TWI681242B - Electrochromic devices - Google Patents

Abstract

Conventional electrochromic devices frequently suffer from poor reliability and poor performance. Improvements are made using entirely solid and inorganic materials. Electrochromic devices are fabricated by forming an ion conducting electronically insulating interfacial region that serves as an IC layer. In some methods, the interfacial region is formedafter formation of an electrochromic and a counter electrode layer. The interfacial region contains an ion conducting electronically insulating material along with components of the electrochromic and/or the counter electrode layer. Materials and microstructure of the electrochromic devices provide improvements in performance and reliability over conventional devices.

Description

Electrochromic device

Electrochromism is a phenomenon in which a material exhibits a reversible change in optical properties when it is in a different electronic energy state (usually by undergoing a voltage change), which is electrochemically mediated. The optical property is usually one or more of color, transmittance, absorbance, and reflectance. For example, a well-known electrochromic material is tungsten oxide (WO ₃ ). Tungsten oxide is a cathode electrochromic material, in which a color transition (blue permeation) occurs through electrochemical reduction. Electrochromic materials can be incorporated into, for example, windows and mirrors. The color, transmittance, absorbance and/or reflectivity of these windows and mirrors can be changed by inducing changes in electrochromic materials. For example, a well-known application of electrochromic materials is rearview mirrors in some automobiles. In these electrochromic rearview mirrors, the reflectivity of the mirror changes at night, so that the front lights of other vehicles do not distract the driver’s attention. Although the electrochromic system was discovered in the 1960s, unfortunately, electrochromic devices still suffer from various problems and have not yet begun to realize their full commercial potential. Advances in electrochromic technology, equipment and related methods of manufacturing and/or using such equipment are required.

A typical electrochromic device includes an electrochromic ("EC") electrode layer and a counter electrode ("CE") layer separated by an ion conducting ("IC") layer that is highly conductive to ions and highly resistant to electrons. In other words, the ion conducting layer allows the transport of ions, but blocks the current. As generally understood, the ion conducting layer thus prevents a short circuit between the electrochromic layer and the counter electrode layer. The ion conductive layer allows the electrochromic electrode and the counter electrode to maintain charge, and thereby maintain their faded or colored state. In the conventional electrochromic device, the components form a stack, wherein the ion conductive layer is sandwiched between the electrochromic electrode and the counter electrode. The boundaries between these three stacked components are defined by sudden changes in composition and/or microstructure. Therefore, these devices have three distinct layers with two abrupt interfaces. Quite surprisingly, the inventors have discovered that high-quality electrochromic devices can be manufactured without depositing an ion-conducting electrically insulating layer. According to certain embodiments, the counter electrode and the electrochromic electrode are formed immediately adjacent to each other (often in direct contact) without depositing an ion conducting layer separately. Xianxin, various manufacturing processes and/or physical or chemical mechanisms create an interface region between the contacting electrochromic layer and the counter electrode layer, and this interface region serves as at least some of the ion-conducting electrically insulating layers in conventional devices Features. The following describes specific mechanisms that may be key to the formation of the interface area. The interface region usually (though not necessarily) has a heterostructure including at least two discrete components represented by different phases and/or compositions. In addition, the interface region may include gradients among these two or more discrete components. The gradient can provide, for example, variable composition, microstructure, resistivity, dopant concentration (eg, oxygen concentration), and/or stoichiometry. In addition to the above findings, the inventors have observed that in order to improve device reliability, two layers of electrochromic devices (electrochromic (EC) layer and counter electrode (CE) layer) can be fabricated to include each A defined amount of lithium. In addition, careful selection of materials and morphology and/or microstructures of some components of electrochromic devices provides improvements in performance and reliability. In some embodiments, all layers of the device are all solid and inorganic. Consistent with the above observations and findings, the inventors have found that the formation of the EC-IC-CE stack does not need to be performed in a conventional sequence (EC→IC→CE or CE→IC→EC), but can be performed in the electrochromic layer and opposite After the formation of the electrode layer, an ion conductive electrically insulating region serving as an IC layer is formed. That is, the EC-CE (or CE-EC) stack is formed first, and then one or a combination of the two layers is formed between the EC layer and the CE layer at the interface between the EC layer and the CE layer. Interface area for some uses to the IC layer. The method of the present invention not only reduces manufacturing complexity and cost by eliminating one or more processing steps, but also provides a device that exhibits improved performance characteristics. Therefore, one aspect of the present invention is a method of manufacturing an electrochromic device, the method comprising: forming an electrochromic layer including an electrochromic material; forming an opposite electrode layer in contact with the electrochromic layer, and Without first providing an ion-conducting electrically insulating layer between the electrochromic layer and the counter electrode layer; and forming an interface region between the electrochromic layer and the counter electrode layer, wherein the interface region is substantially ionic Conductive and substantially electrically insulating. The electrochromic layer and the counter electrode layer are usually (but not necessarily) made of one or more materials that are more conductive than the interface region but may have certain anti-electron properties. The interface region may contain component materials of the EC layer and/or the CE layer, and in some embodiments, the EC layer and the CE layer contain component materials of the interface region. In one embodiment, the electrochromic layer includes WO ₃ . In some embodiments, the EC layer includes WO ₃ , the CE layer includes nickel tungsten oxide (NiWO), and the IC layer includes lithium tungstate (Li ₂ WO ₄ ). Heating may be applied during the deposition of at least a portion of the electrochromic layer. In one embodiment, where the EC layer includes WO ₃ , heating is applied after each of a series of depositions via sputtering to form an EC layer with a substantially polycrystalline microstructure. In one embodiment, the thickness of the electrochromic layer is between about 300 nm and about 600 nm, but the thickness may vary depending on the desired result of forming the interface region after depositing the EC-CE stack. In some embodiments, WO ₃ is substantially polycrystalline. In some embodiments, an oxygen-rich layer of WO ₃ can be used as a precursor to the interface region. In other embodiments, the WO ₃ layer is a graded layer with varying oxygen concentration in the layer. In some embodiments, lithium is the preferred ionic species for driving electrochromic transitions, and stacking or layer lithiation schemes are described. The details of the formation parameters and layer characteristics will be described in more detail below. Another aspect of the present invention is a method of manufacturing an electrochromic device, the method comprising: (a) forming an electrochromic layer including an electrochromic material or a counter electrode layer including a counter electrode material; (b) Forming an intermediate layer above the electrochromic layer or the counter electrode layer, wherein the intermediate layer includes an oxygen-rich form of at least one of the electrochromic material, the counter electrode material, and additional materials, wherein the additional materials Including different electrochromic materials and/or counter electrode materials, the intermediate layer is not substantially electrically insulating; (c) forming the other of the electrochromic layer and the counter electrode layer; and ( d) Allow at least a portion of the intermediate layer to become substantially electrically insulating and substantially ionically conductive. The details of the formation parameters and layer characteristics used in this method will also be described in more detail below. Another aspect of the present invention is an apparatus for manufacturing an electrochromic device, which includes: an integrated deposition system, which includes: (i) a first deposition station containing a source of material, which is configured to deposit an electrochromic device An electrochromic layer of a color-changing material; and (ii) a second deposition station configured to deposit an opposite electrode layer including the opposite electrode material; and a controller containing a layer for sequentially depositing the stack on the substrate Transfer the programming instructions of the substrate through the first deposition stage and the second deposition stage, the stack has an intermediate layer sandwiched between the electrochromic layer and the counter electrode layer; wherein the first deposition stage and the Either or both of the second deposition stations are also configured to deposit the intermediate layer over the electrochromic layer or the counter electrode layer, and wherein the intermediate layer includes the electrochromic material or the counter electrode material Oxygen-rich form, and wherein the first deposition stage and the second deposition stage are interconnected in series and are operable to transfer the substrate from one stage to the next without exposing the substrate to the external environment. In one embodiment, the apparatus of the present invention is operable to transfer the substrate from one stage to the next without breaking the vacuum, and may include operable to deposit lithium from a lithium-containing material source in the electrochromic device One or more lithiation stations on one or more layers. In one embodiment, the apparatus of the present invention is operable to deposit the electrochromic stack on a building glass substrate. The apparatus of the present invention does not need to have a separate target for manufacturing the ion conductive layer. Another aspect of the present invention is an electrochromic device including: (a) an electrochromic layer including an electrochromic material; (b) an opposing electrode layer including an opposing electrode material; and (c) in An interface region between the electrochromic layer and the counter electrode layer, wherein the interface region includes at least one of an electrically insulating ion conductive material and the electrochromic material, the counter electrode material, and additional materials, wherein the The additional materials include different electrochromic materials and/or counter electrode materials. In some embodiments, the additional material is not included; in these embodiments, the interface region includes at least one of the electrochromic material and the counter electrode material. Changes in the composition and morphology and/or microstructure of the interface area will be described in more detail herein. The electrochromic devices described herein can be incorporated into windows (in one embodiment, architectural glass scale windows). These and other features and advantages of the present invention will be described in more detail below with reference to the associated drawings.

The present invention claims the rights and priority of the US applications No. 12/772,055 and No. 12/772,075, each filed on April 30, 2010 and entitled "Electrochromic Devices", these applications Each of them is incorporated by reference in full text. The following detailed description can be more fully understood when considered in conjunction with the drawings. FIG. 1A is a schematic cross-section depicting a stack 100 of conventional electrochromic devices. The electrochromic device 100 includes a substrate 102, a conductive layer (CL) 104, an electrochromic (EC) layer 106, an ion conductive (IC) layer 108, a counter electrode (CE) layer 110, and a conductive layer (CL) 112. The elements 104, 106, 108, 110, and 112 are collectively referred to as the electrochromic stack 114. Generally, the CL layers are made of transparent conductive oxide, and are often referred to as "TCO" layers. Since the TCO layer is transparent, the coloring behavior of the EC-IC-CE stack can be observed, for example, through the TCO layer, allowing these devices to be used on windows to obtain reversible shading. A voltage source 116 operable to apply a potential across the electrochromic stack 114 realizes the transition of the electrochromic device from, for example, a faded state (ie, transparent) to a colored state. The order of these layers can be reversed with respect to the substrate. That is, the layers may be in the following order: substrate, transparent conductive layer, counter electrode layer, ion conductive layer, electrochromic material layer, and (another) transparent conductive layer. Referring again to FIG. 1A, in a conventional method of manufacturing an electrochromic stack, individual layers are deposited on top of another layer in a sequential format as depicted in the schematic diagram on the left side of FIG. 1A. That is, the TCO layer 104 is deposited on the substrate 102. Next, the EC layer 106 is deposited on the TCO 104. Next, the IC layer 108 is deposited on the EC layer 106, followed by the CE layer 110 on the IC layer 108, and finally the TCO layer 112 is deposited on the CE layer 110 to form the electrochromic device 100. Of course, the order of the steps can be reversed to form a "reverse" stack, but the point is that in the conventional method, the IC layer must be deposited on the EC layer, followed by the CE layer on the IC layer, or the IC layer is deposited on The CE layer, followed by the EC layer is deposited on the IC layer. The transition between the layers of material in the stack is abrupt. One of the significant challenges of the above procedures is the processing required to form the IC layer. In some previous methods, the IC layer is formed by a sol-gel process that is difficult to incorporate into the CVD or PVD process used to form the EC layer and the CE layer. In addition, IC layers created by sol-gel and other liquid-based processes tend to have defects that degrade the quality of the device and may need to be removed by, for example, engraving. In other methods, the IC layer is deposited by PVD from a ceramic target that may be difficult to manufacture and use. FIG. 1B is a graph depicting the% composition of material versus the position in the electrochromic stack of FIG. 1A (ie, layers 106, 108, and 110, ie, EC layer, IC layer, and CE layer). As mentioned, in conventional electrochromic stacks, the transition between the layers of material in the stack is abrupt. For example, the EC material 106 is deposited as a distinct layer with little or no composition seepage to the adjacent IC layer. Similarly, the IC material 108 and the CE material 110 are different in composition with little or no seepage to adjacent layers. Therefore, these materials are substantially homogeneous (except for the specific composition of CE materials described below) and have abrupt interfaces. The conventional idea is that each of these three layers should be laid as distinct, uniformly deposited and smooth layers to form a stack. The interface between each layer should be "clear", where there is little intermixing of materials from each layer. Those skilled in the art can generally recognize that FIG. 1B is an ideal depiction, and in the practical sense, there is a certain degree of unavoidable material mixing at the layer interface. The point is that in conventional manufacturing methods, any such mixing is unintentional and minimal. The inventors have discovered that an interface region serving as an IC layer can be formed, where the interface region intentionally includes a large amount of one or more electrochromic materials and/or counter electrode materials. This is a fundamental deviation from self-study manufacturing methods. As mentioned above, the inventors have found that the formation of the EC-IC-CE stack does not have to be performed in a conventional sequence (EC→IC→CE or CE→IC→EC), but can be performed in the electrochromic layer and opposite After the deposition of the electrode layer, an interface region serving as an ion conductive layer is formed. That is, the EC-CE (or CE-EC) stack is formed first, and then the layers are used at the interface of the layers (in some embodiments, and/or another electrochromic material or counter electrode material ) One or both components form an interface region between the EC layer and the CE layer (which may possess at least some functions of the IC layer). The interface area serves at least some of the functions of the conventional IC layer because the interface area is substantially ionically conductive and substantially electrically insulating. However, it should be noted that the interface region as described may have a leakage current higher than that accepted by the conventional art, but despite this, these devices exhibit good performance. In one embodiment, the electrochromic layer is formed to have an oxygen-rich region that is converted into an interface region or layer that serves as an IC layer during subsequent processing after depositing the counter electrode layer. In some embodiments, an oxygen-rich dissimilar layer including an electrochromic material is used to (eventually) form an interface layer between the EC layer and the CE layer that acts as an IC layer. In other embodiments, an oxygen-rich dissimilar layer including a counter electrode material is used to (finally) form an interface region between the EC layer and the CE layer that serves as an IC layer. All or part of the oxygen-rich CE layer is converted into an interface area. In other embodiments, a dissimilar layer including an oxygen-rich version of the counter electrode material and an oxygen-rich form of the electrochromic material is used (finally) to form an interface region between the EC layer and the CE layer that acts as an IC layer. In other words, some or all of the oxygen-rich material acts as a precursor to the interface region that serves as the IC layer. The method of the present invention not only reduces processing steps, but also produces electrochromic devices that exhibit improved performance characteristics. As mentioned, Xianxin, some of the EC layer and/or CE layer in the interface area are converted to provide one or more functions of the IC layer (especially high conductivity to ions and high resistivity to electrons) Of material. The IC functional material in the interface region may be, for example, a salt of a conductive cation; for example, a lithium salt. 2A, 2B, and 2C show the composition curves of three possible examples of electrochromic device stacks (each containing an EC layer, a CE layer, and an interface region serving as an IC layer), where the EC material is tungsten oxide (denoted here Is WO ₃ , but is intended to include WO _x , where x is between about 2.7 and about 3.5, in one embodiment, x is between about 2.7 and about 2.9), the CE material is nickel tungsten oxide (NiWO), and the interface The region mainly includes lithium tungstate (herein expressed as Li ₂ WO ₄ , in another embodiment, the interface region is between about 0.5% and about 50 (atomic)% Li ₂ O, between about 5% and about Between 95% of Li ₂ WO ₄ and between about 5% and about 70% of WO ₃ nanocomposite) and a certain amount of EC material and/or CE material. More generally, the interface region usually (but not necessarily) has a heterostructure including at least two discrete components represented by different phases and/or compositions whose concentration varies across the width of the interface region. For this reason, in this article, the interface region that serves as the IC layer is sometimes referred to as the "gradient region", "heterogeneous IC layer" or "dispersed IC layer". Although described with respect to specific materials, the illustrations in FIGS. 2A, 2B, and 2C more generally represent changes in the composition of any suitable materials used in the electrochromic device of the present invention. FIG. 2A depicts the electrochromic stack of the present invention, where the EC material is an important component serving as the interface region of the IC layer, and the CE material is not an important component. Referring to FIG. 2A, starting from the origin and moving from left to right along the x- axis, one can see that a part of the EC material WO ₃ (which is substantially all tungsten oxide) serves as an EC layer. There is a transition into the interface area where there is gradually decreasing tungsten oxide and correspondingly increasing lithium tungstate up to and including the end near the interface area, where there is a substance with a certain minimum amount of tungsten oxide All of the above are parts of lithium tungstate. Although the transition from the EC layer to the interface region is distinguished by a combination of substantially all tungsten oxide and a minimum amount of lithium tungstate, it is obvious that the transition is not as sudden as in conventional devices. In this example, in fact, the transition begins to occur when the composition has a sufficient amount of lithium tungstate to enable the material to perform at least some functions of the IC layer, such as ion conduction and electrical insulation. Undoubtedly, the composition closer to the CE layer (wherein the composition is substantially lithium tungstate) functions as an IC layer, because it is known that lithium tungstate exhibits these properties. However, certain IC layer functions also exist in other parts of the interface area. The inventors have discovered that these "heterogeneous IC layers" improve the switching characteristics and possible thermal cycling stability of electrochromic devices compared to conventional devices with sudden transitions. The CE layer in this example mainly contains nickel tungsten oxide as the active material, and has a relatively sudden transition to the nickel tungsten oxide composition at the edge of the interface region. The method for manufacturing a stack with these interface areas will be described in more detail below. It should be noted that, for example, the nickel tungsten oxide CE layer in FIG. 2A is depicted as having about 20% lithium tungstate. Without wishing to be bound by theory, Xianxin believes that the nickel tungsten oxide CE layer exists as a core or particle of nickel oxide surrounded by a shell or matrix of lithium tungstate (which imparts a fairly good ion conductivity to the CE layer), and thereby Helps the electrochromic transition of the CE layer during the operation of the electrochromic stack. The exact stoichiometry of lithium tungstate in the CE layer can vary significantly between examples. In some embodiments, some tungsten oxide may also be present in the CE layer. Also, because lithium ions travel from the EC layer and the CE layer via the interface region serving as the IC layer, there may be a large amount of lithium tungstate in the EC layer, for example, as depicted in FIG. 2A. FIG. 2B depicts the electrochromic stack of the present invention, in which the CE material is an important component serving as the interface region of the IC layer, and the EC material is not an important component. Referring to FIG. 2B, starting from the origin and moving from left to right along the x- axis, one can see that in this case, substantially all EC materials that are tungsten oxide act as EC layers. There is a sudden transition into the interface region where there is little (if any) tungsten oxide, but there is a large amount of lithium tungstate and at least some nickel tungsten oxide (CE material). The composition of the interface region changes along the x- axis with decreasing lithium tungstate and corresponding increasing nickel tungsten oxide. The transition from the interface area to the CE layer is arbitrarily distinguished by a composition of approximately 80% nickel tungsten oxide and approximately 20% lithium tungstate, but this is only one example of the transition that occurs with a graded composition. When no or few additional changes in the composition occur during further processing of the stack, the interface area can be considered terminated. In addition, the transition actually ends when the composition has a sufficient amount of nickel-tungsten oxide so that the material no longer performs at least a certain function that the different IC layer can perform. Undoubtedly, the composition closer to the CE layer (as distinguished) (where the composition is 80% nickel tungsten oxide) functions as the CE layer. Similarly, the composition closer to the interface region of the EC layer (where lithium tungstate is a substantial component) acts as an ion-conducting electrically insulating material. FIG. 2C depicts the electrochromic stack of the present invention, where both the EC material and the CE material are important components that serve as the interface region of the IC layer. Referring to FIG. 2C, starting from the origin and moving from left to right along the x- axis, one can see that a part of the EC material WO ₃ (which is substantially all tungsten oxide) serves as an EC layer. There is a transition into the interface region where there is gradually decreasing tungsten oxide and correspondingly increasing lithium tungstate. In this example, there is also a growing amount of nickel tungsten oxide counter electrode material in the vicinity of one-third of the way through the part divided into the interface region. At about the middle position of the portion divided by the interface region, there are about 10% of each of tungsten oxide and nickel tungsten oxide and 80% of lithium tungstate. In this example, there is no abrupt transition between the EC layer and the IC layer or between the IC layer and the CE layer, but there is an interface region with a continuous graded composition of both CE material and EC material. In this example, the lithium tungstate component peaks approximately midway through the interface area, and therefore, this area is likely to be the strongest electrically insulating portion of the interface area. As mentioned in [Summary of the Invention] above, the EC layer and the CE layer may include a material composition that imparts a certain resistivity to the EC layer and the CE layer; at least a certain amount spans all of the materials described in FIGS. 2A to 2C Lithium tungstate in the three regions is an example of such materials that impart resistivity to the EC layer and the CE layer. 2A to 2C only show three non-limiting examples of the graded composition that serves as the interface region of the IC layer in the electrochromic device of the present invention. Those of ordinary skill in the art will understand that many variations are possible without departing from the scope of the present invention. In each of the examples in FIGS. 2A to 2C, there is at least one layer in which there are only two material components and one of the components is the least. The invention is not limited to this approach. Therefore, an embodiment of the present invention is an electrochromic device including an electrochromic layer, an interface region serving as an IC layer, and a counter electrode layer, wherein each of the aforementioned two layers and one region of the device At least one component of the material is present in each of the electrochromic layer, the interface region, and the counter electrode layer in the following amount: at least about 25% by weight, in another embodiment, at least about 15 % By weight, in another embodiment, at least about 10% by weight, in another embodiment, at least about 5% by weight, and in yet another embodiment, at least about 2% by weight. The amount of electrochromic material and/or counter electrode material in the interface area may be significant, in one embodiment, up to 50% by weight of the interface area. However, in many embodiments, the ion-conducting electrically insulating material is usually a plurality of components, and the remaining part of the interface region is the electrochromic material and/or the counter electrode material. In one embodiment, the interface region includes between about 60% and about 95% by weight ionically conductive electrically insulating material, and the remaining portion of the interface region is electrochromic material and/or counter electrode material. In one embodiment, the interface region includes between about 70% and about 95% by weight ionically conductive electrically insulating material, and the remaining portion of the interface region is the electrochromic material and/or counter electrode material. In one embodiment, the interface region includes between about 80% and about 95% by weight ionically conductive electrically insulating material, and the remaining portion of the interface region is an electrochromic material and/or counter electrode material. In some embodiments, the interface regions in the devices described herein may be relatively different, that is, when analyzed, for example, by a microscope, there are relatively distinguishable boundaries at adjacent layers, even if the interface region contains The same is true for a certain amount of electrochromic material and/or counter electrode material. In these embodiments, the thickness of the interface region can be measured. In embodiments where the interface region is formed by the oxygen-rich (superstoichiometric) region of the EC layer and/or the CE layer, the ratio of the thickness of the interface region to the layer or layers forming the interface region is used to characterize the interface One of the zones is measured. For example, the electrochromic layer is deposited with an oxygen-rich upper layer. The EC layer may include a single metal oxide or two or more metal oxides mixed homogeneously or heterogeneously in the layer or more diffusion regions. The EC layer is 550 nm thick, which includes an oxygen-rich layer (or region). If about 150 nm of the EC layer is converted into the interface region, then about 27% of the EC is converted into the interface region, that is, 150 nm divided by 550 nm. In another example, the EC layer includes a first metal oxide region (or layer) and an oxygen-rich second metal oxide layer (or region). If all or part of the oxygen-rich metal oxide layer is converted into an interface region, the thickness of the interface region divided by the total thickness of the first metal oxide layer and the second metal oxide layer (before the interface region is formed) is Measurement of the interface area. In one embodiment, the interface region includes between about 0.5% and about 50% by thickness of the precursor region (EC and/or CE, including the oxygen-rich portion) used to form the interface region, in another embodiment Between about 1% and about 30%, in yet another embodiment between about 2% and about 10%, and in another embodiment between about 3% and about 7%. The inventors have found that the graded composition has many benefits as an IC layer. Although not wishing to be bound by theory, Xianxin, by having such grading zones, the efficiency of electrochromic transition is greatly improved. As will be described in more detail below, there are other benefits. Although not wishing to be bound by theory, Xianxin believes that one or more of the following mechanisms can achieve the conversion of EC and/or CE materials into IC functional materials in the interface region. However, the implementation or application of the present invention is not limited to any of these mechanisms. Each of these mechanisms is consistent with the process of never depositing IC layer material during the manufacturing of the stack. As clearly stated elsewhere herein, the device of the present invention need not have a separate target containing materials for the IC layer. In the first mechanism, direct lithiation of the electrochromic material or the counter electrode material produces an IC material (eg, lithium tungstate) in the interface region. As will be explained more fully below, various embodiments use the direct lithiation of one of these active layers at some point in the manufacturing process between the formation of the EC layer and the CE layer. This operation involves the exposure of the EC layer or the CE layer (formed first) to lithium. According to this mechanism, ion-conducting electron-resistant materials such as lithium salts are generated through the flux of lithium in the EC or CE layer. Heat or other energy can be applied to drive this flux of lithium. The described mechanism converts the top or exposed portion of the first formed layer (EC or CE layer) before forming the second layer (CE or EC layer). In the second mechanism, lithium diffusing from one of EC or CE to another layer causes EC and/or after both layers have been formed and/or during the formation of the second layer on the lithiated first layer The part of one of the CEs is converted to the interface area with IC functional materials at its interface. The lithium diffusion may occur after the entire second layer has been formed or after only a certain portion of the second layer has been formed. In addition, the diffusion of lithium and the subsequent conversion to the functional material of the IC occur in the first or the second deposited layer and in the EC or CE layer. In one example, the EC layer is formed first, and then the EC layer is lithiated. When the CE layer is subsequently deposited over the EC layer, some lithium diffuses from the underlying EC layer toward the CE layer and/or into the CE layer, resulting in conversion into an interface region containing IC functional materials. In another example, an EC layer (with an oxygen-rich upper region as appropriate) is formed first, then, a CE layer is formed and the CE layer is lithiated. Subsequently, some lithium from the CE layer diffuses into the EC layer, where it forms an interface region with IC functional materials. In yet another example, an EC layer is first deposited, and then the EC layer is lithiated to produce a certain IC functional material according to the first mechanism described above. Next, when the CE layer is formed, some lithium diffuses from the underlying EC layer toward the CE layer to produce an IC material in the interface region of the CE layer. In this way, the functional IC material nominally resides in both the CE layer and the EC layer immediately following the interface of the CE layer and the EC layer. In the third mechanism, the EC layer and the CE layer are formed to completion (or at least the moment when the second formed layer is partially completed). Next, the device structure is heated, and the heating converts at least some of the materials in the interface area into IC functional materials (eg, lithium salts). Heating (e.g., as part of the multi-step thermochemical conditioning (MTCC) described further herein) can be performed during deposition or after completion of deposition. In one embodiment, heating is performed after the transparent conductive oxide is formed on the stack. In another embodiment, heating is applied after the second layer is partially or completely completed, but before the transparent conductive oxide is applied to the second layer. In some cases, heating is direct and primarily responsible for conversion. In other cases, heating mainly promotes the diffusion or flow of lithium ions. As described in the second mechanism, this creates an IC functional material area. Finally, in the fourth mechanism, the current flowing between the EC layer and the CE layer drives at least one of the electrochromic material and the counter electrode material into an IC functional material in the interface region. This conversion may occur because, for example, the ion flux associated with the flowing current is so large that it drives the chemical conversion of the EC and/or CE material to the IC material in the interface region. For example, as will be explained below, a large lithium flux through tungsten oxide in the EC layer can produce lithium tungstate, which acts as an IC material. The lithium flux can be introduced, for example, during the initial activation cycle of the newly formed device. However, this need not be the case, because other opportunities for driving high ion fluxes may be more appropriate for achieving the conversion. The method of the present invention can be performed by those skilled in the art without using any one or more of the above mechanisms. FIG. 3A is a program flow 300 of the method according to the present invention. Specifically, see 305, (on the CL of TCO, for example) to deposit an EC layer. Next, referring to 310, a CE layer is deposited. After depositing the EC layer and the CE layer, then, referring to 315, an interface region serving as an IC layer is formed between the EC layer and the CE layer. An embodiment of the present invention is a similar method (not depicted) in which steps 305 and 310 are reversed. The main point of this method is that the interface region serving as the IC layer is formed after the EC layer and the CE layer (in some embodiments, at least part of one of the EC layer and the CE layer is used to form the interface region). For this reason, the interface region formed in this way is sometimes referred to as the "essential" IC layer. In other embodiments, for example, an oxygen-enriched version of EC material or CE material is used to form a different layer between the EC layer and the CE layer, wherein the layer is completely or partially converted into an interface region after forming the EC layer and the CE layer . Various methods for forming the interface region after forming the EC-CE stack will be described below. Therefore, as mentioned, one aspect of the present invention is a method of manufacturing an electrochromic device, the method comprising: forming an electrochromic layer including an electrochromic material; and forming an opposing surface in contact with the electrochromic layer An electrode layer without first providing an ion-conducting electrically insulating layer between the electrochromic layer and the counter electrode layer, wherein the counter electrode layer includes a counter electrode material; and between the electrochromic layer and the pair An interface region is formed between the electrode layers, wherein the interface region is substantially ion conductive and substantially electrically insulating. The interface region may contain the EC layer, the CE layer, or a component material of both. As will be described in more detail below, this interface region can be formed in many ways. FIG. 3B is a process flow showing the process flow according to the method described with respect to FIG. 3A (in detail, a process flow for depositing an EC layer, then depositing a CE layer, and finally forming an interface region serving as an IC layer between the layers) Procedure 320. More specifically, in this embodiment, the EC layer includes WO ₃ with various amounts of oxygen (specifically, composition and configuration); the CE layer includes NiWO, the interface region includes Li ₂ WO ₄ , and uses such as oxidation TCO materials of indium tin and fluorinated tin oxide. It should be noted that the layers of the electrochromic device will be described below with regard to solid materials. Solid-state materials are required due to reliability, consistent characteristics and process parameters, and device performance. Exemplary solid-state electrochromic devices, methods, and equipment for manufacturing the same, and methods for manufacturing electrochromic windows using these devices are described in Kozlowski et al., US Non-Provisional Patent Application entitled "Fabrication of Low Defectivity Electrochromic Devices" No. 12/645,111 and Wang et al. US Non-Provisional Patent Application No. 12/645,159 entitled "Electrochromic Devices". These two patent applications are incorporated herein by reference for all purposes. In certain embodiments, the electrochromic devices of the present invention are all solid state and are manufactured in equipment that allows one or more layers of the stack to be deposited in a controlled ambient environment. That is, in equipment that deposits these layers without leaving the equipment and, for example, without breaking the vacuum between the deposition steps, thereby reducing contaminants and ultimately improving device performance. In a particular embodiment, the device of the present invention does not require the separate target for depositing the IC layer required in the conventional device. As those skilled in the art will understand, the present invention is not limited to these materials and methods. However, in certain embodiments, the materials that make up the electrochromic stack and the precursor stack (as described below) are all inorganic, Solid (that is, solid) or inorganic and solid. Because organic materials tend to degrade over time, such as when exposed to ultraviolet light and heat associated with window applications, inorganic materials provide the advantage of a reliable electrochromic stack that can work for long periods of time. Solid materials also provide the advantage of not having the contaminants and leakage problems that liquid materials often have. It should be understood that any one or more of the layers in the stack may contain a certain amount of organic material, but in many implementations, one or more of the layers contain little or no organic material. The same can be true for 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 processes using liquid components (such as specific processes using sol-gel or chemical vapor deposition). Referring again to FIG. 3B, see 325, the EC layer of WO ₃ is first deposited. 4A to 4C are schematic cross-sections depicting the formation of an electrochromic device according to a specific method and apparatus of the present invention, and in particular, according to the program flow 320. FIG. Specifically, FIGS. 4A to 4C are used to show three non-limiting examples of how an EC layer including WO ₃ can be formed as part of a stack, where an interface region serving as an IC layer is formed after depositing other layers of the stack . In each of FIGS. 4A to 4C, the substrate 402, the first TCO layer 404, the CE layer 410, and the second TCO layer 412 are substantially the same. Also, in each of the three embodiments, a stack without an IC layer is formed, and then the stack is further processed to form an interface region serving as an IC layer within the stack between the EC layer and the CE layer . Referring to each of FIGS. 4A to 4C, layered structures 400, 403, and 409 are depicted, respectively. Each of these layered structures includes a substrate 402 that is, for example, glass. As the substrate 402, any material having suitable optical, electrical, thermal, and mechanical properties may be used. Such substrates include, for example, glass, plastic, and mirror materials. Suitable plastic substrates include, for example, acrylic, polystyrene, polycarbonate, allyl diethylene glycol carbonate, SAN (styrene acrylonitrile copolymer), poly(4-methyl-1- Pentene), polyester, polyamide, etc., and preferably, the plastic should be able to withstand high temperature processing conditions. If a plastic substrate is used, it is preferably hard-coated with, for example, a diamond-like protective coating, a silica/polysilicon wear-resistant coating, or the like (such as a coating well known in plastic glazing technology) Layer to provide barrier protection and wear protection. Suitable glasses include transparent or colored soda lime glass, including soda lime floating glass. The glass can be tempered or untempered. In some embodiments, commercially available substrates such as glass substrates contain a transparent conductive layer coating. Examples of such glasses include conductive layer coated glasses sold under the trademarks TEC Glass™ (Pilkington of Toledo, Ohio) and SUNGATE™ 300 and SUNGATE™ 500 (PPG Industries of Pittsburgh, Pennsylvania). TEC Glass™ is glass coated with a conductive layer of fluorinated tin oxide. In some embodiments, the optical transmittance of the substrate 402 (ie, the ratio of transmitted radiation or spectrum to incident radiation or spectrum) is about 90% to 95%, for example, about 90% to 92%. The substrate may have any thickness as long as it has suitable mechanical properties to support the electrochromic device. Although the substrate 402 may have any size, in some embodiments, it is about 0.01 mm to 10 mm thick, preferably about 3 mm to 9 mm thick. In some embodiments of the invention, the substrate is architectural glass. Architectural glass is glass used as a building material. Architectural glass is usually used in commercial buildings, but can also be used in residential buildings, and usually (but not necessarily) separate indoor and outdoor environments. In certain embodiments, the architectural glass is at least 20 inches by 20 inches, and may be larger, for example, up to about 72 inches by 120 inches. Architectural glass is usually at least about 2 mm thick. Architectural glass less than about 3.2 mm thick cannot be tempered. In some embodiments of the invention using architectural glass as the substrate, the substrate can still be tempered even after the electrochromic stack has been fabricated on the substrate. In some embodiments using architectural glass as the substrate, the substrate is soda lime glass from a tin float line. The percentage of transmission in the visible spectrum of architectural glass substrates (ie, overall transmission across the visible spectrum) is generally 80% greater than that of neutral substrates, but it may be lower than the percentage of transmission of colored substrates. Preferably, the percentage transmission of the substrate in the visible spectrum is at least about 90% (eg, about 90% to 92%). The visible spectrum is the spectrum that the typical human eye will respond to, generally about 380 nm (purple) to about 780 nm (red). In some cases, the glass has a surface roughness between about 10 nm and about 30 nm. In one embodiment, the substrate 402 is a soda glass with a sodium diffusion barrier (not shown) to prevent sodium ions from diffusing into the electrochromic device. For the purpose of this description, this configuration is referred to as "substrate 402". Referring again to the layered structures 400, 403, and 409, for example, a first TCO layer 404 made of fluorinated tin oxide or other suitable material (which is especially conductive and transparent) is deposited on the substrate 402. Transparent conductive oxides include metal oxides and metal oxides doped with one or more metals. Examples of such metal oxides and doped metal oxides include indium oxide, indium tin oxide, doped indium oxide, tin oxide, doped tin oxide, zinc oxide, aluminum zinc oxide, doped Zinc oxide, ruthenium oxide, doped ruthenium oxide and the like. In one embodiment, the thickness of this second TCO layer is between about 20 nm and about 1200 nm, in another embodiment between about 100 nm and about 600 nm, in another embodiment, about 350 nm thick. The TCO layer should have an appropriate sheet resistance (R _s ) due to the relatively large area spanned by these layers. In some embodiments, the sheet resistance of the TCO layer is between about 5 ohms and about 30 ohms per square. In some embodiments, the sheet resistance of the TCO layer is about 15 ohms per square. In general, it is desirable that the sheet resistance of each of the two conductive layers is approximately the same. In one embodiment, the two layers (eg, 404 and 412) each have a sheet resistance of about 10-15 ohms per square. Each of the layered structures 400, 403, and 409 includes stacks 414a, 414b, and 414c, respectively, and each of these stacks includes a first TCO layer 404, a CE layer 410, and a second TCO above the substrate 402 Level 412. The difference between each of the layered structures 400, 403, and 409 is how the EC layer is formed, which in each case affects the shape of the resulting interface area. Consistent with the process flow 320 of FIG. 3B, each of the stacks 414a, 414b, and 414c includes an electrochromic layer deposited on the first TCO layer 404. The electrochromic layer may contain any one or more of many different 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 ), copper oxide (CuO), iridium oxide (Ir ₂ O ₃ ) , Chromium oxide (Cr ₂ O ₃ ), manganese oxide (Mn ₂ O ₃ ), vanadium oxide (V ₂ O ₅ ), nickel oxide (Ni ₂ O ₃ ), cobalt oxide (Co ₂ O ₃ ) and the like. In some embodiments, the metal oxide is doped with one or more dopants, such as lithium, sodium, potassium, molybdenum, niobium, vanadium, titanium, and/or other suitable metals or metal-containing compounds. Mixed oxides (eg, W-Mo oxides, WV oxides) can also be used in specific embodiments, that is, the electrochromic layer includes two or more of the above metal oxides. The electrochromic layer including metal oxide can receive ions transferred from the counter electrode layer. In some embodiments, tungsten oxide or doped tungsten oxide is used for the electrochromic layer. In one embodiment of the invention, the electrochromic layer is substantially made of WO _x , where " x " refers to the atomic ratio of oxygen to tungsten in the electrochromic layer, and x is between about 2.7 and 3.5. It has been proposed that tungsten oxide that is only below the stoichiometric amount exhibits electrochromism; that is, stoichiometric tungsten oxide (WO ₃ ) does not exhibit electrochromism. In a more specific embodiment, WO _x (where x is less than 3.0 and at least about 2.7) is used for the electrochromic layer. In another embodiment, the electrochromic layer is WO _x , where x is between about 2.7 and about 2.9. Techniques such as Rutherford Backscattering Spectroscopy (RBS) can identify the total number of oxygen atoms including oxygen atoms bonded to tungsten and oxygen atoms not bonded to tungsten. In some examples, the tungsten oxide layer (where x is 3 or greater) exhibits electrochromism, which may be due to unbound excess oxygen and sub-stoichiometric tungsten oxide. In another embodiment, the tungsten oxide layer has stoichiometric or more oxygen, where x is from 3.0 to about 3.5. In some embodiments of the invention, at least a portion of the EC layer has excess oxygen. This more highly oxidized region of the EC layer is used as a precursor to form an ion-conducting electrically insulating region that acts as an IC layer. In other embodiments, a dissimilar layer of highly oxidized EC material is formed between the EC layer and the CE layer for at least partial final conversion to the ion-conducting electrically insulating interface region. In certain embodiments, the tungsten oxide is crystalline, nanocrystalline, or amorphous. In some embodiments, the tungsten oxide is substantially nanocrystalline and has an average grain size of about 5 nm to 50 nm (or about 5 nm to 20 nm), characterized by transmission electron microscopy (TEM) . The tungsten oxide morphology or microstructure can also be characterized as nanocrystalline using x-ray diffraction (XRD) and/or electron diffraction (such as selected area electron diffraction (SAED)). For example, the nanocrystalline electrochromic tungsten oxide may be characterized by the following XRD characteristics: a crystal size of about 10 to 100 nm (eg, about 55 nm). In addition, nanocrystalline tungsten oxide can exhibit limited long-range order, for example, about several (about 5 to 20) tungsten oxide unit cells. Therefore, for convenience, the remainder of the program flow 320 in FIG. 3B will be further described in relation to the first embodiment (including the formation of the EC layer 406 shown in FIG. 4A). Next, the second and third embodiments shown in FIGS. 4B and 4C, respectively, will be described below, with particular emphasis on the formation and morphology and/or microstructure of their respective EC layers. As mentioned with reference to FIG. 3B, see 325, an EC layer is deposited. In the first embodiment (represented in FIG. 4A), a substantially homogeneous EC layer 406 (including WO ₃ ) is formed as part of the stack 414a, where the EC layer is in direct contact with the CE layer 410. In one embodiment, as described above, the EC layer includes WO ₃ . In one embodiment, heating is applied during at least part of the deposition of WO ₃ . In a particular embodiment, a sputtering target is passed several times, wherein a portion of WO ₃ is deposited as each pass passes, and after each deposition, heating is applied to, for example, the substrate 402 to deposit WO ₃ on the deposition layer 406 Adjust WO ₃ before the next section. In other embodiments, the WO ₃ layer can be continuously heated during deposition and can be deposited in a continuous manner instead of going through the sputtering target several times. In one embodiment, the thickness of the EC layer is between about 300 nm and about 600 nm. As mentioned, the thickness of the EC layer depends on the desired result and the method of forming the IC layer. In the embodiment described with respect to FIG. 4A, the EC layer is a tungsten target with a thickness between about 500 nm and about 600 nm and includes between about 40% and about 80% O ₂ and about 20% and about Between 60% of the Ar ₃ sputter gas sputtered WO ₃ , and the substrate in which WO ₃ is deposited is heated at least intermittently between about 150° C. and about 450° C. during the formation of the EC layer. In a specific embodiment, the EC layer is about 550 nm thick WO ₃ using a tungsten target sputtering, wherein the sputtering gas includes about 50% to about 60% O ₂ and about 40% to about 50% Ar, and the substrate on which WO ₃ is deposited is heated at least intermittently between about 250°C and about 350°C during the formation of the electrochromic layer. In these embodiments, the WO ₃ layer is substantially homogeneous. In one embodiment, WO ₃ is substantially polycrystalline. Xianxin, heating the WO ₃ at least intermittently during the deposition helps the formation of WO ₃ in polycrystalline form. As mentioned, many materials are suitable for the EC layer. In general, in electrochromic materials, the coloration of electrochromic materials (or any optical properties, such as changes in absorbance, reflectance, and transmittance) is through reversible ion insertion (eg, intercalation) into the material ) And the corresponding injection of charge balance electrons. Usually, a small part of the ions responsible for the optical transition are irreversibly bound together in the electrochromic material. As described herein, some or all of the irreversibly bound ions are used to compensate for "blind charge" in the material. In most electrochromic materials, suitable ions include lithium ions (Li ⁺ ) and hydrogen ions (H ⁺ ) (ie, protons). However, in some cases, other ions will be appropriate. This plasma includes, for example, deuterium ions (D ⁺ ), sodium ions (Na ⁺ ), potassium ions (K ⁺ ), calcium ions (Ca ⁺⁺ ), barium ions (Ba ⁺⁺ ), strontium ions (Sr ⁺⁺ ) And magnesium ions (Mg ⁺⁺ ). In various embodiments described herein, lithium ions are used to generate electrochromism. The intercalation of lithium ions to tungsten oxide (WO _3-y (0<y£~0.3)) changes tungsten oxide from transparent (fading state) to blue (coloring state). In a typical process where the EC layer includes or is tungsten oxide, a lithium system is deposited on the EC layer 406 (for example, via sputtering) to meet the blind charge (see FIG. 6 and FIG. 7 for more details), see FIG. 3B 330 of the program flow. In one embodiment, lithiation is performed in an integrated deposition system (where vacuum is not broken between deposition steps). It should be noted that in some embodiments, lithium is not added at this stage, but may be added after the counter electrode layer is deposited, or in other embodiments, lithium is added after the TCO is deposited. Referring again to FIG. 4A, next, a CE layer 410 is deposited on the EC layer 406. In some embodiments, the counter electrode layer 410 is inorganic and/or solid. The counter electrode layer may include one or more of many different materials capable of acting as a reservoir of ions when the electrochromic device is in a faded state. During the electrochromic transition initiated by, for example, applying an appropriate potential, the counter electrode layer transfers some or all of the ions it holds to the electrochromic layer, thereby changing the electrochromic layer to a colored state. At the same time, in the case of NiO and/or NiWO, the counter electrode layer is colored due to the loss of ions. In some embodiments, suitable materials for the counter electrode include nickel oxide (NiO), nickel tungsten oxide (NiWO), nickel vanadium oxide, nickel chromium oxide, nickel aluminum oxide, nickel manganese oxide, nickel magnesium oxide, chromium oxide (Cr ₂ O ₃ ), manganese oxide (MnO ₂ ) and Prussian blue. Optical passive counter electrodes include cerium titanium (CeO ₂ -TiO ₂ ), cerium zirconium oxide (CeO ₂ -ZrO ₂ ), nickel oxide (NiO), nickel tungsten oxide (NiWO), vanadium oxide (V ₂ O ₅ ) and A mixture of oxides (for example, a mixture of Ni ₂ O ₃ and WO ₃ ). Doping formulations of these oxides can also be used, where the dopant includes, for example, tantalum and tungsten. Since the counter electrode layer 410 contains ions used to generate electrochromism in the electrochromic material when the electrochromic material is in a faded state, the counter electrode preferably has a high level when it maintains a significant amount of this plasma Transmittance and neutral color. The shape of the counter electrode can be crystalline, nanocrystalline or amorphous. In some embodiments, where the counter electrode layer is nickel tungsten oxide, the counter electrode material is amorphous or substantially amorphous. Compared to the crystalline counterpart of the substantially amorphous nickel-tungsten oxide counter electrode, it has been found that these substantially amorphous nickel-tungsten oxide counter electrodes perform better under certain conditions. As described below, the amorphous state of nickel tungsten oxide can be obtained by using specific processing conditions. Although not wishing to be bound by any theory or mechanism, Xianxin believes that amorphous nickel-tungsten oxide is produced by relatively high-energy atoms in the sputtering process. Higher energy atomic systems are obtained, for example, in sputtering processes with higher target power, lower chamber pressure (ie, higher vacuum), and smaller source-to-substrate distance. Under the described processing conditions, a higher density film with better stability under UV/heat exposure is produced. In certain embodiments, the amount of nickel present in nickel tungsten oxide can be up to about 90% by weight of nickel tungsten oxide. In a particular embodiment, the mass ratio of nickel to tungsten in nickel tungsten oxide is between about 4:6 and 6:4, in one example about 1:1. In one embodiment, NiWO contains between about 15% (atomic) and about 60% Ni, and between about 10% and about 40% W. In another embodiment, NiWO contains between about 30% (atomic) and about 45% Ni, and between about 15% and about 35% W. In another embodiment, NiWO contains between about 30% (atomic) and about 45% Ni, and between about 20% and about 30% W. In one embodiment, NiWO contains about 42% (atomic) Ni and about 14% W. In one embodiment, as described above, referring to 335 of FIG. 3B, the CE layer 410 is NiWO. In one embodiment, the thickness of the CE layer is between about 150 nm and about 300 nm, in another embodiment between about 200 nm and about 250 nm, and in another embodiment about 230 nm. In a typical process, lithium is also applied to the CE layer until the CE layer fades. It should be understood that the description of the transition between the colored state and the faded state is non-limiting and implies only one of many examples of electrochromic transitions that may be implemented. Unless otherwise stated herein, whenever a fade-color transition is mentioned, the corresponding device or process covers other optical state transitions such as non-reflective-reflective, transparent-opaque, etc. In addition, the term "fading" refers to an optically neutral state, such as uncolored, transparent, or translucent. Furthermore, unless otherwise stated herein, the "color" of the electrochromic transition is not limited to any particular wavelength or range of wavelengths. As generally understood by those skilled in the art, the selection of appropriate electrochromic materials and counter electrode materials controls the related optical transitions. In a particular embodiment, see 340 of FIG. 3B, lithium (eg, via sputtering) is added to the NiWO CE layer. In a particular embodiment, see 345 of FIG. 3B, an additional amount of lithium is added after sufficient lithium has been introduced to completely fade the NiWO (this procedure is optional, and in one embodiment, at this stage of the procedure Add excess lithium). In one embodiment, this additional amount is between about 5% and about 15% based on the amount required to discolor the counter electrode layer. In another embodiment, the excess lithium added to the CE layer is about 10% excess based on the amount required to discolor the counter electrode layer. After depositing the CE layer 410, discoloring it with lithium, and adding additional lithium, referring to 350 of FIG. 3B, a second TCO layer 412 is deposited over the counter electrode layer. In one embodiment, the transparent conductive oxide includes indium tin oxide. In another embodiment, the TCO layer is indium tin oxide. In one embodiment, the thickness of this second TCO layer is between about 20 nm and about 1200 nm, in another embodiment between about 100 nm and about 600 nm, in another embodiment about 350 nm. Referring again to FIG. 4A, once the layered structure 400 is completed, it is subjected to thermochemical adjustment to convert at least a portion of the stack 414a into an IC layer (if it is not converted due to lithium diffusion or other mechanisms). The stack 414a is a precursor rather than an electrochromic device, because the stack does not yet have an ion conductive/electrically insulating layer (or region) between the EC layer 406 and the CE layer 410. In this particular embodiment, in a two-step process, a portion of the EC layer 406 is converted into an IC layer 408 to form a functional electrochromic device 401. Referring to FIG. 3B and see 355, the layered structure 400 is subjected to MTCC. In one embodiment, the stack is first subjected to heating between about 150°C and about 450°C under an inert atmosphere (eg, argon) for between about 10 minutes and about 30 minutes, and then heated under O ₂ for a duration Between about 1 minute and about 15 minutes. In another embodiment, the stack is heated at about 250° C. under an inert atmosphere for about 15 minutes, and then heated under O ₂ for about 5 minutes. Next, the layered structure 400 is subjected to heating in air. In one embodiment, the stack is heated in air at between about 250°C and about 350°C for between about 20 minutes and about 40 minutes, in another embodiment, the stack is at about 300°C in air The heating lasted about 30 minutes. The energy required to implement MTCC need not be radiant heat. For example, in one embodiment, MTCC is implemented using ultraviolet radiation. Other energy sources can also be used without departing from the scope of the present invention. After the multi-step thermochemical adjustment, the procedure 320 is completed, and the functional electrochromic device is established. As mentioned, and although not wishing to be bound by theory, it is believed that the lithium in the stack 414a is combined with a portion of the EC layer 406 and/or the CE layer 410 to form an interface region 408 that serves as an IC layer. The Xianxin interface region 408 is mainly lithium tungstate (Li ₂ WO ₄ ), which is known to have good ion conduction and electrical insulation properties compared to traditional IC layer materials. As discussed above, it is not clear how this phenomenon occurs. There is a chemical reaction that must occur during the multi-step thermochemical conditioning to form an ion-conducting electrically insulating region 408 between the EC layer and the CE layer, but it is also believed that the initial flux of lithium traveling through the stack (eg, as described above The excess lithium added to the CE layer described above) plays a role in the formation of the IC layer 408. The thickness of the ion-conducting electrically insulating region may vary depending on the materials used and the processing conditions used to form the layer. In some embodiments, the thickness of the interface region 408 is between about 10 nm and about 150 nm, in another embodiment between about 20 nm and about 100 nm, and in other embodiments between about 30 nm and Between about 50 nm. As mentioned above, there are many suitable materials for forming the EC layer. Therefore, by using, for example, lithium or other suitable ions in the above method, one can make other interface regions that serve as IC layers starting from the oxygen-rich EC material. Suitable EC materials for this purpose include (but are not limited to) SiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , ZrO ₂ and CeO ₂ . In specific embodiments using lithium ions, ion conducting materials (such as, but not limited to, lithium silicate, lithium aluminum silicate, lithium aluminum borate, lithium aluminum fluoride, lithium borate, lithium nitride, lithium zirconium silicate, Lithium niobate, lithium borosilicate, lithium phosphosilicate and other such lithium-based ceramic materials, silica or silicon oxide (including lithium oxide silicon) can be made to serve as the interface region of the IC layer. As mentioned, in one embodiment, the precursor of the ion conduction region is an oxygen-rich (superstoichiometric) layer converted into an ion conduction/electrical insulation region by lithiation and MTCC as described herein. Although not wishing to be bound by theory, Xianxin believes that after lithiation, excess oxygen forms lithium oxide, which further forms lithium salts (ie, lithium electrolytes), such as lithium tungstate (Li ₂ WO ₄ ), lithium molybdate (Li ₂ MoO ₄ ), lithium niobate (LiNbO ₃ ), lithium tantalate (LiTaO ₃ ), lithium titanate (Li ₂ TiO ₃ ), lithium zirconate (Li ₂ ZrO ₃ ) and the like. In one embodiment, the interface region includes at least one of the following: tungsten oxide (WO _3+x , 0≤x≤1.5), molybdenum oxide (MoO _3+x , 0≤x≤1.5), niobium oxide (Nb ₂ O _5+x , 0≤x≤2), titanium oxide (TiO _2+x , 0≤x≤1.5), tantalum oxide (Ta ₂ O _5+x , 0≤x≤2), zirconium oxide ( ZrO _2+x , 0≤x≤1.5) and cerium oxide (CeO _2+x , 0≤x≤1.5). However, any material can be used for the ion-conducting interface region, as long as the material can be manufactured with a low degree of defect and it substantially prevents electrons from passing while allowing ions to pass between the counter electrode layer 410 and the electrochromic layer 406 can. The material can substantially conduct ions and substantially resist electrons. In one embodiment, the ion conductor material has an ion conductivity between about 10 ^-10 Siemens/cm (or ohm ^-1 cm ^-1 ) and about 10 ^-3 Siemens/cm and is greater than 10 ⁵ ohm-cm resistivity. In another embodiment, the ion conductor material has an ionic conductivity between about ^10-8 Siemens/cm and about ^10-3 Siemens/cm and a resistivity greater than 10 ¹⁰ ohm-cm. Although the ion-conducting layer should be substantially resistant to leakage current (for example, providing a leakage current no greater than about 15 μA/cm ² ), it has been found that some devices manufactured as described herein have surprisingly high leakage currents (for example , Between about 40 μA/cm and about 150 μA/cm), but still provide good color variation across the device and operate efficiently. As mentioned above, there are at least two other ways to establish an ion-conducting electrically insulating region between the EC layer and the CE layer after forming the stack. These additional embodiments will be described below with reference to specific examples of using tungsten oxide for the IC layer. Also, as mentioned above, when, for example, lithium diffusion or heat converts some of the EC and/or CE layers into interface regions, interface regions with IC properties may be formed in situ during the manufacturing stack. Often, there are specific benefits to establishing the ion conducting region later in the process. First, the ion conductive material can be protected from some of the harsh processes that occur during the deposition and lithiation of the EC and CE layers. For example, depositing these layers through a plasma process is often accompanied by a large voltage drop next to the stack, often around 15-20 volts. These large voltages can damage sensitive ion conductive materials or cause decomposition of sensitive ion conductive materials. By moving the IC material formation to a later stage in the process, the material is not exposed to potential damage to voltage extremes. Second, by forming IC materials later in the process, we can better control some processing conditions that are not possible before completing both the EC layer and the CE layer. These conditions include lithium diffusion and current between electrodes. Controlling these and other conditions in the middle and late stages of the process provides additional flexibility to adapt the physical and chemical properties of IC materials to specific applications. Therefore, not all the benefits of the present invention are due to the unique interface area that acts as an IC layer, that is, there are also manufacturing and other benefits. It has been observed that ion conducting materials formed according to some of the embodiments described herein are superior to devices fabricated using conventional techniques for forming IC layers (eg, PVD from IC material targets) efficacy. For example, it has been found that the device switching speed is very fast (eg, less than 10 minutes, in one example about 8 minutes) to achieve a final state of about 80% compared to 20-25 minutes or more for conventional devices. In some examples, the devices described herein have an order of magnitude faster than conventional devices. This may be due to the large amount of lithium disposed in the interface area and/or the graded interface that can be easily transferred (eg, between EC and interface area and/or between CE and interface area). Such lithium may be in EC and/or CE phases that are mixed with ICs present in the interface region. It may also be attributed to the relatively thin layer or network of IC materials present in the interface area. To support this view, it has been observed that some devices manufactured according to the teachings in this article have high leakage currents, but still surprisingly exhibit good color changes and good efficiency. In some cases, the leakage current density of devices that have been robustly implemented has been found to be at least about 100 μA/cm. Referring now to FIG. 4B, in the second embodiment, the initially laid EC material of the stack 414b is actually two layers: the first WO ₃ layer 406, which is similar to the layer 406 in FIG. 4A, but with a thickness of about 350 nm Between about 450 nm and the first layer is sputtered with a tungsten target and a first sputtering gas including between about 40% and about 80% O ₂ and between about 20% and about 60% Ar ; And the second WO ₃ layer 405, whose thickness is between about 100 nm and about 200 nm, the second layer uses a tungsten target and includes between about 70% and 100% of O ₂ and 0% and about 30 The second sputtering gas sputtering of Ar between %. In this embodiment, heat is applied by heating the substrate 402 at least intermittently to between about 150°C and about 450°C during the deposition of the first WO ₃ layer 406, but during the deposition of the second WO ₃ layer 405 No heating or no heating during the period. In a more specific embodiment, the layer 406 is about 400 nm thick, and the first sputtering gas includes between about 50% and about 60% O ₂ and between about 40% and about 50% Ar; The two WO ₃ layers 405 are about 150 nm thick, and the second sputtering gas is substantially pure O ₂ . In this embodiment, heat is applied at least intermittently between about 200°C and about 350°C during the formation of the first WO ₃ layer 406, but is not heated or substantially not during the formation of the second WO ₃ layer 405 heating. In this way, the first WO ₃ layer is substantially polycrystalline, while the second WO ₃ layer need not be. Referring again to FIG. 4B, as described above with respect to FIGS. 3B and 4A, the stacking is completed by the following operations: lithiating EC layers 406 and 405 to substantially or substantially satisfy the blind charge, depositing the CE layer 410, lithiating the CE layer To the faded state, additional lithium is added and the second TCO layer 412 is deposited to complete the layered stack 403. Similar thermochemical adjustments are performed on the layered stack 403 to provide a layered stack 407, a functional electrochromic device including an ion-conducting electrically insulating region 408a. Although not wishing to be bound by theory, in this example, the oxygen-rich layer 405 of Xianxin WO ₃ mainly charges the source of the current driver material to form the interface region 408a. In this example, the entire oxygen-enriched WO ₃ layer is depicted as converted to the interface region 408a, however, it has been found that this is not always the case. In some embodiments, only a portion of the oxygen-rich layer is converted to form an interface region that functions as an IC layer. Referring now to FIG. 4C, in the third embodiment, the layered stack 409 includes an EC layer 406a (which has a graded composition of WO ₃ and is formed as part of the stack 414c), where the graded composition includes varying content Oxygen. In a non-limiting example, there is a higher oxygen concentration in the EC layer 406a at the interface of the EC-CE layer (410) than at the interface of the TCO layer 404 and the EC layer 406a. In one embodiment, the EC layer 406a is a layered composition WO ₃ layer with a thickness of between about 500 nm and about 600 nm using a tungsten target and sputtering gas sputtering, wherein the sputtering gas is electroplated during sputtering The color change layer starts with about 40% and about 80% O ₂ and between about 20% and about 60% Ar, and the sputtering gas includes about 70% and about 70% at the end of sputtering the electrochromic layer O ₂ between 100% and Ar between 0% and about 30%, and wherein at least intermittently heat is applied to, for example, the substrate 402 to about 150°C and about 450°C during the beginning of the formation of the EC layer 406a Between, but not or substantially not applying heat during the deposition of at least a last portion of the EC layer 406a. In a more specific embodiment, the WO ₃ layer of the graded composition is about 550 nm thick; the sputtering gas includes between about 50% and about 60% O ₂ and 40% at the beginning of sputtering the electrochromic layer Between about 50% and Ar, and the sputtering gas is substantially pure O ₂ at the end of sputtering the electrochromic layer; and wherein at least intermittently heat is applied to the beginning of the formation of the electrochromic layer to For example, the substrate 402 is between about 200°C and about 350°C, but no or substantially no heat is applied during the deposition of at least a final portion of the electrochromic layer. In one embodiment, heat is applied at the temperature range at the beginning of deposition, and gradually decreases to not apply heat when about half of the EC layer is deposited, while the sputtering gas composition is along the The substantially linear rate is adjusted from O ₂ between about 50% and about 60% and Ar between about 40% and about 50% to substantially pure O ₂ . More generally, the interface region usually (but not necessarily) has a heterostructure including at least two discrete components represented by different phases and/or compositions. In addition, the interface region may include gradients in these two or more discrete components, such as ion conductive materials and electrochromic materials (eg, a mixture of lithium tungstate and tungsten oxide). The gradient can provide, for example, variable composition, microstructure, resistivity, dopant concentration (eg, oxygen concentration), stoichiometry, density, and/or grain size range. The gradient can have many different forms of transition, including linear transition, S-type transition, Gaussian transition, and so on. In one example, the electrochromic layer includes a tungsten oxide region that transitions into a superstoichiometric tungsten oxide region. Part or all of the superstoichiometric oxide zone is converted into an interface zone. In the final structure, the tungsten oxide region is substantially polycrystalline, and the microstructure transitions to substantially amorphous at the interface region. In another example, the electrochromic layer includes a tungsten oxide region that transitions into (superstoichiometric) niobium oxide regions. Part or all of the niobium oxide region is converted into an interface region. In the final structure, the tungsten oxide region is substantially polycrystalline, and the microstructure transitions to substantially amorphous at the interface region. Referring again to FIG. 4C, as described above with respect to FIGS. 3B and 4A, the stacking is completed by the following operations: the lithiated EC layer 406a substantially or substantially meets the blind charge, deposits the CE layer 410, and the lithiated CE layer to a faded state 2. Add additional lithium and deposit the second TCO layer 412 to complete the layered stack 409. A similar multi-step thermochemical adjustment is performed on the layered stack 409 to provide at least a portion of the layered stack 411, including the ion-conducting electrically insulating region 408b, and the original layered EC layer 406a (which serves as an EC in the functional electrochromic device 411 Layer) functional electrochromic device. Although not wishing to be bound by theory, in this example, Xianxin, the uppermost oxygen-rich portion of the graded layer of WO ₃ mainly forms a graded interface region 408b. Although not wishing to be bound by theory, there is a possibility that the formation of the interface region is limited by itself and depends on the relative amounts of oxygen, lithium, electrochromic materials, and/or counter electrode materials in the stack. In the various embodiments described herein, the electrochromic stack is described as not or substantially not heated during certain processing stages. In one embodiment, after the heating step, the stack is actively or passively cooled (eg, using heat sinks). The apparatus of the present invention includes active and passive cooling components. For example, active cooling may include a platen cooled by fluid circulation, cooling by exposure to cold (eg, by expanding) gas, a refrigeration unit, and the like. Passive cooling components may include heat sinks, such as metal blocks and the like, or only remove the substrate from heat exposure. Another aspect of the present invention is a method of manufacturing an electrochromic device, the method comprising: (a) forming an electrochromic layer including an electrochromic material or a counter electrode layer including a counter electrode material; (b) Forming an intermediate layer above the electrochromic layer or the counter electrode layer, wherein the intermediate layer includes an oxygen-rich form of at least one of the electrochromic material, the counter electrode material, and additional materials, wherein the additional materials Including different electrochromic materials or counter electrode materials, where the intermediate layer is not substantially electrically insulating; (c) forming the other of the electrochromic layer and the counter electrode layer; and (d ) Allows at least a portion of the intermediate layer to become substantially electrically insulating. In one embodiment, the electrochromic material is WO ₃ . In another embodiment, (a) includes sputtering a WO using a tungsten target and a first sputtering gas including between about 40% and about 80% of O ₂ and between about 20% and about 60% of Ar ₃ to achieve a thickness between about 350 nm and about 450 nm, and at least intermittently heated to between about 150°C and about 450°C during the formation of the electrochromic layer. In another embodiment, (b) includes the use of a tungsten target without heating and second sputtering including between about 70% and 100% of O ₂ and between 0% and about 30% of Ar The gas sputters WO ₃ to achieve a thickness between about 100 nm and about 200 nm. In yet another embodiment, the method further includes sputtering lithium onto the intermediate layer until the blind charge is substantially or substantially satisfied. In one embodiment, the counter electrode layer includes NiWO with a thickness between about 150 nm and about 300 nm. In another embodiment, lithium is sputtered onto the counter electrode layer until the counter electrode layer fades. In another embodiment, an additional amount of lithium between about 5% and about 15% based on the amount required to discolor the counter electrode layer is sputtered onto the counter electrode layer. In another embodiment, a transparent conductive oxide layer is deposited over the counter electrode layer. In one embodiment, the transparent conductive oxide includes indium tin oxide, and in another embodiment, the transparent conductive oxide is indium tin oxide. In another embodiment, the stack formed according to the above embodiment is heated under Ar at between about 150°C and about 450°C for between about 10 minutes and about 30 minutes, and then heated under O ₂ for about 1 Between about 15 minutes and about 15 minutes, and then heated in the air between about 250°C and about 350°C for between about 20 minutes and about 40 minutes. In another embodiment, (a) includes a sputtered MO _x first electrochromic material, where M is a metallic or non-metallic element, and x indicates the stoichiometric oxygen to M ratio, and (b) includes The second electrochromic material of sputtered NO _y is used as an intermediate layer, where N is the same or different metal or non-metal element, and y indicates the ratio of superstoichiometric oxygen to N. In one embodiment, M is tungsten and N is tungsten. In another embodiment, M is tungsten, and N is selected from the group consisting of niobium, silicon, tantalum, titanium, zirconium, and cerium. Another embodiment of the present invention is an electrochromic device, including: (a) an electrochromic layer including an electrochromic material; (b) an opposing electrode layer including an opposing electrode material; and (c) in An interface region between the electrochromic layer and the counter electrode layer, wherein the interface region includes at least one of an electrically insulating ion conductive material and the electrochromic material, the counter electrode material, and additional materials, wherein the The additional materials include different electrochromic materials or counter electrode materials. In one embodiment, at least one of the electrically insulating ion conductive material and the electrochromic material, the counter electrode material, and the additional material is substantially evenly distributed within the interface area. In another embodiment, at least one of the electrically insulating ion conducting material and the electrochromic material, the counter electrode material and the additional material includes a composition gradient in a direction perpendicular to the layers. In another embodiment, consistent with any of the two previous embodiments, the electrically insulating ion conductive material includes lithium tungstate, the electrochromic material includes tungsten oxide, and the counter electrode material includes nickel tungsten oxide . In one specific implementation of the foregoing embodiment, no additional material is present. In one embodiment, the thickness of the electrochromic layer is between about 300 nm and about 500 nm, the thickness of the interface region is between about 10 nm and about 150 nm, and the thickness of the counter electrode layer is about Between 150 nm and about 300 nm. In another embodiment, the thickness of the electrochromic layer is between about 400 nm and about 500 nm; the thickness of the interface region is between about 20 nm and about 100 nm, and the thickness of the counter electrode layer is between Between about 150 nm and about 250 nm. In yet another embodiment, the thickness of the electrochromic layer is between about 400 nm and about 450 nm; the thickness of the interface region is between about 30 nm and about 50 nm, and the thickness of the counter electrode layer is between Between about 200 nm and about 250 nm. Another embodiment is a method of manufacturing an electrochromic device, the method comprising: by using a sputtering gas containing between about 40% and about 80% of O ₂ and between about 20% and about 60% of Ar Sputtering a tungsten target to produce WO ₃ to a thickness between about 500 nm and about 600 nm to deposit an electrochromic layer, wherein the substrate on which the WO ₃ is deposited is at least intermittently during the formation of the electrochromic layer Heated to between about 150°C and about 450°C; sputtering lithium onto the electrochromic layer until the blind charge is satisfied; depositing an opposing electrode layer on the electrochromic layer without first An ion-conducting electrically insulating layer is provided between the electrochromic layer and the counter electrode layer, wherein the counter electrode layer includes NiWO; sputtering lithium onto the counter electrode layer until the counter electrode layer substantially fades; And forming an interface region between the electrochromic layer and the counter electrode layer, wherein the interface region is substantially ion conductive and substantially electrically insulating. In one embodiment, forming the interface region includes the stack of MTCCs alone or together with the substrate, conductive layer, and/or encapsulation layer. The electrochromic device of the present invention may include one or more additional layers (not shown) such as one or more passive layers (for example) to improve specific optical properties (provide moisture resistance or scratch resistance) in an airtight manner Seal the electrochromic device and the like. Usually (but not necessarily), a capping layer is deposited on the electrochromic stack. In some embodiments, the cap layer is SiAlO. In some embodiments, the cap layer is deposited by sputtering. In one embodiment, the thickness of the cover layer is between about 30 nm and about 100 nm. It should be understood from the above discussion that the electrochromic device of the present invention can be sputtered in a single chamber device (eg, with (for example) tungsten target, nickel target and lithium target, and oxygen and argon sputtering gas) Tool). As mentioned, due to the nature of the interface region formed to serve the purpose of a conventionally distinct IC layer, a separate target for sputtering the IC layer is not necessary. The inventor is particularly interested in, for example, manufacturing the electrochromic device of the present invention in a high-throughput manner. Therefore, there is a need for equipment that can sequentially manufacture the electrochromic device of the present invention when the substrate passes through an integrated deposition system. For example, the inventors are particularly interested in manufacturing electrochromic devices on windows, especially architectural glass slat windows (above). Therefore, another aspect of the present invention is an apparatus for manufacturing an electrochromic device, which includes: an integrated deposition system including: (i) a first deposition station containing a material source, which is configured to deposit including An electrochromic layer of electrochromic material; and (ii) a second deposition station configured to deposit a counter electrode layer including a counter electrode material; and a controller, which contains a substrate for sequentially on the substrate A deposition stack is used to transfer programming commands of the substrate through the first deposition stage and the second deposition stage, the stack has an intermediate layer sandwiched between the electrochromic layer and the counter electrode layer; wherein the first deposition Either or both of the stage and the second deposition stage are also configured to deposit the intermediate layer over the electrochromic layer or the counter electrode layer, and wherein the intermediate layer includes the electrochromic material or the pair The oxygen-rich form of the electrode material, and wherein the first deposition stage and the second deposition stage are interconnected in series and are operable to transfer the substrate from one stage to the next stage without exposing the substrate to the external environment. In one embodiment, the apparatus of the present invention is operable to transfer the substrate from one stage to the next without breaking the vacuum, and may include operable to deposit lithium from a lithium-containing material source in the electrochromic device One or more lithiation stations on one or more layers. In one embodiment, the apparatus of the present invention is operable to deposit the electrochromic stack on a building glass substrate. In one embodiment, the apparatus is operable to transfer the substrate from one stage to the next without breaking the vacuum. In another embodiment, the integrated deposition system further includes one operable to deposit one of lithium from a lithium-containing material source on at least one of the electrochromic layer, the intermediate layer, and the counter electrode layer or Multiple lithium stations. In yet another embodiment, the integrated deposition system is operable to deposit the stack on a building glass substrate. In another embodiment, the integrated deposition system further includes a substrate holder and a transport mechanism operable to hold the architectural glass substrate in a vertical orientation when passing the architectural glass substrate through the integrated deposition system. In another embodiment, the apparatus further includes one or more vacuum load locks for transferring the substrate between the external environment and the integrated deposition system. In another embodiment, the apparatus further includes at least one slit valve operable to permit at least one of the one or more lithium deposition stations and the first deposition station and the second deposition station者 Isolated. In one embodiment, the integrated deposition system includes one or more heaters configured to heat the substrate. 5 depicts a simplified representation of an integrated deposition system 500 in a perspective view and includes a cross-sectional view of the interior in more detail. In this example, the system 500 is a module, wherein the inlet vacuum pre-evacuation chamber 502 and the outlet vacuum pre-evacuation chamber 504 are connected to the deposition module 506. There is an inlet port 510 for loading, for example, a building glass substrate 525 (the vacuum pre-extraction chamber 504 has a corresponding outlet port). The base plate 525 is supported by the pallet 520 traveling along the rail 515. In this example, the pallet 520 is supported by rails 515 via suspension, but the pallet 520 may also be supported on rails located near the bottom of the equipment 500 or (for example) between the rails between the top and bottom of the equipment 500 On top. The pallet 520 can be translated forward and/or backward in the system 500 (as indicated by the double-headed arrow). For example, during lithium deposition, the substrate may move forward and backward in front of the lithium target 530, thereby generating multiple passes to achieve the desired lithiation. However, this function is not limited to a lithium target, for example, a tungsten target can pass through a substrate multiple times, or the substrate can pass in front of the tungsten target via a forward/backward motion path to deposit, for example, an electrochromic layer. The pallet 520 and the substrate 525 are in a substantially vertical orientation. The substantially vertical orientation is not restrictive, but it can help prevent defects because particulate matter that may be generated, for example, from coalescence of atoms from the sputtering will tend to be subject to gravity and therefore will not be deposited on the substrate 525 . Also, because architectural glass substrates tend to be large, the vertical orientation of the substrate realizes the coating of thinner glass substrates as it traverses the stages of the integrated deposition system, which occurs because of the thicker hot glass There are fewer worries. Target 530 (a cylindrical target in this case) is oriented substantially parallel to and in front of the surface of the substrate on which deposition will occur (for convenience, other sputtering methods are not depicted here). The substrate 525 can translate through the target 530 during deposition, and/or the target 530 can move in front of the substrate 525. The moving path of the target 530 is not limited to translation along the path of the substrate 525. The target 530 can rotate along an axis passing through its length, translate along the path of the substrate (forward and/or backward), translate along the path perpendicular to the path of the substrate, circular in a plane parallel to the substrate 525 Path movement, etc. The target 530 need not be cylindrical, it can be flat or any shape required to deposit the desired layer with the desired properties. Also, there may be more than one target in each deposition station, and/or the target may move between stations depending on the desired process. The various stages of the integrated deposition system of the present invention may be modules, but once connected, they form a continuous system in which a controlled ambient environment is established and maintained to process substrates at various stages within the system. A more detailed description of how to deposit the electrochromic material using the integrated deposition system 500 is described in the aforementioned US Non-Provisional Patent Application Nos. 12/645,111 and 12/645,159. The integrated deposition system 500 also has various vacuum pumps, gas inlets, pressure sensors, and the like that establish and maintain a controlled surrounding environment within the system. These components are not shown, but can be understood by those skilled in the art. The system 500 is controlled by a computer system or other controller represented by an LCD and a keyboard 535 in FIG. 5, for example. Those of ordinary skill in the art will understand that embodiments of the present invention may use various processes involving data stored in or transmitted through one or more computer systems. Embodiments of the present invention also relate to equipment, computers and microcontrollers for performing these operations. Such equipment and processes can be used to deposit the electrochromic materials of the methods of the invention and equipment designed to implement such methods. The control device of the present invention may be specially constructed for the required purpose, or the control device may be a general-purpose computer that is selectively activated or reconfigured by computer programs and/or data structures stored in the computer. The programs presented in this article are not inherently related to any particular computer or other device. In particular, various general-purpose machines can be used with programs written according to the teachings herein, or it may be more convenient for constructing more specific devices to execute and/or control the required methods and procedures. As can be seen from the above description (especially FIGS. 3A to 3B), using the method of the present invention, we can not only manufacture electrochromic devices, but also pre-manufacture layered stacks (e.g., 400, 403, and 409). In this case, it can be converted into an electrochromic device via a subsequent process such as described herein. Although it is not a functional electrochromic device because there is no ion-conducting and electrically insulating region between the EC layer and the CE layer, these "electrochromic device precursors" may have special value. This is particularly the case where the device precursors are manufactured with high purity in an integrated processing facility as described herein, where the material layers are all deposited in a controlled ambient environment where, for example, the vacuum has never been destroyed. In this way, high-purity, low-defect materials are stacked and essentially "sealed" by the final TCO layer and/or cover layer, for example, before leaving the integrated system. Like the electrochromic device of the present invention described above, the electrochromic device precursor may also include one or more additional layers (not shown) such as one or more passive layers (for example) to improve specific optical properties (provided (Moisture resistance or scratch resistance) hermetically seal the device precursors and the like. In one embodiment, a cap layer is deposited on the TCO layer of the precursor stack. In some embodiments, the cap layer is SiAlO. In some embodiments, the cap layer is deposited by sputtering. In one embodiment, the thickness of the cover layer is between about 30 nm and about 100 nm. Subsequent processing of the top cover layer in place forms an IC layer without pollution from the environment, that is, with additional protection of the cover layer. The conversion to a functional electrochromic device can occur outside the integrated system if necessary. This is because the internal stack structure is protected from the external environment, and the slightly lower purity conditions are used to use the precursor Necessary for the final adjustment step of the conversion of the stack into a functional device. These stacked electrochromic device precursors can have advantages, for example, due to the longer lifetime of switching to electrochromic devices only when needed, by having (for example) storable and conversion parameters that depend on the final product The quality standards required and must be met to improve or feed to different conversion chambers and/or consumption points for flexibility resulting from a single precursor stack used for conversion. Again, these precursor stacks can be used for testing purposes, such as quality control or research efforts. Therefore, one embodiment of the present invention is a precursor of an electrochromic device, which includes: (a) a substrate; (b) a first transparent conductive oxide layer on the substrate; (c) the first transparent conductive oxide A stack on a layer, the stack including: (i) an electrochromic layer including an electrochromic material, and (ii) an opposite electrode layer including an opposite electrode material; wherein the stack does not include a layer between the electrochromic layer A region of ion conduction and electrical insulation between the counter electrode layer; and (d) a second transparent conductive oxide layer above the stack. In one embodiment, the electrochromic layer includes tungsten oxide, and the counter electrode layer includes nickel tungsten oxide. In one embodiment, at least one of the stack and the electrochromic layer contains lithium. In another embodiment, the electrochromic layer is tungsten oxide having a superstoichiometric oxygen content at least at the interface with the counter electrode layer. In another embodiment, the stack includes an IC precursor layer between the counter electrode layer and the electrochromic layer, the IC precursor layer includes an oxygen content that has a higher oxygen content than the electrochromic layer Oxygen tungsten oxide. In one embodiment, in the absence of an IC precursor layer between the EC layer and the CE layer, the thickness of the electrochromic layer is between about 500 nm and about 600 nm, and the thickness of the counter electrode layer Between about 150 nm and about 300 nm. In another embodiment, where there is an IC precursor layer between the EC layer and the CE layer, the thickness of the electrochromic layer is between about 350 nm and about 400 nm, and the thickness of the IC precursor layer is between Between about 20 nm and about 100 nm, and the thickness of the counter electrode layer is between about 150 nm and about 300 nm. In one embodiment, the prior-displacement devices described herein are exposed to heat to convert the devices into functional electrochromic devices. In one embodiment, the heating is part of MTCC. Another embodiment is an electrochromic device, which includes: (a) an electrochromic layer including an electrochromic material; and (b) an opposite electrode layer including an opposite electrode material, wherein the device is not contained in the The electrically insulating ion conducting material between the electrochromic layer and the counter electrode is composed of a homogeneous layer. In one embodiment, the electrochromic material is tungsten oxide, the counter electrode material is nickel tungsten oxide, and between the electrochromic layer and the counter electrode layer are lithium tungstate and tungsten oxide And the interface region of the mixture of at least one of nickel tungsten oxide. In another embodiment, the thickness of the electrochromic layer is between about 300 nm and about 500 nm; the thickness of the interface region is between about 10 nm and about 150 nm, and the thickness of the counter electrode layer is between Between about 150 nm and about 300 nm. Example FIG. 6 is a graph of a procedure flow used as a scheme for manufacturing the electrochromic device of the present invention. The y- axis unit is optical density, and the x- axis unit is time/program flow. In this example, an electrochromic device similar to the electrochromic device described with respect to FIG. 4A was fabricated, in which the substrate was a glass with fluorinated tin oxide as the first TCO, and the EC layer was one with excess oxygen in the matrix WO ₃ (for example, using tungsten target sputtering, in which the sputtering gas is about 60% O ₂ and about 40% Ar), the CE layer is formed on the EC layer and is made of NiWO, and the second TCO is Indium tin oxide (ITO). Lithium is used as an ion source for electrochromic transition. The optical density is used to determine the end point during the manufacture of the electrochromic device. From the origin of the graph, as the EC layer (WO ₃ ) is deposited on the substrate (glass + TCO), the optical density is measured. The optical density of the glass substrate has a baseline optical density of about 0.07 (absorbance unit). As the EC layer is built, the optical density increases from this point, because tungsten oxide (although substantially transparent) absorbs some visible light. For the desired thickness of the tungsten oxide layer about 550 nm thick, as described above, the optical density rises to about 0.2. After depositing the tungsten oxide EC layer, lithium is sputtered on the EC layer, as indicated by the first time period indicated by "Li". During this period, the optical density further increased to 0.4 along the curve, which indicates that the blind charge of tungsten oxide has been satisfied, because the tungsten oxide is colored with the addition of lithium. The time period indicated by "NiWO" indicates the deposition of the NiWO layer, and the optical density increases during this period, because NiWO is colored. Due to the addition of a NiWO layer about 230 nm thick, the optical density further increased from about 0.4 to about 0.9 during NiWO deposition. Note that as NiWO is deposited, some lithium can diffuse from the EC layer to the CE layer. This serves to maintain the optical density at a relatively low value during NiWO deposition or at least during the initial phase of deposition. The second time period indicated by "Li" indicates the addition of lithium to the NiWO EC layer. The optical density decreased from about 0.9 to about 0.4 during this stage, due to the discoloration of NiWO due to lithiation of NiWO. Lithization is performed until NiWO fades (including a local minimum of about 0.4 optical density). The optical density started to pick up at about 0.4, because the WO ₃ layer was still lithiated and affected the optical density. Next, as indicated by the time period "Extra Li", extra lithium is sputtered onto the NiWO layer. In this example, about 10% of the extra lithium compared to the lithium added to the NiWO discolors the NiWO layer. During this stage, the optical density increases slightly. Next, add indium tin oxide TCO as indicated by "ITO" in the graph. Again, the optical density continued to rise slightly to about 0.6 during the formation of the indium tin oxide layer. Next, as indicated by the time period indicated by "MSTCC", the device was heated to about 250 °C under Ar for about 15 minutes, and then heated under O ₂ for about 5 minutes. Next, the device was annealed in air at about 300°C for about 30 minutes. During this time, the optical density decreased to about 0.4. Therefore, the optical density is used for manufacturing the device of the present invention (for example, for determining the thickness of the layer based on the deposited material and morphology, and in particular for titrating lithium onto various layers to satisfy the blind charge and/or to achieve discoloration State) is a useful tool. Consistent with the scheme described with respect to FIG. 6, FIG. 7 shows a cross-sectional TEM of an electrochromic device 700 manufactured using the method of the present invention. The device 700 has a glass substrate 702 on which an electrochromic stack 714 is formed. The substrate 702 has an ITO layer 704 serving as a first TCO. The tungsten oxide EC layer 706 is deposited on the TCO 704. Layer 706 is formed with a thickness of about 550 nm (ie, WO ₃ formed by sputtering tungsten with oxygen and argon), as described above with respect to FIG. 6. Add lithium to the EC layer. Next, a NiWO CE layer 710 about 230 nm thick is added, followed by lithium to discolor and then about 10% excess lithium. Finally, an indium tin oxide layer 712 is deposited, and the stack is subjected to multi-step thermochemical conditioning, as described above with respect to FIG. 4A. After MSTCC, this TEM is performed. As seen, a new zone 708 of ion conduction and electrical insulation is formed. Figure 7 also shows five selected area electron diffraction (SAED) patterns for various layers. First, 704a indicates that the ITO layer is highly crystalline. Pattern 706a shows that the EC layer is polycrystalline. Pattern 708a shows that the IC layer is substantially amorphous. Pattern 710a shows that the CE layer is polycrystalline. Finally, pattern 712a shows that the indium tin oxide TCO layer is highly crystalline. 8 is a cross-section of the device 800 of the present invention analyzed by scanning transmission electron microscope (STEM). In this example, consistent with the solution described with respect to FIG. 4B, the device 800 is manufactured using the method of the present invention. The device 800 is an electrochromic stack formed on a glass substrate (not marked). On the glass substrate is a fluorinated tin oxide layer 804, which serves as the first TCO (for transparent electronic conductors, this layer is sometimes referred to as a "TEC" layer). The tungsten oxide EC layer 806 is deposited on the TCO 804. In this example, the layer 806 is formed with a thickness of about 400 nm (that is, WO ₃ formed by sputtering tungsten using oxygen and argon, as described above with respect to FIG. 6), and then depositing the oxygen-rich precursor layer 805 to Thickness of about 150 nm. Add lithium to layer 805. Next, a NiWO CE layer 810 about 230 nm thick is added, followed by lithium to discolor and then about 10% excess lithium. Finally, an indium tin oxide layer 812 is deposited and the stack is subjected to multi-step thermochemical conditioning, as described above with respect to FIG. 4B. After MSTCC, perform this STEM. As seen, a new area 808 of ion-conducting electrical insulation is formed. The difference between this example and the embodiment described with respect to FIG. 4B is that, unlike the similar layer 405 in FIG. 4B, the oxygen-rich layer 805 is only partially converted into the interface region 808. In this case, only about 40 nm of the 150 nm oxygen-rich precursor layer 405 is converted into a region that serves as an ion conductive layer. 8B and 8C show a "front-to-back" comparison of the device 800 of the present invention (FIG. 8C) and the device precursor (FIG. 8B) before multi-step thermochemical conditioning as analyzed by STEM. In this example, only layers 804-810 (EC to CE) are depicted. These layers are numbered the same as in Figure 8A, with some exceptions. The dotted line in FIG. 8B is used to roughly distinguish the interface between the EC layer 806 and the oxygen-rich layer 805 (this is more clear in FIG. 8C). Referring again to FIG. 8B, it appears that there is at least lithium concentrated at the interface between the oxygen-rich layer 805 and the CE layer 810 (approximately 10-15 nm thick region), as indicated by 808a. After MTCC (FIG. 8C), it is clear that the interface area 808 has been formed. Although the foregoing invention has been described in some detail to promote understanding, the described embodiments should be considered illustrative rather than restrictive. It will be obvious to those familiar with this technology in general, within the scope of additional patent applications, specific changes and modifications can be practiced.

100‧‧‧Electrochromic device 102‧‧‧Substrate 104‧‧‧Conductive layer (CL) 106‧‧‧Electrochromic (EC) layer 108‧‧‧Ion conductive (IC) layer 110‧‧‧Counter electrode (CE) layer 112‧‧‧ conductive layer (CL) 114‧‧‧ electrochromic stack 116‧‧‧ voltage source 300‧‧‧ program flow 320‧‧‧ program flow 400‧‧‧ layered structure 401‧‧‧ Functional electrochromic device 402‧‧‧Substrate 403‧‧‧Layered structure 404‧‧‧First TCO layer 405‧‧‧Second WO ₃ layer 406‧‧‧EC layer 406a‧‧‧EC layer 407‧‧ ‧Layered stack 408‧‧‧IC layer/interface area 408a‧‧‧Ion conductive electrical insulation area/interface area 408b‧‧‧ hierarchical interface area 409‧‧‧layer structure 410‧‧‧CE layer 411‧‧‧ points Layer stack/functional electrochromic device 412‧‧‧Second TCO layer 414a‧‧‧Stack 414b‧‧‧Stack 414c‧‧‧Stack 500‧‧‧Integrated deposition system 502‧‧‧Inlet vacuum pre-extraction chamber 504 ‧‧‧Exhaust vacuum pre-exhaust chamber 506‧‧‧Deposition module 510‧‧‧ Entry port 515‧‧‧Orbit 520‧‧‧pallet 525‧‧‧Substrate 530‧‧‧Lithium target 535‧‧‧LCD And keyboard 700‧‧‧Electrochromic device 702‧‧‧glass substrate 704‧‧‧indium tin oxide (ITO) layer 704a‧‧‧pattern 706‧‧‧tungsten oxide EC layer 706a‧‧‧pattern 708‧‧‧ 708a‧‧‧pattern 710‧‧‧CE layer 710a‧‧‧pattern 712‧‧‧indium tin oxide layer 712a‧‧‧pattern 714‧‧‧electrochromic stack 800‧‧‧device 804‧‧‧fluorinated Tin oxide layer 805‧‧‧Oxygen-rich precursor layer 806‧‧‧Tungsten oxide EC layer 808‧‧‧New area/interface area 808a‧‧‧Li 810‧‧‧CE layer 812‧‧‧Indium tin oxide layer

FIG. 1A is a schematic cross-section depicting a conventional formation of electrochromic device stacks. FIG. 1B is a graph showing the composition of the EC layer, IC layer, and CE layer in a conventional electrochromic stack. 2A to 2C are graphs showing representative component compositions used in the electrochromic device of the present invention. 3A and 3B are the program flow according to the embodiment of the invention. 4A to 4C are schematic cross sections depicting the formation of an electrochromic device according to certain embodiments of the present invention. Figure 5 depicts the integrated deposition system of the present invention in a perspective view. 6 is a graph showing how program parameters and end point readings are related during the formation of an electrochromic stack according to an embodiment of the invention. 7 and 8A to 8C are actual cross-sections of an electrochromic device manufactured using a method according to an embodiment of the present invention.

320‧‧‧Procedure flow

Claims (18)

An electrochromic device, comprising: (a) an electrochromic layer including an electrochromic material; and (b) an opposite electrode layer including an opposite electrode material, wherein the opposite electrode material can undergo an electrochromic transition (electrochromic transition); wherein the device does not contain a homogeneous layer on the composition of the electrically insulating ion conducting material between the electrochromic layer and the counter electrode. The electrochromic device according to claim 1, wherein the electrochromic material includes tungsten oxide, the counter electrode material includes nickel tungsten oxide, and the one between the electrochromic layer and the counter electrode layer includes the following The interface area of the mixture of: (i) lithium tungstate and/or lithium oxide and (ii) at least one of tungsten oxide and nickel tungsten oxide. The electrochromic device according to claim 2, wherein the thickness of the electrochromic layer is between about 300 nm and about 500 nm; the thickness of the interface region is between about 10 nm and about 150 nm, and the thickness of the counter electrode layer is between Between about 150nm and about 300nm. The electrochromic device according to claim 1, wherein the electrochromic device is completely inorganic. A precursor of an electrochromic device, comprising: (a) a substrate; (b) a first transparent conductive oxide layer on the substrate; (c) a stack on the first transparent conductive oxide layer, the stack including: (i) an electrochromic layer including an electrochromic material; (ii) an opposing electrode layer including an opposing electrode material, wherein the pair The electrode material can undergo an electrochromic transition; wherein the stack does not contain a region of ion conduction and electrical insulation between the electrochromic layer and the counter electrode layer; and (d) the second on top of the stack Transparent conductive oxide layer. The electrochromic device precursor of claim 5, wherein the electrochromic layer includes tungsten oxide, and the counter electrode layer includes nickel tungsten oxide. The electrochromic device precursor of claim 6, wherein at least one of the electrochromic layer and the counter electrode layer contains lithium. The electrochromic device precursor according to claim 7, wherein the electrochromic layer contains an oxygen content having a superstoichiometric amount at least at the interface with the counter electrode layer. The electrochromic device precursor of claim 7, wherein the thickness of the electrochromic layer is between about 500 nm and about 600 nm, and the thickness of the counter electrode layer is between about 150 nm and about 300 nm. The electrochromic device precursor according to claim 5, wherein the electrochromic device precursor is completely inorganic. An apparatus for manufacturing an electrochromic device, comprising: an integrated deposition system, comprising: (i) a first deposition station containing a material source, which is configured to deposit an electrochromic layer including electrochromic materials; (ii) a second deposition station configured to deposit a counter electrode layer including a counter electrode material, wherein the counter electrode material can withstand electrochromic transitions; and (iii) a controller, which contains The programming instructions of the substrate passing through the first deposition table and the second deposition table are sequentially deposited on the substrate in a stacked manner. The stack includes an intermediate layer sandwiched between the electrochromic layer and the counter electrode layer; the The intermediate layer is not substantially electrically insulating; wherein either or both of the first deposition table and the second deposition table are also configured to deposit the intermediate layer over the electrochromic layer or the counter electrode layer , And wherein the intermediate layer includes the electrochromic material or the oxygen-rich form of the counter electrode material, and wherein the first deposition stage and the second deposition stage are interconnected in series and operable to transfer the substrate from one stage to The next stage without exposing the substrate to the external environment. As in the equipment of claim 11, it is operable to transfer the substrate from one stage to the next without breaking the vacuum. The apparatus of claim 12, wherein the integrated deposition system further includes one operable to deposit one of lithium from a lithium-containing material source on at least one of the electrochromic layer, the intermediate layer, and the counter electrode layer Or more lithium stations. The apparatus of claim 13, wherein the integrated deposition system is operable to deposit the stack on a building glass substrate. The apparatus of claim 14, wherein the integrated deposition system further includes a substrate holder and transport operable to hold the architectural glass substrate in a substantially vertical orientation when passing the architectural glass substrate through the integrated deposition system mechanism. The apparatus of claim 15, further comprising one or more vacuum pre-exhaust chambers (load locks) for transferring the substrate between the external environment and the integrated deposition system. The apparatus of claim 16, wherein the integrated deposition system includes one or more heaters configured to heat the substrate and one or more cooling components configured to cool the substrate in an active or passive manner. The device of claim 11, wherein the electrochromic device is completely inorganic.

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