Counter electrode for electrochromic device

Abstract

The invention relates to a counter electrode for an electrochromic device. Embodiments herein relate to electrochromic stacks, electrochromic devices, and methods and apparatus for making such stacks and devices. In various embodiments, an anodically colored layer in an electrochromic stack or device is fabricated to include a heterostructure, e.g., a heterogeneous composition and / or morphology. Such heterogeneous anodically colored layers may be used to better tune the properties of the device.

Description

[0001] This application is a divisional application of an application with a filing date of July 7, 2016, application number 202111168365.1, and invention name “Counter electrode for electrochromic device”. The application with application number 202111168365.1 is a divisional application of an application with a filing date of July 7, 2016, application number 201680047325.2, and invention name “Counter electrode for electrochromic device”. Technical Field

[0002] The present application relates to a counter electrode for an electrochromic device.

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] This application claims the benefit of priority to U.S. Provisional Patent Application No. 62 / 192,443, filed on July 14, 2015, and entitled “COUNTER ELECTRODE FOR ELECTROCHROMIC DEVICES,” which is incorporated herein by reference in its entirety and for all purposes. This application is a continuation-in-part of U.S. Patent Application No. 12 / 645,111, filed on December 22, 2009, and entitled “FABRICATION OF LOW DEFECTIVITY ELECTROCHROMIC DEVICES,” which claims the benefit of priority to U.S. Provisional Application No. 61 / 165,484, filed on March 31, 2009, and entitled “ALL-SOLID-STATE ELECTROCHROMIC DEVICE,” each of which is incorporated herein by reference in its entirety and for all purposes. This application is also a continuation-in-part of U.S. patent application No. 14 / 683,541, filed on April 10, 2015, and entitled “ELECTROCHROMIC DEVICES,” which is a continuation-in-part of U.S. patent application No. 13 / 462,725, filed on May 2, 2012, and entitled “ELECTROCHROMIC DEVICES,” now issued as U.S. Patent No. 9,261,751, which is a continuation-in-part of U.S. patent application No. 12 / 772,055, filed on April 30, 2010, and entitled “ELECTROCHROMIC DEVICES,” now issued as U.S. Patent No. 8,300,298; and U.S. Patent No. 11,673,979, filed on June 11, 2010, and entitled “ELECTROCHROMIC DEVICES.” No. 12 / 814,277, filed on June 11, 2010, entitled “ELECTROCHROMIC DEVICES” (now issued as U.S. Patent No. 8,764,950); and U.S. Patent Application No. 12 / 814,279, filed on June 11, 2010, entitled “ELECTROCHROMIC DEVICES” (now issued as U.S. Patent No. 8,764,951), each of which is incorporated herein by reference in its entirety and for all purposes.This application is also a continuation-in-part of PCT Application No. PCT / US15 / 61995, filed on November 20, 2015, and entitled “COUNTER ELECTRODE FOR EL ECTROCHROMIC DEVICES,” which claims the priority benefit of U.S. Provisional Patent Application No. 62 / 085,096, filed on November 26, 2014, and entitled “COUNTER ELECTRODE FOR ELE CTROCHROMIC DEVICES,” and U.S. Provisional Patent Application No. 62 / 192,443, filed on July 14, 2015, and entitled “COUNTER ELECTRO DE FORELECTROCHROMIC DEVICES,” which are also incorporated herein by reference in their entirety and for all purposes. This application is also a continuation-in-part of U.S. Patent Application No. 14 / 885,734, filed on October 16, 2015, and entitled “DEFECT-MITIGATION LAYERS IN ELECTROCHROMIC DEVICES,” which is a continuation-in-part of U.S. Patent Application No. 14 / 601,141, filed on January 20, 2015, and entitled “DEFECT-MITIGATION LAYERS IN ELECTROCHROMIC DEVICES,” now issued as U.S. Patent No. 9,229,291, which is a continuation-in-part of U.S. Patent Application No. 13 / 763,505, filed on February 8, 2013, and entitled “DEFECT-MITIGATION LAYERS IN ELECTROCHROMIC DEVICES,” now issued as U.S. Patent No. 9,007,674, which is a continuation-in-part of U.S. Patent Application No. 13 / 763,505, filed on February 8, 2013, and entitled “DEFECT-MITIGATION LAYERS IN ELECTROCHROMIC DEVICES,” now issued as U.S. Patent No. 9,007,674, which is a continuation-in-part of U.S. Patent Application No. 13 / 763,505, filed on February 8, 2013, and entitled “DEFECT-MITIGATION LAYERS IN ELECTROCHROMIC DEVICES,” now issued as U.S. Patent No. 9,007,674, DE VICE FABRICATION”, which claims the benefit of priority to U.S. Provisional Patent Application No. 61 / 541,999, filed on September 30, 2011, and entitled “OPTICAL DEVICE FABRICATION”, each of which is incorporated herein by reference in its entirety and for all purposes. Background of the Invention

[0006] Electrochromism is the phenomenon in which a material exhibits a reversible electrochemically mediated change in an optical property when placed in a different electronic state (usually as a result of being subjected to a voltage change). The optical property is typically one or more of color, transmittance, absorptivity, and reflectivity. A well-known electrochromic material, for example, is tungsten oxide (WO 3 ). Tungsten oxide is a cathode electrochromic material that undergoes a color change that allows blue light to pass through it through electrochemical reduction.

[0007] Electrochromic materials can be incorporated into, for example, windows and mirrors. The color, transmittance, absorptivity, and / or reflectivity of such windows and mirrors can be changed by inducing changes in the electrochromic material. One well-known application of electrochromic materials is, for example, rearview mirrors in some cars. In these electrochromic rearview mirrors, the reflectivity of the mirror changes at night so that the headlights of other vehicles do not distract the driver.

[0008] Although electrochromism was discovered in the 1960s, electrochromic devices have historically encountered a variety of problems that have prevented the technology from realizing its enormous commercial potential. Summary of the invention

[0009] Embodiments herein relate to electrochromic materials, electrochromic stacks, electrochromic devices, and methods and apparatus for making such materials, stacks, and devices. In various embodiments, the counter electrode material may have a heterogeneous composition. In some cases, the counter electrode may be deposited to include multiple sublayers, which may have different compositions and / or morphologies. In these or other cases, the counter electrode may be deposited to include a composition gradient. The gradient, if present, is typically in a direction perpendicular to the plane of the counter electrode. In various embodiments, the composition is heterogeneous with respect to the concentration of one or more metals in the counter electrode material. The composition gradient may extend over the entire thickness of the counter electrode or over only a portion (e.g., sublayer) of the counter electrode.

[0010] In one aspect of the disclosed embodiment, an electrochromic device is provided, comprising: a substrate; an electrochromic layer disposed on or above the substrate, the electrochromic layer comprising a cathode-dying electrochromic material; and a counter electrode layer also disposed on or above the substrate, the counter electrode layer comprising (a) a first sublayer comprising a first anode-dying material, and (b) a second sublayer comprising a second anode-dying material, wherein the first and second anode-dying materials have different compositions but each comprises an oxide of at least one transition metal, and wherein the first sublayer is disposed between the electrochromic layer and the second sublayer.

[0011] In certain implementations, each of the first and second anodic dyeing materials may include the at least one transition metal and another non-alkali metal. In some such implementations, the first and second anodic dyeing materials may each include nickel and tungsten. The second anodic dyeing material may further include tantalum. The second anodic dyeing material may further include niobium. The second anodic dyeing material may further include tin. In some embodiments, the second anodic dyeing material may include the at least one transition metal, the other non-alkali metals and the second non-alkali metal, wherein the first anodic dyeing material contains the at least one transition metal and the other non-alkali metals as its only metal. In certain cases, the first and second anodic dyeing materials may each include the at least one transition metal, the other non-alkali metals and the second non-alkali metal, wherein the second anodic dyeing material has a higher atomic concentration of the second non-alkali metal compared to the first anodic dyeing material.

[0012] The at least one transition metal may be selected from the group consisting of tungsten (W), tantalum (Ta), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), rhodium (Rh), ruthenium (Ru), vanadium (V), iridium (Ir), and combinations thereof. The other non-alkali metals may be selected from the group consisting of silver (Ag), aluminum (Al), arsenic (As), gold (Au), boron (B), barium (Ba), beryllium (Be), bismuth (Bi), calcium (Ca), cadmium (Cd), cerium (Ce), cobalt (Co), chromium (Cr), copper (Cu), europium (Eu), iron (Fe), gallium (Ga), gadolinium (Gd), germanium (Ge), hafnium (Hf), mercury (Hg), indium (In), iridium (Ir), lanthanum (La), magnesium (Mg), manganese (Mn), molybdenum (Mo), niobium (Nb), neodymium (Nd) , osmium (Os), protactinium (Pa), lead (Pb), palladium (Pd), praseodymium (Pr), promethium (Pm), polonium (Po), platinum (Pt), radium (Ra), rhenium (Re), rhodium (Rh), ruthenium (Ru), antimony (Sb), scandium (Sc), selenium (Se), silicon (Si), samarium (Sm), tin (Sn), strontium (Sr), tantalum (Ta), terbium (Tb), technetium (Tc), tellurium (Te), thorium (Th), titanium (Ti), thallium (Tl), uranium (U), vanadium (V), tungsten (W), yttrium (Y), zinc (Zn), zirconium (Zr), and combinations thereof. In certain embodiments, the other non-alkali metals may be selected from the group consisting of silver (Ag), arsenic (As), gold (Au), boron (B), cadmium (Cd), copper (Cu), europium (Eu), gallium (Ga), gadolinium (Gd), germanium (Ge), mercury (Hg), osmium (Os), lead (Pb), palladium (Pd), promethium (Pm), polonium (Po), platinum (Pt), radium (Ra), terbium (Tb), technetium (Tc), thorium (Th), thallium (Tl), and combinations thereof. In some cases, the other non-alkali metals may be selected from the group consisting of tantalum (Ta), tin (Sn), and niobium (Nb). In a specific example, the other non-alkali metal is tantalum (Ta). In another example, the other non-alkali metal is tin (Sn). In another example, the other non-alkali metal is niobium (Nb).

[0013] In some embodiments, the first and second anodic dyeing materials may each include a first transition metal, a second transition metal, and oxygen, wherein the ratio of the first transition metal to the second transition metal is different in the first and second anodic dyeing materials. In these or other embodiments, the counter electrode layer may further include a third sublayer, the third sublayer including a third anodic dyeing electrochromic material, wherein the first, second, and third anodic dyeing materials have different compositions but each include the at least one transition metal, and wherein the second sublayer is disposed between the first sublayer and the third sublayer. The first anodic dyeing material may include the at least one transition metal, the second transition metal, but no other transition metals, and include oxygen; the second anodic dyeing material may include the at least one transition metal, the second transition metal, the third transition metal, and oxygen; and the third anodic dyeing material may include the at least one transition metal, the second metal, the third transition metal, and oxygen, and the second and third anodic dyeing materials may have different concentrations of the third transition metal. In certain implementations, the first and second sublayers of the counter electrode layer may be in physical contact with each other. In some cases, the first and second sublayers of the counter electrode layer may be separated from each other by a defect mitigation insulating layer having a thickness of about 1×10 10 Ohm-cm vs. 5×10 10 Resistivity between ohms-cm. In various embodiments, the first anodically coloring material has a first affinity for lithium and the second anodically coloring material has a second affinity for lithium, wherein the first affinity for lithium and the second affinity for lithium can be different.

[0014] The electrochromic device can have specific visual properties. In some embodiments, when the electrochromic device is in its clearest state, the transmission b* value of the electrochromic device can be about 14 or less. For example, when the electrochromic device is in its clearest state, the transmission b* value of the electrochromic device can be about 10 or less. When the electrochromic device is in its clearest state, the visible light transmittance of the electrochromic device can be at least about 55%.

[0015] The counter electrode layer may have a specific total thickness. In some embodiments, the counter electrode layer may have a total thickness between about 50 nm and about 650 nm, such as between about 100 nm and about 400 nm, or between about 150 nm and about 300 nm. The first and second sublayers of the counter electrode layer may each have a morphology that is a mixture of an amorphous phase and a nanocrystalline phase having nanocrystals with a diameter less than about 50 nm. In some cases, the second sublayer may have a morphology of about 1×10 10 Ohm-cm vs. 5×1010 The defect mitigating insulating layer has a resistivity between ohms-cm. The electrochromic device may further include a transparent conductive layer disposed on or above the electrochromic layer and the counter electrode layer. The transparent conductive layer may include doped indium oxide.

[0016] In some embodiments, at least one of the first and second anodic dyeing materials may include nickel, aluminum and oxygen. In an example, the first anodic dyeing material includes nickel, tungsten and oxygen, and the second anodic dyeing material includes nickel, aluminum and oxygen. In certain embodiments, at least one of the first and second anodic dyeing materials includes nickel, silicon and oxygen. For example, the first anodic dyeing material may include nickel, tungsten and oxygen, and the second anodic dyeing material may include nickel, silicon and oxygen.

[0017] In another aspect of the disclosed embodiment, an electrochromic device is provided, comprising: a substrate; an electrochromic layer disposed on or over the substrate, the electrochromic layer comprising a cathode-dyed electrochromic material; and an anodically-dyed counter electrode layer also disposed on or over the substrate, the counter electrode layer comprising (a) a first sublayer comprising a first nickel-tungsten oxide composition, and (b) a second sublayer comprising a second nickel-tungsten oxide composition, wherein the first and second nickel-tungsten oxide compositions have different relative amounts of nickel and / or tungsten, and wherein the first sublayer is disposed between the electrochromic layer and the second sublayer.

[0018] In certain implementations, the second nickel tungsten oxide composition may further include tantalum, niobium, tin, or a combination thereof. In one example, the second nickel tungsten oxide composition includes tantalum. In another example, the second nickel tungsten oxide composition includes niobium. In another example, the second nickel tungsten oxide composition includes tin. In many embodiments, the first nickel tungsten oxide composition may further include tantalum, wherein the second nickel tungsten oxide composition includes a higher tantalum concentration than the first nickel tungsten oxide composition. The first nickel tungsten oxide composition may further include tantalum, and the second nickel tungsten oxide composition may include a higher niobium concentration than the first nickel tungsten oxide composition. In some cases, the first nickel tungsten oxide composition may further include tin, and the second nickel tungsten oxide composition may include a higher tin concentration than the first nickel tungsten oxide composition.

[0019] The counter electrode layer may include a third sublayer. The third sublayer may include a third nickel tungsten oxide composition. The first, second and third nickel tungsten oxide compositions may have different relative amounts of nickel and / or tungsten. The second sublayer may be disposed between the first sublayer and the third sublayer. In some embodiments, the third nickel tungsten oxide composition may further include tantalum, niobium, tin or a combination thereof. In one example, the third nickel tungsten oxide composition includes tantalum. In another example, the third nickel tungsten oxide composition includes niobium. In another example, the third nickel tungsten oxide composition includes tin. In certain embodiments, the second and third nickel tungsten oxide compositions may each include tantalum, and the third nickel tungsten oxide composition may include a higher tantalum concentration than the second nickel tungsten oxide composition. In these or other embodiments, the second and third nickel tungsten oxide compositions may each include niobium, and the third nickel tungsten oxide composition may include a higher niobium concentration than the second nickel tungsten oxide composition. In some cases, the second and third nickel tungsten oxide compositions may each include tin, and the third nickel tungsten oxide composition may include a higher tin concentration than the second nickel tungsten oxide composition. In some embodiments, the counter electrode layer may include a third sublayer, the third sublayer including a third nickel tungsten oxide composition, wherein the second nickel tungsten oxide composition further includes a metal M1, the third nickel tungsten oxide composition further includes a metal M2, and wherein the metals M1 and M2 may be different from each other. In some such cases, the second nickel tungsten oxide composition may be substantially free of metal M2, and the third nickel tungsten oxide composition may be substantially free of metal M1.

[0020] The first sublayer of the counter electrode layer may be a flash layer having a thickness between about 10 nm and about 80 nm. In some cases, the thickness of the flash layer may be more limited, such as between about 10 nm and about 50 nm, or between about 10 nm and about 30 nm. The first sublayer may have a specific resistivity, such as between about 1×10 10 Ohm-cm vs. 5×10 10 In some embodiments, each of the first and second sublayers of the counter electrode layer may have a thickness between about 20 nm and about 200 nm. In some such cases, the thickness of the first sublayer may differ from the thickness of the second sublayer by between about 50 nm and about 200 nm.

[0021] In certain implementations, the second nickel tungsten oxide composition may include between about 2% and 10% atomic tantalum, and the third nickel tungsten oxide composition may include between about 5% and 20% atomic tantalum. In certain embodiments, the first sublayer may consist essentially of nickel tungsten oxide, the second sublayer may consist essentially of nickel tungsten tantalum oxide having between about 2% and 10% atomic tantalum, and the third sublayer may consist essentially of nickel tungsten tantalum oxide having between about 5% and 20% atomic tantalum. For example, the nickel tungsten tantalum oxide in the second sublayer may have about 4% atomic tantalum, and the nickel tungsten tantalum oxide in the third sublayer may have about 8% atomic tantalum. In another example, the second nickel tungsten oxide composition may include between about 2% and 10% atomic niobium, and the third nickel tungsten oxide composition may include between about 5% and 20% atomic niobium. The first sublayer may consist essentially of nickel tungsten oxide, the second sublayer may consist essentially of nickel tungsten niobium oxide having between about 2% and 10% atomic niobium, and the third sublayer may consist essentially of nickel tungsten niobium oxide having between about 5% and 20% atomic niobium. For example, the nickel tungsten niobium oxide in the second sublayer may have about 4% atomic niobium, and the nickel tungsten niobium oxide in the third sublayer may have about 8% atomic niobium. In another embodiment, the second nickel tungsten oxide composition may include about 2% to 10% atomic tin, and the third nickel tungsten oxide composition may include about 5% to 20% atomic tin. The first sublayer may consist essentially of nickel tungsten oxide, the second sublayer may consist essentially of nickel tungsten tin oxide having between about 2% and 10% atomic tin, and the third sublayer may consist essentially of nickel tungsten tin oxide having between about 5% and 20% atomic tin. For example, the nickel tungsten tin oxide in the second sublayer may have about 4% atomic tin, and the nickel tungsten tin oxide in the third sublayer may have about 8% atomic tin.

[0022] In various embodiments, the second nickel tungsten oxide composition may further include a metal that is not present in the first nickel tungsten oxide composition. In certain implementations, at least one of the first and second sublayers of the counter electrode layer may include a graded composition. In many embodiments, the first and second sublayers of the counter electrode layer may each have a morphology that is a mixture of an amorphous phase and a nanocrystalline phase having nanocrystals with a diameter less than about 50 nm.

[0023] In another aspect of the disclosed embodiment, a method for making an electrochromic device is provided, the method comprising: depositing an electrochromic layer, the electrochromic layer comprising a cathodically coloring electrochromic material; depositing a counter electrode layer by the following operations: depositing a first anode coloring sublayer, and depositing a second anode coloring sublayer, wherein the first anode coloring sublayer is located between the electrochromic layer and the second anode coloring sublayer, and wherein the first and second anode coloring sublayers have different compositions and each comprises an oxide of at least one transition metal.

[0024] In certain implementations, the second anodic dyeing sublayer may include one or more metals that are not present in the first sublayer. For example, the second anodic dyeing sublayer may include tantalum, and the first anodic dyeing sublayer may not include tantalum. In various embodiments, the first anodic dyeing sublayer may be substantially free of tantalum. In some instances, the second anodic dyeing sublayer may include niobium, and the first anodic dyeing sublayer may not include niobium. In various embodiments, the first anodic dyeing sublayer may be substantially free of niobium. In certain implementations, the second anodic dyeing sublayer may include tin, and the first anodic dyeing sublayer may not include tin. In various embodiments, the first anodic dyeing sublayer may be substantially free of tin. In some implementations, the second anodic dyeing sublayer may include aluminum, and the first anodic dyeing sublayer may not include aluminum. The first anodic dyeing sublayer may be substantially free of aluminum. In these or other cases, the second anodic dyeing sublayer may include silicon, and the first anodic dyeing sublayer may not include silicon. The first anodic dyeing sublayer may be substantially free of silicon.

[0025] In certain embodiments, depositing the counter electrode layer may further include depositing a third anodic dyeing sublayer, the third anodic dyeing sublayer including an oxide of at least one transition metal, wherein the second anodic dyeing sublayer is located between the first and third anodic dyeing sublayers. In some such embodiments, the second and third anodic dyeing sublayers may each include a metal that is not present in the first anodic dyeing sublayer, and the atomic concentration of the metal that is not present in the first anodic dyeing layer is higher in the third anodic dyeing sublayer than in the second anodic dyeing sublayer. For example, the first anodic dyeing sublayer may consist essentially of nickel tungsten oxide, the second and third anodic dyeing sublayers may consist essentially of nickel tungsten tantalum oxide, and the concentration of tantalum may be higher in the third anodic dyeing sublayer than in the second anodic dyeing layer.

[0026] In some embodiments, different conditions can be used to deposit different sublayers. For example, the first anodized sublayer can be deposited at a higher deposition rate than the second anodized sublayer. In these or other cases, the first anodized sublayer can be deposited at a sputtering power lower than the sputtering power used to deposit the second anodized sublayer. In some embodiments, the first anodized sublayer can be deposited at a sputtering power of about 5 kW / m 2 Up to 20kW / m 2 The second sublayer may be deposited at a sputtering power of about 20 kW / m 2 Up to 45kW / m 2 In these or other implementations, the temperature of the partially fabricated electrochromic device is lower during deposition of the first anodically dyeing sublayer than during deposition of the second anodically dyeing sublayer.

[0027] The method may also include lithiation of one or more layers and / or sublayers. For example, the method may further include lithiation of the first anode dyeing sublayer prior to depositing the second anode dyeing sublayer. In one embodiment, the method further includes depositing lithium on the second anode dyeing sublayer, and then optionally depositing a third anode dyeing sublayer on the second anode dyeing sublayer. In another embodiment, the method further includes depositing a third anode dyeing sublayer on the second anode dyeing sublayer, and then depositing lithium on the third anode dyeing sublayer.

[0028] In another aspect of the disclosed embodiment, a method for making an electrochromic device is provided, the method comprising: depositing an electrochromic layer, the electrochromic layer comprising a cathode-coloring electrochromic material; depositing a counter electrode layer by: depositing a first anode dyeing sublayer, lithiating the first anode dyeing sublayer, and after lithiating the first anode dyeing layer, depositing a second anode dyeing sublayer, wherein the first anode dyeing layer is located between the electrochromic layer and the second anode dyeing sublayer, and wherein the first and second anode dyeing layers have different compositions and each comprises an oxide of at least one transition metal.

[0029] In another aspect of the disclosed embodiment, an apparatus for making an electrochromic device is provided, the apparatus comprising: (a) an integrated deposition system comprising: (i) a first deposition station comprising one or more first targets, the first targets being used to deposit a layer of electrochromic material on a substrate when the substrate is in the first deposition station, (ii) a second deposition station comprising one or more second targets, the second targets being used to deposit a first sublayer of a first pair of electrode material on the substrate when the substrate is in the second deposition station; (iii) a third deposition station comprising one or more third targets, the third targets being used to deposit a second sublayer of a second pair of electrode material on the substrate when the substrate is in the third deposition station, the second pair of electrode material having a different composition from the first pair of electrode material; and (b) a controller comprising executable program instructions for passing the substrate through the first, second and third deposition stations in a manner to sequentially deposit a stack on the substrate, the stack comprising the layer of electrochromic material, the first sublayer of the first pair of electrode material and the second sublayer of the second pair of electrode material.

[0030] In some embodiments, the one or more second targets and the one or more third targets may each include at least one pair of rotatable cylindrical targets. The controller may include executable instructions for depositing the first pair of electrode materials at a sputtering power lower than the sputtering power used to deposit the second pair of electrode materials. In some embodiments, the controller may include instructions for depositing the first pair of electrode materials at a sputtering power of about 10 kW / m 2 Up to 20kW / m 2 The first pair of electrode materials are deposited at a sputtering power of about 20 kW / m 2 Up to 45kW / m 2 The executable instructions are to deposit the second pair of electrode materials at a sputtering power between.

[0031] These and other features and advantages of the disclosed embodiments will be described in more detail below with reference to the associated drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The following detailed description may be more fully understood when considered in conjunction with the drawings, in which:

[0034] Figure 1 is a schematic cross-sectional view of an electrochromic device according to certain embodiments.

[0035] Figure 2 is a schematic cross-sectional view of an electrochromic device according to certain embodiments, wherein the counter electrode layer includes two sub-layers.

[0036] Figure 3is a schematic cross-sectional view of an electrochromic device according to certain embodiments, wherein the counter electrode layer includes three sub-layers.

[0037] Figures 4A-4I Shown are diagrams illustrating the composition of one or more layers in an electrochromic device according to various embodiments.

[0038] Figure 5 Depicted are methods of making an electrochromic stack that is part of an electrochromic device, according to certain embodiments.

[0039] Fig. 6A A rotating sputtering target according to certain embodiments is shown.

[0040] Figure 6B A top-down view of two rotating sputtering targets depositing material onto a substrate is shown in accordance with certain embodiments.

[0041] Figures 7A-7C Embodiments are directed to embodiments in which an auxiliary sputtering target is used to deposit material onto a primary sputtering target, which is then deposited onto a substrate, according to certain embodiments.

[0042] Figure 8 Hysteresis curves for the deposition of various optically switchable materials are shown.

[0043] Figures 9A-9E Various embodiments of integrated deposition systems are shown. DETAILED DESCRIPTION

[0044] Electrochromic device

[0045] A schematic cross-sectional view of an electrochromic device 100 according to some embodiments is shown in FIG. Figure 1In. The electrochromic device includes a substrate 102, a conductive layer (CL) 104, an electrochromic layer (EC) 106 (sometimes also referred to as a cathode coloring layer or an anode coloring layer), an ion conducting layer (IC) 108, a counter electrode layer (CE) 110 and a conductive layer (CL) 114. The counter electrode layer 110 can be an anode coloring / dying layer and is sometimes referred to as an "ion storage" layer because ions reside therein when the electrochromic device is not dyed. The counter electrode layer is sometimes referred to as an anode coloring / dying counter electrode layer in this article, or even as an anode coloring / dying electrochromic layer. When the counter electrode layer 110 is described as an "electrochromic" layer, it is understood that the counter electrode layer is dyed when driven by an anode potential because ions are driven out of this layer, and alternatively, becomes clear and substantially transparent when driven by a cathode potential because ions are re-embedded. Elements 104, 106, 108, 110 and 114 are collectively referred to as an electrochromic stack 120. A voltage source 116 operable to apply a potential across the electrochromic stack 120 effects a transition of the electrochromic device from, for example, a clear state to a dyed state. In other embodiments, the order of the layers is reversed relative to the substrate. That is, the layers are in the following order: substrate, conductive layer, counter electrode layer, ion conducting layer, electrochromic material layer, conductive layer. The conductive layer is generally a transparent conductive layer, but in a reflective device the conductive layer may be reflective, such as a metal layer.

[0046] It should be understood that reference to transitions between a clear state and a dyed state is non-limiting and indicates only one example of many examples of electrochromic transitions that can be achieved. Unless otherwise specified herein, whenever a clear-dyed transition is mentioned, the corresponding device or process includes other optical state transitions, such as non-reflective-reflective, transparent-opaque, etc. In addition, the terms "clear" and "bleached" refer to optically neutral states, for example, undyed, transparent, or translucent. In addition, unless otherwise specified herein, the "color" or "hue" of the electrochromic transition is not limited to any particular wavelength or wavelength range. As will be appreciated by those skilled in the art, the selection of appropriate electrochromic materials and counter electrode materials controls the associated optical transitions. In various embodiments herein, the counter electrode is deposited to include heterogeneous compositions and / or morphologies. For example, in some cases, the counter electrode may include two or more sublayers having different compositions and / or morphologies. In these or other cases, the entire counter electrode or sublayers of the counter electrode may include a composition gradient. Although Figure 1 The counter electrode layer 110 is shown as comprising a single layer, but it is understood that various embodiments herein utilize counter electrode layers that are not homogeneous.

[0047] In certain embodiments, the electrochromic device reversibly cycles between a clear state and a dyed state. In the clear state, an electrical potential is applied to electrochromic stack 120 such that available ions in the stack that can cause electrochromic material 106 to be in the dyed state reside primarily in counter electrode 110. When the electrical potential on the electrochromic stack is reversed, ions are transported through ion conducting layer 108 to electrochromic material 106 and cause the material to enter the dyed state.

[0048] In certain embodiments, all materials that make up the electrochromic stack 120 are inorganic, solid (i.e., in a solid state), or inorganic and solid. Because organic materials tend to degrade over time, inorganic materials provide the advantage of a reliable electrochromic stack that can work over an extended period of time. The material in a solid state also provides the advantage that there is no often blockage and leakage problem like the material in a liquid state. Each layer in the electrochromic device is discussed in detail below. It should be understood that any one or more layers in the stack can contain a certain amount of organic material, but in many implementations, one or more of the layers contain little or no organic matter. The same situation can be applied to liquids that may be present in small amounts in one or more layers. It should also be understood that solid materials can be deposited or otherwise formed by a process using a liquid component, such as using certain processes of sol-gel or chemical vapor deposition.

[0049] See again Figure 1 , voltage source 116 is typically a low voltage power source and can be configured to work in conjunction with radiation sensors and other environmental sensors. Voltage source 116 can also be configured to interface with an energy management system (e.g., 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 combined with large areas of electrochromic devices (i.e., electrochromic windows) can dramatically reduce the energy consumption of a building.

[0050] Any material with suitable optical, electrical, thermal and mechanical properties can be used as substrate 102. Such substrates include, for example, glass, plastic and mirror materials. Suitable plastic substrates include, for example, acrylic plastics, polystyrene, polycarbonate, allyl diglycol carbonate, SAN (styrene acrylonitrile copolymer), poly (4-methyl-1-pentene), polyester, polyamide, etc. If a plastic substrate is used, a hard coating such as a diamond-like protective coating, a silica / silicone anti-abrasion coating, etc., as is well known in the field of plastic glass, is used to provide barrier protection and prevent abrasion of the plastic substrate. Suitable glass includes clear or stained soda-lime glass, including soda-lime float glass. The glass may be tempered or untempered. In some embodiments of the electrochromic device 100 in which glass (e.g., soda-lime glass) is used as substrate 102, there is a sodium diffusion barrier layer (not shown) between substrate 102 and conductive layer 104 to prevent sodium ions from diffusing from the glass into conductive layer 104. The substrate may also include alkali-free (e.g., sodium) molten glass, such as Gorilla Glass TM 、Willow Glass TM and similar commercial products from Corning Incorporated, Corning, NY If such alkali-free substrates are used, no diffusion barrier is required, but an optical tuning layer may be used between the substrate and the electrochromic device to optimize the color and reflective properties of, for example, a window.

[0051] In some embodiments, the optical transmittance (i.e., the ratio of transmitted radiation or spectrum to incident radiation or spectrum) of substrate 102 is about 40% to 95%, for example, about 90% to 92%. The substrate can be of any thickness as long as it has suitable mechanical properties to support electrochromic device 120. Although substrate 102 can be of any size, in some embodiments, it is about 0.01 mm to 10 mm thick, and in some cases between about 3 mm and 9 mm thick.

[0052] In some embodiments, 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 usually, but not necessarily, isolates the indoor environment from the outdoor environment. In certain embodiments, architectural glass is at least 20 inches by 20 inches, and can be larger, for example, as large as about 72 inches by 120 inches. Architectural glass is usually at least about 2mm thick. Architectural glass less than about 3.2mm thick cannot be tempered. In some embodiments of architectural glass as substrate, even after the electrochromic stack has been made on the substrate, the substrate can still be tempered. In some embodiments of architectural glass as substrate, the substrate is soda-lime glass from a tin bath float glass production line.

[0053] Conductive layer 104 is provided on the top of substrate 102. In certain 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. Typically, conductive layers 104 and 114 are transparent at least in the wavelength range in which electrochromicity is exhibited by the electrochromic layer. Transparent conductive oxides include metal oxides and metal oxides doped with one or more metals. Examples of such metal oxides and doped metal oxides include indium oxide, indium tin oxide, doped indium oxide, tin oxide, doped tin oxide, zinc oxide, aluminum zinc oxide, doped zinc oxide, ruthenium oxide, doped ruthenium oxide, etc.

[0054] Because oxides are commonly used for these layers, they are sometimes referred to as "transparent conductive oxide" (TCO) layers. The function of the conductive layer is to diffuse the potential provided by the voltage source 116 on the surface of the electrochromic stack 120 to the interior regions of the stack with little ohmic potential drop. Additional details and examples of TCO layers are provided in U.S. Patent Application No. 12 / 645,111, filed December 22, 2009, entitled "FABRICATION OF LOW DEFECTIVITY ELECTROCHROMIC DEVICES," which is incorporated herein by reference in its entirety.

[0055] Cathodically colored layer 106 (also referred to as electrochromic layer 106) covers conductive layer 104. In certain embodiments, electrochromic layer 106 is inorganic and / or solid, and in typical embodiments is inorganic and solid. The electrochromic layer can contain any one or more of a number of different cathodically colored electrochromic materials, including metal oxides. Such metal oxides include tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), niobium oxide (Nb 2 O 5 ), titanium oxide (TiO 2 ), vanadium oxide (V 2 O 5 ), Tantalum Oxide (Ta 2 O 5) and so on. In some embodiments, the metal oxide is doped with one or more dopants, such as lithium, sodium, potassium, molybdenum, vanadium, titanium, and / or other suitable metals or metal-containing compounds. In certain embodiments, mixed oxides (e.g., W-Mo oxides, W-V oxides) are also used. The cathodically coloring electrochromic layer 106 including the metal oxide is capable of receiving ions transferred from the anodically coloring counter electrode layer 110. Other details regarding the cathodically coloring electrochromic layer are provided in U.S. Patent Application No. 12,645,111 incorporated herein by reference above.

[0056] Generally, in cathodically coloring electrochromic materials, the coloring / staining of the electrochromic material (or any change in optical properties - e.g., absorbance, reflectance, and transmittance) is caused by reversible ion insertion (e.g., intercalation) into the material and the corresponding injection of charge-balancing electrons. Typically, a portion of the ions responsible for the optical transition are irreversibly bound within the electrochromic material. As explained below, some or all of the irreversibly bound ions are used to compensate for "blind charges" in the material. In most electrochromic materials, suitable ions include lithium ions (Li + ) and hydrogen ions (H + ) (i.e., protons). However, in some cases, other ions will be suitable. These ions include (e.g.) deuterium ions (D + ), sodium ions (Na + ), potassium ions (K + ), calcium ions (Ca ++ ), barium ions (Ba ++ ), strontium ions (Sr ++ ), and magnesium ions (Mg ++ ). In the various embodiments described herein, lithium ions are used to produce the electrochromic phenomenon. The intercalation of lithium ions into tungsten oxide (WO 3-y (0 < y ≤ ~0.3)) causes the tungsten oxide to change from transparent (clear state) to blue (stained state).

[0057] Referring again to Figure 1 , in the electrochromic stack 120, the ion-conducting layer 108 covers the electrochromic layer 106. In certain embodiments, during the deposition of the layers in the stack, this ion-conducting layer 108 is omitted, and the cathodically coloring electrochromic layer 106 is deposited to be in direct physical contact with the anodically coloring counter electrode layer 110. The interface region where the cathodically coloring electrochromic layer 106 meets the anodically coloring counter electrode layer 110 can be formed due to specific processing steps, thereby allowing the interface region to serve as the ion-conducting layer in the finished device.

[0058] The ion conducting layer 108 serves as a medium through which ions are transported (in the form of an electrolyte) when the electrochromic device transitions between the clear state and the dyed state. In various cases, the ion conducting layer 108 is highly conductive to the relevant ions for 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 (sometimes also referred to as ion conductor layers) with high ionic conductivity permit rapid ion conduction and therefore allow rapid switching to achieve high performance electrochromic devices. In certain embodiments, the ion conducting layer 108 is inorganic and / or solid. When made from 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 implementations, the ion conductor material has a thickness of about 10 8 Siemens / cm or Ohm -1 cm -1 With about 10 9 Siemens / cm or Ohm -1 cm -1 The ionic conductivity is between 10 11 Resistivity in ohms-cm.

[0059] In other embodiments, the ion conductor layer can be omitted. In such embodiments, when forming an electrochromic stack for an electrochromic device, a separate ion conductor material is not deposited. Instead, in these embodiments, a cathode coloring electrochromic material can be deposited to make it in direct physical contact with an anodically coloring counter electrode material. One or both of the anodically coloring and cathode coloring materials can be deposited to include a portion that is oxygen-rich compared to the rest of the material.

[0060] Typically, the oxygen-rich portion is in contact with other types of layers. For example, the electrochromic stack may include an anode coloring material in contact with a cathode coloring material, wherein the cathode coloring material includes an oxygen-rich portion in direct physical contact with the anode coloring material. In another example, the electrochromic stack includes an anode coloring material in contact with a cathode coloring material, wherein the anode coloring material includes an oxygen-rich portion in direct physical contact with the cathode coloring material. In another example, the anode coloring material and the cathode coloring material include an oxygen-rich portion, wherein the oxygen-rich portion of the cathode coloring material is in direct physical contact with the oxygen-rich portion of the anode coloring material.

[0061] The oxygen-rich portions of these layers can be provided as different sublayers (e.g., the cathode or anode coloring material includes an oxygen-rich sublayer and a less oxygen-rich sublayer). The oxygen-rich portions of the layers can also be provided in graded layers (e.g., the cathode or anode coloring material can include a gradient of oxygen concentration, the gradient being along a direction perpendicular to the surface of the layer). Embodiments in which the ion conductor layer is omitted and the anode coloring counter electrode material is in direct contact with the cathode coloring electrochromic material are further discussed in the following U.S. patents, each of which is incorporated herein by reference in its entirety: U.S. Patent No. 8,300,298 and U.S. Patent No. 8,764,950.

[0062] On the top of ion conducting layer 108 (when present), an anode coloring layer 110 (also referred to as counter electrode layer 110) is provided. In various embodiments herein, the counter electrode layer is deposited to include a heterogeneous structure. In terms of composition and / or morphology, the structure can be heterogeneous. Other details of the disclosed counter electrode structure and composition are provided below. In some embodiments, the counter electrode layer 110 is inorganic and / or solid. The counter electrode layer can include one or more of many different materials, which can be used as a reservoir of ions when the electrochromic device is in a clear state. During the electrochromic transition initiated by (for example) applying an appropriate potential, the anode coloring counter electrode layer transfers some or all of the ions it retains to the cathode coloring electrochromic layer, thereby changing the electrochromic layer to a dyed state. At the same time, the counter electrode layer is dyed because of the loss of ions.

[0063] In various embodiments, one or more defect mitigation insulating layers (DMILs) may be provided. Such DMILs may be provided at Figure 1 In some specific embodiments, the DMIL can be disposed between sublayers of the counter electrode layer, but the DMIL can also be disposed at alternative or additional locations. The DMIL can help minimize the risk of making a defective device. In certain embodiments, the insulating layer has a thickness of about 1×10 10 Ohm-cm vs. 5×10 10The insulating layer may have a resistivity between 100 and 200 ohms-cm. In certain embodiments, the insulating layer contains one or more of the following metal oxides: cerium oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, silicon aluminum oxide, tungsten oxide, nickel tungsten oxide, tantalum oxide, and oxidized indium tin oxide. In certain embodiments, the insulating layer contains a nitride, carbide, oxynitride, or oxycarbide, such as a nitride, carbide, oxynitride, or oxycarbide analog of the listed oxides. As an example, the insulating layer includes one or more of the following metal nitrides: titanium nitride, aluminum nitride, silicon nitride, and tungsten nitride. The insulating layer may also contain a mixture or other combination of oxide and nitride materials (e.g., silicon oxynitride). DMIL is further described in U.S. Patent No. 9,007,674, which is incorporated by reference above.

[0064] The electrochromic devices in the embodiments herein are also scalable to accommodate substrates smaller or larger than architectural glass. The electrochromic stack can be deposited on substrates having a wide range of sizes, up to about 12 inches by 12 inches, or even 80 inches by 120 inches.

[0065] In some embodiments, electrochromic glass is integrated into an insulating glass unit (IGU). An insulating glass unit is composed of a plurality of glass window panels assembled into a unit, generally in the hope of maximizing the insulating properties of the gas contained in the space formed by the unit while providing clear vision through the unit. In addition to the electrical leads for connecting the electrochromic glass to a voltage source, the insulating glass unit incorporating the electrochromic glass will be similar to the insulating glass unit currently known in the art. Due to the higher temperatures that the electrochromic insulating glass unit may experience (due to the absorption of radiant energy by the electrochromic glass), a sealant that is more durable than the sealant used in a conventional insulating glass unit may be necessary. For example, stainless steel spacers, high temperature polyisobutylene (PIB), new secondary sealants, foil-coated PIB tapes for spacer seams, and the like. In some cases, the electrochromic glass can be incorporated into a laminate; the laminate can be constructed separately or incorporated into the IGU as one of the window panels of the IGU.

[0066] Counter electrode layer

[0067] In many embodiments herein, the anodically colored counter electrode layer is heterogeneous in composition or physical characteristics such as morphology. Such heterogeneous counter electrode layers can exhibit improved color, switching behavior, service life, uniformity, process window, etc.

[0068] In certain embodiments, the electrode layer includes two or more sublayers, wherein the sublayers have different compositions and / or morphologies. One or more of such sublayers may also have a graded composition. Composition and / or morphological gradients may have any form of transition, including linear transition, inverse transition, Gaussian transition, etc. Many advantages may be achieved by providing the electrode as two or more sublayers. For example, the sublayers may be different materials with complementary properties. A material may promote better color quality, while another material promotes high-quality, long-life switching behavior. The combination of materials may promote high-degree film quality and uniformity while achieving high-rate deposition (and therefore high throughput). Some of the methods outlined herein may also promote better control of lithium distribution in electrochromic devices, and in some cases may result in improvements in the morphology of the electrode (e.g., higher transmission) and overall reduction of defects in the electrochromic device. Another benefit that may be caused by various embodiments herein is the availability of one or more intermediate states. The difference in potential between the various sublayers can allow lithium to reside in discrete locations (e.g., within a particular sublayer to a certain extent), thereby enabling the electrochromic device to achieve intermediate dyeing states between, for example, a fully dyed device and a fully clear device. In some cases, the intermediate states can be achieved by applying different voltages to the device. Including multiple sublayers within the counter electrode layer can reduce or eliminate the need to apply different voltages to achieve different intermediate dyeing states. These and other benefits of the disclosed embodiments are further described below.

[0069] In some cases, the electrode includes the first sublayer of the first anode coloring electrode material and one or more additional sublayers of the second anode coloring electrode material. In various cases, the first sublayer of the CE layer can be in a position closer to the cathode coloring electrochromic material than the second (and optional additional) sublayer of the CE layer. In some implementations, the first sublayer is a flash coating, which is generally characterized as a thin and generally fast-deposited layer, which generally has a thickness of not more than about 100nm, not more than about 80nm in various cases. The flash coating can be between about 5nm thick and about 100nm thick, between about 10nm thick and about 80nm thick, or between about 10nm thick and about 50nm thick, or between about 10nm thick and about 30nm thick. In some other cases, a separate flash coating (which can be an anode coloring electrode material) can be set between the electrochromic layer and the first sublayer of the electrode. In some embodiments, the flash coating can be set between the second sublayer and the transparent conductor layer. The flash layer, if present, may or may not exhibit electrochromic properties. In certain embodiments, the flash layer is made of a counter electrode material that does not change color with the rest of the electrochromic / counter electrode layer (although this layer may have a composition very similar to other layers, such as the anodically colored layer). In some embodiments, the first sublayer (which is or is thicker than the flash layer) has a relatively high resistivity, for example, about 1×10 10 Ohm-cm vs. 5×10 10 Between ohm-cm.

[0070] In general, the first and second anode coloring to electrode materials can be any anode coloring to electrode material independently of one another. The first and / or second to electrode material can be a binary metal oxide (for example, in addition to lithium or other transported ions also including the oxide of two metals, NiWO is an example), a ternary metal oxide (for example, including the oxide of three kinds of metals, NiWTaO is an example) or even more complicated material. In many cases, the material also includes lithium, which can move in the device to a certain extent. The specific example of anode coloring to electrode material is provided hereinafter. As used in this article, the term metal is intended to include metal and nonmetal (for example, B, Si, Ge, As, Sb, Te and Po).

[0071] In some embodiments, the first anodizing material may include at least one transition metal selected from the group consisting of chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), rhodium (Rh), ruthenium (Ru), vanadium (V), and iridium (Ir). In addition to one or more of the transition metals just listed, the first anodizing material may include at least one or more additional metals (in many cases, at least one non-alkali metal). In some embodiments, the additional metal may be selected from the group consisting of silver (Ag), aluminum (Al), arsenic (As), gold (Au), barium (Ba), beryllium (Be), bismuth (Bi), calcium (Ca), cadmium (Cd), cerium (Ce), cobalt (Co), chromium (Cr), copper (Cu), europium (Eu), iron (Fe), gallium (Ga), gadolinium (Gd), germanium (Ge), hafnium (Hf), mercury (Hg), indium (In), iridium (Ir), lanthanum (La), magnesium (Mg), manganese (Mn), molybdenum (Mo), niobium (Nb), neodymium (Nd), ), osmium (Os), protactinium (Pa), lead (Pb), palladium (Pd), praseodymium (Pr), promethium (Pm), polonium (Po), platinum (Pt), radium (Ra), rhenium (Re), rhodium (Rh), ruthenium (Ru), antimony (Sb), scandium (Sc), selenium (Se), silicon (Si), samarium (Sm), tin (Sn), strontium (Sr), tantalum (Ta), terbium (Tb), technetium (Tc), tellurium (Te), thorium (Th), titanium (Ti), thallium (Tl), uranium (U), vanadium (V), tungsten (W), yttrium (Y), zinc (Zn), zirconium (Zr), and combinations thereof.

[0072] In these or other embodiments, the second anode coloring material can be a first anode coloring material doped with one or more additional elements or otherwise combined with one or more additional elements. In various cases, the additional elements can include at least one non-alkali metal. In some embodiments, the one or more additional elements are selected from the group consisting of silver (Ag), aluminum (Al), arsenic (As), gold (Au), barium (Ba), beryllium (Be), bismuth (Bi), calcium (Ca), cadmium (Cd), cerium (Ce), cobalt (Co), chromium (Cr), copper (Cu), europium (Eu), iron (Fe), gallium (Ga), gadolinium (Gd), germanium (Ge), hafnium (Hf), mercury (Hg), indium (In), iridium (Ir), lanthanum (La), magnesium (Mg), manganese (Mn), molybdenum (Mo), niobium (Nb), neodymium ( In some embodiments, the additional element may include at least one element selected from the group consisting of tantalum, tin, niobium, zirconium, silicon, aluminum, and combinations thereof. In some embodiments, the additional element may include at least one element selected from the group consisting of tantalum, tin, niobium, zirconium, silicon, aluminum, and combinations thereof. Although the additional element may be a dopant in the second anode coloring material, this may not necessarily be the case. In some compositions, the additional element forms a compound or salt with other elements in the material.

[0073] In a particular example, the first anode coloring material is NiWO. In these or other examples, the second anode coloring material can be NiWO doped with or otherwise including an additional metal (e.g., non-alkali metal, transition metal, post-transition metal, or non-metal in some cases), wherein the additional metal is selected from the list presented above, wherein an example material is NiWTaO. Other examples of the second anode coloring material (wherein the first anode coloring material is NiWO) include but are not limited to NiWSnO, NiWNbO, NiWZrO, NiWAlO and NiWSiO. In some similar embodiments, the first anode coloring material can be NiWO, and the second anode coloring material can be nickel oxide doped with or otherwise including an additional metal (e.g., non-alkali metal, transition metal, post-transition metal, or non-metal in some cases), wherein the additional metal is selected from the list presented above. Example materials for the second anode coloring material include but are not limited to NiTaO, NiSnO, NiNbO, NiZrO, NiAlO, NiSiO and combinations thereof. In one example, the second anodically coloring material can be selected from the group consisting of NiTaO, NiSnO, NiNbO, NiAlO, NiSiO, and combinations thereof. In another example, the second anodically coloring material can be selected from the group consisting of NiAlO and NiSiO.

[0074] In some embodiments, the first and second anodizing materials contain the same elements, but in different proportions. For example, both materials can contain Ni, W and Ta, but two or three of the elements are present in different mass ratios or atomic ratios. The examples below further illustrate this selection.

[0075] In some other embodiments, the first and second sublayers can differ more significantly from each other in composition. For example, the first and second sublayers (and any additional sublayers) can each be any anodizing material, regardless of the composition of the other sublayers. As noted, additional examples of anodizing materials are provided below.

[0076] The two or more sub-layers may have different physical properties. In various cases, the material used in one or more of the sub-layers is a material that would not perform as well as the electrode material if not provided with a companion sub-layer (e.g., would exhibit poor color quality, poor lifetime performance, slow switching speed, slow deposition rate, etc.).

[0077] Figure 2A cross-sectional view of a deposited electrochromic stack according to an embodiment is provided. The stack includes transparent conductive oxide layers 204 and 214. A cathode coloring electrochromic layer 206 is in contact with the transparent conductive oxide layer 204. An anode coloring counter electrode layer 210 is in contact with the transparent conductive oxide layer 214, and the anode coloring counter electrode layer includes two sublayers 210a and 210b. The first sublayer 210a of the counter electrode is in contact with the electrochromic layer 206, and the second sublayer 210b is in contact with the transparent conductive oxide layer 214. In this embodiment, a separate ion conductor layer is not deposited (but an interface region that acts as an ion conductor layer can be formed in situ thereby, as described in more detail herein).

[0078] The first and second sublayers 210a and 210b of the anodizing electrode layer 210 can have different compositions and / or morphologies. In various examples, the second sublayer 210b includes at least one metal and / or metal oxide that is not present in the first sublayer 210a. In a specific example, the first sublayer 210a is NiWO, and the second sublayer 210b is NiWO (e.g., NiWTaO, NiWSnO, NiWNbO, NiWZrO, NiWAlO, NiWSiO, etc.) doped with another metal or otherwise combined with another metal. In another example, the first sublayer 210a is NiWO, and the second sublayer 210b is nickel oxide (NiO) (e.g., NiTaO, NiSnO, NiNbO, NiZrO, NiAlO, NiSiO, etc.) doped with another metal or otherwise combined with another metal. In another embodiment, the first and second sublayers 210a and 210b include the same element in different relative concentrations.

[0079] In some embodiments, the first sublayer 210a is a flash coating. Flash coatings are generally thin layers (and thus they are generally, but not necessarily, deposited relatively quickly). In some embodiments, the first sublayer of the anodically colored counter electrode is a flash coating that is between about 5 nm thick and about 100 nm thick, between about 10 nm thick and about 80 nm thick, between about 10 nm thick and about 50 nm thick, or between about 10 nm thick and about 30 nm thick.

[0080] The thickness of the flash layer (or other counter electrode sublayers that are not deposited as flash layers) can depend on the materials selected for the various sublayers. One consideration that may affect the maximum thickness of each sublayer is the color quality of each sublayer compared to the color quality of the remaining sublayers. In many cases, the remaining sublayers will have superior color performance (e.g., a less yellow clear state) compared to the first sublayer / flash layer. In a specific example, the NiWTaO sublayer has superior color performance compared to the NiWO sublayer (which can be deposited as a flash layer). Thus, it is desirable that the NiWO sublayer is relatively thin to achieve the desired overall color performance in the device, for example, a thin flash layer made of NiWO will have a color that is less yellow than a thicker NiWO layer.

[0081] A competing issue with the thickness of each sublayer is the relative deposition rates of the materials in the sublayers. In many embodiments, the first sublayer / flash layer can be a material that is deposited at a higher deposition rate than the materials of the remaining sublayers. Similarly, the first sublayer / flash layer can be deposited at a lower power than the remaining sublayers. These factors make it advantageous to use a relatively thick first sublayer, thereby achieving higher throughput and / or reducing the amount of power used. These issues are weighed against those described above to select an appropriate sublayer thickness.

[0082] In many embodiments, the remaining sublayers can be thicker than the first sublayer 210a. In certain embodiments where the counter electrode layer 210 includes two sublayers (e.g., 210a and 210b), the second sublayer 210b can be between about 20nm and about 300nm thick, such as between about 150nm and about 250nm thick, or between about 125nm and about 200nm thick.

[0083] In certain embodiments, the second sub-layer 210b is homogeneous in composition. Figure 4A The presented diagrams show that in a specific embodiment where the first sublayer is NiM1O and the second sublayer is compositionally homogeneous NiM1M2O Figure 2 Concentrations of various elements present in the first sublayer 210a and the second sublayer 210b are shown. The first sublayer 210a is labeled CE1, and the second sublayer 210b is labeled CE2. In this example, the first sublayer has a composition of about 25% nickel, about 8% M1, and about 66% oxygen, and the second sublayer has a composition of about 21% nickel, about 3% M1, about 68% oxygen, and about 8% M2. In various embodiments, M2 can be a metal.

[0084] In other embodiments, the second sublayer 210b may include a graded composition. The composition may be graded in terms of the relative concentration of the metals therein. For example, in some cases, the second sublayer 210b has a graded composition for metals that are not present in the first sublayer. In a specific example, the first sublayer is NiWO, and the second sublayer is NiWTaO, wherein the concentration of tantalum is graded in the second sublayer. The relative concentrations of the remaining elements (except tantalum) may be uniform in the second sublayer, or they may also vary in this sublayer. In a specific example, the concentration of oxygen may also be graded in the second sublayer 210b (and / or in the first sublayer 210a).

[0085] Figure 4B The presented diagram shows a specific embodiment of a graded layer in which the first sublayer is NiM1O and the second sublayer is NiM1M2O. Figure 2 The concentration of M2 present in the first sub-layer 210a and the second sub-layer 210b is shown. Figure 4A Similarly, the first sublayer 210a is labeled CE1, and the second sublayer is labeled CE2. In this example, the concentration of M2 increases across the thickness of the second sublayer to a value of about 15% (atomic) at the face of the second sublayer farthest from the EC layer. Other elements are omitted from the figure; however, in one embodiment, they substantially reflect the same as described above. Figure 4A or Figure 4D The composition described is adjusted as appropriate to accommodate the varying M2 concentration. In certain embodiments, the concentration of M2 decreases across the thickness of the second sublayer, that is, the concentration of M2 is highest at the face of the second sublayer closest to the EC layer and decreases, reaching a minimum concentration at the face of the second sublayer farthest from the EC layer. In yet another embodiment, the concentration of M2 is highest in the middle region across the thickness of the second sublayer, that is, the concentration of M2 is highest (for example) at the center of the second sublayer and decreases across the second sublayer toward the two faces of the second sublayer. In this embodiment, the concentration of M2 at the faces of the second sublayer is not necessarily the same.

[0086] In certain embodiments, the first and second sublayers can have compositions that are more different from each other. Figure 4C The presented diagram shows that in an embodiment where the first sublayer is NiM1O and the second sublayer is NiM2O Figure 2 The concentrations of various elements present in the first sublayer 210a and the second sublayer 210b are shown. In the specific case, M1 is tungsten and M2 is vanadium, but other metals and materials may also be used. Figure 4C The concentrations of oxygen and nickel are shown to remain constant in both sub-layers of the counter electrode layer, but this is not always the case. Figures 4A-4CThe specific compositions described are provided as examples only and are not intended to be limiting. Different materials and concentrations / compositions may also be used.

[0087] Figure 3 Shown with Figure 2 Additional examples of electrochromic stacks similar to the electrochromic stack shown in . Figure 3 The stack in FIG. 1 includes transparent conductive oxide layers 304 and 314, a cathode coloring electrochromic layer 306, and an anodically coloring counter electrode layer 311. Here, the counter electrode layer 311 is composed of three sublayers 311a-c. The first sublayer 311a can be as described above with respect to Figure 2 The flash layer described for the first sublayer 210a of the embodiment of the present invention. Each of the sublayers 311a-c may have a different composition. In some embodiments, the second sublayer 311b and the third sublayer 311c may include the same element in different relative concentrations. In another embodiment, all sublayers 311a-c include the same element in different relative concentrations. There may be an IC layer (not shown) between the electrochromic layer 306 and the counter electrode layer 311. Figure 3 middle).

[0088] In one example, first sublayer 311a is a first anodically coloring counter electrode material, and second sublayer 311b and third sublayer 311c are second anodically coloring counter electrode materials (each deposited at a different composition). The composition of second sublayer 311b and third sublayer 311c may be homogeneous within each sublayer.

[0089] Figure 4D The presented diagram shows the different compositions in the case where the first sublayer is NiM1O and the second and third sublayers are homogeneous NiM1M2O Figure 3 The concentration of M2 present in the first, second and third sub-layers 311a-c is shown. The first sub-layer is labeled CE1, the second sub-layer is labeled CE2, and the third sub-layer is labeled CE3. The other elements (M1, Ni and O) are Figure 4D In one embodiment, these elements substantially reflect the Figure 4A or Figure 4C The compositions described are adjusted as appropriate to accommodate varying concentrations of M2. In a related embodiment, the concentration of M2 may be lower in the third sublayer than in the second sublayer.

[0090] In other cases, the composition within one or more of the second sub-layer 311b and the third sub-layer 311c can be graded, such as with respect to the concentration of a metal (in some cases, a metal not present in the first sub-layer 311a). Figure 4EThe presented diagram shows that in the case where the first sublayer (CE1) is NiM1O, the second sublayer (CE2) is NiM1M2O with a graded composition of M2 and the third sublayer (CE3) is compositionally homogeneous NiM1M2O Figure 3 The concentration of M2 present in the first, second and third sub-layers 311a-c is shown. The other elements (M1, Ni and O) are removed from Figure 4E In one embodiment, these elements substantially reflect the Figure 4A or Figure 4C The compositions described are adjusted as appropriate to accommodate the varying M2 concentrations. In a related embodiment, the composition may be graded in the opposite direction. For example, the concentration of M2 may decrease in the second sublayer rather than increase (when moving from CE1 to CE3).

[0091] As noted, in some implementations, the second anode coloring pair electrode material can be the first pair electrode material with additional metal. In a particular embodiment, the concentration of this additional metal is lower in the second sublayer 311b and higher in the third sublayer 311c. In a particular example, the first sublayer 311a is NiWO, the second sublayer 311b is NiWTaO, the third sublayer 311c is NiWTaO, and the concentration of tantalum is higher in the third sublayer 311c than in the second sublayer 311b. In a similar example, the first sublayer 311a is NiWO, the second sublayer 311b and the third sublayer 311c are NiWSnO, and the concentration of tin is higher in the third sublayer 311c than in the second sublayer 311b. A variety of anode coloring materials and material combinations can be used. In different embodiments, the concentration of the additional metal can be higher in the second sublayer than in the third sublayer. For any number of sublayers, these trends (increasing or reducing the concentration of the additional metal) can continue.

[0092] See also Figure 2 In another example, the first sublayer 210a is NiWO, and the second sublayer 210b is NiAlO or NiWAlO. In another example, the first sublayer 210a is NiWO, and the second sublayer 210b is NiSiO or NiWSiO. Figure 3, in one example, the first sub-layer 311a is NiWO, the second sub-layer 311b is NiAlO, the third sub-layer 311c is NiAlO, and the concentration of aluminum in the third sub-layer 311c is higher (or lower) than that in the second sub-layer 311b. In another example, the first sub-layer 311a is NiWO, the second sub-layer 311b is NiSiO, the third sub-layer 311c is NiSiO, and the concentration of silicon in the third sub-layer 311c is higher (or lower) than that in the second sub-layer 311b. As noted above, for any number of sub-layers, the trend of the concentration of additional (or different) metals (e.g., aluminum or silicon in these examples) can continue.

[0093] In some cases, the concentration (atomic %) of the additional metal in the third sub-layer 311c is at least 1.2× the concentration of the additional metal in the second sub-layer 311b. For example, the concentration of the additional metal in the third sub-layer 311c can be at least about 1.5×, or at least about 2×, or at least about 2.5× the concentration of the additional metal in the second sub-layer 311b. In some embodiments, one or more additional metals not present in the first sub-layer 311a can be provided in the second and / or third sub-layers 311b / 311c. In some particular embodiments, the third sub-layer 311c can include another additional material (e.g., a metal or another element) not present in the first sub-layer 311a or the second sub-layer 311b.

[0094] To further illustrate the examples provided above, in one embodiment, the first sub-layer 311a can be NiWO (in any suitable composition), the second sub-layer 311b can be NiWTaO (having a composition with any suitable relative composition including about 7% (atomic) tantalum and nickel, tungsten, and oxygen), and the third sub-layer 311c can also be NiWTaO (having a composition with any suitable relative composition including about 14% (atomic) tantalum and nickel, tungsten, and oxygen). This example is shown in Figure 4D (where M1 is tungsten and M2 is tantalum). In a similar example, tantalum and / or tungsten can be replaced with different metals.

[0095] As mentioned, a variety of different materials can be provided for the first sub-layer. In various embodiments, the first sub-layer is NiM1O. In the case where the first sub-layer is NiM1O, it can be provided in any suitable composition. In certain implementations, the NiM1O sub-layer can have the composition Ni x M1 y O z , where 0.2 < x < 0.3, 0.02 < y < 0.1, and 0.5 < z < 0.75. In many implementations, M1 is tungsten (W), but the embodiments are not limited thereto. In the case where M1 is tungsten and the first sub-layer is NiWO, NIWO can have the composition Ni x Wy O z , where 0.2 < x < 0.3, 0.05 < y < 0.1 and 0.6 < z < 0.7.

[0096] Similarly, many different materials can be provided for the second (and optional additional) sublayer. As noted, these sublayers will generally include the materials of the first sublayer having additional metal (M2) and / or metal oxide. In the case where the first sublayer includes NiM1O and the second / additional sublayer includes NiM1M2O, the second / additional sublayer can have the composition Ni a M1 b M2 c O d , where 0.2 < a < 0.3, 0.05 < b < 0.1, 0.01 < c < 0.1 and 0.5 < d < 0.75. In many embodiments, the subscript c is lower in the sublayer closer to the electrochromic layer and higher in the sublayer farther from the electrochromic layer.

[0097] The thickness of the sublayer is generally determined by the total desired thickness of the CE layer and the number of sublayers used. The total desired thickness of the CE layer is at least partially determined by the desired charge capacity of the CE layer, and example thicknesses are provided below. In the case where the counter electrode layer is provided as three sublayers as shown in Figure 3 , the first sublayer 311a can be a relatively thin flash coating as described above. The second sublayer 311b and the third sublayer 311c can have any relative thickness. For example, the second sublayer 311b can be thinner than, thicker than, or approximately the same thickness as the third sublayer 311c.

[0098] In some embodiments, additional sublayers can be provided. The additional sublayers can be homogeneous in composition, or as described above, they can be graded. In various embodiments where such additional sublayers are provided, with respect to Figure 2 and Figure 3The trends described for the first, second, and third sublayers may also hold true in additional sublayers. In one example, the counter electrode is deposited to include four sublayers, wherein the first sublayer (positioned closest to the electrochromic layer) includes a first material (e.g., NiM1O), and the second, third, and fourth sublayers include a second material (e.g., NiM1M2O), the second material including an additional element (e.g., a metal) that is not present in the first sublayer. The concentration of this additional element may be higher in the sublayer farther from the electrochromic layer and lower in the sublayer closer to the electrochromic layer. As a specific example, the first sublayer (closest to the electrochromic layer) is NiWO, the second sublayer is NiWTaO with 3% (atomic) Ta, the third sublayer is NiWTaO with 7% (atomic) Ta, and the fourth sublayer (farthest from the electrochromic layer) is NiWTaO with 10% (atomic) Ta.

[0099] In yet another embodiment, the electrode can be arranged as a single layer, but the composition of the electrode layer can be hierarchical. The composition can be hierarchical with respect to one or more elements present in the material. In some embodiments, the electrode has a hierarchical composition with respect to one or more metals in the material. In these or other embodiments, the electrode can have a hierarchical composition with respect to one or more non-metals (e.g., oxygen). Figure 4F The presented graph shows the concentration of M2 present in the counter electrode layer in the case where the counter electrode is arranged as a single layer with graded composition. In this example, the composition is graded in terms of the metal (M2) therein. The other elements (Ni, M1, O) are removed from Figure 4F In one embodiment, these elements substantially reflect the Figure 4A or Figure 4C The compositions described are adjusted as appropriate to accommodate varying M2 compositions.

[0100] Without wishing to be bound by theory or mechanism of action, it is believed that the disclosed first sublayer can help protect the ion conducting layer and / or the electrochromic layer from damage due to excessive heating or other harsh conditions during deposition of the counter electrode layer. The first sublayer can be deposited under milder conditions than those used to deposit the remaining sublayers. For example, in some embodiments, the first sublayer can be deposited at about 5 kW / m 2 Up to 20kW / m 2 The first sub-layer is deposited with a sputtering power between 20 kW / m 2 Up to 45kW / m 2The second sublayer may be deposited using a sputtering power between 0.1 and 0.25 W. In a specific example where the first sublayer is NiWO and the second sublayer is NiWTaO, NiWTaO may be deposited using a sputtering power higher than that of NiWO. This high power process (if performed to deposit directly on the ion conducting layer and / or electrochromic layer) may in some implementations degrade the ion conducting layer and / or electrochromic layer, for example, due to overheating and premature crystallization of associated materials, and / or due to loss of oxygen in the ion conducting layer and / or electrochromic layer. However, in the case where a thin flash layer made of NiWO is provided as the first sublayer, this NiWO layer may be deposited under milder conditions. The NiWO sublayer may then protect the underlying ion conducting and / or electrochromic layer during deposition of a subsequent NiWTaO sublayer. This protection may result in a more reliable, better functioning electrochromic device.

[0101] In some embodiments, the electrochromic device includes a cathode-colored, tungsten oxide-based electrode layer; and an anodically colored, nickel oxide-based counter electrode layer; wherein the nickel oxide-based counter electrode layer includes at least a first sublayer and a second sublayer, each of the first and second sublayers of the counter electrode layer having a chemical formula Li a NeA x A y O z , wherein: a is 1 to 10; x is 0 to 1; y is 0 to 1; and z is at least 1; and wherein a, x, y, z and A are independently selected for each of the first and second sublayers of the counter electrode layer.

[0102] In some embodiments, for at least one of the first and second sublayers of the counter electrode layer, y may be greater than 0. In some examples, y may be zero in the first sublayer of the counter electrode layer and greater than zero in the second sublayer of the counter electrode layer. In these or other embodiments, for at least one of the first and second sublayers of the counter electrode layer, x may be greater than 0. For example, x may be greater than zero in the first sublayer of the counter electrode layer and zero in the second sublayer of the counter electrode layer.

[0103] In various embodiments, the first and second sublayers have different compositions. For each of the first and second sublayers of the counter electrode layer, A can be independently selected from the group consisting of silver (Ag), aluminum (Al), arsenic (As), gold (Au), boron (B), barium (Ba), beryllium (Be), bismuth (Bi), calcium (Ca), cadmium (Cd), cerium (Ce), cobalt (Co), chromium (Cr), copper (Cu), europium (Eu), iron (Fe), gallium (Ga), gadolinium (Gd), germanium (Ge), hafnium (Hf), mercury (Hg), indium (In), iridium (Ir), lanthanum (La), magnesium (Mg), manganese (Mn), molybdenum (Mo), niobium (Nb), and the like. In some embodiments, A can be a first metal in the first sublayer, a second metal in the second sublayer, and the first metal is different from the second metal. In some implementations, y can be zero in the first sublayer, so that the first sublayer is LiNiWO. In some embodiments, A in the first and / or second sublayer of the counter electrode layer may be selected from the group consisting of Ta, Nb, Sn, Al, and Si. In these or other embodiments, A in each of the first and second sublayers of the counter electrode layer may be selected from the group consisting of Ta, Nb, Sn, Al, and Si, wherein A in the first sublayer of the counter electrode layer is different from A in the second sublayer of the counter electrode layer. In some implementations, for at least one of the first and / or second sublayers of the counter electrode layer, y may be between about 0.1 and 1. In a specific embodiment, for each of the first and second sublayers of the counter electrode layer, y may be between about 0.1 and 1.

[0104] In some embodiments, the first sublayer of the electrode can be NiWO, and the second sublayer of the electrode can be a material selected from the group consisting of NiWTaO, NiWNbO, NiWSnO, NiWAlO, NiWSiO, NiTaO, NiNbO, NiSnO, NiAlO, NiSiO, and combinations thereof. In certain implementations, the second sublayer of the electrode can be a material selected from the group consisting of NiWTaO, NiWNbO, NiWSnO, NiWAlO, NiWSiO, and combinations thereof. The second sublayer of the electrode can be a material selected from the group consisting of NiTaO, NiNbO, NiSnO, NiAlO, NiSiO, and combinations thereof. In various implementations, the first and second sublayers of the electrode can each independently be selected from the group consisting of NiWO, NiWTaO, NiWNbO, NiWSnO, NiWAlO, NiWSiO, NiTaO, NiNbO, NiSnO, NiAlO, NiSiO, and combinations thereof, wherein the material of the first sublayer is different from the material of the second sublayer. In certain embodiments, the first and second sublayers of the counter electrode can each independently be selected from the group consisting of NiWO, NiWTaO, NiWNbO, NiWSnO, NiWAlO, NiWSiO, and combinations thereof, wherein the material of the first sublayer is different from the material of the second sublayer. In some cases, the first and second sublayers of the counter electrode can each independently be selected from the group consisting of NiWO, NiTaO, NiNbO, NiSnO, NiAlO, NiSiO, and combinations thereof, wherein the material of the first sublayer is different from the material of the second sublayer.

[0105] The disclosed embodiment can also show the improved performance produced by the morphology of higher quality and improved morphology control in the anodizing material.As described herein, the electrode material can be crystal, nanocrystal, amorphous or its certain combination.Usually it is desired that the crystallinity is relatively low, and it is desired that any crystal present is relatively small.By setting the electrode to two or more sublayers, one or more additional interfaces (for example, the interface where the sublayer contacts each other) are introduced in the electrode.These interfaces can destroy the formation of crystal, for example, due to nucleation again and related grain growth effect.This type of effect can be used to prevent crystal growth from being larger and limiting the size of any crystal formed.This effect to morphology may cause the device with less space or other defects to be produced.

[0106] Similarly, in the case where the counter electrode is deposited as one or more sublayers, the sublayers can be used to smooth out the bumps / pits / stripes in the underlying layer. In the case where the counter electrode layer is deposited as a single homogeneous layer in a single step, most of the bumps / pits / stripes present on the underlying layer (in some cases, the underlying layer can be derived from the substrate) are transferred to / through the counter electrode layer. In contrast, by depositing the counter electrode layer in several steps (e.g., using multiple sublayers), the sublayers can promote a smoother surface because the bumps / pits / stripes are less obvious with each additional layer deposited. Several benefits can be achieved by reducing the transfer of such surface non-uniformities through the layers of the device. For example, the airtightness can be improved, which leads to improved humidity control. Accordingly, the waiting time during production can be reduced, thereby increasing production volume.

[0107] Without wishing to be bound by theory or mechanism of action, it is also believed that the disclosed method can be used to achieve improved control of the distribution of lithium in an electrochromic device. Different counter electrode materials exhibit different affinities for lithium, so the selection of counter electrode materials affects how lithium ions are distributed in an electrochromic device. By selecting specific materials and material combinations, the distribution of lithium in the device can be controlled. In devices made without depositing a separate ion-conducting layer, the distribution of lithium in the device may be particularly important. In such embodiments, the distribution of lithium in the device may affect whether an ion-conducting / substantially electronically insulating region is formed in the interface region between the electrochromic layer and the counter electrode layer after depositing the electrochromic stack and further processing the stack. In certain embodiments, the sublayers of the counter electrode include materials with different affinities for lithium. For example, the material of the first sublayer may have a higher or lower affinity for lithium than the material of the second (or additional) sublayer of the counter electrode.

[0108] Accordingly, the disclosed methods can be used to achieve improved control of the total amount of lithium used to make an electrochromic device. In various cases, lithium can be added during the deposition of an electrode layer. In some embodiments, lithium can be added during the deposition of one or more sublayers of the electrode. In these or other embodiments, lithium can be added between the deposition of subsequent sublayers of the electrode. By controlling the distribution of lithium and the total amount of lithium within the electrochromic device, the uniformity and appearance of the device can be improved.

[0109] Another benefit that the disclosed technology can produce is improved color and switching performance. As mentioned above, some electrode materials show better performance in color (e.g., a clearer clear state, a more attractive dyed state, etc.), switching speed, service life, and other properties. However, some materials that promote high-quality results in one property may have disadvantages in other properties. For example, a material that is desired because it exhibits a very transparent and colorless clear state may encounter problems related to slow switching speeds and / or short service lives. By combining this material with another electrode material (which may have its own problems, such as a relatively yellow clear state), electrodes with improved properties can be achieved in various implementations. The disadvantages associated with a pair of electrode materials can be mitigated by the properties of another pair of electrode materials.

[0110] For example, in certain embodiments, the first sublayer / flash layer may be made of a material that has acceptable (but not uncommon) color quality in the clear state, and the second sublayer (and optional additional sublayers) may be made of a material that has excellent color quality in the clear state (compared to the material of the flash layer). Color quality may be assessed based on the a* and / or b* values ​​of the materials, with higher quality colors generally corresponding to a* and b* values ​​that are closer to zero, and lower quality colors generally corresponding to a* and b* values ​​that are farther from zero. In various embodiments, the a* and / or b* values ​​of the first and second sublayers (in their clearest state) may differ by at least about 6, or at least about 3. In these or other cases, the a* and / or b* values ​​of the first and second sublayers (in their clearest state) may differ by about 10 or less.

[0111] In some cases, the flash layer can be deposited at a relatively high rate using a low sputtering power, and the second sublayer can be deposited at a relatively low rate using a higher sputtering power. The first sublayer can help fabricate the device more quickly while also protecting the ion-conducting and / or electrochromic layer during formation of the counter electrode (e.g., by preventing the ion-conducting and / or electrochromic layer from being exposed to high temperatures generated during high sputtering power deposition of the second sublayer), and the second sublayer can help provide high quality color performance to the device.

[0112] In some cases, splitting the electrode into multiple layers can lead to improved reliability or reduced defectivity by adjusting the film stress in the film. The film stress in the electrode layer can improve or degrade the adhesion of the subsequent layers, which may affect the long-term reliability of the device when the device undergoes changes in voltage, temperature, humidity, ambient light, etc. Changes in film stress may also affect the appearance defects of the device. Particles present on the substrate before or during the deposition of the device may cause short circuits between electrode layers, which lead to local areas of reduced staining. Defect mitigation insulating layers (DMILs) can be used to reduce the occurrence of these short circuits, and some embodiments of the DMIL require manipulating the stress in the electrode to drive out particles before applying the DMIL. This situation is described in U.S. Patent Application No. 13 / 763,505, filed on February 8, 2013 and entitled "DEFECT-MITIGATION LAYERS IN ELECTROCHROMIC DEVICES". A multilayer counter electrode may incorporate an initial layer of high stress that may deform or dislodge particles, and a final layer of low stress that may fill in any open areas created by the dislodged particles.

[0113] In some embodiments, the anodic coloring counter electrode layer (or one or more sublayers herein) is a material including nickel, tungsten, tantalum and oxygen. The material can be provided as NiWTaO together in any appropriate composition (or in the combination / arrangement of the composition in the counter electrode). Materials based on nickel tungsten tantalum oxide are particularly beneficial as anodic coloring materials because they may be particularly clear or color neutral in a clear state. Many counter electrode materials are also slightly dyed (colored) even in their clear state. For example, NiWO generally has a light yellow color in a clear state. For aesthetic reasons, in various situations, the situation that is beneficial is that the cathode coloring and anodic coloring materials in the electrochromic device are very clear (transparent) and colorless when the device is in a clear state.

[0114] In addition, some electrode materials show good color quality (that is, very clear under their clear state), but are not suitable for commercial use, because the ability of the material to carry out rapid optical conversion weakens over time. In other words, for these materials, the duration of optical conversion increases with the age / use of device. In this case, the newly made window will show a switching speed higher than the same window used for (for example) six months. An example of an anode coloring electrode material showing good color quality but the speed of conversion decreases over time is nickel tantalum oxide (NiTaO). It has been shown that tungsten is included in this type of material and significantly reduces the reduction in switching speed over time. Thus, NiWTaO is a valuable candidate for one or more anode coloring electrode materials.

[0115] NiWTaO can have various compositions when used as an anode coloring material. In certain embodiments, a specific balance can be achieved between the various components of NiWTaO. For example, the Ni:(W+Ta) atomic ratio in the material can fall between about 1.5:1 and 3:1, such as between about 1.5:1 and 2.5:1, or between about 2:1 and 2.5:1. In a specific example, the Ni:(W+Ta) atomic ratio is between about 2:1 and 3:1. The Ni:(W+Ta) atomic ratio refers to the ratio of the sum of the number of tungsten and tantalum atoms in (i) the material and (ii) the material.

[0116] The NiWTaO material may also have a specific W:Ta atomic ratio. In certain embodiments, the W:Ta atomic ratio is between about 0.1:1 and 6:1, for example, between about 0.2:1 and 5:1, or between about 1:1 and 3:1, or between about 1.5:1 and 2.5:1, or between about 1.5:1 and 2:1. In some cases, the W:Ta atomic ratio is between about 0.2:1 and 1:1, or between about 1:1 and 2:1, or between about 2:1 and 3:1, or between about 3:1 and 4:1, or between about 4:1 and 5:1. In some implementations, specific Ni:(W+Ta) and W:Ta atomic ratios are used. All combinations of the disclosed Ni:(W+Ta) compositions and the disclosed W:Ta compositions are contemplated, but only certain combinations are explicitly listed herein. For example, the Ni:(W+Ta) atomic ratio may be between about 1.5:1 and 3:1, wherein the W:Ta atomic ratio is between about 1.5:1 and 3:1. In another example, the Ni:(W+Ta) atomic ratio may be between about 1.5:1 and 2.5:1, wherein the W:Ta atomic ratio is between about 1.5:1 and 2.5:1. In another example, the Ni:(W+Ta) atomic ratio may be between about 2:1 and 2.5:1, wherein the W:Ta atomic ratio 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.

[0117] Other exemplary materials for the counter electrode include, but are not limited to, nickel oxide, nickel tungsten oxide, nickel vanadium oxide, nickel chromium oxide, nickel aluminum oxide, nickel manganese oxide, nickel magnesium oxide, chromium oxide, iron oxide, cobalt oxide, rhodium oxide, iridium oxide, manganese oxide, Prussian blue. The materials (e.g., metal and oxygen) can be provided in different stoichiometric ratios as appropriate for a given application. In some other implementations, the counter electrode material may include a mixture of cerium titanium oxide, cerium zirconium oxide, nickel oxide, nickel tungsten oxide, vanadium oxide, and oxides (e.g., Ni 2 O 3 with WO 3Doped formulations of these oxides may also be used, wherein the dopants include, for example, tantalum and tungsten as well as the other elements listed above.

[0118] Because the anodically coloring counter electrode layer contains ions for producing electrochromic phenomena in the cathodically coloring electrochromic material when the cathodically coloring counter electrode is in a clear state, the anodically coloring counter electrode may have high transmittance and neutral color when the anodically coloring counter electrode retains a large amount of these ions.

[0119] When charge is removed from the anodically coloring counter electrode (ie ions are transported from the counter electrode to the electrochromic layer), the counter electrode layer will change from a (more or less) transparent state to a dyed state.

[0120] The morphology of the counter electrode layer or any one or more sublayers thereof can be crystalline, amorphous or a mixture thereof. The crystalline phase can be nanocrystalline. In some embodiments, the counter electrode material layer (or one or more sublayers thereof) is amorphous or substantially amorphous. It has been found that various substantially amorphous counter electrodes perform better under some conditions than their crystalline counterparts. The amorphous state of one or more counter electrode oxide materials can be obtained by using certain processing conditions described below. Although it is not desired to be bound by any theory or mechanism, it is believed that amorphous counter electrode materials such as nickel tungsten oxide or nickel tungsten tantalum oxide are produced by relatively low energy atoms in the sputtering process. For example, low energy atoms are obtained with lower target power, higher chamber pressure (i.e., lower vacuum) and / or larger source to substrate distance in the sputtering process. It is also more likely to form an amorphous film in which there is a relatively high portion / concentration of heavy atoms (e.g., W). Under the described process conditions, a film with better stability under UV / heat exposure is produced. Substantially amorphous materials can have some crystals, usually but not necessarily nanocrystalline materials dispersed in an amorphous matrix. The grain size and amount of such crystalline material are described in more detail below.

[0121] In some embodiments, the morphology of the electrode or any sublayer thereof can include microcrystals, nanocrystals and / or amorphous phases. For example, the electrode can be a material of an amorphous matrix with nanocrystals distributed therein, for example. In certain embodiments, the nanocrystals make up 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 (depending on the embodiment and by weight or by volume). In certain embodiments, the maximum diameter of the nanocrystals is less than about 50nm, in some cases less than about 25nm, less than about 10nm or less than about 5nm. In some cases, the average diameter of the nanocrystals is about 50nm or less, or about 10nm or less, or about 5nm or less (e.g., about 1nm to 10nm).

[0122] In certain embodiments, it is desirable to have a distribution of nanocrystal sizes wherein at least about 50% of the nanocrystals have diameters that are within 1 standard deviation of the average nanocrystal diameter, e.g., wherein at least about 75% of the nanocrystals have diameters that are within 1 standard deviation of the average nanocrystal diameter or wherein at least about 90% of the nanocrystals have diameters that are within 1 standard deviation of the average nanocrystal diameter.

[0123] It has been found that, compared with relatively more crystalline counter electrode materials, the counter electrode materials including amorphous matrix tend to work more efficiently. In certain embodiments, a kind of material / additive can form a host matrix, in which the crystalline domains of basic anode coloring materials 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 the basic anode coloring electrochromic material in the form of (for example) oxide. An example of the basic anode coloring electrochromic material in the form of oxide is nickel tungsten oxide. Additive can contribute to the formation of an amorphous host matrix that is not substantially crystalline, but the host matrix has merged the crystalline domains (for example, nanocrystals in some cases) of basic anode coloring electrochromic materials. An exemplary additive is tantalum. In other embodiments, additive and anode coloring basic material form chemical compounds together by covalent and / or ionic bonding. The compound can be crystalline, amorphous or its combination. In other embodiments, the anode coloring basic material forms a host matrix in which the crystalline domains of the additive exist in the form of discrete phases or capsules. For example, certain embodiments include an amorphous counter electrode having an amorphous matrix of a first material, wherein a second material (also amorphous) is distributed in the first material in the form of capsules (e.g., capsules of the diameter described herein for crystalline material distributed in the amorphous matrix).

[0124] In various embodiments, the sublayers within the counter electrode layer can have different crystallinity. For example, the first sublayer can be more crystalline, less crystalline, or approximately equally crystalline than the second (or additional) sublayer of the counter electrode. For example, the first sublayer can have an average grain size that is larger, smaller, or approximately equal to that of the second (or additional) sublayer. The first sublayer can also have more, less, or approximately the same proportion of crystalline material as the second (or additional) sublayer.

[0125] In some embodiments, the thickness of the counter electrode is about 50 nm to about 650 nm. In some embodiments, the thickness of the counter electrode is about 100 nm to about 400 nm, sometimes in the range of about 150 nm to 300 nm, or between about 200 nm to 300 nm. The thickness of the counter electrode layer is also substantially uniform. In one embodiment, the substantially uniform counter electrode layer varies only about 10 nm in each of the aforementioned thickness ranges. + In another embodiment, the substantially uniform counter electrode layer varies by only about 10% in each of the aforementioned thickness ranges. + In another embodiment, the substantially uniform counter electrode layer varies by only about 5% in each of the aforementioned thickness ranges. + 3%.

[0126] The amount of ions that are retained in the counter electrode layer during the clear state (and correspondingly in the electrochromic layer during the dyed state) and that can be used to drive the electrochromic transition depends on the composition of the layer as well as the thickness and fabrication method of the layer. The electrochromic layer and the counter electrode layer can support tens of millicoulombs of available charge (in the form of lithium ions and electrons) per square centimeter of layer surface area in the adjacent area. The charge capacity of the electrochromic film is the amount of charge per unit area and unit thickness of the film that can be reversibly loaded and unloaded by applying an external voltage or potential. In one embodiment, WO 3 The layer has about 30mC / cm 2 / micron and about 150mC / cm 2 In another embodiment, WO 3 The layer has about 50mC / cm 2 / micron and about 100mC / cm 2 In one embodiment, the counter electrode layer has a charge capacity of about 75 mC / cm 2 / micron and about 200mC / cm 2 In another embodiment, the counter electrode layer has a charge capacity of about 100 mC / cm 2 / micron and about 150mC / cm 2 / micron charge capacity.

[0127] When considering all layers / sublayers in the counter electrode layer and / or electrochromic device, the counter electrode layer and / or electrochromic device can have specific properties. For example, in some embodiments, when the counter electrode is in its clearest state (when the counter electrode is maintained at its maximum cathode potential and the ions are completely resident in the counter electrode layer of the device), the counter electrode will have a b* value between about 2 and 10 or between about 4 and 6. When the electrochromic device made according to the disclosed embodiments is in its clearest state, the device can have a b* value between about 6 and 14 or between about 9 and 12. These values ​​take color into account, which can be caused by the counter electrode layer as well as the electrochromic layer. When the electrochromic window made according to the disclosed technology is in its clearest state, the electrochromic window can have a b* value between about 6 and 14 or between about 9 and 12. The b* value of such a window can be less than 10. In various cases, when an electrochromic device and / or electrochromic window according to the disclosed embodiments is in its clearest state, the device or window can have a transmittance b* value of about 14 or less, 12 or less, or 10 or less. These values ​​take into account color, which can be caused by the counter electrode layer, the electrochromic layer, the substrate (e.g., glass, etc.), the conductive oxide layer, and any other layers present in the window.

[0128] Similarly, the counter electrode layer and / or electrochromic device can have a particular transmittance when in its clearest state. In some embodiments, the counter electrode layer will have a visible light transmittance of at least about 65% when in its clearest state. An electrochromic device as disclosed herein can have a visible light transmittance of at least about 55% when in its clearest state. An electrochromic window made as disclosed herein can have a visible light transmittance of at least about 50% when in its clearest state.

[0129] In certain embodiments, as described for the counter electrode layer, the electrochromic layer can be implemented as two or more sub-layers. The details of the differences between the sub-layers and the details of the changes within the layer can also be applied to the electrochromic layer (instead of the counter electrode layer or in addition to the counter electrode layer).

[0130] Other aspects related to the various components within the EC device

[0131] Most of the above discussion focuses on embodiments including a counter electrode layer with a heterogeneous composition. Typically, the composition of the counter electrode is heterogeneous with respect to the metal therein. Alternatively or additionally, with respect to another element (such as oxygen), the counter electrode (or another layer / area in the electrochromic device) can be made to include a heterogeneous composition. In various embodiments, for example, an electrochromic layer and / or a counter electrode layer can be deposited to include an oxygen-rich portion. The oxygen-rich portion (in some cases this portion is set to different sublayers, and in other cases, different sublayers are not set) can be in contact with other electrode layers (for example, the oxygen-rich portion of the electrochromic layer can be deposited to make it directly contact with the counter electrode layer, and / or the oxygen-rich portion of the counter electrode layer can be deposited to make it directly contact with the electrochromic layer). The heterogeneous structure of the electrochromic layer and / or the counter electrode layer can promote the formation of the interface zone between the two layers, wherein (after further treatment) the interface zone is used as a zone that can conduct ions and is essentially electronically insulating. In terms of composition and / or morphology, the interface zone itself can be heterogeneous.

[0132] Generally speaking, in certain embodiments, the interface region can have a heterogeneous structure including at least two different components represented by different phases and / or compositions. In addition, the interface region can include a gradient between these two or more different components, such as an ion conductive material and an electrochromic material (e.g., a mixture of lithium tungstate and tungsten oxide). The gradient can provide, for example, a variable composition, microstructure, resistivity, dopant concentration (e.g., oxygen concentration), stoichiometry, density, and / or grain size. The gradient can have many different forms of transitions, including linear transitions, inverse transitions, Gaussian transitions, and the like.

[0133] Since the interface region may be formed by a portion of the electrochromic layer and / or the counter electrode layer, these layers may also be deposited to include such a heterostructure.

[0134] In certain implementations, the electrochromic stack can be configured as a graded electrochromic element. The EC element does not have an abrupt transition between the EC layer and the IC layer or between the IC layer and the CE layer, but rather has a single layer graded composition of the EC region, which transitions to the IC region (interface region), which transitions to the CE region. Since the EC element is a single layer with a graded composition, the EC element can be described in many ways, including those described below. The following description is intended to illustrate certain embodiments of the EC element.

[0135] One embodiment is an EC element, which is a monolayer hierarchical composition including EC, IC and CE regions, respectively. In one embodiment, the EC element is all solid and inorganic. A single EC element can be described in many ways to understand the hierarchical composition it includes. In various embodiments, the monolayer hierarchical composition EC element does not have abrupt boundaries between EC / IC or between IC / CE. Instead, as discussed herein, these two interfaces are characterized by hierarchical composition. In some cases, the monolayer hierarchical composition EC element has a continuously variable composition across all regions of the element. In other cases, the element has at least one region or at least two regions with a constant composition. Figure 4G-4I are examples of how the composition of a class of EC elements can be determined. In these specific examples, the EC region of the EC element includes a first transition metal; the IC region includes an alkali metal, and the CE region includes a mixed transition metal oxide. After depositing the EC region and the CE region in contact with each other, the IC region can be formed. In specific examples, the mixed transition metal oxide includes a first transition metal and an additional transition metal, but in other examples, the mixed transition metal oxide does not include a first transition metal. In some devices, Figure 4G-4I The same EC element is described, but described in different ways. Each of these ways illustrates how any number of EC elements according to the embodiments described herein may be described. In this example, some of the components depicted in the figure are present in the graded composition and some are not present in the graded composition. For example, a transition metal is continuously present in significant concentrations across the entire device from the EC region through the CE region. The invention is not limited in this regard. In some embodiments, some or all of the components are present in the EC element at least in some very small amount (or even significant amount). In Figure 4G-4I In certain examples within the scope of the invention, each component is present to at least some extent in each zone of the EC element.

[0136] See also Figure 4G , EC elements are described in terms of the mole fractions of the elemental components that make up the EC element as a function of the region EC, IC, or CE in which the component occurs. Starting at the origin and moving from left to right across the diagram, in the EC region, the mole fraction of oxygen (O) is greater than that of the first transition metal (TM 1 ) is high. For example, this can represent tungsten oxide with an oxygen to tungsten ratio of about 3:1. Moving further to the right, the mole fraction of the first transition metal starts to decrease from somewhere in the EC region. At some point in the CE region, the mole fractions of oxygen and the first transition metal become stable. For example, this can represent nickel tungsten oxide with a stable composition in the CE region. In this example, the second transition metal (TM 2 ) is present in the EC element, in this particular example, in a higher molar fraction in the CE region than in other regions of the EC element.碱 ) are present in the EC element. For the purposes of this description, "alkali metal" is intended to include neutral elemental alkali metals as well as cations thereof, e.g., bound in a material matrix or unbound and thus capable of intercalation / transport during device operation. In this example, the alkali metal has the highest mole fraction in the IC region. In one example, this may correspond to the lithium in the lithium tungstate present in this region. Figure 4G As shown in , the oxygen concentration may also be highest in the IC region. This high oxygen concentration may be the result of depositing the material in the IC region superstoichiometrically with respect to oxygen. In certain embodiments, the material in the IC region may include a superstoichiometric (with respect to oxygen) form of the material in the EC region and / or the CE region. It is important to note that Figure 4G The mole fractions of the components depicted in are those components identified in the EC element, e.g., alkali metal components do not include mobile lithium ions, which can be used to drive coloration or bleaching of the EC element (e.g., because such ions are mobile and their position in the EC element will change depending on the applied charge). This example illustrates how the composition of an EC element can be described.

[0137] One embodiment is an EC element comprising: a) a first transition metal, which has a higher mole fraction in the composition in the EC zone than the second transition metal (if present) in the EC zone, b) an alkali metal, which has the largest mole fraction in the composition in the IC zone compared to the EC zone and the CE zone; and c) a second transition metal, which has its largest mole fraction in the composition of any zone of the EC element in the CE zone.

[0138] See also Figure 4H If you want to consider Figure 4G If the composition of the same EC element described above is not considered, but the oxygen content is not taken into account, then there is another way to describe the embodiments described herein. For example, in this figure, the y-axis is not the mole fraction, but the metal concentration, that is, each metal TM in each zone with a graded composition 1 、M 碱 and TM 2 In this example, each of the first transition metal and the alkali metal is described in terms of its concentration relative to the other two metals. The second transition metal is described in terms of its absolute concentration. Figure 4H In the EC region, the first transition metal has its maximum concentration relative to the other metals. In the IC region, the alkali metal has its maximum concentration relative to the other metals. In the CE region, the second transition metal has its maximum (absolute) concentration. In this example, in the CE region, TM 1 With TM 2 have substantially the same concentration, this could represent NiWO, for example.

[0139] One embodiment is an EC element comprising: a) a first transition metal, which has a maximum concentration in the EC region relative to other metals in the EC element, b) an alkali metal, which has a maximum concentration in the IC region relative to other metals in the EC element, and c) a second transition metal, which has its absolute maximum concentration in the CE region of the EC element.

[0140] Fig. 4I Description as about Figure 4G and Figure 4H The composition of the same EC element described above, but looking at the actual composition, e.g., compounds, that make up each zone. For example, in this figure, the y-axis is the % composition of each compound in each zone with graded composition, the compound being an oxide of the first transition metal (TM 1 - oxide), a mixture of oxides comprising an alkali metal and a first and a second transition metal (M 碱 -TM 1 -TM 2 oxide mixtures) and mixed transition metal oxides (TM 1 -TM 2 As mentioned, the mixed transition metal oxide need not include a first transition metal (e.g., it may include a second and a third transition metal), but in this example includes a first transition metal. In this example, TM 1 -Oxide is the most abundant in the EC region, and it is the main component of the EC region. 碱 -TM 1 -TM 2 The oxide mixture is the main component of the IC area, and the TM 1 -TM 2 Oxide is the main component of CE region. Please note that M 碱 -TM 1 -TM 2 The oxide mixture may include more than one compound in the matrix of the material, for example, this may represent a graded mixture of lithium tungstate, tungsten oxide, and nickel tungsten oxide. The morphology of the EC element may vary across the layers, i.e., in any one or more of the zones, the graded zones may have amorphous portions, crystalline portions, and / or mixed amorphous crystalline portions. In some embodiments, the CE zone is substantially amorphous.

[0141] One embodiment is an EC element comprising: a) a first transition metal oxide, the first transition metal oxide being the major constituent of the EC zone, b) a mixed transition metal oxide, the mixed transition metal oxide being the major constituent of the CE zone, and c) a mixture, the mixture comprising a first transition metal and a mixed transition metal oxide, the mixture being the major constituent of the IC zone. One embodiment is an EC element comprising: a) a first transition metal oxide, the first transition metal oxide being the major constituent of the EC zone, b) a mixed transition metal oxide, the mixed transition metal oxide being the major constituent of the CE zone, and c) a mixture comprising an alkali metal compound, a first transition metal, and a mixed transition metal oxide, the mixture being the major constituent of the IC zone. In one embodiment, the mixed transition metal oxide comprises a first transition metal and a second transition metal selected from the group consisting of nickel, tantalum, titanium, vanadium, chromium, cerium, cobalt, copper, iridium, iron, manganese, molybdenum, niobium, palladium, praseodymium, rhodium, and ruthenium. In one embodiment, the mixed transition metal oxide does not include a first transition metal. In one embodiment, the alkali metal is a lithium ion, associated with a compound or associated with a material matrix, as a transportable ion during operation of the EC element.

[0142] One embodiment is a method of making an electrochromic device, the method comprising: (a) forming an electrochromic layer comprising an electrochromic material or a counter electrode layer comprising a counter electrode material; (b) forming an intermediate layer on the electrochromic layer or the counter electrode layer, wherein the intermediate layer comprises an oxygen-rich form of at least one of the electrochromic material, the counter electrode material, and an additional material, wherein the additional material comprises a different electrochromic or counter electrode material, and the intermediate layer is not substantially electronically insulating; (c) exposing the intermediate layer to lithium; and (d) heating the formed stack so as to convert at least a portion of the intermediate layer into a region coextensive with a region of the intermediate layer, the region comprising an electronically insulating ion-conducting material and a material of the intermediate layer.

[0143] Because the intermediate layer may be formed from an oxygen-enriched form of the EC and / or CE material, the EC layer and / or CE layer may be understood to be formed to include a heterogeneous composition (eg, including oxygen-enriched portions and non-oxygen-enriched portions).

[0144] Method for making electrochromic window

[0145] Deposition of electrochromic stacks

[0146] As mentioned above, one aspect of the embodiment is the method for making electrochromic window. In a broad sense, the method includes sequentially depositing (i) cathode coloring electrochromic layer, (ii) optional ion conducting layer and (iii) anode coloring counter electrode layer on substrate to form a stack, in which (a) ion conducting layer is spaced apart cathode coloring electrochromic layer from anode coloring counter electrode layer, or (b) cathode coloring electrochromic layer is physically contacted with anode coloring counter electrode layer. In various embodiments, in terms of composition and / or morphology, the counter electrode layer is deposited as heterogeneous. For example, in some cases, the counter electrode can be deposited to include sublayer. In some embodiments, the counter electrode layer is deposited to include graded composition. The gradient can be along the direction perpendicular to the surface of the layer.

[0147] The sequential deposition may employ a single integrated deposition system having a controlled ambient environment in which pressure, temperature, and / or gas composition are controlled independently of the external environment outside the integrated deposition system, and the substrate may not leave the integrated deposition system at any time during the sequential deposition of the electrochromic layer, the optional ion-conducting layer, and the counter electrode layer. (hereinafter referred to as 9A to 9E Examples of integrated deposition systems that maintain a controlled ambient environment are described in more detail in the accompanying drawings. The gas composition can be characterized by the partial pressures of the various components in the controlled ambient environment. The controlled ambient environment can also be characterized by the number of particles or the density of particles. In certain embodiments, the controlled ambient environment contains 100% by volume of the particles per m 3 In some embodiments, the controlled environment meets the requirements of a Class 1000 clean room (US FED STD 209E) or a Class 100 clean room (US FED STD 209E). In some embodiments, the controlled environment meets the requirements of a Class 10 clean room (US FED STD 209E). The substrate can enter and / or leave a controlled environment in a clean room that meets Class 1000, Class 100, or even Class 10 requirements.

[0148] Typically, but not necessarily, this method of making is integrated into a multi-step process for making electrochromic windows using architectural glass as a substrate, but the method is not so limited. Electrochromic mirrors and other devices may be made using some or all of the operations and methods described herein. Additional details about the process for making electrochromic windows are discussed in U.S. Patent Application No. 12 / 645,111, incorporated by reference above.

[0149] The method for depositing an electrochromic stack may include sequentially depositing (i) a cathode coloring EC layer, (ii) an optional IC layer, and (iii) an anodically coloring CE layer on a substrate to form a stack, in which (a) the IC layer separates the EC layer from the CE layer, or (b) the EC layer and the CE layer are in physical contact with each other. The method may be performed in a single integrated deposition system with a controlled ambient environment, in which the pressure and / or gas composition are controlled independently of the external environment outside the integrated deposition system, and the substrate may not leave the integrated deposition system at any time during the sequential deposition of the EC layer, the optional IC layer, and the CE layer in various cases. In one embodiment, each of the sequentially deposited layers is physically vapor deposited. In general, the layers of the electrochromic device can be deposited by various techniques, including physical vapor deposition, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition, to name just a few. The term physical vapor deposition as used herein includes the entire range of PVD techniques recognized in the art, including sputtering, evaporation, ablation, and the like.

[0150] Figure 5 Describe an embodiment of process 720 for forming an electrochromic stack. First, a cathode coloring EC layer is deposited on a substrate (process 722), followed by an optional IC layer (process 724) (as noted above, in certain embodiments, the IC layer is omitted, so process 724 is omitted), followed by a heterogeneous anode coloring CE layer (process 726). In some cases, a heterogeneous CE layer can be deposited in two or more steps. For example, in the case where the CE layer includes a sublayer, each of the sublayers can be deposited in a different process / step. Deposition in the opposite order is also an embodiment, that is, wherein the CE layer is deposited first, followed by an optional IC layer and then an EC layer. In one embodiment, each of the electrochromic layer, the optional ion conductive layer, and the counter electrode layer is a solid phase layer. In these or other embodiments, each of the electrochromic layer, the optional ion conductive layer, and the counter electrode layer can include only inorganic materials.

[0151] It should be understood that while certain embodiments are described in terms of counter electrode layers, ion conductor layers, and electrochromic layers, any one or more of these layers may be comprised of one or more sub-layers that may have different compositions, sizes, morphologies, charge densities, optical properties, etc. Additionally, any one or more of the layers of the device may have a graded composition or a graded morphology, wherein the composition or morphology, respectively, varies over at least a portion of the thickness of the layer.

[0152] Many embodiments herein are presented in the context of a counter electrode layer comprising heterogeneous composition and / or morphology. The described heterogeneous counter electrode layer can be used in combination with other layers or regions (e.g., electrochromic layers, interface regions where EC layers contact CE layers, etc.) comprising gradients and / or sublayers having different compositions and / or morphologies.

[0153] In one example, the concentration of oxygen, dopants, or charge carriers varies within a given layer, at least when the layer is made. In another example, the morphology of the layer changes from crystalline to amorphous. Such graded composition or morphology can be selected to affect the functional properties of the device. In some cases, additional layers can be added to the stack. In one example, a heat sink layer is inserted between one or two TCO layers and the EC stack. The heat sink layer is made of a material that has high thermal conductivity and can therefore effectively spread heat over the stack.

[0154] In addition, as described above, the electrochromic device of certain embodiments utilizes ion movement between the electrochromic layer and the counter electrode layer via an ion conductive layer. In some embodiments, these ions (or their neutral precursors) are introduced into the stack with one or more layers that are finally embedded in the stack. Such layers can be deposited before, during and / or after the deposition of other layers (e.g., EC layer, IC layer, CE layer) in the stack. Alternatively (or additionally), one or more lithiation steps can be performed as an intermediate step occurring between steps performed to deposit an electrode. For example, the counter electrode layer can be deposited by depositing a first sublayer, then depositing lithium thereon, and then finally depositing one or more additional sublayers. In one embodiment, the first sublayer is deposited, a flash layer is optionally deposited, then a second sublayer is deposited, then lithiation is performed, and then a third sublayer is deposited on the second sublayer. In another embodiment, the first sublayer is deposited, a flash layer is optionally deposited, then a second sublayer is deposited, then a third sublayer is deposited on the second sublayer, and then lithium is deposited on the third sublayer. In some embodiments, a DMIL or a capping layer is deposited on the third sublayer.

[0155] Sublayers deposited before and after lithiation may have the same or different compositions and / or morphologies. Lithiation may also be performed during deposition of a single sublayer, e.g., where the material of the sublayer includes an excess of lithium, such that deposition of the sublayer provides, e.g., sufficient lithium for the remainder of the electrochromic device stack. This result may be achieved, e.g., by co-sputtering lithium with the sublayer material or where the sublayer material already includes lithium. Such methods may have certain advantages, such as better separation of lithium from indium tin oxide (ITO) or other materials of the conductive layer, which improves adhesion and prevents undesirable side effects.

[0156] In some embodiments, the ions are introduced into the stack simultaneously with one or more of the electrochromic layer, the ion conducting layer, and the counter electrode layer. In one embodiment, where lithium ions are used, lithium is sputtered, for example, with the material used to make one or more of the stack layers, or as part of the material comprising lithium (e.g., by a process employing lithium nickel tungsten tantalum oxide or another lithium-containing material). In one embodiment, the IC layer is deposited via sputtering of a lithium oxide silicon aluminum target. In another embodiment, Li is co-sputtered with silicon aluminum to achieve the desired film.

[0157] Reference again Figure 5 In process 722, in one embodiment, depositing the electrochromic layer includes depositing WO x , for example, wherein x is less than 3.0 and at least about 2.7. In this embodiment, WO x The electrochromic layer has a substantially non-crystalline morphology. In some embodiments, the electrochromic layer is deposited to a thickness between about 200 nm and 700 nm. In one embodiment, depositing the electrochromic layer comprises sputtering tungsten from a tungsten-containing target. x Specific deposition conditions for the electrochromic layer are further discussed in U.S. Patent Application Serial No. 12 / 645,11, incorporated by reference above.

[0158] It should be understood that although the deposition of the EC layer is described in terms of sputtering from a target, other deposition techniques are employed in some embodiments. For example, chemical vapor deposition, atomic layer deposition, etc. may be employed. As known to those skilled in the art, each of these techniques, as well as PVD, has its own source of materials in the form of.

[0159] See again Figure 5 , operation 724, once the EC layer is deposited, the optional IC layer may be deposited. Electrochromic devices that operate by lithium ion insertion are well suited for the harsh conditions of architectural windows. Suitable lithium ion conductor layer materials 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 tantalum oxide, lithium zirconium oxide, lithium silicon carbon oxynitride (LiSiCON), lithium titanium phosphate, lithium germanium vanadium oxide, lithium zinc germanium oxide, and other ceramic materials that allow lithium ions to pass therethrough while having a high resistance (blocking electrons from moving therethrough). Specific deposition conditions for forming the IC layer in situ are further discussed in U.S. Patent Application No. 12 / 645,111 and U.S. Patent No. 9,261,751, each of which is incorporated by reference above. In certain embodiments, depositing the ion conducting layer includes depositing the ion conducting layer to a thickness between about 10 nm and 100 nm.

[0160] See again Figure 5 , operation 726, after depositing the optional IC layer, deposit the anodized CE layer. In some embodiments where the IC layer is omitted, operation 726 may follow operation 722. As described above, the anodized CE layer may be deposited to include heterogeneous composition and / or morphology. In various cases, operation 726 involves depositing two or more sublayers of anodized counter electrode material. As described above, one of these sublayers may be a flash layer. In these or other cases, the counter electrode may be deposited to include a graded composition.

[0161] In one embodiment, depositing the counter electrode layer comprises depositing a layer or sublayer of nickel tungsten tantalum oxide (NiWTaO). In a specific embodiment, depositing the counter electrode layer comprises sputtering a target comprising about 30% (by weight) to about 70% tungsten in nickel and / or tantalum in an oxygen-containing environment to produce a layer of nickel tungsten tantalum oxide (tantalum is provided by a tungsten / nickel / tantalum target of appropriate composition or by another target or by another source (such as an evaporated tantalum source)). In another embodiment, the target is between about 40% and about 60% tungsten in nickel (and / or tantalum), between about 45% and about 55% tungsten in nickel (and / or tantalum) in another embodiment, and about 51% tungsten in nickel (and / or tantalum) in yet another embodiment.

[0162] In certain embodiments where the anodizing counter electrode layer includes a layer or sublayer of NiWTaO, many deposition targets or target combinations can be used to deposit NiWTaO material. For example, separate metal targets of nickel, tungsten and tantalum can be used. In other cases, at least one of the targets includes an alloy. For example, an alloy target of nickel-tungsten can be used with a metal tantalum target. In another case, an alloy target of nickel-tantalum can be used with a metal tungsten target. In another case, an alloy of tungsten-tantalum can be used with a metal nickel target. In yet another case, an alloy target containing nickel-tungsten-tantalum material can be used. In addition, any one of the listed targets can be provided as an oxide. Typically, sputtering occurs when oxygen is present, and such oxygen is incorporated into the material. Alternatively or in addition to an oxygen-containing sputtering atmosphere, an oxygen-containing sputtering target can also be used.

[0163] The sputtering target used to form the anodically colored counter electrode material can have a composition that allows the counter electrode layer or sublayer to be formed according to any composition described herein. In addition, as described herein, the sputtering target used to form the anodically colored counter electrode material can be positioned in a manner that allows the material to be formed as needed, such as to form a heterogeneous counter electrode layer (e.g., having a heterogeneous composition, heterogeneous morphology, sublayers, graded composition, etc.). In an example of using a single sputtering target to form a NiWTaO material, the sputtering target can have a composition that matches the composition of any one of the NiWTaO materials disclosed herein. In other examples, a combination of sputtering targets is used, and the composition of the combined target allows deposition according to any one of the NiWTaO compositions (or other counter electrode materials) disclosed herein.

[0164] In one embodiment, the gas composition used in forming the CE (or its sublayer) contains between about 30% and about 100% oxygen, in another embodiment between about 75% and about 100% oxygen, in yet another embodiment between about 95% and about 100% oxygen, and in another embodiment about 100% oxygen. In one embodiment, the power density used to sputter the CE target is about 2 Watts / cm 2 With about 50 watts / cm 2 (determined based on the applied power divided by the surface area of ​​the target); in another embodiment, between about 5 watts / cm 2 With about 20 watts / cm 2 and in yet another embodiment at about 8 watts / cm 2 With about 10 watts / cm 2 In another embodiment, about 8 watts / 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 using pulsed DC / AC reactive sputtering, the frequency is between about 20 kHz and about 400 kHz, between about 20 kHz and about 50 kHz in another embodiment, between about 40 kHz and about 50 kHz in yet another embodiment, and about 40 kHz in another embodiment.

[0165] The pressure in the deposition station or chamber is between about 1 mTorr and about 50 mTorr in one embodiment, between about 20 mTorr and about 40 mTorr in another embodiment, between about 25 mTorr and about 35 mTorr in another embodiment, and about 30 mTorr in another embodiment. In some cases, a nickel tungsten oxide NiWO ceramic target is sputtered with, for example, argon and oxygen. 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 about 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. In another embodiment, depositing the counter electrode layer comprises depositing the counter electrode layer to a thickness between about 150 nm and 350 nm; in yet another embodiment about 200 nm to about 250 nm thick. The above conditions can be used in any combination with each other to achieve deposition of a heterogeneous counter electrode layer.

[0166] The sputtering process for forming each portion of the CE layer can utilize one or more sputtering targets. Different sputtering targets can be used to form various CE materials. In general, the sputtering target used to form the CE layer includes elements that will be present in the deposited CE layer (wherein oxygen is optionally provided in the target itself and / or provided by the sputtering gas). In some cases, the elements of the CE layer are all provided together in a single target. In other cases, all elements in the CE layer except oxygen are provided together in a single target. In other cases, different sputtering targets may include different materials, and the targets can be used together to form the desired CE material. Most of the discussion about sputtering targets herein is conducted in the context of forming NiWTaO materials. However, the teachings herein are applicable to forming any of the disclosed materials, as long as the provided target includes appropriate elements in appropriate composition.

[0167] In an example of using a sputtering target to form a layer of NiWTaO, the target may include nickel, tungsten, and tantalum. In some cases, the sputtering target also includes oxygen. In some cases, multiple targets may be provided, wherein the compositions of the targets are the same or different from each other. In one example, in the case of forming a NiWTaO layer, at least one of the nickel, tungsten, and tantalum materials may be provided in a separate target. Similarly, in the case of using a sputtering target to form a layer of NiWO, the target may include nickel and tungsten, optionally with oxygen. Nickel and tungsten may also be provided in separate targets. Other CE materials may be similarly deposited using one or more targets, which may have compositions that are the same or different from each other.

[0168] The sputtering target may include a grid or other overlapping shapes, wherein different portions of the grid include different related materials (e.g., in the case of forming a NiWTaO layer or sublayer, certain portions of the grid may include elemental nickel, elemental tungsten, elemental tantalum, nickel-tungsten alloy, nickel-tantalum alloy, and / or tungsten-tantalum alloy). In some cases, the sputtering target may be an alloy of related materials (e.g., in the case of forming a NiWTaO layer or sublayer, two or more of nickel, tungsten, and tantalum may be provided as an alloy). In the case of using two or more sputtering targets, each sputtering target may include at least one of the related materials (e.g., in the case of forming a NiWTaO layer or sublayer, at least one element and / or alloy form of nickel, tungsten, and / or tantalum may be present in each target, any of which may be provided in the form of an oxide). The sputtering targets may overlap in some cases. In some embodiments, the sputtering target may also rotate. As noted, the counter electrode layer is typically an oxide material. Oxygen may be provided as part of the sputtering target and / or the sputtering gas. In certain cases, the sputtering target is a substantially pure metal and the sputtering is performed in the presence of oxygen to form an oxide.

[0169] In one embodiment, to normalize the deposition rate of the CE layer, multiple targets are used in order to avoid requiring too high a power (or other improper adjustments to the desired process conditions) to increase the deposition rate. In one embodiment, the distance between the CE target (cathode or source) and the substrate surface is between about 35 mm and about 150 mm; in another embodiment, between about 45 mm and about 130 mm; and in another embodiment, between about 70 mm and about 100 mm.

[0170] As noted, one or more rotating targets may be used in some cases. In various cases, the rotating target may include an internal magnet. Fig. 6AA view of a rotating target 900 is presented. Inside the rotating target 900 are magnets 902 that (when appropriate power is supplied to the target) cause material to be sputtered from the target surface 904 in a sputtering cone 906 (the sputtering cone is sometimes also referred to as a sputtering plasma). The magnets 902 can extend along the length of the sputtering target 900. In various embodiments, the magnets 902 can be oriented to extend radially outward so that the resulting sputtering cone 906 emanates from the sputtering target 900 in a direction perpendicular to the surface 904 of the target (the direction is measured along the central axis of the sputtering cone 906, which generally corresponds to the average direction of the sputtering cone 906). The sputtering cone 906 can be v-shaped when viewed from above and can extend along the height of the target 900 (or the height of the magnets 902, if not the same as the height of the target 900). The magnets 902 inside the rotating target 900 may be stationary (i.e., although the surface 904 of the target 900 rotates, the magnets 902 inside the target 900 do not rotate), so that the sputtering cone 906 is also stationary. The small circles / dots depicted in the sputtering cone 906 represent the sputtered material emanating from the sputtering target 900. The rotating target may be combined with other rotating targets and / or planar targets as desired.

[0171] In one example, two rotating targets are used to deposit a NiWTaO anodically coloring CE layer (or a sublayer within an anodically coloring CE layer): a first target comprising nickel and tungsten and a second target comprising tantalum (either or both optionally in oxide form). Figure 6B A top-down view of a deposition system for depositing anodically colored layers or sublayers in this manner is presented. Nickel tungsten target 910 and tantalum target 912 each include internal magnets 914. Magnets 914 are angled toward each other so that sputtering cones 916 and 918 from nickel tungsten target 910 and tantalum target 912, respectively, overlap. Figure 6B Also shown is a substrate 920 passing in front of targets 910 and 912. As shown, sputter cones 916 and 918 closely overlap where they strike substrate 920. In some embodiments, the sputter cones from the various sputter targets can overlap closely with each other (e.g., the non-overlapping area reached by only a single sputter cone when depositing on the substrate 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 can be offset from each other to a greater extent, such that either or both of the sputter cones have a non-overlapping area that is at least about 10% (e.g., at least about 20%, or at least about 30%, or at least about 50%) of the total area reached by either sputter cone.

[0172] In the case of forming a NiWTaO CE layer (or sublayer), Figure 6BIn an embodiment similar to the embodiment shown in , one sputtering target is tungsten, and the other is an alloy of nickel and tantalum (either one or both targets are optionally in oxide form). Similarly, one sputtering target can be nickel, and the other can be an alloy of tungsten and tantalum (either one or both targets are optionally in oxide form). In a related embodiment, three sputtering targets are used: a tantalum target, a nickel target, and a tungsten target (any one of which can be optionally in oxide form). The sputtering cones from each of the three targets can overlap by angling the magnet as appropriate. In addition, shielding, grids, and / or other additional plasma shaping elements can be used to help produce a suitable plasma mixture to form NiWTaO. Similarly, in the case of other anodic coloring counter electrode materials, any combination of targets including elemental metals, alloys, and / or oxides can be used, assuming that the target includes materials (except oxygen) that will be merged into the relevant layer or sublayer being formed.

[0173] Various sputtering target designs, orientations, and implementations are further discussed in US Pat. No. 9,261,751, incorporated by reference above.

[0174] The density and orientation / shape of the material sputtered from the sputtering target depends on various factors, including, for example, the shape and strength of the magnetic field, pressure, and power density used to generate the sputtering plasma. The distance between adjacent targets and the distance between each target and the substrate may also affect how the sputtering plasma mixes and how the resulting material is deposited on the substrate.

[0175] In certain embodiments, two different types of sputtering targets are provided to deposit a single layer or sublayer in an electrochromic stack: (a) a main sputtering target, which sputters material onto a substrate, and (b) an auxiliary sputtering target, which sputters material onto the main sputtering target. The main and auxiliary sputtering targets may include any combination of metals, metal alloys, and metal oxides that are to be formed in the deposited layer. In a specific example, in the case of a NiWTaO counter electrode material, the main sputtering target includes an alloy of nickel and tungsten, and the auxiliary sputtering target includes tantalum. In another example, the main sputtering target includes tantalum, and the auxiliary sputtering target includes an alloy of nickel and tungsten. These sputtering targets can be used together to deposit a NiWTaO anode coloring layer (or sublayer). Other combinations of alloys (e.g., nickel-tantalum, tungsten-tantalum, and other metal alloys) and metals (e.g., nickel, tungsten, and other metals) may also be used as appropriate to form NiWTaO or other desired materials. Any sputtering target may be provided in the form of an oxide.

[0176] When using primary and secondary sputtering targets, many different setups are possible. Fig. 7A and Figure 7BA top-down view of one embodiment of a deposition station for depositing a multi-component anodizing counter electrode material is presented. Although presented in the specific context of depositing counter electrode materials, the sputtering target configuration discussed herein can be used to deposit any material in an electrochromic stack, as long as the target has an appropriate composition for depositing the desired material in the stack. A main sputtering target 1001 and an auxiliary sputtering target 1002 are provided, each having an internal magnet 1003. In this example each sputtering target is a rotating sputtering target, but flat or other shaped targets may also be used. The targets may rotate in the same direction or in opposite directions. As Fig. 7A As shown in FIG. 1 , when there is no substrate 1004 between the two targets, the auxiliary sputtering target 1002 sputters material onto the main sputtering target 1001. In this way, the material from the auxiliary sputtering target 1002 is deposited onto the main sputtering target 1001. Next, as shown in FIG. Figure 7B As shown in , when the substrate 1004 moves to a position between the two targets, sputtering from the auxiliary sputtering target 1002 stops, and sputtering from the main sputtering target 1001 onto the substrate 1004 starts.

[0177] When material is sputtered from the main sputtering target 1001 and deposited onto the substrate 1004, the deposited material includes materials originating from the main and auxiliary sputtering targets 1001 and 1002, respectively. In fact, this method involves the in-situ formation of a hybrid sputtering target surface on the main sputtering target 1001. One advantage of this method is that a flash coating of material from the auxiliary sputtering target 1002 is periodically deposited on the surface of the main sputtering target 1001. The hybrid material is then delivered together to the substrate 1004. In a specific example, in the case of forming a NiWTaO counter electrode material, each of the main and auxiliary sputtering targets can include any combination of tantalum, tungsten, nickel and / or alloys thereof (optionally in the form of oxides).

[0178] exist Figure 7CIn a related embodiment shown in , the auxiliary sputtering target 1022 is located behind the main sputtering target 1021, and the substrate 1024 passes in front of the main sputtering target 1021 so that it does not block the line of sight between the two targets 1021 and 1022. Each of the sputtering targets may include a magnet 1023. In this embodiment, it is not necessary to periodically stop sputtering from the auxiliary sputtering target 1021 to the main sputtering target 1022. Instead, such sputtering can occur continuously. In the case where the main sputtering target 1021 is located between the substrate 1024 and the auxiliary sputtering target 1022 (for example, there is no line of sight between the auxiliary sputtering target 1022 and the substrate 1024), the main sputtering target 1021 will rotate so that the material deposited on the main sputtering target 1021 can be sputtered onto the substrate 1024. There is more flexibility in the design of the auxiliary sputtering target 1022. In a related embodiment, the auxiliary sputtering target can be a planar or other non-rotating target. Where two rotating targets are used, the targets may rotate in the same direction or in opposite directions.

[0179] In similar embodiments, the auxiliary sputtering target may be replaced with another auxiliary material source (e.g., Figures 7A-7C Auxiliary target in the main sputtering target). The auxiliary material source can provide material to the main sputtering target by means other than sputtering. In one example, the auxiliary material source provides evaporation material to the main sputtering target. The evaporation material can be any component of the deposited layer. In various examples, the evaporation material is an elemental metal or a metal oxide. Specific examples of evaporation materials include tantalum, tungsten and nickel, which can be used to form NiWTaO anode coloring counter electrode materials. In one embodiment, elemental tantalum is evaporated onto a main sputtering target comprising a mixture and / or alloy of nickel and tungsten. Other materials can also be provided in this way to form layers or sublayers of other compositions. In the case where the auxiliary material source provides the evaporation material, the auxiliary material source can be located at any position relative to the main sputtering target and the substrate. In some embodiments, an auxiliary material source is provided so that it is behind the main sputtering target and is primarily deposited on the main sputtering target, with Figure 7C The setup shown in is very similar.

[0180] In the case of using a primary and secondary sputtering target, the secondary sputtering target can be operated at a potential that is cathodic compared to the potential of the primary sputtering target (which is already cathodic). Alternatively, the targets can be operated independently. Furthermore, the neutral chemical species 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 beam and will be deposited on the cathodic primary target regardless of the relative potential.

[0181] In various embodiments, reactive sputtering may be used to deposit one or more materials in the electrochromic stack. Figure 8 is a graph showing the rate of sputtering deposition from a sputtering target as a function of oxygen concentration at a fixed power. Figure 8As shown in , there is a strong hysteresis effect related to the oxygen concentration profile to which the target has been exposed and / or operated. For example, when starting from a low oxygen concentration and increasing to a higher oxygen concentration, the deposition rate remains quite high until the oxygen concentration reaches a point where the sputtering target forms an oxide that cannot be removed from the target quickly enough. At this point, the deposition rate drops and the sputtering target essentially forms a metal oxide target. All other conditions being equal, the deposition rate of an oxide target is generally much lower than the deposition rate of a metal target. Figure 8 The region of relatively high deposition rate in corresponds to the metal deposition regime, while the region of relatively low deposition rate corresponds to the metal oxide deposition regime. When the target is initially exposed to / operated at a high oxygen concentration and then exposed to / operated at a relatively low concentration, the deposition rate remains relatively low until the oxygen concentration reaches a point where the deposition rate jumps to a higher level. Figure 8 As shown in , the oxygen concentration at which these changes occur is different depending on whether the oxygen concentration is increasing or decreasing. The exact oxygen concentration at which the mode change occurs can be controlled by changing the target power density and the magnetic strength of the internal magnet 1003. For example, if a target sputters a substantially higher beam of metal atoms from the surface (due to higher power and / or magnetic strength), then the target will likely remain in the metal deposition mode compared to a target sputtering a very low beam of metal atoms. Such hysteresis effects can be used to facilitate the deposition process.

[0182] In certain embodiments where two or more sputtering targets are used to deposit materials in an electrochromic stack, one target may be operated in a metal deposition mode, while another target may be operated in a metal oxide deposition mode. By controlling the target power density, the magnetic strength of the internal magnet 1003, and the atmosphere to which each target is exposed / operated over time, it is possible to operate in both of these modes simultaneously. In one example, a first nickel-tungsten target is exposed to a relatively low concentration of oxygen and then brought to an intermediate concentration of oxygen so that it operates in a metal deposition mode. A second tantalum target is exposed to a relatively high concentration of oxygen and then brought to an intermediate concentration of oxygen so that it operates in a metal oxide deposition mode. The two targets may then be brought together, still exposing them to an intermediate oxygen concentration, where they are used to deposit materials onto a substrate in two modes (the first target continues to operate in a metal deposition mode and the second target continues to operate in a metal oxide deposition mode).

[0183] In many cases it may not be necessary to expose each target to a different atmosphere. Other factors besides different historical oxygen exposures may cause the targets to operate in different deposition modes. For example, the targets may have different hysteresis curves due to different materials in the targets. Thus, the targets may be able to operate in different modes even if they were historically exposed to the same atmospheric oxygen conditions and operated under the same atmospheric oxygen conditions. In addition, the amount of power applied to each target can significantly affect the deposition mode experienced by each target. Therefore, in one example, due to the different powers applied to each target, one target is operated in a metal deposition mode and the other target is operated in a metal oxide deposition mode. This method may be easier because there is no need to separate the targets from each other so that they can be exposed to different oxygen concentrations. One advantage of operating the targets at different points in the hysteresis curve is that the composition of the deposited material can be closely controlled.

[0184] It should be understood that although the order of deposition operations is Figure 5 , as described herein as a first EC layer, a second IC layer, and finally a CE layer, but the order may be reversed in various embodiments. In other words, when the "sequential" deposition of stacked layers is described as described herein, it is intended to cover the following "reverse" order, i.e., a first CE layer, a second IC layer, and a third EC layer, as well as the "forward" order described above. Both the forward and reverse orders can function as reliable, high-quality electrochromic devices. In addition, it should be understood that the conditions for depositing the various EC, IC, and CE materials described herein are not limited to depositing such materials. In some cases, other materials may be deposited under the same or similar conditions. Furthermore, in some cases, the IC layer may be omitted. In addition, in some embodiments, non-sputtering deposition conditions may be used to form deposited materials that are the same or similar to those described herein.

[0185] Since the amount of charge that each of the EC layer and the CE layer can safely hold varies, the relative thickness of each of the layers can be controlled as appropriate to match the capacity, depending on the materials used. In one embodiment, the electrochromic layer includes tungsten oxide and the counter electrode includes nickel tungsten tantalum oxide (provided in the counter electrode layer or sublayer), and the ratio of the thickness of the electrochromic layer to the thickness of the counter electrode layer is between about 1.7:1 and 2.3:1 or between about 1.9:1 and 2.1:1 (where about 2:1 is a specific example).

[0186] As mentioned, the EC stack is made in an integrated deposition system, wherein the substrate does not leave the integrated deposition system at any time during the fabrication of the stack. In one embodiment, the second TCO layer is also formed using the integrated deposition system, wherein the substrate does not leave the integrated deposition system during the deposition of the EC stack and the TCO layer. In one embodiment, all layers are deposited in an integrated deposition system, wherein the substrate does not leave the integrated deposition system during deposition; that is, in one embodiment, the substrate is a glass plate, and the stack comprising the EC layer, the optional IC layer, and the CE layer sandwiched between the first and second TCO layers is made on the glass, wherein the glass does not leave the integrated deposition system during deposition. In another implementation of this embodiment, the substrate is glass with a diffusion barrier deposited prior to entering the integrated deposition system. In another implementation, the substrate is glass, and the stack comprising the EC layer, the optional IC layer, and the CE layer sandwiched between the first and second TCO layers is all deposited on the glass, wherein the glass does not leave the integrated deposition system during deposition.

[0187] As mentioned above, when EC, CE and / or IC layers are formed on a substrate, lithium can be provided with EC, CE and / or IC layers. This may involve, for example, co-sputtering of lithium with other materials of a given layer (e.g., tungsten and oxygen, optionally with additional or different elements in some cases). In certain embodiments, lithium is delivered via a separate process and allowed to diffuse or otherwise merge into EC, CE and / or IC layers. In some embodiments, only a single layer in the electrochromic stack is lithiated. For example, in some instances, only the anode coloring CE layer (or the sublayer therein) is lithiated. In other cases, only the cathode coloring EC layer is lithiated. In yet other cases, only the IC layer is lithiated. In other embodiments, two or more of the EC layer, IC layer and CE layer (including sublayers) are lithiated. The specific conditions for lithiation are further discussed in U.S. Patent Application No. 12 / 645,111, incorporated by reference above.

[0188] In some embodiments, the electrochromic stack includes a counter electrode layer or sublayer in direct physical contact with the electrochromic layer, without an ion conducting layer between the two. In some such cases, the electrochromic layer and / or the counter electrode layer may include an oxygen-rich portion (e.g., in various cases, an oxygen-rich sublayer or an oxygen-rich portion of a graded layer) in contact with the others of these layers. The oxygen-rich portion may include an electrochromic material or a counter electrode material having an oxygen concentration higher than that in the rest of the electrochromic layer and / or the counter electrode layer. Electrochromic devices made according to such designs are further discussed and described in U.S. Patent No. 8,300,298 filed on April 30, 2010, which is incorporated by reference above.

[0189] In one aspect of the disclosed embodiment, a method of making an electrochromic device is provided, the method comprising: depositing an electrochromic layer, the electrochromic layer comprising a cathode coloring electrochromic material; and depositing a counter electrode layer by the following steps: depositing a first anode coloring sublayer, the first anode coloring sublayer comprising Ni a W b A c O d , wherein a, b and d are greater than zero; depositing a second anodic dyeing sublayer, the second anodic dyeing sublayer comprising Ni e W f B g O h, wherein e, f and h are greater than zero, wherein at least one of c and g is greater than zero, and wherein each of A and B, when present, is independently selected from the group consisting of silver (Ag), aluminum (Al), arsenic (As), gold (Au), boron (B), barium (Ba), beryllium (Be), bismuth (Bi), calcium (Ca), cadmium (Cd), cerium (Ce), cobalt (Co), chromium (Cr), copper (Cu), europium (Eu), iron (Fe), gallium (Ga), gadolinium (Gd), germanium (Ge), hafnium (Hf), mercury (Hg), indium (In), iridium (Ir), lanthanum (La), magnesium (Mg), manganese (Mn), molybdenum (Mo), niobium (Nb), neodymium (Nd), osmium (Os), protactinium (Pa), lead (Pb), Palladium (Pd), praseodymium (Pr), promethium (Pm), polonium (Po), platinum (Pt), radium (Ra), rhenium (Re), rhodium (Rh), ruthenium (Ru), antimony (Sb), scandium (Sc), selenium (Se), silicon (Si), samarium (Sm), tin (Sn), strontium (Sr), tantalum (Ta), terbium (Tb), technetium (Tc), tellurium (Te), thorium (Th), titanium (Ti), thallium (Tl), uranium (U), vanadium (V), tungsten (W), yttrium (Y), zinc (Zn) and zirconium (Zr); and one or more anodic dyeing sublayers of a lithiated counter electrode layer, wherein the first anodic dyeing sublayer is located between the electrochromic layer and the second anodic dyeing sublayer, and wherein the first and second anodic dyeing sublayers have different compositions. The electrochromic device can be made to include any of the materials / material combinations / structures described herein.

[0190] As mentioned above, in certain embodiments, the making of electrochromic stacking is carried out in an integrated deposition system. Such integrated systems can allow the various layers in the deposition stacking to be deposited without destroying vacuum. In other cases, one or more layers in the deposition stacking can be deposited by the process that needs to be removed from a protected vacuum environment. For example, in some cases, one or more layers (such as cathode coloring EC layer) are deposited on a substrate under vacuum using physical vapor deposition, then the substrate is removed from vacuum and ion conductor layers are deposited using sol-gel (or other non-vacuum) processes, and then the substrate is returned to the vacuum environment to deposit anodically colored counter electrode layers. The sol-gel process involves producing solid materials from small molecules. Monomers are converted into colloidal solutions, which serve as precursors for the integrated network or network polymers of discrete particles. Examples of ionic conductor materials that can be deposited include, for example, silicate-based structures, lithium silicate, lithium aluminum silicate, lithium aluminum borate, lithium borate, lithium zirconium silicate, lithium niobate, lithium borosilicate, lithium phosphosilicate, lithium nitride, lithium aluminum fluoride and other such lithium-based ceramic materials, silica, or silicon oxide, silicon dioxide and tantalum oxide.

[0191] Multi-step thermochemical regulation

[0192] Once the stack is deposited, the device can undergo a multi-step thermochemical conditioning (MTC) process. In embodiments where the device is deposited without a separate ion-conducting layer itself, this conditioning process can promote the formation of ion-conducting regions within the device. The MTC process is further described in U.S. Patent Application No. 12 / 645,111, incorporated by reference above.

[0193] In certain embodiments, different process flows may be used to fabricate electrochromic devices. Alternative process flows are further discussed in U.S. Patent Application No. 14 / 362,863, filed on June 4, 2014, and entitled “THIN-FILM DEVICES AND FABRICATION,” which is incorporated herein by reference in its entirety.

[0194] Integrated deposition system

[0195] As explained above, an integrated deposition system can be used to make electrochromic devices on (for example) architectural glass. As described above, an electrochromic device is used to make an IGU, which is in turn used to make an electrochromic window. The term "integrated deposition system" refers to an apparatus for making an electrochromic device on an optically transparent and translucent substrate. The apparatus has a plurality of stations, each of which is responsible for a specific unit operation, such as a specific component (or part of a component) of the deposition electrochromic device, and cleaning, etching, and temperature control of such a device or part thereof. The plurality of stations are fully integrated so that the substrate on which the electrochromic device is made can be transferred from one station to the next station without being exposed to the external environment. The integrated deposition system works with a controlled ambient environment inside the system, wherein the processing station is located in the environment. A fully integrated system achieves better control of the interface quality between the deposited layers. Interface quality refers to the lack of contaminants in the adhesion quality and interface area between the layers in addition to other factors. The term "controlled ambient environment" refers to a sealed environment spaced apart from an external environment (such as an open atmospheric environment or a clean room). In a controlled ambient environment, at least one of pressure and gas composition is controlled independently of conditions in the external environment. Generally, but not necessarily, a controlled ambient environment has a pressure below atmospheric pressure; for example, at least a partial vacuum. The conditions in the controlled ambient environment can remain constant during a processing operation or can vary over time. For example, the layers of an electrochromic device can be deposited under vacuum in a controlled ambient environment, and at the end of the deposition operation, the environment can be backfilled with a purge gas or a reagent gas and the pressure increased to, for example, atmospheric pressure for processing at another station, and then the vacuum is reestablished for the next operation, and so on.

[0196] In one embodiment, the system includes a plurality of deposition stations that are continuously aligned and interconnected and operable to transfer a substrate from one station to the next station without exposing the substrate to an external environment. The plurality of deposition stations include (i) a first deposition station containing one or more targets for depositing a cathode coloring electrochromic layer; (ii) a second (optional) deposition station containing one or more targets for depositing an ion conducting layer; and (iii) a third deposition station containing one or more targets for depositing a counter electrode layer. In some cases the second deposition station may be omitted. For example, the apparatus may not include any targets for depositing a separate ion conductor layer.

[0197] In addition, any layer in the stack can be deposited in two or more stations. For example, in the case of depositing a counter electrode to include two or more sublayers, each of the sublayers can be deposited in different stations. Alternatively or additionally, two or more sublayers in a layer can be deposited in the same station, using different targets in the same station in some cases. In one example, the counter electrode is deposited in a single station and includes sublayers of different compositions (e.g., NiWO sublayer and one or more NiWTaO sublayers, but other material combinations can also be used). Targets of different compositions can be provided at different parts of the station to deposit the sublayers as needed. In another example, the counter electrode can be deposited in two stations, a first station depositing a first sublayer (e.g., a thin flash coating) of a first counter electrode material (e.g., NiWO or another anode coloring counter electrode material) and a second station depositing one or more additional sublayers (e.g., NiWTaO or another anode coloring counter electrode material) of a second (or additional) counter electrode material. In another embodiment, a dedicated station is provided to deposit each layer or sublayer with different compositions. For example, a first station may be provided to deposit a first sublayer having a first composition (e.g., NiWO), a second station may be provided to deposit a second sublayer having a second composition (e.g., NiWTaO including approximately 7% tantalum), and a third station may be provided to deposit a third sublayer having a third composition (e.g., NiWTaO including approximately 14% tantalum).

[0198] The system also includes a controller containing program instructions for sequentially depositing (i) an electrochromic layer, (ii) (optional) an ion-conducting layer, and (iii) a counter electrode layer (as described herein) on the substrate to form a stack by transferring the substrate through the multiple stations. In one embodiment, the multiple deposition stations are operable to transfer the substrate from one station to the next station without breaking the vacuum. In another embodiment, the multiple deposition stations are configured to deposit an electrochromic layer, an optional ion-conducting 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 hold the architectural glass substrate in a vertical orientation when in the multiple deposition stations. In yet another embodiment, the integrated deposition system includes one or more loading chambers for transferring substrates between an external environment and the integrated deposition system. In another embodiment, the multiple deposition stations include at least two stations for depositing a layer selected from the group consisting of a cathode coloring electrochromic layer, an ion-conducting layer, and an anodically coloring counter electrode layer.

[0199] In some embodiments, the integrated deposition system includes one or more lithium deposition stations, each of which includes a target containing lithium. In one embodiment, the integrated deposition system contains two or more lithium deposition stations. In one embodiment, the integrated deposition system has one or more isolation valves for isolating individual processing stations from each other during operation. In one embodiment, the one or more lithium deposition stations have an isolation valve. In this document, the term "isolation valve" means a device used in the integrated deposition system to isolate the deposition or other treatment performed at one station from the treatment at other stations. In one example, the isolation valve is a physical (solid) isolation valve engaged in the integrated deposition system when lithium is deposited. The actual physical solid valve can be used to completely or partially isolate (or shield) lithium deposition from other treatments or stations in the integrated deposition system. In another embodiment, the isolation valve can be a gas knife or 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 evacuated area between a lithium deposition station and other processing stations, such that lithium ions entering the evacuated area or ions from other stations are removed to (for example) a waste stream rather than contaminating adjacent processes. This is achieved, for example, via differential pressure in the lithiation station of the integrated deposition system via fluid dynamics in the controlled surrounding environment, such that lithium deposition is adequately isolated from other processes in the integrated deposition system. Furthermore, the isolation valve is not limited to lithium deposition stations.

[0200] Fig.9AAn integrated deposition system 800 according to certain embodiments is schematically depicted. In this example, the system 800 includes an inlet loading chamber 802 for introducing a substrate into the system and an outlet loading chamber 804 for removing a substrate from the system. The loading chamber allows a substrate to be introduced into and removed from the system without disturbing the controlled surrounding environment of the system. The integrated deposition system 800 has a module 806, which has a plurality of deposition stations; an EC layer deposition station, an IC layer deposition station, and a CE layer deposition station. In the broadest sense, the integrated deposition system does not need to have a loading chamber, for example, the module 806 can be used alone as an integrated deposition system. For example, a substrate can be loaded into the module 806, a controlled surrounding environment can be established, and then the substrate can be passed through various stations in the system for processing. Individual stations in the integrated deposition system can contain heaters, coolers, various sputtering targets and components for moving them, RF and / or DC power supplies and power delivery mechanisms, etching tools (e.g., plasma etching), gas sources, vacuum sources, glow discharge sources, process parameter monitors and sensors, robots, power supplies, and the like.

[0201] Fig. 9B A section (or simplified version) of an integrated deposition system 800 is depicted in perspective and in more detail, including a cutaway view of the interior. In this example, the system 800 is modular, with a sample loading chamber 802 and a sample loading chamber 804 connected to a deposition module 806. There is an inlet 810 for loading, for example, an architectural glass substrate 825 (the loading chamber 804 has a corresponding outlet). The substrate 825 is supported by a pallet 820, which travels along a track 815. In this example, the pallet 820 is supported by the track 815 via suspension, but the pallet 820 can also be supported on a track near the bottom of the device 800 or on top of a track located between the top and bottom of the device 800, for example. The pallet 820 can be translated forward and / or backward (as indicated by double arrows) through the system 800. For example, during lithium deposition, the substrate can move back and forth in front of the lithium target 830, causing multiple passes to achieve desired lithiation. The support plate 820 and substrate 825 are in a substantially vertical orientation. The substantially vertical orientation is not limiting, but it can help prevent defects because particulate matter that may be generated, for example, by agglomeration of atoms from sputtering will tend to succumb to gravity and therefore not deposit on the substrate 825. In addition, because architectural glass substrates tend to be larger, the vertical orientation of the substrate as it traverses the stations of the integrated deposition system enables coating of thinner glass substrates because there are fewer issues with sagging, which can occur with thicker hot glass.

[0202] Target 830 (in this case a cylindrical target) is oriented substantially parallel to and in front of the substrate surface where deposition will occur (other sputtering components are not depicted here for convenience). Substrate 825 may translate past target 830 during deposition, and / or target 830 may move in front of substrate 825. The path of movement of target 830 is not limited to translation along the path of substrate 825. Target 830 may rotate along an axis passing through its length, translate along the path of the substrate (forward and / or backward), translate along a path perpendicular to the path of the substrate, move in a circular path in a plane parallel to substrate 825, etc. Target 830 need not be cylindrical, it may be planar or any shape required for depositing a desired layer with desired properties. Furthermore, there may be more than one target in each deposition station, and / or the target may be moved from station to station depending on the desired process.

[0203] The integrated deposition system 800 also has various vacuum pumps, gas inlets, pressure sensors, etc. to 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. For example, via a computer system or other controller (in Fig. 9B The system 800 is controlled by a computer (represented by an LCD and keyboard) 835. Those skilled in the art will appreciate that the embodiments herein may employ various processes involving data stored in or transmitted through one or more computer systems. The embodiments also relate to devices, such computers, and microcontrollers for performing these operations. These devices and processes may be employed to deposit the electrochromic materials of the methods herein and devices designed to implement them. The control device may be specially constructed for the desired purpose, or it may be a general-purpose computer that is selectively activated or reconfigured by a computer program and / or data structure stored in the computer. The processes presented herein are not inherently related to any particular computer or other device. Specifically, various general-purpose machines may be used with programs written in accordance with the teachings herein, or it may be more convenient to construct more specialized devices to perform and / or control the desired methods and processes.

[0204] 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. Fig. 9CAn integrated deposition system 800a is depicted, which is similar to system 800, but in this example each of the stations is modular, specifically EC layer station 806a, optional IC layer station 806b, and CE layer station 806c. In similar embodiments, IC layer station 806b is omitted. A modular format is not required, but it is convenient because, depending on the need, the integrated deposition system can be assembled according to custom needs and emerging process advances. For example, a lithium deposition station (not shown) can be inserted at relevant locations to provide lithium for various layers and sub-layers as needed.

[0205] Fig.9D The embodiment of integrated deposition system 800d is shown. In this embodiment, integrated deposition system 800d includes injection loading chamber 802, two stations 850 and 851 for depositing the sublayer of cathode coloring electrochromic material, two stations 852 and 853 for depositing the sublayer of anode coloring counter electrode material, and sample loading chamber 804. The first sublayer of cathode coloring electrochromic material is deposited in station 850. The second sublayer of cathode coloring electrochromic material is deposited in station 851, and can be the oxygen-rich form of the electrochromic material deposited in station 850 in some cases. In this embodiment, there is no separate station for depositing ion conductor layer. After depositing the second sublayer of electrochromic material, the first sublayer of anode coloring counter electrode material can be deposited in station 852. The first sublayer can be a flash coating, (for example) made of NiWO or another anode coloring material as described herein. Next, the second sublayer of anode coloring counter electrode material can be deposited in station 853. As described herein, this layer can have any composition, and is NiWTaO in one embodiment. In various cases, the second CE layer station 853 (or any other station configured for depositing CE material) is configured for depositing sub-layers having a graded composition.

[0206] Fig.9E An additional embodiment of an integrated deposition system 800e is shown. Fig.9D The embodiments shown in are similar and for the sake of brevity only the differences will be described. Fig.9E In the deposition system of FIG. 8 , a lithiation station 854 is included after the second electrode station 853. In similar embodiments, an additional lithiation station may be provided. In addition, the lithiation station may be located at Fig.9E , for example, between stations 850 and 851, between stations 851 and 852, between stations 852 and 853, between station 853, and / or between stations 855 and 856.

[0207] In addition, a capping layer station 855 is included after the lithiation station 854. The capping layer station 855 can be used to deposit the capping layer. The capping layer is defined as a layer added to the electrochromic device between the EC layer or the CE layer and the TCO. In some embodiments, the capping layer is an anode coloring material. For example, in some cases, the capping layer includes the same element as the anode coloring material in one or more of the sublayers of the counter electrode layer (for example, the capping layer can include the same element present in the first sublayer, the second sublayer, etc.). In one example, the capping layer is made of NiWO, wherein the composition of NiWO in the capping layer can be the same or different from the composition of NiWO used elsewhere in the device (for example, in the first sublayer of the counter electrode layer). In another example, the capping layer can be made of NiWTaO, NiWSnO, NiWNbO or another anode coloring counter electrode material, wherein the composition of the capping layer can be the same or different from the composition of this material used in other parts of the device (for example, in the second sublayer of the counter electrode layer). Although the cover layer can be made of anodically coloring materials, in various embodiments, the cover layer does not exhibit electrochromic behavior in the finished device. In certain embodiments, the cover layer can have a thickness of about 1×10 10 Ohm-cm vs. 5×10 10 The resistivity is between ohms-cm. The integrated deposition system 800e also includes a station 856 for depositing a layer of a transparent conductive oxide (TCO). In some embodiments, this layer may be indium tin oxide (ITO).

[0208] Integrated deposition systems (such as Figures 9A-9E ) may also have a TCO layer station (not shown in FIG) for depositing a TCO layer on the EC stack. Figures 9A-9D Depending on the process requirements, additional stations can be added to the integrated deposition system, for example, stations for heating / annealing process, cleaning process, laser writing, spin process, capping layer, defect mitigation insulating layer (DMIL), MTC, etc.

[0209] Although the foregoing embodiments have been described in some detail to facilitate understanding, the described embodiments should be considered illustrative rather than restrictive. It will be apparent to one of ordinary skill in the art that certain changes and modifications may be practiced within the scope of the appended claims.

Claims

1. An electrochromic device, comprising: substrate; an electrochromic layer disposed on or over the substrate, the electrochromic layer comprising a cathodically dyed electrochromic material; as well as A counter electrode layer is also disposed on or above the substrate, the counter electrode layer comprising (a) a first sublayer comprising a first anodic dyeing material, and (b) a second sublayer comprising a second anodic dyeing material, wherein the first and second anodic dyeing materials have different compositions but each comprises an oxide of at least one transition metal, and wherein the first sublayer is disposed between the electrochromic layer and the second sublayer.

2. The electrochromic device of claim 1, wherein each of the first and second anodizing materials comprises the at least one transition metal and another non-alkali metal.

3. The electrochromic device of claim 2, wherein the first and second anodic dye materials each comprise nickel and tungsten.

4. The electrochromic device of claim 3, wherein the second anodizing material further comprises tantalum.

5. The electrochromic device of claim 3, wherein the second anodizing material further comprises niobium.

6. The electrochromic device of claim 3, wherein the second anodizing material further comprises tin.

7. An electrochromic device according to claim 2, wherein the second anodic dyeing material comprises the at least one transition metal, the another non-alkali metal and a second non-alkali metal, and wherein the first anodic dyeing material contains the at least one transition metal and the another non-alkali metal as its only metals.

8. An electrochromic device according to claim 2, wherein the first and second anodic dyeing materials each include the at least one transition metal, the another non-alkali metal and the second non-alkali metal, and wherein the second anodic dyeing material has a higher atomic concentration of the second non-alkali metal compared to the first anodic dyeing material.

9. The electrochromic device of claim 2, wherein one of the at least one transition metal is selected from the group consisting of tungsten (W), tantalum (Ta), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), rhodium (Rh), ruthenium (Ru), vanadium (V), iridium (Ir), and combinations thereof.

10. The electrochromic device of claim 9, wherein the other non-alkali metal is selected from the group consisting of silver (Ag), aluminum (Al), arsenic (As), gold (Au), boron (B), barium (Ba), beryllium (Be), bismuth (Bi), calcium (Ca), cadmium (Cd), cerium (Ce), cobalt (Co), chromium (Cr), copper (Cu), europium (Eu), iron (Fe), gallium (Ga), gadolinium (Gd), germanium (Ge), hafnium (Hf), mercury (Hg), indium (In), iridium (Ir), lanthanum (La), magnesium (Mg), manganese (Mn), molybdenum (Mo), Niobium (Nb), neodymium (Nd), osmium (Os), protactinium (Pa), lead (Pb), palladium (Pd), praseodymium (Pr), promethium (Pm), polonium (Po), platinum (Pt), radium (Ra), rhenium (Re), rhodium (Rh), ruthenium (Ru), antimony (Sb), scandium (Sc), selenium (Se), silicon (Si), samarium (Sm), tin (Sn), strontium (Sr), tantalum (Ta), terbium (Tb), technetium (Tc), tellurium (Te), thorium (Th), titanium (Ti), thallium (Tl), uranium (U), vanadium (V), tungsten (W), yttrium (Y), zinc (Zn), zirconium (Zr), and combinations thereof.

11. The electrochromic device of claim 10, wherein the other non-alkali metal is selected from the group consisting of silver (Ag), arsenic (As), gold (Au), boron (B), cadmium (Cd), copper (Cu), europium (Eu), gallium (Ga), gadolinium (Gd), germanium (Ge), mercury (Hg), osmium (Os), lead (Pb), palladium (Pd), promethium (Pm), polonium (Po), platinum (Pt), radium (Ra), terbium (Tb), technetium (Tc), thorium (Th), thallium (Tl), and combinations thereof.

12. The electrochromic device of claim 10, wherein the another non-alkali metal is selected from the group consisting of tantalum (Ta), tin (Sn) and niobium (Nb).

13. The electrochromic device of claim 12, wherein the another non-alkali metal is tantalum (Ta).

14. The electrochromic device of claim 12, wherein the another non-alkali metal is tin (Sn).

15. The electrochromic device of claim 12, wherein the another non-alkali metal is niobium (Nb).

16. The electrochromic device of claim 1, wherein the first and second anodic dye materials each comprise a first transition metal, a second transition metal, and oxygen, and wherein a ratio of the first transition metal to the second transition metal is different in the first and second anodic dye materials.

17. An electrochromic device according to claim 1, wherein the counter electrode layer further includes a third sublayer, the third sublayer including a third anodized electrochromic material, wherein the first, second and third anodized materials have different compositions but each include the at least one transition metal, and wherein the second sublayer is disposed between the first sublayer and the third sublayer.

18. An electrochromic device according to claim 17, wherein the first anodic dyeing material includes the at least one transition metal, the second transition metal, but no other transition metals, and includes oxygen; the second anodic dyeing material includes the at least one transition metal, the second transition metal, a third transition metal and oxygen; and the third anodic dyeing material includes the at least one transition metal, the second metal, the third transition metal and oxygen, and wherein the second and third anodic dyeing materials have different concentrations of the third transition metal.

19. The electrochromic device of claim 1, wherein the first and second sub-layers of the counter electrode layer are in physical contact with each other.

20. The electrochromic device of claim 1, wherein the first and second sublayers of the counter electrode layer are separated from each other by a defect mitigation insulating layer having a thickness of about 1×10 10 Ohm-cm vs. 5×10 10 Resistivity between ohms-cm.

21. The electrochromic device of claim 1, wherein the first anodizing material has a first affinity for lithium and the second anodizing material has a second affinity for lithium, wherein the first affinity for lithium is different than the second affinity for lithium.

22. The electrochromic device of claim 1, wherein the transmission b* value of the electrochromic device is about 14 or less when the electrochromic device is in its clearest state.

23. The electrochromic device of claim 1, wherein the transmission b* value of the electrochromic device is about 10 or less when the electrochromic device is in its clearest state.

24. The electrochromic device of claim 1, wherein the visible light transmittance of the electrochromic device is at least about 55% when the electrochromic device is in its clearest state.

25. The electrochromic device of claim 1, wherein at least one of the first and second anodizing materials comprises nickel, aluminum, and oxygen.

26. The electrochromic device of claim 25, wherein the first anodizing material comprises nickel, tungsten, and oxygen, and wherein the second anodizing material comprises nickel, aluminum, and oxygen.

27. The electrochromic device of claim 1, wherein at least one of the first and second anodizing materials comprises nickel, silicon, and oxygen.

28. The electrochromic device of claim 27, wherein the first anodizing material comprises nickel, tungsten, and oxygen, and wherein the second anodizing material comprises nickel, silicon, and oxygen.

29. The electrochromic device of claim 1, wherein the first anodizing material is NiWO and the second anodizing material is selected from NiWTaO, NiWSnO, NiWNbO, NiTaO, NiSnO, or NiNbO.

30. An electrochromic device comprising: substrate; an electrochromic layer disposed on or over the substrate, the electrochromic layer comprising a cathodically dyed electrochromic material; as well as Also disposed on or above the substrate is an anodically dyed counter electrode layer, the counter electrode layer comprising (a) a first sublayer comprising a first nickel tungsten oxide composition, and (b) a second sublayer comprising a second nickel tungsten oxide composition, wherein the first and second nickel tungsten oxide compositions have different relative amounts of nickel and / or tungsten, and wherein the first sublayer is disposed between the electrochromic layer and the second sublayer.

31. The electrochromic device of claim 30, wherein the second nickel tungsten oxide composition further comprises tantalum, niobium, tin, or a combination thereof.

32. The electrochromic device of claim 31, wherein the second nickel tungsten oxide composition comprises tantalum.

33. The electrochromic device of claim 31, wherein the second nickel tungsten oxide composition comprises niobium.

34. The electrochromic device of claim 31, wherein the second nickel tungsten oxide composition comprises tin.

35. The electrochromic device of claim 32, wherein the first nickel tungsten oxide composition further comprises tantalum, and wherein the second nickel tungsten oxide composition comprises a higher concentration of tantalum than the first nickel tungsten oxide composition.

36. The electrochromic device of claim 33, wherein the first nickel tungsten oxide composition further comprises niobium, and wherein the second nickel tungsten oxide composition comprises a higher concentration of niobium than the first nickel tungsten oxide composition.

37. The electrochromic device of claim 34, wherein the first nickel tungsten oxide composition further comprises tin, and wherein the second nickel tungsten oxide composition comprises a higher concentration of tin than the first nickel tungsten oxide composition.

38. An electrochromic device according to claim 31, wherein the counter electrode layer further includes a third sublayer, the third sublayer including a third nickel tungsten oxide composition, wherein the first, second and third nickel tungsten oxide compositions have different relative amounts of nickel and / or tungsten, and wherein the second sublayer is disposed between the first sublayer and the third sublayer.

39. The electrochromic device of claim 38, wherein the third nickel tungsten oxide composition further comprises tantalum, niobium, tin, or a combination thereof.

40. The electrochromic device of claim 39, wherein the third nickel tungsten oxide composition comprises tantalum.

41. The electrochromic device of claim 39, wherein the third nickel tungsten oxide composition comprises niobium.

42. The electrochromic device of claim 39, wherein the third nickel tungsten oxide composition comprises tin.

43. The electrochromic device of claim 40, wherein the second and third nickel tungsten oxide compositions each include tantalum, and wherein the third nickel tungsten oxide composition includes a higher concentration of tantalum than the second nickel tungsten oxide composition.

44. The electrochromic device of claim 41, wherein the second and third nickel tungsten oxide compositions each include niobium, and wherein the third nickel tungsten oxide composition includes a higher niobium concentration than the second nickel tungsten oxide composition.

45. The electrochromic device of claim 42, wherein the second and third nickel tungsten oxide compositions each include tin, and wherein the third nickel tungsten oxide composition includes a higher concentration of tin than the second nickel tungsten oxide composition.

46. ​​An electrochromic device according to claim 30, wherein the counter electrode layer further includes a third sublayer, the third sublayer includes a third nickel tungsten oxide composition, wherein the second nickel tungsten oxide composition further includes a metal M1, wherein the third nickel tungsten oxide composition further includes a metal M2, and wherein the metals M1 and M2 are different from each other.

47. The electrochromic device of claim 46, wherein the second nickel tungsten oxide composition is substantially free of metal M2, and wherein the third nickel tungsten oxide composition is substantially free of metal M1.

48. The electrochromic device of claim 30, wherein at least one of the first and second sublayers of the counter electrode layer comprises a graded composition.

49. The electrochromic device of claim 30, wherein the first and second sublayers of the counter electrode layer each have a morphology that is a mixture of an amorphous phase and a nanocrystalline phase having nanocrystals having diameters less than about 50 nm.

50. A method of making an electrochromic device, the method comprising: depositing an electrochromic layer, the electrochromic layer comprising a cathodically coloring electrochromic material; The counter electrode layer was deposited by: depositing a first anodic dyed sublayer, and A second anodically dyeing sublayer is deposited, wherein the first anodically dyeing sublayer is located between the electrochromic layer and the second anodically dyeing sublayer, and wherein the first and second anodically dyeing layers have different compositions and each include an oxide of at least one transition metal.

51. The method of claim 50, wherein the second anodized sublayer comprises one or more metals not present in the first sublayer.

52. The method of claim 50, wherein depositing the counter electrode layer further comprises depositing a third anodic dyeing sublayer, the third anodic dyeing sublayer comprising an oxide of at least one transition metal, wherein the second anodic dyeing sublayer is located between the first and third anodic dyeing sublayers.

53. A method according to claim 52, wherein the second and third anodic dyeing sublayers each include a metal that is not present in the first anodic dyeing sublayer, and wherein the atomic concentration of the metal that is not present in the first anodic dyeing sublayer is higher in the third anodic dyeing sublayer than in the second anodic dyeing sublayer.

54. A method according to claim 53, wherein the first anodic dyeing sublayer is essentially composed of nickel tungsten oxide, wherein the second and third anodic dyeing sublayers are essentially composed of nickel tungsten tantalum oxide, and wherein the concentration of tantalum is higher in the third anodic dyeing sublayer than in the second anodic dyeing sublayer.

55. The method of claim 50, wherein the first anodically dyed sublayer is deposited at a higher deposition rate than the second anodically dyed sublayer.

56. The method of claim 50, wherein the first anodic dye sublayer is deposited at a sputtering power lower than a sputtering power used to deposit the second anodic dye sublayer.

57. The method of claim 50, wherein the temperature of the partially fabricated electrochromic device is lower during deposition of the first anodically dyeing sublayer than during deposition of the second anodically dyeing sublayer.

58. The method of claim 50, further comprising lithiating the first anodic dyeing sublayer prior to depositing the second anodic dyeing sublayer.

59. The method of claim 50, further comprising: Lithium is deposited on the second anodic dyeing sublayer, and then A third anodically dyed sublayer is deposited on the second anodically dyed sublayer.

60. The method of claim 50, further comprising: A third anodic dyeing sublayer is deposited on the second anodic dyeing sublayer, and then lithium is deposited on the third anodic dyeing sublayer.

61. A method of making an electrochromic device, the method comprising: depositing an electrochromic layer, the electrochromic layer comprising a cathodically coloring electrochromic material; The counter electrode layer was deposited by: depositing a first anodic dyeing sublayer, Lithiating the first anodic dyeing sublayer, and After lithiation of the first anodic dyeing sublayer, a second anodic dyeing sublayer is deposited, wherein the first anodic dyeing sublayer is located between the electrochromic layer and the second anodic dyeing sublayer, and wherein the first and second anodic dyeing sublayers have different compositions and each include an oxide of at least one transition metal.

62. A method according to claim 61, wherein depositing the counter electrode layer also includes depositing a third anode dyeing sublayer comprising an oxide of at least one transition metal, wherein the second dyeing sublayer is disposed between the first and third anode dyeing sublayers, wherein the first anode dyeing sublayer is substantially composed of nickel tungsten oxide, wherein the second and third anode dyeing sublayers are substantially composed of nickel tungsten tantalum oxide, and wherein the concentration of tantalum is higher in the third anode dyeing sublayer than in the second anode dyeing sublayer.

63. The method of claim 61, wherein the first anodized sublayer is deposited at a higher deposition rate than the second anodized sublayer.

64. The method of claim 61, wherein the first anodic dyeing sublayer is deposited at a sputtering power lower than the sputtering power used to deposit the second anodic dyeing sublayer.

65. The method of claim 64, wherein the first anodically dyed sublayer is heated at about 5 kW / m 2 Up to 20kW / m 2 and wherein the second sublayer is deposited at a sputtering power of about 20 kW / m 2 Up to 45kW / m 2 Deposition is performed with a sputtering power between 0.

66. The method of claim 61, wherein the temperature of the partially fabricated electrochromic device is lower during deposition of the first anodically dyeing sublayer than during deposition of the second anodically dyeing sublayer.

67. The method of claim 61, further comprising: Lithium is deposited on the second anodic dyeing sublayer, and then A third anodically dyed sublayer is deposited on the second anodically dyed sublayer.

68. The method of claim 61, further comprising: A third anodic dyeing sublayer is deposited on the second anodic dyeing sublayer, and then lithium is deposited on the third anodic dyeing sublayer.

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