TW201222119A - 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 formed after 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

201222119 VI. INSTRUCTIONS: The present invention claims the rights and priority of US Application Nos. 12/772,055 and 12/772,075, filed on Apr. 30, 2010, entitled "Electrochromic Devices" Each of these applications is incorporated by reference in its entirety. • [Prior Art] Electrochromism is a phenomenon in which a material exhibits a reversible electrochemical change in optical properties when it is in a different electronic energy state (usually by undergoing a voltage change). Optical properties are typically one or more of color, transmittance, absorbance, and reflectance. For example, one well known electrochromic material is tungsten oxide (WO3). Tungsten oxide is a cathodic electrochromic material in which a color transition (blue permeable) occurs by electrochemical reduction. Electrochromic materials can be incorporated into, for example, windows and mirrors. The color, transmittance, absorbance and/or reflectivity of such windows and mirrors can be varied by inducing changes in the electrochromic material. For example, one of the well-known applications of electrochromic materials is the rearview mirrors in some automobiles. In these electrochromic rearview mirrors, the reflectivity of the mirror changes at night, so that other vehicle headlights do not distract the driver. Although electrochromic 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. SUMMARY OF THE INVENTION A typical electrochromic device includes an electrochromic ("ec") electrode layer and a counter electrode separated by an ion-conducting ("IC") layer that is highly conductive to ions and resistant to an electron height of 155961.doc 201222119 (" CE") layer. In other words, the ion conducting layer permits ion transport but blocks current flow. As is generally understood, the ion conducting layer thus prevents short circuits between the electrochromic layer and the counter electrode layer. The ion conducting layer allows the electrochromic electrode and the counter electrode to retain charge and thereby maintain their complex or colored state. In conventional electrochromic devices, the components form a stack' wherein the ion conducting layer is between the electrochromic electrode and the counter electrode. The boundaries between these three stacked components are defined by abrupt changes in composition and/or microstructure. Thus, the devices have two distinct layers with two abrupt interfaces. Quite surprisingly, the inventors have discovered that high quality electrochromic devices can be fabricated without the deposition of ionically conductive electrically insulating layers. According to a particular embodiment, the counter electrode and the electrochromic electrode are formed adjacent to each other (often in direct contact) without the separate deposition of the ion conducting layer. A variety of 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 functions as at least some of the functions of the ion conducting electrically insulating layer in conventional devices. . The following describes specific mechanisms that may be key to forming an interface zone. The interfacial region typically, although not necessarily, has a heterostructure comprising at least two discrete components that are represented by different phases and/or compositions. Additionally, the interface region can include gradients in two or more discrete components. The gradient can provide, for example, a variable composition, microstructure, resistivity, dopant concentration (e.g., oxygen concentration), and/or stoichiometry. In addition to the above findings, the inventors have observed that in order to improve the device, two layers (electrochromic (EC) layer and counter electrode (CE) layer) of the electrochromic device can be fabricated by the method of 155961.doc 201222119. Each of them includes a defined amount of lithium, and in addition, careful selection of materials and morphology and/or microstructure of some components of the electrochromic device provides an improvement 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 discovered that the formation of the EC-IC-CE stack does not need to be performed by conventional sequences (EC-IC->CE or CE->IC-»EC), but can be electro After the formation of the color-changing layer and the counter-electrode layer, an ion-conducting electrically insulating region serving as 1 (: layer is formed. That is, an EC-CE (or CE-EC) stack is first formed] and then the interface is used at the interface between the EC layer and the CE layer. One or both of the equal layers form an interface region between the EC layer and the CE layer for some use of the ic layer. The method of the present invention not only reduces manufacturing complexity by eliminating one or more processing steps And a device for providing improved performance characteristics. Accordingly, one aspect of the present invention is a method of fabricating an electrochromic device, the method comprising: forming an electrochromic layer comprising an electrochromic material; The electrochromic layer contacts the counter electrode layer without first providing an ion conductive electrically insulating layer between the electrochromic layer and the counter electrode layer; and forming between the electrochromic layer and the counter electrode layer An interface region, wherein the interface region is substantially ion conducting and The substantially electrically insulating, electrochromic layer and the counter electrode layer are typically, but not necessarily, made of one or more materials that are more conductive than the interface region but may have some electrical resistance. The interface region may contain germanium. The EC layer and/or the component material of the CE layer, and in some embodiments, the EC layer and the CE layer contain component materials of the interface region. In an embodiment 155961.doc 201222119 'the electrochromic The layer comprises W03. In some embodiments, the EC layer comprises WO3, the CE layer comprises nickel tungsten oxide (Niw〇), and the layer comprises lithium tungstate (Li2W〇4). Heating is applied during deposition of at least a portion of the layer. In one embodiment 'in the case where the EC layer comprises w〇3, heating is applied after each of a series of depositions via a splash bond to form a continuum An epitaxial microstructure of the EC layer. In one embodiment, the electrochromic layer has a thickness between about 300 nm and about 600 nm, but the thickness may depend on the formation of the EC-CE stack after deposition. The desired result of the interface area changes. In some embodiments ' w 〇 3 is substantially polycrystalline. In some embodiments 'an oxygen-rich layer of W 〇 3 can be used as the interface precursor. In other embodiments, the WO 3 layer has a varying oxygen in the layer a grading layer of concentration. In some embodiments, lithium is the preferred ionic species for driving electrochromic transitions, and a stack or layer lithiation scheme is described. 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 fabricating an electrochromic device, the method comprising: (a) forming an electrochromic layer comprising an electrochromic material or a counter electrode layer comprising a counter electrode material; (8) Forming an intermediate layer over the electrochromic layer or the counter electrode layer, wherein the intermediate layer comprises an oxygen-rich form of at least one of the electrochromic material, the counter electrode material, and an additional material, wherein the cough additional material comprises a difference The intermediate layer of electrochromic material and/or counter electrode material is not substantially electrically insulating; (c) forming the other of the electrochromic layer and the counter electrode layer; and (4) allowing at least the intermediate layer Part of the change: Substantially electrically insulating and substantially ion conducting. The details of the formation parameters for this method 155961.doc 201222119 and the layer characteristics are also described in more detail below. Another aspect of the invention is an apparatus for fabricating an electrochromic device comprising: an integrated deposition system comprising: (丨) a first deposition station containing a source of material configured to deposit including electricity An electrochromic layer of a color-changing material, and (ii) a second deposition station configured to deposit a counter electrode layer comprising a counter electrode material; and a controller 'containing a layer for sequentially depositing the stack on the substrate Passing 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 first Either or both of the deposition stations are also configured to deposit the intermediate layer over the electrochromic layer or the counter electrode layer, and wherein the intermediate layer comprises the electrochromic material or the counter electrode material is rich An oxygen form, and wherein the first deposition station and the second deposition station are interconnected in series and are operable to transfer the substrate from one station to the next without exposing the substrate to an external environment. In one embodiment, the apparatus of the present invention is operable to transfer the substrate from one station to the next without breaking the vacuum' and may include operable to deposit lithium from a source of lithium-containing material in the electrochromic One or more chemistries on one or more layers of the device. In an embodiment, the apparatus of the present invention is operable to deposit an electrochromic stack on a building glass substrate. The apparatus of the present invention does not require a separate stem for the fabrication of the ion conducting layer. Another aspect of the invention is an electrochromic device comprising: (4) an electrochromic layer comprising an electrochromic material; (b) an anti-electrode layer comprising a counter electrode material; and (4) in the electrochromic layer An interface region between the counter electrode layers, wherein the interface region comprises at least one of an electrically insulating ion conductive material and the electrochromic material, the counter electrode material and an additional material, wherein the additional material Including a dissimilar electrochromic material and/or a counter electrode material. In some embodiments, the additional material is not included; in such embodiments, the interfacial region comprises the electrochromic material and the counter electrode material At least one of the changes in composition and morphology and/or microstructure of the interface region will be described in more detail herein. The electrochromic device described herein can be incorporated into a window (in an embodiment, 'architecture Glass scale window: The same and other features and advantages of the present invention will be described in more detail below with reference to the associated drawings. [Embodiment] The following detailed description can be incorporated in the drawings. Figure 1A is a schematic cross-section depicting a stack of conventional electrochromic devices. Electrochromic device 100 includes substrate 1 2, conductive layer (CL) 1〇4, electro-induced Color change (EC) layer 106 'ion conduction (ic) layer 1〇8, counter electrode (CE) layer 110 and conductive layer (CL) 112. The elements 1〇4, 1〇6, 1〇8, 110 and 112 are common This is called electrochromic stack 114. Typically, these CL layers are made of a transparent conductive oxide 'and are often referred to as 'TC0' layers. Since the TCO layer is transparent', the coloring behavior of the EC-IC-CE stack This can be observed, for example, via a tc layer to allow for the use of such devices on the window to achieve reversible shading. The voltage source 丨 16 that is operable to apply a potential across the electrochromic stack 114 effects the electrochromic device from, for example, fading The transition from the state (ie, transparent) to the colored state. The order of the layers can be reversed relative to the substrate. That is, the layers can be in the following order: substrate, transparent conductive layer, counter electrode layer, ion conduction 155961.doc 201222119 layer, electrochromic material layer and (other) transparent conductive layer Referring again to Figure 1A', in a conventional method of fabricating an electrochromic stack, individual layers are deposited on top of another layer in the sequential format depicted in the schematic of the left side of Figure 1A. That is, the TCO layer 104 is deposited on the substrate. Next, an EC layer 106 is deposited on the TCO 104. Next, a 1C layer 108 is deposited on the EC layer 106, followed by a CE layer 110 deposited on the ic layer 108, and finally a TCO layer 112 deposited on the CE layer. 11〇 to form an electrochromic device 1〇〇. 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 1C layer must be deposited on the EC layer, followed by The CE layer is deposited on the 1C layer' or the 1C layer is deposited on the CE layer, followed by the EC layer deposited on the 1C layer. The transition between the layers of material in the stack is abrupt. One of the above procedures significantly challenges the processing required to form the IC layer. In some prior methods, the '1C layer was formed by a sol-gel process that was difficult to incorporate into the CVD or PVD process used to form the ec layer and the CE layer. In addition, the sol gel and other liquid-based processes produce 1 (the layer tends to have the disadvantage of reducing the quality of the device and may require removal by, for example, engraving. In other methods the '1C layer is made by pvd Ceramic dry deposits from which it may be difficult to manufacture and use. Figure 1B is a depiction of the % composition of the material in the electrochromic stack of Figure 1A (i.e., layers 106, 108, and 11 〇 ', ie, EC layer, IC layer, and CE The graph of the layer) As mentioned, in the conventional electrochromic stack, the transition between the layers of material in the stack is abrupt. For example, EC material 1〇6 is deposited as a different layer. There is little or no percolation of the composition to the adjacent 1C layer. Similarly, the ic material 108 and the CE material 11〇 differ in composition with little or no percolation to the adjacent layer 15596l.doc 201222119. Therefore, 'these materials are substantial Upper homogenized (except for the specific composition of the CE material described below) and having a mutated interface. It is conventionally thought that each of the two layers of shai should be laid as a uniform uniformly deposited and smooth layer to form Stacking. Interface between each layer To be "clear", there is little intermixing of material from each layer at the interface. One skilled in the art will recognize that Figure 1B is an idealized depiction and, in the sense of practice, the layer interface exists. A certain degree of inevitable material mixing. The point is that 'in the conventional manufacturing method, any such mixing is unintentional and minimal. The inventors have found that an interface region serving as an IC layer can be formed, wherein the interface region intentionally includes a large number of One or more electrochromic materials and/or counter electrode materials. This is a fundamental deviation from the conventional manufacturing method. As mentioned above, the 'inventors have found that the formation of the EC-IC-CE stack does not have to be in the conventional sequence (EC). - IC - CE or CE - IC - EC), but can form an interface region serving as an ion conducting layer after deposition of the electrochromic layer and the counter electrode layer. That is, 'first form EC-CE (or CE-EC) Stacking, then 'using one or both of the layers (in some embodiments, and/or another electrochromic material or counter electrode material) at the interface of the layers at the EC layer Forming an interface region with the CE layer It may have at least some functions of the IC layer. The interface region functions as at least some of the functions of the conventional 1C layer because the interface region is substantially ion-conducting and substantially electrically insulating. However, it should be noted that The described interface regions may have leakage currents that are higher than conventionally accepted leakage currents. However, such devices exhibit good performance. In one embodiment, the electrochromic layer is formed to have an oxygen-rich region, which is rich. The oxygen region is converted to a 155961.doc -10·201222119 interface region or layer that serves as an IC layer after subsequent deposition of the counter electrode layer. In some embodiments, an electrochromic material is used.

The opposite layer of the oxygen-rich pattern (finally) forms an interface layer acting as an IC layer between the EC layer and the CE layer. In other embodiments, a dissimilar layer comprising an oxygen-rich version of the counter electrode material is used (finally) to form an interfacial region that acts as an IC layer between the EC layer and the CE layer. All or part of the meta-oxygen CM is converted into an interface region. In other embodiments, an oxygen-rich version comprising a counter electrode material and a phase layer of the field oxygen form of the electrochromic material are used (finally) to form an interfacial region that acts as a 1C layer between the EC layer and the CE layer. In other words, some or all of the oxygen-rich material acts as a precursor to the interface region that acts as the 1C layer. The method of the present invention not only reduces the number of processing steps, but also produces an electrochromic device that exhibits improved performance characteristics. As mentioned, some of the EC layers and/or CE layers in the interface region are converted to provide one or more functions of the 1C layer (especially for the high conductivity of ions and the resistance to electrons). ) material. The ic functional material in the interfacial zone can be, for example, a salt of a conductive cation; for example, a lithium salt. 2A, 2B, and 2C show compositional 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), wherein the EC material is tungsten oxide (here indicated Is w〇3, but is intended to include \νοΛ 'where x is between about 27 and about 35, in one embodiment, X is between about 2.7 and about 2.9) 'The CE material is nickel oxide tungsten (NiW〇) And the interface region mainly comprises lithium tungstate (here denoted Li2W〇4, in another embodiment the 'interfacial zone is between about 0.5% and about 5 〇 (atomic)% of Li2〇, at about 5 /〇 and llwO4 between about 95% and about 7% and about 70% of the W03 nanocomposite) and a certain amount of EC material and / or CE material. More generally, 155961.doc 201222119, the interface region typically, but not necessarily, has a heterostructure comprising at least two discrete components represented by different phases and/or compositions, the concentration of the phases or compositions being over the width of the interface region Variety. For this reason, the interface area that serves as the ic layer is sometimes referred to as "gradient zone", "heterogeneous redundancy layer" or "distributed layer" in this paper. Although it describes the specific material, Figure 2A, Figure 2B and The illustration in Figure 2C more generally represents the compositional variation of any suitable material for use in the electrochromic device of the present invention. Figure 2A depicts an electrochromic stack of the present invention in which the Ec material is an important component of the interface region that acts as an ic layer, while the CE material is not an important component. Referring to Fig. 2A, starting from the origin and moving from left to right along the ^ axis, it can be seen that a portion of the EC material W〇3 (which is substantially all tungsten oxide) acts as the Ec layer. There is a transition to the interface region in which there is a gradual decrease in yttrium oxide and a correspondingly increasing amount of lithium tungstate up to and including the end near the interface region where there is a substantial amount of tungsten oxide substantially All of them are part of lithium tungstate. Although the transition from the EC layer to the interface region is distinguished by a combination of substantially all of the tungsten oxide and the minimum amount of lithium tungstate, it is apparent that the transition is not as abrupt as in conventional devices. In this example, in practice, the transition begins with the composition having a sufficient amount of lithium tungstate to enable the material to function as at least some of the IC layer, such as ion conduction and electrical insulation. Undoubtedly, a composition closer to the CE layer (wherein the composition is substantially lithium tungstate) functions as a layer (1: layer because it is known that lithium tungstate exhibits such properties. But in other parts of the interface region There is also a certain 1C layer function. The inventors have found that the switching characteristics of these "heterogeneous 1C layers" improved electrochromic devices compared with the conventional devices with sudden transitions and 155961.doc 12 201222119 possible thermal cycling Stability. The CE layer in this example mainly contains an oxide-recorded crane as an active material and has a relatively abrupt transition to the nickel-tungsten oxide composition at the edge of the interface region. A method for fabricating a stack having such interface regions will It will be described in more detail below. It should be noted that 'for example, the nickel-nickel-tungsten CE layer of Figure 2A is depicted as having about 20% lithium tungstate. Without wishing to be bound by theory, it is believed that the nickel-tungsten oxide ce layer acts as tungsten. The outer shell of the acid chain or the nickel oxide core or particles surrounding the matrix, which imparts a relatively good ionic conductivity to the CE layer, exists and thereby assists in the electrochromic transition of the CE layer during operation of the electrochromic stack. The exact stoichiometry of lithium tungstate in the cE layer can vary significantly between the examples. In some embodiments, some tungsten oxide may also be present in the CE layer. Again, because lithium ions pass through the interface region that acts as the IC layer And traveling from the EC layer and the ce layer, so there may be a large amount of lithium tungstate in the EC layer, for example, as depicted in Figure 2-8. Figure 2B depicts the electrochromic stack of the present invention, wherein the CE material acts as an ic layer The important component of the interface area, and the Ec material is not an important component. Referring to Figure 2B, starting from the origin and moving from left to right along the axis, we can see that in this case, substantially all of the oxidation The tungsten EC material acts as an EC layer. There is a sudden transition into the interface region where there is little, if any, tungsten oxide, but a large amount of lithium tungstate and at least some nickel oxide tungsten (CE material) are present. The composition of the zone varies along the sense axis with a gradual decrease in lithium tungstate and a corresponding increase in nickel oxide tungsten. The transition from the interface zone to the CE layer is a combination of about 80% oxygen (four) cranes and about 2G% of cranes. Objects are arbitrarily divided, but this is only a transition One of the conditions in which the composition occurs is 155961.doc 201222119. The interface zone can be considered to be terminated when no additional changes to the composition occur when further processing of the stack occurs. Additionally, the transition actually has in the composition Sufficient amount of nickel oxide tungsten is terminated so that the material no longer functions as at least one of the functions of the distinct ic layer. Undoubtedly, the composition of the CE layer is closer (as distinguished) (wherein the composition is 8 〇% of nickel oxide tungsten) functions as a CE layer. Likewise, a 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. Figure 2C depicts the invention The electrochromic stack, in which the Ec material and the material are all important components of the interface region of the ic layer. See Figure 2C, from the origin

Starting and moving from left to right along the X axis, we can see that a portion of the ECM material WO3 (which is essentially all tungsten oxide) acts as a £: layer. There is a transition into the interface region where there is a gradual decrease in oxidation. Tungsten and correspondingly increasing lithium tungstate. In this example, there is also a growth amount of nickel oxide tungsten counter electrode material in the vicinity of one-half of the path divided into portions of the interface region. At about the middle of the portion of the region, there are about 10% each of tungsten oxide and nickel oxide tungsten and 8% by weight of lithium tungstate. In this example, between the EC layer and the 1C layer or 1 (: layer and CE layer) There is no abrupt transition between them, but there is an interfacial zone with a continuous grading composition of both the CE material and the EC material. In this example, the lithium tungstate component peaks around the middle of the interface region, and thus This region is likely to be the strongest electrically insulating portion of the interface region. As mentioned in the above [Summary], the EC layer and the CE layer may include a material component that imparts a certain resistivity to the EC layer and the CE layer; Crossing at least a certain amount as described in Figure 2C There are three regions of lithium tungstate which are examples of such materials which impart a resistivity of 155961.doc 201222119 to the EC layer and the CE layer. Figures 2A to 2C show only the [c layer] in the electrochromic device of the present invention. Three non-limiting examples of hierarchical compositions of the interface regions. It will be appreciated by those skilled in the art that many variations are possible without departing from the scope of the invention. Examples in Figures 2A-2C In each of them, there are only two material components present in H and one of the components is the least. The present invention is not limited to this manner. Therefore, an embodiment of the present invention is an electrochromic. a device comprising an electrochromic layer 'acting as an interface region of an IC layer, and a counter electrode layer, wherein at least one of the two layers of the device and one of the regions - the material component is present in the amount In each of the electrochromic layer, the interfacial region, and the counter electrode layer: at least about wt%, in another embodiment, at least about 15 wt%, and in another embodiment, at least about 1 wt. %, in another embodiment, at least about 5% by weight, in yet In embodiments, at least about 2 weights per Å. The amount of electrochromic t-color material and/or counter electrode material in the interface region can be significant 'in one embodiment' up to 5 〇 weight of the interface region 0/ However, in many embodiments, the ionically conductive electrically insulating material is typically in multiple layers, and the remainder of the interface region is an electrochromic material and/or a counter electrode material. In one embodiment, the interface region is included Between 6% by weight and about 95% by weight of the ionically conductive electrically insulating material, and the remainder of the interface region is an electrochromic material and/or a counter electrode material. In one embodiment, the interface region is comprised at about 70% by weight. The ion conductive electrically insulating material is between about 95% by weight, and the remainder of the interface region is an electrochromic material and/or a counter electrode material. In one embodiment, the 'interface region includes about 8 G ff % and about 95 wt. Between 5%, 155961.doc •15· 201222119 ion-conducting electricity, and rim materials, while the remainder of the interface region is an electrochromic material and/or a counter electrode material. In some embodiments, the interface regions in the devices described herein can be relatively distinct, that is, when analyzed, for example, by microscopy, there are relatively distinguishable boundaries at adjacent layers, even if the interface region The same applies to a certain amount of electrochromic material and/or counter electrode material. In these embodiments, the thickness of the interface region can be measured. In the embodiment in which the interface region is formed by the EC layer and or the oxygen-rich meter 4) region of 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 region. One measure. 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 which are homogeneously or heterogeneously mixed in one or more diffusion regions. The EC layer is 55 〇 nm thick and includes an oxygen layer (or region). If about 15 〇 nm of the EC layer is converted into an interface region, about 27% of Ec is converted into an interface region, that is, 丨5〇 nm divided by wo nm. In another example, the EC layer includes a first metal oxide region (or layer) and an oxygen-enriched second metal oxide layer (or region) β if the oxygen-rich metal oxide layer is all or the enthalpy is converted into The 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 forming the interface region) is a measure of the interface region. In one embodiment, the interface region comprises between about 0.5 Å/〇 and about 50% of the thickness to form the interface region precursor region (EC and/or CE 'including the oxygen-rich portion), in another implementation In an example between about 1% and about 30% 'in 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 acts as a 1 (: layer has many benefits. 155961.doc • 16-201222119 B does not wish to limit the literary arts, but Xianxin, 胄 by having such grading areas, the efficiency of electrochromic transition Greatly improved. There are other benefits as described in more detail in y. Although not wishing to be bound by theory, it is believed that one or more of the following mechanisms can be used to achieve EC and/or CE materials in the interface region. (: Conversion of Functional Materials. However, the execution 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 1 C layer material during fabrication of the stack. As is clear elsewhere herein, the apparatus of the present invention need not have a separate target comprising a material for the layer (1: layer). In the first mechanism, direct lithiation of the electrochromic material or counter electrode material creates an interface region. IC material (eg, lithium tungstate). As will be more fully explained below, various embodiments use direct lithium in one of the active layers at some point in the manufacturing process between the formation of the EC layer and the CE layer. Chemical. The operation involves the exposure of the EC layer or the CE layer (formerly formed) to lithium. According to this mechanism, an ion-conducting electron-resistant material, such as a lithium salt, is generated by the flux of lithium in the EC or CE layer. Heat or other may be applied. Energy to drive the lithium. This mechanism describes the conversion of 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, One of the EC or CE that diffuses to another layer after the formation of both layers and/or during the formation of the second layer on the lithiated first layer results in a portion of one of the EC and/or CE Switching to an interface region having a 1C functional material at its interface" may occur after the entire second layer has been formed or after only a portion of the layer has been formed. Further 'lithium diffusion and to 1C functionality Subsequent conversion of the material occurs in the first deposited layer of the first or 155961.doc • 17· 201222119 and in the EC or CE layer. In one example, the EC layer is first formed 'and then the EC layer is lithiated. Then when the CE layer is deposited on top of the EC layer, some The underlying EC layer diffuses and/or diffuses into the CE layer toward the CE layer, resulting in conversion to an interfacial region containing the IC functional material. In another example, the EC layer is first formed (as appropriate with an oxygen-rich upper region) Then, 'the CE layer is formed and the CE layer is lithiated. Subsequently, some of the layer from the Ce layer is diffused into the EC layer where it forms an interfacial region with an IC functional material. In yet another example, the first deposition An EC layer, and then lithiation of the £ (: layer to produce a certain 1C functional material according to the first mechanism described above. Then, when the CE layer is formed, some of the lithium diffuses from the underlying EC layer toward the CE layer to A certain 1C material is produced in the interface region of the CE layer. In this manner, the interface of the IC functional material nominally next to the CE layer and the EC layer resides in both the CE layer and the EC layer. In the third mechanism, the formation of the EC layer and the CE layer is completed (or at least the time when the layer portion of the second formation is completed). Next, the device structure is heated and the heating converts at least some of the material in the interface region into an IC functional material (e.g., a lithium salt). Heating (e.g., as part of a multi-step thermochemical conditioning (MTCC) as further described herein) can be performed during deposition or after deposition is complete. In an embodiment, the heating is performed after the transparent conductive oxide is formed on the stack. In another embodiment, heating is applied after the second layer portion is fully completed, but prior to applying the transparent conductive oxide to the second layer. In some cases, the heating is directly and primarily responsible for the conversion. In other cases, heating primarily promotes the diffusion or flow of lithium ions, as described in this second mechanism, which establishes a region of functional material. 155961.doc 18- 201222119 Finally, in the fourth mechanism, at least one of the electro-chromic-driven electrochromic material and the counter-electrode material flowing between the Ec layer and the CE layer is transformed into a boundary: IC functionality in the region material. This conversion may occur because, for example, the ion flux associated with the flow current is so large that it drives the sink, or chemical conversion of the CE material to the IC material in the interface region. For example, as will be explained below, the large clock flux through the tungsten oxide in the EC layer can produce lithium oleate, which acts as a 1C material. Lithium flux can be introduced, for example, during the initial activation cycle of a newly formed device. However, the situation does not have to be as & this is because other opportunities for driving the cesium ion flux may be more appropriate to achieve this conversion. The method of the present invention can be performed by those of ordinary skill in the art without employing any one or more of the above mechanisms. Figure 3A is a flow diagram of a process in accordance with the method of the present invention. Specifically, see 305, (for example, on TC〇2 CL) deposit £(: layer. Next, see 31〇, depositing the CE layer. After depositing the Ec layer and the cE layer, then, see 315, in the EC layer with An interface region serving as a 1 (:: layer) is formed between the CE layers. An embodiment of the present invention is a similar method (not depicted) in which steps 305 and 3 10 are reversed. The main point of the method is that 'the interface region serving as the 1C layer is The EC layer and the CE layer are formed after (in some embodiments, at least part of one of the EC layer and the CE layer is used to form an interface region). For this reason, the interface region formed in this way is sometimes referred to as "essence" 1C layer. In other embodiments, an oxygen-rich version, such as an EC material or a CE material, is used to form a distinct layer between the ec layer and the CE layer, wherein the layer is again fully or partially converted after forming the EC layer and the CE layer. Interfacial zone. Various methods for forming an interfacial zone after forming an EC-CE stack will be described below. 155961.doc • 19- 201222119 Thus, as mentioned, one aspect of the present invention is an electrical fabrication Method of color changing device 'This method includes: forming including electricity An electrochromic layer of a color changing material; forming a counter electrode layer in contact with the electrochromic layer without first providing an ion conducting electrically insulating layer between the electrochromic layer and the counter electrode layer, wherein the counter electrode layer Including a counter electrode material; and forming an interface region between the electrochromic layer and the counter electrode layer, wherein the interfacial region is substantially ionically conductive and substantially electrically insulating. The interfacial region may comprise an EC layer, a CE layer or The component materials of both. As will be described in more detail below, the interface region can be formed in a number of ways. Figure 3B is a flow diagram showing the process described in relation to Figure 3A (detailed 'for depositing an EC layer, then A program flow 320 of depositing a Ce layer and ultimately forming a program flow that acts as an interface region for the ic layer between the layers. More specifically, in this embodiment, the EC layer includes oxygen having various amounts (detailed 'Composition and configuration' w〇3; CE layer includes NiWO, interface region includes LhWO4, and TC〇 material such as indium tin oxide and fluorinated tin oxide is used. It should be noted that the following will be about solid materials. Description of electrical alteration A layer of a color device that is required for reliability, consistent characteristics, and program parameters and device performance. Exemplary solid state electrochromic devices, methods, and devices for making the same, and fabricating electrochromic devices therewith The method of the window is described in K〇Zl〇Wski et al. entitled "FabHcati〇n 〇f L〇w Defectivity

Electrochiromic Deviees, U.S. Non-Provisional Patent Application No. 12/645,111, and Wang et al., entitled "Electr〇chr〇mic, US Non-Provisional Patent Application No. 12/645,159, the two patents The invention is incorporated herein by reference for all purposes. In the specific implementation 155961.doc • 20 201222119, the electrochromic devices of the present invention are all solid and are capable of depositing a stack in a documented environment. - or multiple layers of equipment. That is, depositing the layers without leaving the equipment and, for example, without breaking the vacuum between the deposition steps, thereby reducing contaminants and ultimately improving Device Effectiveness. In a particular embodiment, the apparatus of the present invention does not require the conventional apparatus to require a separate target for depositing an IC layer. As will be appreciated by those of ordinary skill in the art, the present invention is not limited to such materials. And methods, but in a particular embodiment, the materials comprising the electrochromic stack and the precursor stack (as described below) are all inorganic, solid (ie, 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 offer the advantage of a reliable electrochromic stack that can operate for extended periods of time. It also provides the advantage of not having the contaminants and bubble problems that liquid cancer materials often have. It should be understood that 'any of the layers in the stack—or more may contain a certain amount of organic material' but in many implementations, The (four) towel may contain little or no organic matter. S may be the same for liquids that may be present in small amounts in one or more layers. It should also be understood that solid materials may be used by using liquid groups. a portion of the process (such as a specific process using sol-gel or chemical vapor deposition) is deposited or otherwise formed. Referring again to Figure 3A, see 325, first depositing (4) of w〇3. Figure to Figure 4C is a depiction based on A particular method and apparatus of the present invention, and in particular a schematic cross-section of an electrochromic device formed according to program flow 32G, is specifically shown in Figures 4A through 4C to illustrate the inclusion of w〇, EC. How to form 155961.doc -21 - 201222119 are three non-limiting examples of portions of the stack in which the interface region acting as the ic layer is formed after depositing the other layers of the stack. Each of Figures 4A-4C The substrate 402, the first TCO layer 404, the CE layer 410, and the second TCO layer 41 2 are substantially identical. Again, in each of the three embodiments, a stack having no 1C layer is formed, and then The stack is further processed to form an interfacial region that acts as a 1C layer within the stack, between the EC layer and the CE layer. Referring to each of Figures 4A-4C, a hierarchical structure 4〇0, 403 is depicted, respectively. And 409. Each of these layers includes, for example, a substrate 402 of glass. Any material having suitable optical, electrical, thermal, and mechanical properties can be used as the substrate 402. Such substrates include, for example, glass, plastic, and mirror materials. Suitable plastic substrates include, for example, acrylic acid, polystyrene, polycarbonate, allyl diethylene glycol carbonate, SAN (styrene acrylonitrile copolymer), poly(4-mercapto-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 vermiculite/polyoxygen wear resistant coating or the like (such as a coating well known in plastic glazing techniques). Layers come with barriers #\ protection and wear protection. Suitable glasses include clear or colored soda lime glass, including soda lime floating glass. The glass can be tempered or untempered. In some embodiments, a commercially available 'substrate, such as a glass substrate, contains a transparent conductive layer coating. Examples of such glasses include those sold under the trademark TEC GlassTM (Pilkington of Toledo, Ohio) and SUNGATETM 300 and SUNGATETM 500 (PPG Industries of Pittsburgh, Pennsylvania) coated with a conductive layer of 155961.doc -22· 201222119 Glass.

TEC

GlassTM is a conductive layer coated with fluorinated tin oxide. In the embodiment, the optical transmittance of the substrate (that is, the ratio of the transmitted radiation or the spectrum to the radiation or spectrum of the human being) is (d) For example, about township to 92%. The substrate may have any thickness as long as it has suitable mechanical properties to support the electrochromic device. Although the substrate can be of any size, it is about (10) money mm thick, preferably about 3 mm to 9 mm thick. In some embodiments of the invention, the substrate is architectural glass. Building glass is glass used as building materials. Building glass is used in commercial buildings, but can also be used in residential buildings' and usually (but not necessarily) separates indoor and outdoor environments. In a particular embodiment, the architectural glass is at least 2 inches by 2 inches, and may be larger, for example, up to about 72 inches by 12 inches. Architectural glass is typically at least about 2 mm thick. Building glass less than about 3.2 mm thick can not be tempered. In some embodiments of the invention in which architectural glass is used as a substrate, the substrate can be tempered after the electrochromic stack has been fabricated on the substrate. In some embodiments of the substrate, the substrate is a lime glass from a tin float line. "The percentage of transmission in the visible spectrum of the architectural glass substrate (ie, the overall transmission across the visible spectrum) is generally better than neutral. The substrate is 80% larger, but it may be lower than the transmission percentage of the colored substrate. Preferably, the substrate has a percent transmission in the visible spectrum of at least about 90°/. (e.g. 'about 90% to 92%). The visible spectrum is a typical human eye that responds to a spectrum 'typically from about 380 nm (purple) to about 780 nm (red). In some cases, the glass has a surface between about 10 nm and about 30 nm 155961.doc • 23- 201222119 roughness. In one embodiment, substrate 402 is a soda glass having 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 layered structures 400, 403 and 409, a first TCO layer 404, for example made of defeated tin oxide or other suitable material, which is especially conductive and transparent, is deposited over substrate 402. The transparent conductive oxide includes a metal oxide and a metal oxide 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, cerium oxide, doped cerium oxide and the like. In one embodiment, the thickness of the second TCO layer is between about 20 nm and about 1200 nm, and in another embodiment between about 1〇〇11111 and about 600 nm, in another embodiment, About 350 nm thick. The TCO layer should have an appropriate sheet resistance (Rs) due to the relatively large area spanned by the layers. In some embodiments, the TCO layer has a sheet resistance between about 5 ohms and about 30 ohms per square. In some embodiments, the TCO layer has a sheet resistance of about 15 ohms per square. In general, it is desirable that the sheet resistance of each of the two conductive layers be substantially the same. In one embodiment, the two layers (eg, 4〇4 and 412) each have a sheet resistance of about 10-15 ohms per square. . Each of the layered structures 400, 403, and 409 includes a stack 414a, 414b, and 414c, each of which includes a first TCO layer 404, a CE layer 410, and a portion over the substrate 4? Two TCO layers 412. The difference in each of the hierarchical structures 400, 403, and 409 is in how the EC layer is formed, which in each case affects the morphology of the resulting interface region. 155961.doc -24- 201222119 Consistent with the program flow 320 of FIG. 3B, the mothers of the stacks 41, 41, and 41 include an electrochromic layer deposited on the first TCO layer 404. " The electrochromic layer may contain any one or more of a number of different electrochromic materials including metal oxides. These metal oxides include tungsten oxide (W〇3), molybdenum oxide (Mo〇3) 'Nb2〇5), titanium oxide (Ti〇2), copper oxide (Cu〇), yttrium oxide (11). 2〇3), chromium oxide (Cr2〇3), manganese oxide (Mn2〇3), oxidative hunger (v2〇5), oxidation record (Ni2〇3), oxidation start (c〇2〇3) 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 (e.g., w_m〇 oxide, W-ν oxide) may also be used in certain embodiments, i.e., the electrochromic layer includes two or more of the above metal oxides. An electrochromic layer comprising a metal oxide is capable of receiving ions transferred from the counter electrode layer. In some embodiments, tungsten oxide or doped tungsten oxide is used in the electrochromic layer. In one embodiment of the invention, the electrochromic layer is substantially made of wo, wherein "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 only below stoichiometric tungsten oxide exhibits electrochromism; that is, stoichiometric tungsten oxide (w〇3) does not exhibit electrochromism. In a more specific embodiment, Xianggong (where χ is less than 3) And at least about 2.7) for the electrochromic layer. In another embodiment, the electrochromic layer is WO, wherein X is between about .2.7 and about 2.9. Such as Rutherford backscattering spectrometry (RBS, Rutherf〇rd BackscatteHng

The technique of Spectroscopy can identify the total number of oxygen atoms that are bonded to the oxygen atom of tungsten and the unbonded 155961.doc •25- 201222119 oxygen atom bound to tungsten. In some instances, the oxidized crane layer (where X is 3 or greater) exhibits electrochromism, which may be due to uncombined excess oxygen and less than stoichiometric tungsten oxide. In another embodiment, the tungsten oxide layer has a stoichiometric or more oxygen, wherein the amount is from about 3 Torr 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 to form a precursor that acts as an ion conducting electrically insulating region of the layer (in other embodiments, a highly oxidized EC material is formed in the EC layer and the ce layer). Between the final conversion for at least partially to the ionically conductive electrically insulating interface region. In a particular embodiment, the tungsten oxide is crystalline, nanocrystalline or amorphous. In some embodiments, the tungsten oxide is substantially Rice crystal-shaped, with an average grain size of about 5 nm to 50 rim (or about 5 nm to 20 nm), characterized by transmission electron microscopy (TEM). X-rays can also be used for tungsten oxide morphology or microstructure. Diffraction (XRD) and/or electron diffraction (such as selected area electron diffraction (SAED)) are characterized as nanocrystalline. For example, the characteristics of nanocrystalline electrochromic tungsten oxide may lie in the following XRD features. : crystal size of about 1 〇 to 1 〇〇 nm (for example, about 55 nm). In addition, nanocrystalline tungsten oxide can exhibit limited long-range order, for example, about several (about 5 to 2 〇) tungsten oxide. Unit cell. Therefore, for the sake of convenience, the program flow in Figure 3B The remainder of 32 进一步 will further describe the illusion of cues represented by ____ (package (4) 4A. Next, the second embodiment and the third respectively shown in Fig. 4β and Fig. 2 will be described below. Examples, which are particularly focused on the formation and morphology and/or microstructure of their respective EC layers. 155961.doc -26- 201222119 As mentioned with reference to Figure 3B, see 325, Deposition of the EC layer. In the first embodiment ( In Fig. 4A), a substantially homogeneous EC layer 406 (including W03) is formed as part of stack 414a, wherein the EC layer is in direct contact with CE layer 410. In one embodiment, as described above, the EC The layer includes W03. In one embodiment, heating is applied during at least a portion of the deposition W03. In a particular embodiment, the sputtering target is passed through several times, wherein one portion of the W〇3 is deposited at each pass, and Heating is applied to, for example, substrate 402 after deposition for each pass to adjust WO3 prior to a portion below W03 of deposited layer 406. In other embodiments, the layer of w〇3 may be continuously heated during deposition and may be deposited in a continuous manner. Instead of being sputtered In a number of embodiments, 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 depicted embodiment, the EC layer is a tungsten target having a thickness between about 500 nm and about 600 nm and includes between about 40% and about 80% 〇2 and between about 20% and about 60%. The sputtered gas sputtered WO3' of Ar and the substrate in which WO3 is deposited are at least intermittently heated to between about 150 ° C and about 450 ° C during formation of the EC layer. In a particular embodiment, the EC layer is about 550 nm thick using tungsten target sputtering, wherein the sputtering gas comprises from about 50% to about 60% 〇2 and from about 40% to about 50%. Ar, and the substrate deposited with WO3 is at least intermittently heated to between about 250 ° C and about 350 ° C during formation of the electrochromic layer. In these embodiments, the W〇3 layer is substantially homogeneous. In one embodiment, w 〇 3 is substantially polycrystalline. Xianxin, at least intermittently heating W〇3 during the deposition to help the formation of polycrystalline 155961.doc -27- 201222119 form of wo3. As mentioned, many materials are suitable for the EC layer. In general, in electrochromic materials, the coloring of an electrochromic material (or any optical property, such as a change in 'absorbance, reflectance, and transmittance') is caused by reversible ion insertion into the material (eg, intercalation). And the corresponding injection of charge balance electrons. Typically, a small portion of the ions responsible for the optical transition are irreversibly bonded together in the electrochromic material. As described herein, some or all of the irreversibly combined ions are used to compensate for the "blind charge" in the material. Among most electrochromic materials, suitable ions include clock ions (Li+) and hydrogen ions (H+) (i.e., protons). However, in some cases, other ions will be suitable. The plasma includes, for example, gas ions (D+), sodium ions (Na+), potassium ions (κ+), calcium ions (ca++), lock ions (Ba++), barium ions (Sr++), and magnesium ions (Mg++p). In the various embodiments described herein, 'lithium ions are used to generate electrochromism. The intercalation of lithium ions to tungsten oxide (W〇3_y (0<yS~0.3)) makes the tungsten oxide self-transparent (faded state) Change to blue (colored state). In the typical process of the EC layer including or for tungsten oxide, 'lithium' is deposited, for example, on the EC layer 406 via sputtering to meet the blind charge (see Figures 6 and 7 below). As will be discussed in more detail), see program flow 330 of Figure 3B. In one embodiment, the lithiation is performed in an integrated deposition system in which the vacuum is not destroyed between deposition steps. It should be noted that 'in some In the embodiment, 'lithium is not added at this stage, but may be added after depositing the counter electrode layer' or in other embodiments, the lithium system is added after depositing the TCO. Referring again to FIG. 4A 'next' on the EC layer 406 Depositing CE layer 410. 155961.doc -28- 201222119 In some implementations The counter electrode layer 410 is inorganic and/or solid. The counter electrode layer may comprise one or more of a number of different materials capable of acting as a reservoir of ions when the electrochromic device is in a discolored state. During the electrochromic transition initiated by the application of a suitable potential, for example, the counter electrode layer transfers some or all of the ions it retains to the electrochromic layer, thereby changing the electrochromic layer to a colored state. Meanwhile, at NiO And/or in the case of 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 (nickel), nickel tungsten oxide (NiWO), nickel vanadium oxide, Nickel oxide chromium, nickel aluminum oxide, nickel manganese oxide, nickel magnesium oxide, chromium oxide ((>2〇3), manganese oxide (Mn〇2), and Prussian blue. The optical passive counter electrode includes titanium ruthenium oxide. a mixture of (Ce〇2-Ti〇2), oxidized 〇(ce〇2_Zr〇2), oxidized (Ni〇), nickel oxynitride (NiW〇), vanadium oxide (V2〇5) and oxide (for example , a mixture of 2〇3 and WO;) can also be used for such oxidation Doping formulations, wherein the dopant comprises, for example, tantalum and tungsten, because the counter electrode layer 41 contains ions for generating electrochromism in the electrochromic material when the electrochromic material is in a discolored state Therefore, the counter electrode preferably has a high transmittance and a neutral color when it maintains a significant amount of the plasma. The counter electrode form may be a crystal form, a nano crystal form or an amorphous form. In some embodiments, the counter electrode layer is In the case of nickel oxide tungsten, the counter electrode material is amorphous or substantially amorphous. Compared to the crystalline counterpart of the substantially amorphous nickel-tungsten tungsten counter electrode, the substantially non-曰曰-shaped oxidation has been found. The nickel tungsten counter electrode is preferably performed under some conditions. As described below, the amorphous form of nickel tungsten oxide can be obtained by using specific processing conditions. 15596] .doc • 29· 201222119 state. Although not wishing to be bound by any theory or mechanism, it is believed that amorphous nickel oxide cranes are produced by relatively high energy atoms in the splash clock process. Higher energy atomic systems are obtained, for example, in a blanking process with higher target power, lower chamber home power (i.e., higher vacuum), and smaller source to substrate distance. Under the described processing conditions, a higher density film with better stability under uv/thermal exposure is produced. In a particular embodiment, the amount of town present in the nickel oxide crane can be as high as about 90% by weight of the oxidized strontium tungsten. In a particular embodiment, the mass ratio of nickel to rhenium in the oxidized log crane is between about 4:6 and 6:4, in one example about Η. In an embodiment, NiWO comprises a valence between about 15% (atoms) and about 6%, and between about 10% and about 4,000%. In another embodiment, the NiWO comprises between about 3% (atoms) and about 45% of the states, and between about 15% and about 35% of w. In another embodiment, Niw(R) comprises between about 30% (atoms) and about 45% Ni, and between about 2% and about 3%. In one embodiment, 'NiWO contains about 42% (atomic) Ni and about 14% W. In a consistent embodiment, as described above, see 335 of Figure 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, and in another embodiment between about 2 〇〇 nrn and about 250 nm 'in another embodiment, about 23 〇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 merely one of many examples of non-limiting and suggesting possible electrochromic transitions. Unless otherwise stated herein, whenever a 155961.doc -30-201222119 color-coloring transition' corresponds to a device or process that covers other optical state transitions such as non-reflective-reflective, transparent-opaque, etc., "Fad" refers to an optically neutral state such as uncolored, transparent or translucent. Furthermore, unless otherwise stated herein, the "color a" of the electrochromic transition is not limited to any particular wavelength or range of wavelengths, as understood by those skilled in the art, the selection of suitable electrochromic materials and counter electrode materials. Tube related optical transitions. In a particular embodiment, referring to 34 of Figure 3B, lithium (e.g., via a bond) is added to the NiWO CE layer. In a particular embodiment, referring to FIG. 345, an additional amount of lithium is added after sufficient lithium has been introduced to completely fade Niw ( (this procedure is optional, and in one embodiment, at this stage of the process Do not add excess lithium). In one embodiment, the additional amount is between about 5% and about 5% excess based on the amount required to fade the counter electrode layer. In another example & example, the excess added to the CE layer is about 10% excess based on the amount required to fade the counter electrode layer. After depositing the layer 410, dissolving it with lithium, and adding additional chains, see 350 of Figure 3B, a second TCO layer 412 is deposited over the counter electrode layer. In one embodiment, the transparent conductive oxide comprises indium tin oxide. In another embodiment, the TCO layer is indium tin oxide. In one embodiment 'this second TCO layer has a thickness between about 20 nm and about 1200 nm, in another embodiment between about 1 〇〇 nm and about 600 nm, in another embodiment About 350 nm. Referring again to Figure 4A', once the layered structure 4 is completed, it is subjected to converting at least a portion of the stack 414a to 1 (the thermochemical adjustment of the layer (if it is not converted due to diffusion or other mechanism) The stack 414a is the precursor 155961.doc • 31·201222119 instead of the electrochromic device because the stack does not have an ion conducting/electrical insulating layer (or region) between the Ec layer 4〇6 and the layer 410. In this particular embodiment, in a two-step process, a portion of the EC layer 4〇6 is converted into a layer 408 to form a functional electrochromic device 4〇1. Referring to Figure 3b, see 355, Layered Structure 4〇 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 3 minutes, and then Heating at 〇 2 lasts 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 at 〇 2 for about 5 minutes. Next, the layered structure 4 is subjected to heating in air. The stack is heated between about 25 (rc and about 35 Torr) for about 20 minutes and about 40 minutes in air, and in another embodiment the stack is about 300 in air. The heating takes about 30 minutes. The energy required to implement the MTCC need not be radiant heat. For example, in one embodiment, the MTCC is implemented using ultraviolet radiation. Other energies may be used without departing from the scope of the invention. After the multi-step thermochemical conditioning, program flow 320 is complete and the work chamber b 1 ± electrochromic device is established. As mentioned, and although not wishing to be bound by theory, the lithium in the stack 414a The knives of the EC layer 406 and/or the CE layer 410 combine to form an interface region 408 that acts as a 1C layer. The smectic interface region 408 is primarily lithium tungstate (Li2W〇4), which is known to be good relative to conventional ic layer materials. Ion conduction and electrical insulation properties. As discussed above, it is not known how this phenomenon occurs. There is a multi-step thermochemical conditioning period that must occur/page to form ion-conducting electrical insulation between the Ec layer and the CE layer. District 155961.doc -32- 201222119 408 The reaction, but it is also believed that the initial flux of lithium traveling through the stack (eg, provided by excess lithium added to the CE layer as described above) acts in the formation of 1 (: layer 4 〇 8). The thickness of the 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 1 〇 nni and about 〇 5 〇 nm, in another It is consistent between about 20 nm and about 100 nm in a consistent embodiment, and between about 30 nm and about 50 nm in other embodiments. As mentioned above, there are many suitable materials for forming an EC layer. Thus, in the above methods, for example, or other suitable ions, we can make other interface regions that act as ic layers starting from the oxygen-rich EC material. Suitable EC materials for this purpose include, but are not limited to, Si〇2, Nb2〇5, Ta205, Ti〇2, Zr〇2, and Ce〇2. In particular embodiments in which ions are used, ion conducting materials such as, but not limited to, lithium niobate, lithium aluminum niobate, lithium borate, lithium aluminum fluoride, lithium borate, lithium nitride, lithium zirconium niobate, Lithium niobate, ruthenium acid, scaly acid and other such ceramic materials based on ceramsite, or cerium oxide (including lithium lanthanum oxide) can be made into an interface region serving as a 1C layer. As mentioned, in one embodiment, the ion-conducting region precursor is an oxygen-rich (superstoichiometric) layer that is converted to an ion conducting/electrically insulating region via the nucleation and MTCC described herein. Although not wishing to be bound by theory, it is believed that after lithiation, excess oxygen forms lithium oxide, which further forms a lithium salt (ie, a lithium electrolyte), such as lithium tungstate (Li2W04), lithium molybdate (Li2Mo04). Lithium niobate (LiNb03), lithium nitrite (LiTa03), lithium titanate (LizTiO3), lithium zirconate (LizZrO3) and the like. In one embodiment, the interface region comprises at least one of: tungsten oxide (W〇3+x, 155961.doc • 33-201222119 OSxSl.5), oxidized turn (m〇03+x, 〇sd5) ), yttrium oxide (Nb2〇5+x, 〇SxS2), oxidized chin (Ti02+x, (^d.5), yttrium oxide (Ta2〇5+x, 〇$x$2), oxidized hammer (Zr02+x) , 〇sd .5) and yttrium oxide (Ce 〇 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 to have low defectivity and it is substantially Blocking electrons while allowing ions to pass between the counter electrode layer 410 and the electrochromic layer 4〇6. The material can conduct ions substantially and be substantially resistant to electrons. In one embodiment, the ion conductor The material has an ionic conductivity between about 1〇-1〇Siemens/cm (or ohn^cnT丨) and about ι〇-3 Siemens/cm and an electron greater than 1〇5 ohm-cm Resistance. In another embodiment, the a ion conductor material has an ionic conductivity between about 1 〇·8 Siemens/cm and about 1 〇3 Siemens/cm. Electrical resistance greater than i 〇 1Q ohm centimeters. Although the ion conducting layer should be substantially resistant to leakage current (e.g., providing a leakage current of no more than about 15 μΑ/cm 2 ), it has been found to be fabricated as described herein. Some devices have surprisingly high leakage currents (eg, between about 40 μΑ/cm and about 150 μΑ/ειη), but still provide good color variation across the device and operate efficiently. As mentioned above, After forming the stack, at least two other ways of establishing an ion conducting electrically insulating region between the EC layer and the ce layer are provided. These additional embodiments will be described below with reference to a specific example of using tungsten oxide for a layer: As mentioned above, when, for example, diffusion or heat is used to convert the EC and/or CE layers into interfacial regions, interface regions having ic properties can be formed in situ during fabrication of the stack. 155961.doc • 34· 201222119 Usually there is a specific benefit in 'making money _ establishing ion transmission (4). First of all, 'enable 4 ion-conducting materials are not affected by some of the harsh treatments that occur during the deposition and clocking of the Ec and ce layers. In other words, the deposition of such layers by a plasma process is often accompanied by a large voltage drop immediately adjacent to the stack, often above and below 15 20 volts. Such large voltages can damage sensitive ion conducting materials or cause decomposition of sensitive ion conducting materials. By moving the (four) material formation to the post-stage phase of the process, the material is not exposed to the potential damage voltage extremes. Secondly, by forming the 1C material later in the process, we can better control the completion of the EC layer and Some processing conditions that were previously impossible for the CE layer. These conditions include clock diffusion and current flow between the electrodes. Controlling these and other conditions during the process provides additional flexibility to tailor the physical and chemical properties of the material to the particular application. Therefore, not all of the benefits of the present invention are due to the unique interface area that acts as the 1C layer, i.e., there are manufacturing and other benefits as well. It has been observed that 'the formation of ion conduction according to the embodiments described herein is compared to devices made using conventional techniques for forming a 1C layer (eg, PVD from a 1C material target). The material has excellent performance. For example, it has been found that the device switches very fast (e.g., less than 10 minutes, in the example - about 8 minutes) to achieve a final state of about 80% compared to 20-15 minutes or more of conventional devices. In some examples, the devices described herein have an order of magnitude that is superior to conventional devices. This can be attributed to a larger amount of placement in the interface zone and/or the grading interface (eg, between the interface zone and/or between the ce and the interface zone). These lithium may be in the EC and/or CE phase mixed with the 1C mutual 155961.doc • 35· 201222119 present in the interface region. It may also be due to a relatively thin layer or network of 1C material present in the interface region. To support this view, it has been observed that some devices fabricated according to the teachings herein have high leakage currents, but still surprisingly exhibit good color variations and good efficiency. In some cases, devices that have been found to perform robustly have a leakage current density of at least about 丨〇〇 pA/cm. Referring now to Figure 4A, in the second embodiment, the initially laid EC material of the stack 41 is actually two layers: a first w〇3 layer 4〇6' which is similar to layer 406' in Figure 4A but thickness Between about 350 nm and about 450 nm, the first layer uses a tungsten target and includes between about 40% and about 80% of 〇2 and between about 2〇0/〇 and about 60% of Ar. a first sputter gas sputtering; and a second w 〇 3 layer 405 ′ having a thickness between about 1 〇〇 nm and about 2 〇〇 nm, the second layer using a tungsten target and including about 70% and 1第二2 between 〇2 and 〇% with about 3〇% of Ar's second sputtering gas sputtering. In this embodiment, heat is applied by at least intermittently heating the substrate 4〇2 to between about 150 C and about 450 °C during deposition of the first WO3 layer 406, but in the second layer of the third The deposition of 4〇5 is not heated or substantially not heated. In a more specific embodiment, layer 406 is about 400 nm thick, and the first sputtering gas comprises between about 5% and about 6% of 〇2 and between about 40% and about 50% of Ar. The second W 〇 3 layer 405 is about 150 nm thick 'and the second sputtering gas is substantially pure 〇 2 . In this embodiment, heat is applied at least intermittently to about 200 ° C and about 350 during formation of the first WO 3 layer 406. (: between, but not heated or substantially not heated during the formation of the second WO3 layer 405. In this way, the first w〇3 layer is substantially polycrystalline, and the second W〇3 layer does not have to Referring again to Figure 4B, as described above with respect to Figures 3B and 4A, the stacking is accomplished by the following operations: lithiated EC layers 406 and 405 to substantially or substantially satisfy blind charge, deposition. The CE layer 410, the CE layer is lithiated to a faded state, an additional clock is added, and a second layer <:0 layer 412 is deposited to complete the layered stack 4〇3 ^ Performing a similar thermochemical adjustment on the layered stack 403 to provide delamination Stack 4〇7, a functional electrochromic device comprising an ion-conducting electrically insulating region 408a. Although not wishing to be bound by theory, in this example, the oxygen-rich layer 405 of the salt-like W〇3 is primarily a source of current precursor material. To form interface region 408a. In this example, the entire oxygen-rich WO3 layer is depicted as being converted into 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 And form an interface area that functions as a 1C layer. Referring to FIG. 4C, in the third embodiment, the layered stack 4〇9 includes an EC layer 406a (which has a hierarchical composition of \v〇3 (3) and is formed as part of the stack 414c) The graded composition includes varying levels of oxygen. In a non-limiting example, there is an EC layer 406a at the interface of the layer (410) that is higher than the interface between the TCO layer 404 and the EC layer 406a. Oxygen concentration. In one embodiment, the 'EC layer 4〇6a is a graded composition w〇3 layer using a tungsten target and a sputtering gas sputtering thickness between about 500 nm and about 600 nm, where the sputtering The gas comprises between about 4% and about 80% of 〇2 and between about 20% and about 60% of Ar at the beginning of the sputtered electrochromic layer, and the sputtering gas is sputtered on the electrochromic layer Included between about 70% and 100% of 〇2 and 〇% and about 30% of Ar, and wherein at least intermittently applies heat to, for example, substrate 402 during the beginning of formation of ec layer 406a Apply heat between about 150 ° C and about 450 ° C 'but not substantially or substantially not at least one of the most 155961.doc -37 - 201222119 after the deposition of the layer. In an embodiment, the graded composition W 〇 3 layer is about 55 〇 nm thick; the sputtering gas comprises between about 50% and about 60% 〇 2 and 40% and about 100% of the beginning of sputtering the electrochromic layer. Between 50% of Ar' and the sputtering gas is substantially pure '2' at the end of sputtering of the electrochromic layer and wherein at least intermittently applies heat to the beginning of the formation of the electrochromic layer (eg Substrate 402 to about 200 eC and about 350. (between, but not or substantially not 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 is gradually reduced to about half of the deposit (the layer is not applied with heat, and the deposition of the sputtering gas composition in the EC layer) During the period of substantially linear, from about 50% to about 60%, and between about 4% and about 5%, to a substantially pure 〇2 material and electrochromic material (eg In addition, the interface region generally (but not necessarily) has a heterostructure comprising at least two discrete components represented by different phases and/or compositions. Furthermore, the interface region is herein One or more discrete components (such as ion conductive materials such as a mixture of lithium tungstate and tungsten oxide)

155961.doc •38· 201222119 Includes a transition to the tungsten oxide zone in the (superstoichiometric) yttrium oxide zone. Part or all of the oxidized sharp region is converted into an interface region. In the final structure, the oxidized crane region is substantially polycrystalline and the microstructure transitions to substantially amorphous at the interfacial region. Referring again to FIG. 4C', as described above with respect to FIG. 3B and FIG. 4A, the stacking is accomplished by lithochemical EC layer 406a to substantially or substantially satisfy the blind charge, deposit CE layer 410, lithiated CE layer to a faded state. Additional lithium is deposited and a second TCO layer 412 is deposited to complete the layered stack 409. A similar multi-step thermochemical conditioning is performed on the layered stack 409 to provide a layered stack 411 comprising at least a portion of the ion conducting electrically insulating region 4 8b and the original layered EC layer 406a (which is in the functional electrochromic device 41 i In the present example, in the example, the uppermost oxygen-rich portion of the graded layer of WO3 mainly forms the graded interface region 408b. It is not desirable to be bound by theory, but there is a possibility that the formation of the interface region is self-limiting and depends on the relative amounts of oxygen, lithium, electrochromic material and/or counter electrode material in the stack. In various embodiments described herein, the electrochromic stack is described as not being heated during a particular processing stage. In 1 =: after the heating step, active or passive (for example, using a heat-dissipating γ cold section stack. The apparatus of the present invention includes active and passive cooling components, such as 'active cooling may include circulation via fluid, exposure to cold (eg The fuse is cooled by the expansion of the gas, the cooling unit, and the like: The passive cooling assembly may include a heat sink, such as a metal block and the like, or the substrate may only be removed from the heat exposure. .doc •39· 201222119 Another aspect of the invention is a method of making an electrochromic device, the method comprising: (a) forming an electrochromic layer comprising an electrochromic material or a counter electrode layer comprising a counter electrode material (13) forming an intermediate layer over the electrochromic layer or the counter electrode layer, wherein the intermediate layer comprises an oxygen-rich form of at least one of the electrochromic material, the counter electrode material, and additional material, wherein Additional materials include dissimilar electrochromic materials or counter electrode materials, wherein the intermediate layer is not substantially electrically insulating; (c) forming the electrochromic layer and the other of the counter electrode layers One, and (d) allows at least a portion of the intermediate layer to become substantially electrically insulated. In one embodiment, the electrochromic material is w 〇 3. In another embodiment, (a) includes the use of tungsten The target and the first splashing gas between the 〇2 and about 20% and about 60% between about 4% and about 80% are reduced by the WO3 to reach about 350 nm and about 450 nm. The thickness between, and during the formation of the electrochromic layer, is at least intermittently heated to between about 15 〇β (: and about 450 ° C. In another embodiment - (b) included without heating In the case of using a tungsten target and a second sputtering gas comprising W between about 70% and 100% between 〇2 and 〇% and about 3〇0/〇, the sputtering is performed to achieve about 1 A thickness between 〇〇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 an embodiment, the The counter electrode layer comprises NiWO having a thickness between about 15 〇 nm and about 300 nm. In another embodiment, lithium is sputtered onto the counter electrode layer until the counter electrode layer fades. In an example, an excess amount of lithium between about 5% and about 5% excess of the amount required to fade the counter electrode layer is sputtered onto the counter electrode layer. In another embodiment, in the opposite A transparent conductive oxide layer is deposited over the electrode layer. In an embodiment, the transparent 155961.doc • 40· 201222119 conductive oxide comprises 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 stacked at Ar at about 15 Torr. (: heating between about 45 CTC and about 45 minutes between about 10 minutes and about 30 minutes, and then heating at 〇2 It lasts between about 1 minute and about 15 minutes' and then in the air at about 25 inches. Heating between about 〇 and about 35 cc takes about 20 minutes and about 40 minutes. In another embodiment, (a) includes a first electrochromic material of the sputtered crucible 'where germanium is a metallic or non-metallic element, and χ indicates a stoichiometric ratio of oxygen to hydrazine' and (b) A second electrochromic material comprising a splash-type N〇y is used as ten layers, wherein N is the same or a different metal or non-metal element, and less refers to a ratio of oxygen to N that is not superstoichiometric. In one embodiment, M is a crane and N is a crane. In another embodiment, μ is a crane and n is selected from the group consisting of sharp, enamel, button, titanium, zirconium, and hafnium. Another embodiment of the invention is an electrochromic device comprising: (a) an electrochromic layer comprising an electrochromic material; (b) a counter electrode layer comprising a counter electrode material, and (c) at the electricity An interface region between the discoloration layer and the counter electrode layer, wherein the interface region comprises at least one of an electrically insulating ion conducting material and the electrochromic material, the counter electrode material, and additional materials, wherein the additional material comprises a phase Different electrochromic materials or counter electrode materials. In one embodiment, at least one of the electrically insulating ion conducting material and the electrochromic material, the counter electrode material, and the additional material are substantially uniformly distributed within the interface region. 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 comprise a compositional gradient in a direction perpendicular to the layers. In another embodiment, in accordance with any of the two preceding embodiments, the electrically insulating ion conducting material comprises lithium tungstate, the electrochromic material comprises tungsten oxide, and the counter The electrode material includes nickel tungsten oxide. In a particular implementation of one of the foregoing embodiments, there is no additional material. In one embodiment, the electrochromic layer has a thickness between about 300 nm and about 500 nm, the interface region has a thickness between about 10 nm and about 15 nm, and the thickness of the counter electrode layer is about Between 15 〇 nm and about 300 nm. In another embodiment, the electrochromic layer has a thickness between about 400 nm and about 500 nm; the interface region has a thickness between about 2 nm and about 100 nm, and the thickness of the counter electrode layer is About 15 〇 ^ ^ claws and about 250 nm. In still another embodiment, the electrochromic layer has a thickness between about 400 nm and about 450 nm; the interface region has a thickness between about 3 〇 nm and about 50 nm, and the thickness of the counter electrode layer is Another embodiment is between about 2 〇〇 nm and about 25 〇 nm. Another embodiment is a method of fabricating an electrochromic device, the method comprising: comprising between about 40% and about 80% 〇2 and about 2溅% and about 6〇% of the sputtering gas of Ar is sputtered with a tungsten target to produce w〇3 to a thickness between about 5 〇〇 nm and about 600 nm to deposit an electrochromic layer, wherein the deposited The substrate of the WO3 is at least intermittently heated to between about 150 ° C and about 450 ° C during formation of the electrochromic layer; the clock is splashed onto the electrochromic layer until the blind charge is satisfied; Depositing a counter electrode layer on the a-electrochromic layer without first providing an ion-conducting electrically insulating layer between the electrochromic layer and the counter-electrode layer, wherein the counter-electrode layer comprises NiWO; 155961.doc • 42 · 201222119 will be sputtered onto the counter electrode layer until the counter electrode layer is substantially discolored; and in the electrochromic layer and the counter electrode It is formed between the interface region, wherein the interfacial region is substantially ion-conducting and electrically substantially insulating. Forming the interface region in the embodiment includes the stack of MTCC alone or with the substrate, conductive layer and/or encapsulation layer. The electrochromic device of the present invention may include one or more additional layers (such as, for example, one or more passive layers) to improve specific optical properties (providing moisture or scratch resistance) to hermetically seal the Electrochromic devices and the like. Typically, but not necessarily, a cap layer is deposited on the electrochromic stack. In some instances, the cap layer is SiAl. In some embodiments, the cap layer is deposited by sputtering. In one embodiment, the thickness of the cap layer is between about 30 nm and about 1 〇〇 nm. It should be understood from the above discussion that the electrochromic device of the present invention can be used in a single chamber device (for example, with, for example, a tungsten target, a nickel target, a lithium target, and a sputtering of oxygen and argon sputtering gases). Manufactured in the tool). As mentioned, due to the nature of the interface region formed to serve the purpose of the conventional IC layer, a separate target for sputtering the 1C layer is not necessary. Of particular interest to the inventors is the fabrication of the electrochromic devices of the present invention, for example, in a high throughput manner, and therefore there is a need for an apparatus that can sequentially fabricate the electrochromic devices of the present invention as it passes through an integrated deposition system. For example, the inventors are particularly interested in the manufacture of electrochromic devices on curved glass window (described above). Therefore, another aspect of the present invention is an apparatus for manufacturing an electrochromic device 155961.doc-43 201222119, including: an integrated deposition system comprising: (1) a first-deposition table containing a source of material Configuring to deposit an electrochromic layer comprising an electrochromic material; and (ii) a second deposition station configured to deposit a counter electrode layer comprising a counter electrode material; and a controller 'containing And sequentially transferring the substrate on the substrate to transfer the substrate through the first deposition stage and the second deposition stage; the stack has an intermediate layer between the electrochromic layer and the counter electrode layer; Any one or both of the first deposition stage and the second deposition stage are configured to deposit the intermediate layer over the electrochromic layer or the counter electrode layer, and wherein the intermediate layer includes the electricity The color change material or the counter electrode material of the palace is exemplified by a rolled form of the leaf, 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 bottom - Station without exposing the substrate Environment. In one embodiment, the apparatus of the present invention is operable to transfer the substrate from one station to the next without disrupting the vacuum, and may include being operable to deposit lithium from the source of the clocked material in the electrolysis One or more layers of one or more layers i of a color changing device. In one embodiment, the apparatus of the present invention is operable to deposit the electrochromic stack on a building glass substrate. In an embodiment, the The apparatus is operable to transfer the substrate from one station to the next without breaking the vacuum. In another embodiment, the integrated deposition system further includes an operative layer in the electrochromic layer, the intermediate layer, and the counter At least one of the electrode layers is deposited from one or more H-stages containing the source of (iv). 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 an operable to hold the architectural glass substrate in a vertical orientation when the architectural glass substrate 155961.doc • 44 201222119 is passed through the integrated deposition system The substrate holder and transport mechanism. In another embodiment, the apparatus further includes one or more vacuum preload chambers 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 the one or more lithium deposition stations and at least one of the first deposition station and the second deposition station Isolation. In one embodiment, the integrated deposition system includes one or more heaters configured to heat the substrate. Figure 5 depicts a simplified representation of the integrated deposition system 5' in a perspective view and includes in more detail Internal cross-sectional view. In this example, system 500 is a module in which inlet vacuum pre-extraction chamber 502 and outlet vacuum pre-extraction chamber 504 are coupled to deposition module 5〇6. There is an inlet port 51 for loading, for example, a building glass substrate 525 (the vacuum pre-extraction chamber 504 has a corresponding outlet port). The substrate 525 is supported by a pallet 520 that travels along the track 5 15 . In this example, the pallet 520 is supported by the track 515 via suspension, but the pallet 520 can also support a track positioned near the bottom of the device 500 or, for example, at the top and bottom of the device 5 On top of the middle track. The pallet 52 can be translated forward and/or backward in the system 5 (as indicated by the double-headed arrow). For example, during lithium deposition, the substrate can move forward and backward in front of the lithium target 530. , thereby producing a multi-person pass in order to achieve the desired bell. However, this function is not limited to a clock target, for example, the tungsten target can pass through the 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 carrier 520 and the substrate 525 are in a substantially vertical orientation. The substantially vertical orientation is not limiting, but it can help prevent defects, which is 155961.doc -45-201222119 because particulate matter that may, for example, arise from agglomeration of atoms from sputtering will tend to be subject to gravity and Therefore, it is not deposited on the substrate 525. Also, because the architectural glass substrate tends to be large, the vertical orientation of the substrate enables coating of the thinner glass substrate as it traverses the stations of the integrated deposition system, as is the case with respect to thicker hot glass. There are fewer concerns about drooping. Target 530 (in this case a cylindrical target) is oriented substantially parallel to the surface of the substrate where deposition will occur and in front of the surface of the substrate (for convenience, other sputtering means are not depicted herein)^ The substrate 525 can be translated through the target 530 during deposition, and/or the target 53 can be moved in front of the substrate 525. The path of movement of the target 530 is not limited to translation along the path of the substrate 525. Target 530 can be translated along a path through its length, along a path of the substrate (forward and/or backward), along a path perpendicular to the path of the substrate, in a plane parallel to substrate 525. Path moves, etc. The target 530 need not be cylindrical, it can be flat or deposit any shape desired for the desired layer of the desired properties. Also, there may be more than one target at each deposition station, and '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 can be modular, but once connected, form a continuous system in which a controlled ambient environment is established and maintained to process the substrate at various stages within the system. A more detailed description of how to deposit an electrochromic material using the integrated deposition system 500 is described in the aforementioned U.S. Non-Provisional Patent Application Serial No. 12/645, filed on Apr. No. 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. I55961.doc • 46· 201222119 ί solution = piece not shown 'but may be The 5GG (for example) is generally controlled by a computer system or other controller represented by LCD and keyboard 535 in FIG. Those skilled in the art will appreciate that embodiments of the present invention may utilize various processes involving the storage of data stored on one or more computer systems or via one or more computer systems. The embodiments of the present invention are also directed to apparatus for performing such operations, such computers and micro-controls, such & preparations and processes for depositing the methods of the present invention and apparatus for performing such methods Electrochromic material. The control device of the present invention may be specially constructed for the purpose required by the poem, or the (4) device may be a general purpose computer' selectively activated or reconfigured by a computer program and/or data structure stored in the computer. The programs presented herein are not inherently related to any particular computer or other device. In particular, various general purpose machines may be used with programs written in accordance with the teachings herein, or may be more convenient for constructing more specific devices to perform and/or control desired methods and procedures. As can be seen from the above description (in particular, FIG. 3A to FIG. 3), with the method of the present invention, not only can an electrochromic device be fabricated, but also a layered stack (eg, 400, 403, and 409) can be pre-manufactured, in some The case can be converted to an electrochromic device via subsequent processing such as described herein. Although "non-functional electrochromic devices" are not provided between the EC layer and the CE layer without ion conduction and electrical insulation, such "electrochromic device precursors" may have particular value. This is especially the case when the device precursor system is manufactured in high purity in an integrated processing apparatus as described herein, wherein the material layers are all sunk in a controlled surrounding environment where, for example, the vacuum is never destroyed 155961.doc • 47- 201222119 Product. In this manner, high purity, low defect materials are stacked and substantially "sealed" by the last TCO layer and/or cap layer, for example, prior to exiting the integrated system. As with the electrochromic devices of the present invention described above, the electrochromic device precursors 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-proof or resistant) seals the device precursor and the like in a gas-tight manner. In one embodiment, a cap layer is deposited on the TC0 layer of the precursor stack. In some embodiments, the cap layer is hAlO. In some embodiments, the cap layer is deposited by ruthenium plating. In one embodiment, the thickness of the cap layer is between about 3 〇 nm and about ι 〇〇 nm. Subsequent processing of the cap layer in place forms a π layer without environmental contamination, i.e., with additional protection of the cap layer. Conversion to a functional electrochromic device can occur outside of the integrated system if necessary because the internal stack structure is protected from the external environment and a slightly lower stringency condition is used to drive the precursor The stack is converted to the necessary adjustment steps for the functional device. Such stacked electrochromic device precursors may have advantages, for example, due to the longer lifetime of switching to an electrochromic device only when needed, by having, for example, storable and depending on the final product. Flexibility due to the single-precursor stack used for conversion or improvement to different conversion chambers and/or consumption points for quality standards that are required and must be met. Again, such precursor stacks can be used for testing purposes' such as quality control or research efforts. Accordingly, an embodiment of the present invention is an electrochromic device precursor comprising '(4) substrate' (b) a first transparent conductive oxide 15596I.doc • 48· 201222119 layer on the substrate; (c) a stack on the first transparent conductive oxide layer 'The stack includes: (:) an electrochromic layer comprising an electrochromic material, and (9) a counter electrode layer comprising a counter electrode material, wherein the stack does not include the electro-electrode a region of ion-conducting and electrically insulating between the color-changing layer and the counter electrode layer; and (4) a second transparent conductive oxide layer on the stack:. In an embodiment, the electrochromic layer comprises an oxidized crane and the counter electrode layer comprises nickel tungsten oxide. In an embodiment, at least one of the stack and the electrochromic layer contains a clock. In another embodiment, the electrochromic layer is a tungsten oxide having a superstoichiometric amount of oxygen at least at the interface with the counter electrode layer. In another embodiment, the stack includes an lc precursor layer between the counter electrode layer and the electrochromic layer, and the S1 1C precursor layer includes an oxygen content having a higher oxygen content than the electrochromic layer. Tungsten oxide. In one embodiment, in the case where there is no 1C 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 is about Between 15 〇 nm and about 300 nm. In another embodiment, in the case where a 1C precursor layer exists 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 1C precursor layer is about 2 Between 〇nm and about 100 nm' and the thickness of the counter electrode layer is between about 15 〇 11111 and about 300 nm. In one embodiment, the precursor devices described herein are exposed to heat to convert the devices into functional electrochromic devices. In one embodiment, the heating is part of the MTCC. Another embodiment is an electrochromic device comprising: (a) an electrochromic layer comprising an electrochromic material; and (b) a counter electrode layer comprising a counter electrode material, wherein the device is not contained in the electro-optical layer A compositionally homogeneous layer of 155961.doc -49· 201222119 electrically insulating ion conducting material between the color changing layer and the counter electrode. In one embodiment, the electrochromic material is tungsten oxide, and the counter electrode material is nickel oxide tungsten, and between the electrochromic layer and the counter electrode layer, including erbium acid and tungsten oxide, and oxidation An interface region of a mixture of at least one of nickel tungsten. In another embodiment, the thickness of the electrochromic layer is between about 3 〇〇 nm and about 5 〇〇 nm; the thickness of the interfacial region is between about 1 〇 nm and about 15 〇 nm, and the inverse The thickness of the electrode layer is between about 15 〇 nm and about 300 nm. EXAMPLES Figure 6 is a graph showing the flow of a procedure for use in the manufacture of the electrochromic device of the present invention. The y-axis unit is optical density, and the λ-axis unit is time/program flow. In this example, an electrochromic device similar to the electrochromic device described with respect to FIG. 4A is fabricated, wherein the substrate has excess oxygen in the matrix of the glass 'Ec layer with fluorinated tin oxide as the first TCO. W〇3 (for example, using tungsten target sputtering, in which the sputtering gas is about 60% 〇 2 and about 40% Ar), the CE layer is formed on the EC layer and made of Niw ,, and One TCO is indium tin oxide (IT〇). Lithium is used as an ion source for electrochromic transition. The optical density is used to determine the endpoint during manufacture of the electrochromic device. From the origin of the graph, the optical density was measured as the Ec layer (w〇3) was deposited on the substrate (glass + TCO). The optical density of the glass substrate has a baseline optical density of about 〇.〇7 (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 550 nm thick tungsten oxide layer, as described above, the optical density increases to about ^2 ^ after depositing the tungsten oxide Ec layer, 15596I.doc •50· 201222119 is sputtered on the EC layer, such as " Lij indicates the first time period indicated. During this period, the optical density is further increased along the curve to 〇4, which means that the blind charge of non-oxidized tungsten has been satisfied because the tungsten oxide is colored with lithium addition. The time period indicated by "NiWO" indicates the deposition of the Niw layer, and the optical density increases during this period because the NiW is colored. Due to the addition of a NiWO layer of about 230 nm thick, the optical density further increased from about 0.4 to about 〇9 during the Niw〇 deposition period. Note that as Niw〇 deposits, some of the lithium can diffuse from the EC layer to the ugly layer. This is used to maintain the optical density at a relatively low value during Niw(R) deposition or at least during the initial stage of deposition. "Li" means that the second time period indicates that the lithium to Niw〇 Ec layer is added. The optical density decreased from about 9.9 to about 〇4 during this stage because NiWO was discolored by lithiation of NiWO. Lithiation is performed until Niw fading (including a local minimum of about 0-4 optical density). The optical density starts to rise at about 〇4. This is because the W〇3 layer is still clocked and affects the optical density. Next, additional lithium is sputtered onto the NiWO layer as indicated by the time period "Extra U". In this example, about 1% of the additional lithium added to the Niw(R) lithium discolors the NiWO layer. During this phase, the optical density increases slightly. Next, add indium tin oxide TCO as indicated by "IT0" in the graph. Again, the optical density continues to rise slightly to about 0.6 during the formation of the indium tin oxide layer. Next, the apparatus was heated to about 25 〇〇c for about 15 minutes under Ar as indicated by the time period indicated by "MSTCC", and then heated at 〇 2 for about 5 minutes. Next, the device was annealed in air for about 30 minutes at about; During this time, the optical density is reduced to 155961.doc -51 _ 201222119 about 0.4 » Therefore, the optical density is used to fabricate the device of the invention (for example, for determining the layer thickness based on the deposited material and morphology, and in particular A useful tool for titrating a clock onto various layers for satisfying blind charge and/or reaching a faded state. Consistent with the scheme described with respect to Figure 6, Figure 7 shows a cross-sectional TEM of an electrochromic device 700 fabricated using the method of the present invention. Apparatus 700 has a glass substrate 702' an electrochromic stack 714 formed on the glass substrate. The substrate 7〇2 has an ITO layer 704 serving as a first TCO. A tungsten oxide EC layer 706 is deposited on the TCO 704. Layer 706 is formed at a thickness of about 550 nm (i.e., W03 formed by a gas mine with oxygen and argon) as described above with respect to Figure 6. Add the clock to the EC layer. Next, a NiWO CE layer 710' of about 230 nm thick was added followed by lithium to fade and then an excess of about 1% excess was added. 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 Figure 4A. After the MSTCC, the TEJV^ is as seen, forming a new region 7-8 of ion-conducting electrical insulation. Figure 7 also shows five selected area electronic diffraction (SAED) patterns for various layers. First, 704a indicates that the ITO layer is highly crystalline. Pattern 7〇6a shows that the EC layer is polycrystalline. Pattern 708a shows that the 1C layer is substantially amorphous. Pattern 710a shows that the CE layer is polycrystalline. Finally, pattern 712a exhibits an indium tin oxide TCO layer that is highly crystalline. Figure 8 is a cross section of an apparatus 800 of the present invention as analyzed by scanning transmission electron microscopy (STEM). In this example, in accordance with the approach described with respect to Figure 4B, device 800 is fabricated using the method of the present invention. Device 8 is an electrochromic stack formed on a glass substrate (not labeled). On the glass substrate 155961.doc • 52· 201222119 is a fluorinated tin oxide layer 804 which acts as a first Tc (for a transparent electronic conductor. The layer is sometimes referred to as a r TEC layer). The tungsten oxide EC layer is deposited on the TCO 804. In this example t, the layer _ is opened at a thickness of about tens of nanometers (i.e., using the oxygen and argon gas to form a boundary 〇3 via a money-plated crane, as described above with respect to Figure 6), followed by deposition of an oxygen-rich precursor. The thickness of the bulk layer from 8 〇 5 to about 15 〇 nm "addition of lithium to the layer 8 〇 5. Next, a NiWO CE layer 81G of about 23 Å thick was added, followed by the addition of a clock to fade and then add about 1% excess lithium. Finally, an indium tin oxide layer 812 is deposited and the stack is subjected to a multi-step thermochemical grading as described above with respect to Figure 4B. After the MSTCC, perform this S TEM » as seen, forming a new region of ion-conducting electrical insulation 8 〇 8. The difference between this example and the embodiment described with respect to Figure 4B is that, unlike the similar layer 405 of Figure 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 acts as an ion conducting layer. Figures 8B and 8C show a "front-back" comparison of the device precursor (Figure 8C) of the present invention with the device precursor (Figure 8B) prior to 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 clearly seen in Figure 8C). Referring again to Figure 8B, it appears that there is at least lithium concentrated at the interface of the oxygen-rich layer 805 and the CE layer 810 (a region approximately 10-15 nm thick) as indicated by 808a. After the MTCC (Fig. 8C), it is apparent that the interface region 808 has been formed. Although the foregoing invention has been described in some detail to facilitate an understanding, the embodiments of the 155961.doc.53.201222119 are described as illustrative and not limiting, and in the appended claims::: Changes and modifications. 4 围范鸣内's practical [simplified description of the drawings] Figure 1A is a schematic cross-sectional view showing the conventional formation of electrochromic surface 0 stacking. Figure 1B shows the composition of a conventional electrochromic stack. Graph. EC layer, 1C layer and CE layer in Figs. 2A to 2C are graphs showing compositions for use in the present invention. Representative of Electrochromic Device Figures 3A and 3B are program flows in accordance with an embodiment of the present invention. 4A-4C are schematic cross sections depicting the formation of an electrochromic device in accordance with certain embodiments of the present invention. Figure 5 depicts the integrated deposition system of the present invention in a perspective view. Figure 6 is a graph of how the program parameters and endpoint readings are correlated during formation of an electrochromic stack in accordance with an embodiment of the present invention. Figures 7 and 8A through 8C are actual cross sections of an electrochromic device fabricated using a method in accordance with an embodiment of the present invention. [Main component symbol description] 100 Electrochromic device 102 Substrate 104 Conductive layer (CL) 106 Electrochromic (EC) layer 108 Ion conduction (1C) layer 155961.doc -54 - 201222119 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 W03 Layer 406 EC Layer 406a EC Layer 407 Layered Stack 408 1C Layer/Interface Zone 408a Ion Conduction Electrical Insulation Zone/Interface Zone 408b Graded Interface Zone 409 Layered Structure 410 CE Layer 411 Layered Stack/Functional Electrochromic Device 412 Second TCO Layer 414a Stack 414b Stacking 155961.doc -55- 201222119 414c Stacking 500 Integrated Deposition System 502 Inlet Vacuum Pre-Draining Chamber 504 Outlet Vacuum Pre-Pulling Chamber 506 Deposition Module 510 Inlet 埠 515 Track 520 Cartridge 525 Substrate 530 Lithium Target 535 LCD and Keyboard 700 electrochromic device 702 glass substrate 704 indium tin oxide (ITO) layer 704a Figure 'case 706 tungsten oxide EC layer 706a pattern 708 new Region 708a Pattern 710 CE Layer 710a Pattern 712 Indium Tin Oxide Layer 712a Pattern 714 Electrochromic Stack - 56-155961.doc 201222119 800 Device 804 Fluorinated Tin Oxide Layer 805 Oxygen-rich Precursor Layer 806 Tungsten Oxide EC Layer 808 New District /Interface area 808a Lithium 810 CE layer 812 Indium tin oxide layer 155961.doc -57-

Claims (1)

201222119 VII. Patent Application Range: 1. An electrochromic device comprising: (a) an electrochromic layer comprising an electrochromic material; (b) a counter electrode layer comprising a counter electrode material; and (c) An interfacial region between the electrochromic layer and the counter electrode layer, wherein the interfacial region comprises (1) a substantially electrically insulating ion conducting material and (ii) at least the electrochromic material, the counter electrode material, and additional materials - A mixture of the materials, wherein the additional material comprises a different electrochromic material or a counter electrode material. 2. The electrochromic device of claim 1, wherein: the electrochromic material comprises an oxide of at least one of: tungsten, molybdenum, niobium, titanium, copper, lanthanum, chromium, manganese, vanadium, Nickel and cobalt; the counter electrode material comprises at least one of the following: oxidation record, oxidation recorded tungsten, oxidation recorded hunger, oxidized chromium, nickel oxide IS, oxidized manganese oxide oxide town, chromium oxide, oxidized, Prussian blue (p call), oxidized enamel, oxidized, oxidized, bismuth and tungsten; and the electrically insulating ion conductive material comprises at least one of the following: lithic acid, material (four), "clock H (4) Lu, boric acid clock, nitriding, (4) (four), 铌 _, acid acid m (four) clock, lithium oxide lanthanum oxide, lithium tungstate, lithium molybdate, lithium nitrite, lithium titanate, calcium acid clock, oxidized crane , oxygen oxide, oxidized sharp, titanium oxide, oxidized group, bismuth oxide and cerium oxide 3. The electrochromic device of claim 2, the electrically insulating ion conductive material and (ii) the interface region containing the substance Electrochromic material and the counter electrode 155961.doc 201222119 - or A mixture of those. 4. The electrochromic device of claim 3, wherein the substantially electrically insulating ion conducting material and one or both of the electrochromic material and the counter electrode material are substantially uniformly distributed in the interface region Inside. 5. The electrochromic device of claim 3, wherein the substantially electrically insulating ion conducting material and the one or both of the electrochromic material and the counter electrode material are included in the interface region perpendicular to The composition gradient in the direction of the layers. 6. The electrochromic device of claim 5, wherein the electrochromic material and the substantially electrically insulating ion conducting material together comprise a majority of the materials in the interface region. The electro-optic device of claim 6, wherein the interfacial region comprises between about 6% by weight and about 95% by weight of the ion-conducting electrically insulating material, and the remainder of the interfacial region is the electrochromic material. 8. The electrochromic device of claim 6, wherein the interface region comprises between about 7% by weight and about 95% by weight of the ion-conducting electrically insulating material, and the remainder of the interface region is the electro-optical 9. The electrochromic device of claim 6, wherein the interface region comprises between about 8% by weight and about 95% by weight of the ion-conducting electrically insulating material and the remaining portion of the S-hai interface region is The electrochromic material 10. The electrochromic device of claim 3 wherein the counter electrode material and the substantially electrically insulating ion conducting material form a majority of the material in the interface region. The electrochromic device of claim 1 wherein the interface region comprises between about 6 〇 155961.doc 201222119% and about 95% by weight of the ion-conducting electrically insulating material, and the remainder of the interface region is Counter electrode material. An electrochromic device according to claim 1 wherein the interfacial region comprises between about 7% by weight and about 95% by weight of the ionically conductive electrically insulating material, and the remainder of the interfacial region is the counter electrode material. The electrochromic device of claim 1 , wherein the interfacial region comprises between about 8% by weight and about 95% by weight of the ionically conductive electrically insulating material, and the remainder of the interfacial region is the counter electrode material. The electrochromic device of claim 3, wherein the substantially electrically insulating ion conducting material comprises lithium tungstate, the electrochromic material comprises tungsten oxide, and the counter electrode material comprises nickel tungsten oxide. The electrochromic device of claim 14, wherein the electrochromic layer has a thickness between about 300 nm and about 500 nm; the interface region has a thickness between about 1 〇 nm and about 150 nm, and the thickness of the counter electrode layer The electrochromic device of claim 14, wherein the electrochromic layer has a thickness between about 400 nm and about 500 nm; the thickness of the interface region is between about 1500 nm and about 300 nm. Between about nm and about 1 〇〇 nm, and the counter electrode layer The thickness is between about i5 〇 and about 250 nm. The electrochromic device of claim 14, wherein the electrochromic layer has a thickness between about 400 nm and about 450 nm; the thickness of the interface region is about Between 3 〇 nm and about 50 nm, and the thickness of the counter electrode layer is between about 2 〇〇〇 and about 250 nm. 18. The electrochromic device of claim 6, wherein the interface region is formed at about 155961.doc 201222119 The combined thickness of the interface region between the 0.5% and about 50% of the electrochromic layer. 19. The electrochromic device of claim 6, wherein the interface region is comprised at about 1% and about 30. The combined thickness of the interface region between the % and the electrochromic layer. 20. The electrochromic device of claim 6, wherein the interface region is comprised at about 2% and about 10[deg.]. The combined thickness of the interface region and the electrochromic layer. 21. The electrochromic device of claim 18, wherein the substantially electrically insulating ion conducting material comprises tungstic acid, the electrochromic material comprises an oxidized crane, and the counter electrode material comprises nickel tungsten oxide. 22. The electrochromic device of claim 21, wherein the electrochromic layer has a thickness between about 300 nm and about 500 nm; the interface region has a thickness between about 1 〇 nm and about 150 nm 'and The thickness of the counter electrode layer is between about 15 Å and about 300 nm. 23. The electrochromic device of claim 21, wherein the electrochromic layer has a thickness between about 400 nm and about 500 nm; the interface region has a thickness between about 2 〇 nm and about 1 〇〇 nm. And the thickness of the counter electrode layer is between about 15 〇 nm and about 250 nm. The electrochromic device of claim 21, wherein the electrochromic layer has a thickness between about 400 nm and about 450 nm; the interface region has a thickness between about 3 〇 nm and about 50 nm 'and The thickness of the counter electrode layer is between about 200 nm and about 250 nm. 25. An electrochromic device comprising: 155961.doc 201222119 (a) an electrochromic layer comprising tungsten oxide; (b) a counter electrode layer comprising nickel tungsten oxide; and (4) in the electrochromic layer An interfacial region between the counter electrode layers, wherein the interfacial region comprises a mixture of at least one of lithium tungstate and tungsten oxide and nickel tungsten oxide. 26. The electrochromic device of claim 25, wherein the electrochromic layer has a thickness between about 300 run and about 500 nm; the interface region has a thickness between about two nm and about 150 nm, and the counter electrode The thickness of the layer is between about 15 〇 11 claws and about 300 nm. 27. The electrochromic device of claim 25, wherein the electrochromic layer has a thickness between about 400 nm and about 500 nm; the interface region has a thickness between about nm and about 100 nm, and the inverse The thickness of the electrode layer is between about 15 〇 nm and about 205 nm. 28. The electrochromic device of claim 25, wherein the electrochromic layer has a thickness between about 400 nm and about 450 nm; the interface region has a thickness between about 3 〇 nm and about 50 nm, and The thickness of the counter electrode layer is between about 2 〇〇 11 〇 1 and about 250 nm. 29. The electrochromic device of claim 26, wherein the electrochromic layer is substantially polycrystalline, the interfacial region is substantially amorphous, and the counter electrode layer is substantially amorphous. 30. The electrochromic device of claim 26, which is fabricated on a glass substrate comprising a fluorinated tin oxide layer&apos; and further comprising an indium tin oxide layer. 31. The electrochromic device of claim 30, which comprises a switching speed of less than 1 minute to achieve a final state of about 80%. 155961.doc 201222119 32. 33. 34. 35. 36. 37. 38. 39. The electrochromic device of claim 30, wherein the interface region is included in about ι〇_8 Siemens/cm (Siemens/cm) The ionic conductivity between about 1 〇 3 Siemens / cm and the electronic resistance greater than l 〇 1Q ohm-cm. The electrochromic device of claim 30, which comprises a leakage current between about 4 〇 μΑ/εηι and about 150 μΑ/cm. An electrochromic device as claimed in claim 30, which is incorporated into an electrochromic window. An electrochromic device as in item 34, wherein the electrochromic window is a building glass scale window. An electrochromic device comprising: (a) an electrochromic layer comprising an electrochromic material; and (b) a counter electrode layer comprising a counter electrode material; wherein the electrochromic device is not contained in the electrochromic layer A layer of electrically insulating ion conducting material between the counter electrode and the counter electrode. The electrochromic device of claim 36, wherein: the electrochromic material comprises an oxide of at least one of: tungsten, molybdenum, sharp, titanium, copper, ruthenium, chromium, manganese, vanadium, nickel, and Cobalt; and the counter electrode material comprises at least one of: nickel oxide, nickel tungsten oxide, nickel nickel oxide, nickel oxide chromium oxide, nickel aluminum oxide, nickel manganese oxide, nickel magnesium oxide, chromium oxide, manganese oxide, Prussian blue, oxidized sputum, yttrium oxide, oxidized, group and tungsten. The electrochromic device of claim 37, wherein the electrochromic material comprises an oxidized crane&apos; and the counter electrode material comprises nickel tungsten oxide. The electrochromic device of claim 38, wherein at least one of the electrochromic layer and the counter electrode layer 155961.doc 201222119 contains lining. 40. The electrochromic device of claim 39, wherein the electrochromic layer has a thickness between about 500 nm and about 600 nm, and the counter electrode layer has a thickness between about 150 nm and about 300 nm. 41. The electrochromic device of claim 38, wherein the electrochromic layer is substantially polycrystalline&apos; and the counter electrode layer is substantially amorphous. 42. The electrochromic device of claim 38, which is fabricated on a glass substrate comprising a fluorinated tin oxide layer and further comprising an indium tin oxide layer. 43. The electrochromic device of claim 38, which comprises a switching speed of less than 1 minute to achieve a final state of about 80%. 44. The electrochromic device of claim 38, which comprises a leakage current between about 4 Torr and about 150 Α/cm. 45. An electrochromic device comprising: (a) an electrochromic layer comprising an electrochromic material; and (b) a counter electrode layer comprising a counter electrode material; wherein the device is not contained in the electrochromic layer A compositionally homogeneous layer of electrically insulating ion conducting material with the counter electrode. The electrochromic device of claim 45, wherein the electrochromic material is tungsten oxide, the counter electrode material is an oxide log, and between the electrochromic layer and the counter electrode layer An interfacial region of a mixture of a chain and at least one of tungsten oxide and oxidized chain crane. 47. The electrochromic device of claim 46, wherein the electrochromic layer is between about (10) and about 500 (10) thick; the thickness of the interface region is between about 四 (4) and about 15 〇 'The thickness of the counter electrode layer is between about 150-155961.doc 201222119 and about 300 nm. 48. An electrochromic device precursor 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 comprises: (i) an electrochromic layer comprising an electrochromic material; (ii) a counter electrode layer comprising a counter electrode material; wherein the stack does not comprise ions between the delta electrochromic layer and the counter electrode layer a region of conductive and electrically insulating; and (d) a second transparent conductive oxide layer over the stack. 49. The electrochromic device precursor of claim 48, wherein the electrochromic layer comprises tungsten oxide and the counter electrode layer comprises nickel tungsten oxide. 50. The electrochromic device precursor of claim 49, wherein at least one of the stack and the electrochromic layer comprises a lining. 51. The electrochromic device precursor of claim 50, wherein the electrochromic layer is a tungsten oxide having a superstoichiometric amount of oxygen at least at the interface with the counter electrode layer. 52. The electrochromic device precursor of claim 50, wherein the electrochromic layer has a thickness between about 500 nm and about 600 nm, and the counter electrode layer has a thickness between about 150 nm and about 300 nm. between. 53. The precursor of an electrochromic device of claim 51, which is exposed to heat. 54. The electrochromic device precursor of claim 53, wherein the heating is part of the MTCC. 55. A method of making an electrochromic device, the method comprising: 155961.doc 201222119 forming an electrochromic layer comprising an electrochromic material; forming a counter electrode layer in contact with the electrochromic layer, without first Providing an ion conductive electrically insulating layer between the electrochromic layer and the counter electrode layer, wherein the counter electrode layer comprises a counter electrode material; and forming an interface region between the electrochromic layer and the counter electrode layer, wherein the interface The regions are substantially ionically conductive and substantially electrically insulating. 56. The method of claim 55, wherein the electrochromic layer is formed prior to the counter electrode layer and the electrochromic layer comprises W〇3. 57. The method of claim 56, wherein the heating is applied during deposition of at least a portion of the w〇3. The method of claim 57, wherein the electrochromic layer has a thickness between about 3 〇〇 nm and about 6 〇〇 nm. 59. The method of claim 58, wherein the electrochromic layer comprises a tungsten target having a thickness between about 350 nm and about 450 nm and comprising about 4% and about 8 Å. Between the 〇2 and about 2% and about 60% of the first sputter gas of the heart minus the first w〇3 layer, and the thickness between about 10 nm and about 200 nm using the tungsten a second w〇3 layer of a target and a second sputtering gas sputtering comprising between about 70% and about 1% 〇2 and 〇% and about 30% of Ar, and wherein the electricity is deposited The substrate of the discoloration layer is at least intermittently heated to between about 15 Å and about 45 Å &lt;»c during deposition of the first layer of w3, but not during formation of the second layer of WO3 heating. 60. The method of claim 59, wherein the first layer 〇 3 is about 4 〇〇 nm thick, and the first sputtering gas comprises between about 50% and about 〇 2 〇 2 and About 40. /. And about 50% of Ar; the second w〇3 layer is about i5〇nm 155961.doc 201222119 thick' and the second sputtering gas is substantially pure 〇2; and the electrochromic layer is deposited therein The substrate is at least intermittently heated to between about 2 Torr (TC and about 350 during the formation of the first wo3 layer. (between, but not during the formation of the second WO3 layer. 01. The method of claim 58, wherein the electrochromic layer comprises a WO3 layer having a thickness of between about 500 nm and about 600 nm using a tungsten target and a sputter gas sputtering composition, wherein the money plating gas is splashed The electrochromic layer initially comprises between about 4% and about 8% of 〇2 and between about 2% and about 6% of Ar' and the splatter gas is sputtered by the electrochromic At the end of the layer, between about 70% and 100% of Ar between A and 〇% and about 3%, and wherein the substrate in which the electrochromic layer is deposited is at the beginning of the formation of the electrochromic layer It is heated at least intermittently to about 2 Torr. 〇 is between about 35 ° C but not heated during deposition of at least a final portion of the electrochromic layer. The method of claim 59, wherein the first layer of w〇3 is substantially polycrystalline. 63. The method of claim 59, further comprising sputtering lithium onto the electrochromic layer until at least the electricity The method of claim 63, wherein the counter electrode layer comprises 65. The method of claim 64, wherein the Niw〇 is substantially amorphous. 66. The method of claim 64, wherein the thickness of the counter electrode layer is between about 〇5 〇nm and about 300 nm. 67. The method of claim 66, further comprising sputtering lithium onto the counter electrode layer until the counter The electrode layer is substantially discolored. 155961.doc 201222119 The method of claim 67, which further comprises placing an additional amount between about 5 〇/〇 and about 5% based on fading the counter electrode layer. The method of claim 68, further comprising depositing a transparent conductive oxide layer over the counter electrode layer. 70. The method of claim 69, wherein the transparent The conductive oxide comprises oxidized sulphur tin. 71. The method of claim 69, The step of including, prior to or after depositing the transparent conductive oxide, the stack formed between about 150 t and about 45 Torr is heated under Ar for about 1 minute and about 3 minutes and then Heating under 〇2 lasts between about 1 minute and about 15 minutes. 72. The method of claim 71, further comprising the step of heating the stack to be formed between about 25 与 and about 35 〇t in air. Between about 2 minutes and about 40 minutes. 73. The method of claim 69, further comprising flowing a current between the electrochromic layer and the 4 counter electrode layer as an initial activation of the electrochromic device Part of the loop. 74. A method of making an electrochromic device, the method comprising: (a) forming an electrochromic layer comprising an electrochromic material or a counter electrode layer comprising a counter electrode material; (b) in the electrochromic layer or Forming an intermediate layer over the counter electrode layer, wherein the intermediate layer includes at least one of the electrochromic material, the counter electrode material, and an additional material, wherein the additional material comprises a different electrochromic material or a counter electrode material, the intermediate 155961.doc 201222119. The layer is not substantially electrically insulating; (C) forming the other of the electrochromic layer and the counter electrode layer; and (d) allowing at least the intermediate layer A part becomes substantially electrically insulated. 75. The method of claim 74, wherein the electrochromic material is w〇3. 76. The method of claim 75, wherein (a) comprises the first recording of the use of tungsten by using tungsten and comprising between about 40% and about 80% of 〇2 and between about 20% and about 60% of Ar. Gas splashing WO3 to form the electrochromic layer at a thickness between about 350 nm and about 4500 nm, and at least intermittently heating to about 150 ° C during formation of the electrochromic layer Between about 450 ° C. 77. The method of § 青求76, wherein (b) comprises using a tungsten target without heating and comprising between about 70% and 100% between 〇2 and 〇% and about 3% The second sputter gas of Ar is sputtered to achieve a thickness between about 10 nm and about 200 nm. 78. The method of claim 77, further comprising sputtering lithium onto the intermediate layer&apos; until the blind charge is satisfied. 79. The method of claim 78, wherein the counter electrode layer comprises NiWO having a thickness between about 1" nm and about 3 〇〇 nm. 80. The method of claim 79, wherein the Niw0 is substantially amorphous 8 1 · The method of claim 8 </ RTI> further comprising sputtering lithium onto the counter electrode layer until the counter electrode layer is substantially discolored. 82. The method of claim 81, further comprising An additional amount of lithium shovel is applied to the counter electrode layer in an excess of between about 5% and about 15% of the amount required to cause the counter electrode layer to fade. 83. The method of claim 82, further comprising The reverse electrode layer is overlaid 155961.doc -12 201222119. The transparent conductive oxide layer is 84. The method of claim 83, wherein the transparent conductive oxide comprises indium tin oxide. 85. The method of claim 83 And further comprising heating the stack formed between about 15 ° C and about 45 ° c before or after depositing the transparent conductive oxide for about 1 〇 minutes and about 30 minutes, And then heating under 〇 2 for about 1 minute and about 15 minutes. The method of claim 85, further comprising heating the stack formed between about 2501: and about 350 C for about 2 minutes and about 40 minutes in air. As in the method of claim 83, further A method comprising flowing a current between the electrochromic layer and the counter electrode layer as an initial activation cycle of the electrochromic device. 88. A method of making an electrochromic device, the method comprising: Sputtering a tungsten target comprising about 40% to about 80% A and between about 2% and about 6% Ar of a sputter gas to produce w〇3 to between about nm and about 600 nm a thickness to deposit an electrochromic layer, wherein the substrate on which the W3 is deposited is at least intermittently heated between about 150 ° C and about 4501 during formation of the electrochromic layer; On the electrochromic layer until the blind charge is satisfied; depositing a counter electrode layer on the electrochromic layer without first providing an ion-conducting H-edge layer between the electrochromic layer and the counter electrode layer, wherein The counter electrode layer comprises NiWO; 'spray the bond onto the counter electrode layer until the opposite The firing electrode layer substantially fades 155961.doc 201222119 color; and an interface region is formed between the electrochromic layer and the counter electrode layer, wherein the S-hai interface region is substantially ion-conducting and substantially electrically insulating. 89. A method of making an electrochromic device, the method comprising: (a) forming an electrochromic layer comprising an electrochromic material; (b) forming a counter electrode layer comprising a counter electrode material; and (c) completing the The electrochromic device is fabricated such that it does not contain a layer of electrically insulating ion conducting material between the electrochromic layer and the counter electrode layer. The method of claim 89, wherein the electrochromic layer is formed in the counter electrode layer, and the electrochromic layer comprises W〇3. 91. The method of claim 90, wherein the applying is applied during deposition of at least a portion of the w〇3. 92. The method of claim 91, wherein the electrochromic layer has a thickness between about 3 〇〇 nm and about 600 nm. 93. The method of claim 92, wherein the electrochromic layer comprises a tungsten target having a thickness between about 3 50 nm and about 450 nm and comprising about 4 〇 0 /. And a first W 〇 3 layer of between about 80% 〇 2 and about 20% and about 60% of the first sputter gas splash clock, and a thickness between about nm and about 2 〇〇 nm Using the tungsten target and the second w〇3 layer containing the second sputtering gas of Ar between about 70% and 1% 〇2 and 〇% and about 30% of Ar, and The substrate in which the electrochromic layer is deposited is at least intermittently heated to about 15 Torr during deposition of the first W 〇 3 layer. 〇 with about 450. Between: and during the formation of the second WO3 layer is not heated. 155961.doc • 14·201222119 94. The method of claim 93, wherein the first w〇3 layer is about 400 nm thick, and The first sputtering gas comprises between about 50% and about 60% 〇2 and between about 40% and about 50% of the Ar; the second w〇3 layer is about 150 nm thick, and The second sputtering gas is substantially pure ruthenium 2; and the substrate in which the electrochromic layer is deposited is at least intermittently heated to between about 200 ° C and about 350 during formation of the first W03 layer. The method of claim 92, wherein the electrochromic layer comprises a tungsten target having a thickness between about 500 nm and about 600 nm, wherein the method of claim 92 is not heated. And a layer of layered composition of sputtered gas sputtering, wherein the splashing gas comprises between about 40% and about 80% of 〇2 and about 2% and about about the beginning of splashing the electrochromic layer. Ar between 6〇〇/〇, and the Tibetan gas contains about 〇2 and 〇% and about 3〇% of Ar between about 7〇% and 100% at the end of splashing the electrochromic layer And where the deposit is The substrate of the chromotropic layer is at least intermittently heated to at least about 2 Torr at the beginning of the formation of the electrochromic layer. Between 〇 and about 35 〇〇c, but at least one last of the electrochromic layer The method of claim 93, wherein the first layer of w〇3 is substantially polycrystalline. 97. The method of claim 93, further comprising sputtering the bell to The method of claim 97, wherein the counter electrode layer comprises a blunder. 99. The method of claim 98, wherein the method of claim 97, wherein the method of claim 97, wherein The method of claim 98, wherein the thickness of the counter electrode layer is between about 15 〇 nm 155961.doc 15 201222119 and about 300 nm. 101. The method of claim 100 , i ^ A, further comprising: sputtering lithium onto the counter electrode layer until the counter electrode layer is substantially discolored. 102. The method of claim 1, wherein the method further comprises: The amount of electrode layer required to fade is an excess of between about 5% and about 15%. (4) The key is applied to the counter electrode layer. 103. As claimed in claim 1 〇 2, 甘, &amp; 万 居 其 其 其 其 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 104 104 104 104 104 104 104 104 104 104 104 104 104 104 104 104 104 104 104 104 The method of claim 1, wherein the transparent conductive oxide comprises oxidized sulphur tin. 105. The method of claim 1, wherein the method further comprises: before or after depositing the transparent conductive oxide at about 15 〇 The stack formed between about 45 Å &lt; t is heated between Ar for about 1 minute and about 3 minutes, and then heated at 〇 2 for between about 1 minute and about 15 minutes. 106. The method of claim 1, wherein the method further comprises heating the stack between about 25 (rc and about 350 C) in air for between about 2 minutes and about 40 minutes. 107. The method of clause 1, further comprising flowing a current between the electrochromic layer and the counter electrode layer as part of an initial activation cycle of the electrochromic device. 108. Apparatus for an apparatus, comprising: an integrated deposition system comprising: (0 a first deposition station containing a source of material configured to deposit an electrochromic layer comprising an electrochromic material; 155961.doc -16 - 201222119 (ii) a second deposition station configured to deposit a counter electrode layer comprising a counter electrode material; and (iii) a controller comprising means for transferring the substrate through the stack by sequentially depositing a stack on the substrate a deposition instruction of the deposition station and the second deposition stage, the stack comprising an intermediate layer sandwiched between the electrochromic layer and the counter electrode layer; the intermediate layer is not substantially electrically insulated; Deposition station and the second sink Either or both of the stacks are also passed through to deposit the intermediate layer ' over the electrochromic layer or the counter electrode layer and wherein the intermediate layer comprises the electrochromic material or the oxygen enrichment of the counter electrode material Form, and wherein the first deposition station and the second deposition station are interconnected in series and are operable to transfer the substrate from one station to the next without exposing the substrate to the external environment. 109. The device of claim 108 The apparatus is operable to transfer the substrate from one station to the next without damaging the vacuum. 110. The apparatus of claim 109, wherein the integrated deposition system further comprises operable to be in the electrochromic layer, the middle And depositing one or more lithiation stations from the lithium-containing material source on at least one of the layer and the counter electrode layer. 111. The apparatus of claim 110, wherein the integrated deposition system is operable to be in architectural glass Depositing the stack on a substrate. 112. The apparatus of claim 1, wherein the integrated deposition system further comprises an operable glass base for passing the architectural glass substrate through the integrated deposition system The substrate is held in a substantially vertical orientation on the substrate 155961.doc -17- 201222119 holder and transport mechanism. 113. The apparatus of the present invention is further included for use in the external environment and the integrated deposition system Transferring one or more vacuum pre-extraction chambers between the substrates. 1H. The apparatus of claim 113, further comprising at least one slit valve, wherein at least one slit valve is operable to permit the one or more lithium The deposition station is isolated from at least one of the first deposition station and the second deposition stage and the third deposition stage. 115. The apparatus of claim 14, wherein the integrated deposition system includes a configuration to heat the substrate One or more heaters and configured to actively or passively cool one or more of the cooling components of the substrate. 155961.doc