optionally be in the form of an oxide). The sputtering cones from each of the three targets can overlap by appropriately tilting the magnets. Moreover, shields, gratings, and / or other additional plasma shaping elements can be used to help produce the appropriate plasma mixture to form the desired composition. As described above, these examples can be applied to the formation of other materials in electrochromic devices as long as the targets are selected to provide the desired composition.

[0166] Table 1 provides various examples of target groups that can be used together to form tungsten titanium molybdenum oxides according to certain embodiments. Any of these materials can be provided in oxide form. When two metals are provided together, they can be provided as elemental metals (e.g., in a grid or other pattern), or can be provided as an alloy.

[0167] Table 1

[0168] Composition of the first target Composition of the second target Composition of the third target Tungsten and Titanium molybdenum - Tungsten and molybdenum titanium - Tungsten molybdenum titanium

[0169] Table 2 provides various examples of target groups that can be used together to form nickel tungsten tantalum oxide according to certain embodiments. Any of these materials can be provided in oxide form. When two metals are provided together, they can be provided as elemental metals (e.g., in a grid or other pattern), or can be provided as an alloy.

[0170] Table 2

[0171] Composition of the first target Composition of the second target Composition of the third target Nickel and tungsten Tantalum - Nickel and Tantalum Tungsten - nickel Tantalum Tungsten

[0172] Table 3 provides various examples of target groups that can be used together to form nickel-tungsten-niobium oxide according to certain embodiments. Any of these materials can be provided in oxide form. When two metals are provided together, they can be provided as elemental metals (e.g., in a grid or other pattern), or can be provided as an alloy.

[0173] Table 3

[0174] Composition of the first target Composition of the second target Composition of the third target Nickel and tungsten niobium - Nickel and Niobium Tungsten - nickel niobium Tungsten

[0175] Table 4 provides various examples of target groups that can be used together to form nickel tungsten tin oxide according to certain embodiments. Any of these materials can be provided in oxide form. When two metals are provided together, they can be provided as elemental metals (e.g., in a grid or other pattern), or can be provided as an alloy.

[0176] Table 4

[0177] Composition of the first target Composition of the second target Composition of the third target Nickel and tungsten tin - Nickel and tin Tungsten - nickel tin Tungsten

[0178] Tables 1 to 4 describe various examples related to the formation of tungsten titanium 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.

[0179] Various sputtering target designs, orientations, and embodiments are further discussed in US Pat. No. 9,261,751, which is incorporated herein by reference in its entirety.

[0180] The density and orientation / shape of the material sputtered from the sputtering target depends on various factors, including, for example, the magnetic field shape and strength, pressure, and 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 how the generated material is deposited on the substrate.

[0181] In certain embodiments, two different types of sputtering targets are provided to deposit a single layer in an electrochromic stack: (a) a main sputtering target that sputters material onto a substrate; and (b) a secondary sputtering target that sputters material onto the main sputtering target. The main sputtering target and the secondary sputtering target may include any combination of metals, metal alloys, and metal oxides that achieve a desired composition in the deposited layer (including but not limited to any of the combinations described in Tables 1 to 4, wherein the "first target" listed in these tables corresponds to the main target or the secondary target). In a specific example in which the target is used to form tungsten titanium molybdenum oxide, the main sputtering target includes an alloy of tungsten and titanium, and the secondary sputtering target includes molybdenum. In a similar example, the main sputtering target includes titanium, and the secondary sputtering target includes an alloy of molybdenum and tungsten. These sputtering targets can be used together to deposit an electrochromic layer comprising tungsten titanium molybdenum oxide. Other combinations of elemental metals and alloys may also be used as desired.

[0182] When using both a primary and a secondary sputtering target, many different setups are possible. Figure 5A and Figure 5BA top view of one embodiment of a deposition station for depositing layers of an electrochromic device (e.g., an electrochromic layer and / or a counter electrode layer) is presented. The sputtering target configuration discussed herein can be used to deposit any material in an electrochromic stack if the target has an appropriate composition to deposit the desired material in the stack. Both the primary sputtering target 501 and the secondary sputtering target 502 are provided with internal magnets 503. Each sputtering target is a rotating sputtering target in this example, but planar or other shaped targets may also be used. The targets may rotate in the same direction or in opposite directions. As Figure 5A As shown in FIG. 5 , when there is no substrate 504 between the two targets, the secondary sputtering target 502 sputters material onto the primary sputtering target 501. This deposits material from the secondary sputtering target 502 onto the primary sputtering target 501. Then, as the substrate 504 moves to a position between the two targets, sputtering from the secondary sputtering target 502 stops, and sputtering from the primary sputtering target 501 to the substrate 504 begins, as shown in FIG. Figure 5B as shown in .

[0183] When material is sputtered from the primary sputtering target 501 and deposited onto the substrate 504, the deposited material includes materials respectively originating from the primary sputtering target 501 and the secondary sputtering target 502. In effect, this method involves in-situ formation of an intermixed sputtering target surface on the primary sputtering target 501. One advantage of this method is that a new coating of material from the secondary sputtering target 502 is periodically deposited on the surface of the primary sputtering target 501. The intermixed materials are then delivered together to the substrate 504.

[0184] exist Figure 5C In the related embodiment shown in , the secondary sputtering target 522 is positioned behind the main sputtering target 521, and the substrate 504 passes in front of the main sputtering target 521 so that the line of sight between the two targets 521 and 522 is not blocked. Each sputtering target may include a magnet 523. In this embodiment, it is not necessary to periodically stop the sputtering from the secondary sputtering target 521 to the main sputtering target 522. On the contrary, such sputtering can occur continuously. In the case where the main sputtering target 521 is located between the substrate 504 and the secondary sputtering target 522 (for example, there is no line of sight between the secondary sputtering target 522 and the substrate 504), the main sputtering target 521 should be rotated so that the material that can be deposited on the main sputtering target 521 can be sputtered onto the substrate 504. The design of the secondary sputtering target 522 has greater flexibility. In a related embodiment, the secondary sputtering target can be a planar or other non-rotating target. In the case of using two rotating targets, the targets can rotate in the same direction or in opposite directions.

[0185] In similar embodiments, a secondary sputtering target (e.g., FIG. 5A to FIG. 5CThe secondary target in the main sputtering target) may be replaced by another secondary material source. The secondary material source may provide material to the main sputtering target by means other than sputtering. In one example, the secondary material source provides evaporated material to the main sputtering target. The evaporated material may be any component of the layer being deposited. In various examples, the evaporated material is an elemental metal or a metal oxide. Specific examples of evaporated materials include nickel, tungsten, tantalum, niobium, tin, titanium, and molybdenum, which may be used to form the various materials described herein. In one embodiment, elemental molybdenum is evaporated onto a main sputtering target comprising a mixture and / or alloy of tungsten and titanium to form tungsten-titanium-molybdenum oxide. In another embodiment, elemental tantalum is evaporated onto a main sputtering target comprising a mixture and / or alloy of nickel and tungsten to form nickel-tungsten-tantalum oxide. In the case where the secondary material source provides evaporated material, the secondary material source may be provided at any position relative to the main sputtering target and the substrate. In some embodiments, the secondary material source is provided so that it is deposited later and primarily on the main sputtering target, much like Figure 5C The settings shown in .

[0186] In the case of using both a primary and secondary sputtering target, the secondary sputtering target can be operated at a potential that is cathode (already cathode) compared to the potential of the primary sputtering target. Alternatively, the targets can be operated independently. Further, the neutrals ejected from the secondary target will be deposited on the primary target regardless of the relative target potential. The neutral atoms will be part of the flux, and these atoms will be deposited on the cathode primary target regardless of the relative potential.

[0187] It should be understood that the configuration and / or method described herein is exemplary in nature, and these specific embodiments or examples are not considered to be restrictive, because many variations are possible. The specific routine or method described herein can represent one or more of any number of processing strategies. Thus, the various actions described can be performed in the sequence described, in other sequences, in parallel, or omitted in some cases. Similarly, the order of the above-mentioned processing can be changed. Certain references have been incorporated herein by reference. It should be understood that any disclaimer or denial made in such references is not necessarily applicable to the embodiments described herein. Similarly, any feature described as necessary in these references can be omitted in the embodiments herein.

[0188] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various methods, systems and configurations, and other features, functions, acts, and / or properties disclosed herein, and any and all equivalents thereof.

[0189] Unless otherwise defined for a particular parameter, the terms "about" and "approximately" as used herein are intended to mean ±10% with respect to the relevant value.

Claims

1. An integrated deposition system for manufacturing an electrochromic stack, the integrated deposition system comprising: a plurality of deposition stations aligned in series and connected to each other and operable to transfer a substrate from one station to the next without exposing the substrate to an external environment, wherein the plurality of deposition stations include A first deposition station comprising a first one or more material sources for depositing an electrochromic layer comprising an electrochromic material having the composition W 1-x-y Ti x Mo y O z Tungsten titanium molybdenum oxide, wherein x is between about 0.05-0.25, y is between about 0.01-0.15, and z is between about 2.5-4.5, and the thickness of the electrochromic layer is between about 200-700 nm; a second deposition station comprising a second one or more material sources for depositing a counter electrode layer comprising nickel tungsten oxide, the counter electrode layer having a thickness between about 100-400 nm; and a controller including program instructions for passing the substrate through the plurality of deposition stations in a manner such that deposition is performed on the substrate: (i) the electrochromic layer, and (ii) the counter electrode layer to form a stack comprising at least the electrochromic layer and the counter electrode layer.

2. The integrated deposition system of claim 1, wherein the plurality of deposition stations comprises a third deposition station comprising a third one or more material sources for depositing a first conductive layer having a thickness between approximately 10-500 nm.

3. The integrated deposition system of claim 2, wherein the plurality of deposition stations comprises a fourth deposition station comprising a fourth one or more material sources for depositing a second conductive layer having a thickness between approximately 100-400 nm.

4. The integrated deposition system of claim 1, wherein at least one of the second one or more material sources used to deposit the counter electrode layer comprises an elemental metal selected from the group consisting of: nickel, tungsten, and tantalum.

5. The integrated deposition system of claim 1, wherein at least one of the second one or more material sources used to deposit the counter electrode layer comprises an elemental metal selected from the group consisting of: nickel, tungsten, and niobium.

6. The integrated deposition system of claim 1, wherein at least one of the second one or more material sources used to deposit the counter electrode layer comprises an elemental metal selected from the group consisting of: nickel, tungsten, and tin.

7. The integrated deposition system of claim 1, wherein at least one of the second one or more material sources used to deposit the counter electrode layer comprises an oxide.

8. The integrated deposition system of claim 1, wherein the controller further comprises program instructions for forming a stack between the electrochromic layer and the counter electrode layer that does not include a homogeneous layer of ion-conducting, electrically insulating material.

9. The integrated deposition system of claim 1, wherein the controller further comprises program instructions for depositing the electrochromic layer and the counter electrode layer in a stack such that the electrochromic layer is in physical contact with the counter electrode layer.

10. The integrated deposition system of claim 1, wherein at least one of the electrochromic layer and the counter electrode layer comprises two or more layers or portions, and wherein one of the layers or portions is superstoichiometric with respect to oxygen.

11. The integrated deposition system of claim 10, wherein: (a) the electrochromic layer comprises the two or more layers, the layer in which the oxygen is superstoichiometric is in contact with the counter electrode layer, or (b) The counter electrode layer includes the two or more layers, and the layer having a stoichiometric excess relative to oxygen is in contact with the electrochromic layer.

12. The integrated deposition system of claim 10, wherein: (a) the electrochromic layer comprises the two or more layers or parts, the two or more layers or parts together form the electrochromic layer as a graded layer, and the layer or part in the electrochromic layer that is in superstoichiometric amount with respect to oxygen is in contact with the counter electrode layer, or (b) The counter electrode layer includes the two or more layers or parts, and the two or more layers or parts together form the counter electrode layer as a graded layer, and the layer or part of the counter electrode layer that is in superstoichiometric proportion with respect to oxygen is in contact with the electrochromic layer.

13. The integrated deposition system of claim 1 , further comprising a fifth deposition station comprising a fifth one or more material sources for depositing an ion-conducting and substantially electrically insulating layer, wherein the ion-conducting and substantially electrically insulating layer is formed in situ at the interface between the electrochromic layer and the counter electrode layer.

14. The integrated deposition system of claim 13, wherein the ion-conducting and substantially electrically insulating layer comprises a material selected from the group consisting of lithium silicate, lithium aluminum silicate, lithium oxide, lithium tungstate, lithium aluminum borate, lithium borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium oxynitride, lithium aluminum fluoride, lithium phospho-nitride (LiPON), lithium lanthanum titanate (LLT), lithium tantalate, lithium zirconium oxide, lithium silicon carbon oxynitride (LiSiCON), lithium titanium phosphate, lithium germanium vanadium oxide, lithium zinc germanium oxide, and combinations thereof.

15. The integrated deposition system of claim 13, wherein the ionically conductive and substantially electrically insulating layer has a thickness between about 5-100 nm.

16. The integrated deposition system of claim 13, wherein the ion-conducting and substantially electrically insulating 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 carbon oxynitride (LiSiCON), and combinations thereof.

17. The integrated deposition system of claim 3, wherein during formation of at least one of the electrochromic layer, the counter electrode layer, and the second conductive layer in at least one of the plurality of deposition stations, the substrate is positioned in a vertical orientation.

18. An electrochromic device or an electrochromic device precursor, comprising: a first conductive layer having a thickness between about 5 and 10,000 nm; The electrochromic layer comprises an electrochromic material, wherein the electrochromic material comprises a composition W 1-x-y Ti x Mo y O z Tungsten titanium molybdenum oxide, wherein x is between about 0.05-0.25, y is between about 0.01-0.15, and z is between about 2.5-4.5, and the thickness of the electrochromic layer is between about 50-2,000 nm; a counter electrode layer, the counter electrode layer comprising a counter electrode material, the counter electrode material comprising nickel tungsten oxide, the counter electrode layer having a thickness between about 50 nm and about 650 nm; and a second conductive layer, wherein the thickness of the second conductive layer is between about 5-10,000 nm, 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.

19. The electrochromic device or electrochromic device precursor according to claim 18, wherein the electrochromic layer is nanocrystals.

20. The electrochromic device or electrochromic device precursor according to claim 18, wherein the electrochromic layer is amorphous.

21. The electrochromic device or electrochromic device precursor according to claim 18, wherein the counter electrode layer is nanocrystal.

22. The electrochromic device or electrochromic device precursor according to claim 18, wherein the counter electrode layer is amorphous.

23. The electrochromic device or electrochromic device precursor according to claim 18, wherein the counter electrode material comprises nickel tungsten tantalum oxide.

24. The electrochromic device or electrochromic device precursor according to claim 18, wherein the counter electrode material comprises nickel tungsten niobium oxide.

25. The electrochromic device or electrochromic device precursor according to claim 18, wherein the counter electrode material comprises nickel tungsten tin oxide. 26 . The electrochromic device or the electrochromic device precursor according to claim 18 , wherein the electrochromic layer, the counter electrode layer and the second conductive layer are all formed by sputtering.

27. The electrochromic device or electrochromic device precursor of claim 18, wherein 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.

28. The electrochromic device or electrochromic device precursor of claim 18, wherein the electrochromic material is in physical contact with the counter electrode material.

29. The electrochromic device or electrochromic device precursor according to claim 18, 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.

30. The electrochromic device or electrochromic device precursor according to claim 29, wherein: (a) the electrochromic layer comprises the two or more layers, the layer in which the oxygen is superstoichiometric is in contact with the counter electrode layer, or (b) The counter electrode layer includes the two or more layers, and the layer having a stoichiometric excess relative to oxygen is in contact with the electrochromic layer.

31. The electrochromic device or electrochromic device precursor according to claim 29, wherein: (a) the electrochromic layer comprises the two or more parts, the two or more parts together form the electrochromic layer as a graded layer, the part 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 includes the two or more parts, the two or more parts together form the counter electrode layer as a graded layer, and the part of the counter electrode layer that is superstoichiometric with respect to oxygen is in contact with the electrochromic layer.

32. The electrochromic device or electrochromic device precursor of claim 18, further comprising an ionically conductive and substantially electrically insulating material formed in situ at the interface between the electrochromic layer and the counter electrode layer.

33. The electrochromic device or electrochromic device precursor according to claim 18, further comprising an ion conductive layer, wherein the ion conductive layer comprises a material selected from the group consisting of lithium silicate, lithium aluminum silicate, lithium oxide, lithium tungstate, lithium aluminum borate, lithium borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium oxynitride, lithium aluminum fluoride, lithium phosphorus oxynitride (LiPON), lithium lanthanum titanate (LLT), lithium tantalate, lithium zirconium oxide, lithium silicon carbon oxynitride (LiSiCON), lithium titanium phosphate, lithium germanium vanadium oxide, lithium zinc germanium oxide and combinations thereof.

34. The electrochromic device or electrochromic device precursor of claim 33, wherein the ion conducting layer has a thickness between about 5-100 nm.

35. An electrochromic device or an electrochromic device precursor according to claim 33, wherein the ion conductive 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 carbon oxynitride (LiSiCON) and combinations thereof.

36. An electrochromic material comprising (a) Tungsten; (b) Titanium; (c) molybdenum; and (d) oxygen, wherein the composition comprises the chemical formula W 1-x-y Ti x Mo y O z , wherein x is between about 0.05-0.25, y is between about 0.01-0.15, and z is between about 2.5-4.

5.

37. The electrochromic material of claim 36, wherein z is between approximately 2.5-3.

0.

38. The electrochromic material of claim 36, wherein z is between approximately 3.0-3.

5.

39. The electrochromic material of claim 36, wherein z is between approximately 3.5-4.

5.

40. The electrochromic material of claim 36, wherein z is greater than 3.

41. The electrochromic material of claim 36 provided in a layer having a thickness between about 50-2,000 nm.

42. The electrochromic material of claim 41, wherein the thickness is between about 200-700 nm.

43. The electrochromic material of claim 36, wherein the composition is formed by sputtering one or more sputtering targets.

44. The electrochromic material of claim 43, wherein the one or more sputtering targets comprise elemental metals, metal alloys, intermetallic mixtures, metal oxide materials, or combinations thereof.

45. The electrochromic material of claim 36, wherein the composition is amorphous.

46. ​​The electrochromic material of claim 36, wherein the composition is nanocrystalline.

47. The electrochromic material of claim 46, wherein the grain size is between about 5 nm and 50 nm.

48. The electrochromic material of claim 46, wherein the grain size is between about 10 nm and 100 nm.

49. The electrochromic material of claim 36, wherein the composition comprises one or more metal ions selected from the group consisting of lithium ions, hydrogen ions, deuterium ions, sodium ions, potassium ions, calcium ions, barium ions, strontium ions, and magnesium ions.

50. The electrochromic material of claim 36, wherein x is between about 0.08 and 0.12, and y is between about 0.02 and 0.

08.

51. An electrochromic device, comprising an electrochromic layer, wherein the electrochromic layer comprises the electrochromic material according to any one of claims 36 to 50.

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