Reducing defects under bus bars in electrochromic devices

Abstract

The present application relates to reducing defects under a bus bar in an electrochromic device. The present application provides a method of making an electrochromic device that reduces the formation of shorts under a top bus bar without predetermining where the top bus bar will be applied on the device. A device made using such a method can be deactivated under the top bus bar, or the device can include active material under the top bus bar. The method of making a device with active material under the top bus bar includes depositing a modified top bus bar; making a self-healing layer in the electrochromic device; and modifying the top transparent conductive layer of the device before applying the bus bar.

Description

[0001] Information about divisional applications

[0002] This case is a divisional application. The parent case of the divisional application is an invention patent application with application date of December 15, 2015, application number 201580074057.9, and invention name “Reducing defects under busbars in electrochromic devices”.

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] This application claims priority to U.S. Provisional Patent Application No. 62 / 094,862, filed on December 19, 2014, and entitled “MITIGATING DEFECTS IN ANELECTROCHROMIC DEVICE UNDER A BUS BAR,” which is incorporated herein by reference in its entirety and for all purposes. Technical Field

[0005] The present application relates to electrochromic devices. More particularly, the present application relates to reducing defects under bus bars in electrochromic devices. Background of the Invention

[0006] Electrochromism is a phenomenon in which a material exhibits a reversible electrochemically mediated change in optical properties when placed in different electronic states, usually by being subjected to a voltage change. The optical properties are usually one or more of color, transmittance, absorbance, and reflectivity. A well-known electrochromic material is tungsten oxide (WO3). Tungsten oxide is a cathode coloring type electrochromic material that is converted from transparent (colorless) to colored (usually blue) by electrochemical reduction. The electrochromic material is converted from colored to transparent by electrochemical oxidation.

[0007] Electrochromic materials can be incorporated into windows and mirrors for residential, commercial, vehicle and other uses, for example. The color, transmittance, absorbance and / or reflectance of such windows can be reversibly changed by applying an electric charge or potential to the electrochromic material. A small voltage applied to the electrochromic device of a window will cause the window to darken; reversing the voltage will cause the window to lighten. This ability allows the amount of light passing through the window to be controlled, and gives the electrochromic device or window sheet the opportunity to be used as an energy-saving device.

[0008] Although electrochromism was discovered in 1960, unfortunately, electrochromic devices and particularly electrochromic devices or windows continue to suffer from various problems and the industry has only recently begun to realize their full commercial potential. SUMMARY OF THE INVENTION

[0009] Methods for making electrochromic devices are provided. One aspect relates to a method of making an electrochromic device, the method comprising making an electrochromic stack on a substrate without first identifying one or more areas on the electrochromic device for bus bar application.

[0010] On the other hand, a method for making an electrochromic device is provided, wherein the electrochromic device includes an electrochromic stack between a first transparent conductive layer and a second transparent conductive layer, wherein the transparent conductive layer is configured to transfer an electric potential on a surface of the electrochromic stack and thereby cause optical switching of the electrochromic device, the method comprising: (a) receiving a substrate; (b) making an electrochromic stack on a first transparent conductive layer disposed on a surface of the substrate, wherein the electrochromic stack includes an electrochromic layer and a counter electrode layer; (c) forming a second transparent conductive layer on the electrochromic stack; (d) forming a bus bar on an area of ​​the second transparent conductive layer, wherein the area is above the first transparent conductive layer; and (e) after making the electrochromic stack and the second transparent conductive layer, (i) deactivating the electrochromic device in an area below the bus bar, but substantially not deactivating the electrochromic device in an area not below the bus bar, or (ii) activating the electrochromic device in an area not below the bus bar, but substantially not activating the electrochromic device in an area below the bus bar. In some embodiments, (e) is performed before performing (d), while in other embodiments, (e) can be performed after performing (d), and in still other embodiments, deactivating the device in the aforementioned area can be done both before applying the bus bar and gradually after applying the bus bar. In some embodiments, one or more of the bus bars are provided on the visible area of ​​the surface of the electrochromic device. One or more of the bus bars can be transparent.

[0011] In various embodiments, the method further includes depositing a first transparent conductive layer on the substrate in an apparatus for making an electrochromic stack.

[0012] In some embodiments, the method further comprises continuously feeding the substrate from a coil of the substrate to an apparatus for coating the electrochromic stack on the substrate. In some implementations, the substrate comprises flexible glass. In certain embodiments, the electrochromic device is coated on the substrate at one facility, whether or not roll-to-roll processing is performed on thin glass, and then the substrate is transported to another facility for subsequent processing, which includes cutting the substrate into sub-devices or windows.

[0013] The method may also include forming a first transparent conductive layer on the surface of the substrate. Forming the first transparent conductive layer, making the electrochromic stack and forming the second transparent conductive layer may be sequentially performed in a sputtering device that applies the first transparent conductive layer, the second transparent conductive layer and the electrochromic stack to the surface of the substrate.

[0014] In some embodiments, operations (b) and (c) are sequentially performed in a sputtering device that coats the surface of the substrate with the first transparent conductive layer and the second transparent conductive layer and the electrochromic stack, and operation (d) is performed outside the sputtering device. In certain embodiments, (e) is also performed outside the sputtering device.

[0015] The method may be performed before depositing the second transparent conductive layer, without scribing or without isolating regions of the first transparent conductive layer. The method may be performed before depositing the second transparent conductive layer, without scribing or without isolating regions of the electrochromic stack. In some embodiments, the method may further include forming one or more additional bus bars on the second transparent conductive layer and / or the first transparent conductive layer. In some embodiments, the method may further include cutting the substrate to provide a plurality of electrochromic devices or windows.

[0016] The method may be performed before the electrochromic device and the second transparent conductive layer are completed without predefining where the bus bars of the second transparent conductive layer are to be formed.

[0017] Fabricating the electrochromic stack may include depositing elemental lithium on the counter electrode layer and / or the electrochromic layer.

[0018] The bus bar can have a length of up to about 144 inches. The second transparent conductive layer can be substantially transparent. In some embodiments, the maximum dimension of the substrate is at least about 144 inches. If a roll-to-roll process is used, the 144 inch dimension refers to the width, and the length of the substrate can be longer, for example, several hundred feet long or more.

[0019] The deactivation in (e) may include reducing the conductivity of the first transparent conductive layer and / or the electrochromic layer and / or the counter electrode layer of the electrochromic device in the region below the bus bar. Reducing the conductivity may include chemically reacting the first transparent conductive layer in the region below the bus bar.

[0020] The chemical reaction may include exposing the first transparent conductive layer to an active oxygen source, and thereby the first transparent conductive layer includes a transparent layer. The transparent layer may be selected from the group consisting of: a metal-doped oxide, an undoped metal oxide, a nitride, and a metal. In some embodiments, the active oxygen source is a substrate.

[0021] The chemical reaction may include forming the passivation layer by contacting the first transparent conductive layer with a component present in a material applied to form the bus bar, or exposing the first transparent conductive layer to an elevated temperature.

[0022] Deactivation may include preventing lithiation of the electrochromic device in the region beneath the bus bar.

[0023] In some embodiments, the electrochromic layer includes an electrochromic metal oxide, and thus the deactivation in (e) includes reacting interstitial oxygen in the electrochromic layer with the electrochromic metal oxide to produce a stoichiometric or oxygen-rich form of the metal oxide that is not electrochromically active. The electrochromic metal oxide may be tungsten oxide.

[0024] The deactivation in (e) may include applying excess oxygen in the area below the bus bar.

[0025] In some embodiments, operation (e) may include: (i) sensitizing the electrochromic stack, the first transparent conductive layer, and / or the second transparent conductive layer during operation (b) and / or (c); and (ii) after operation (c), locally applying a stimulus below or near the bus bar to deactivate the sensitized electrochromic stack, the first transparent conductive layer, and / or the second transparent conductive layer in the area below the bus bar, or to activate the sensitized electrochromic stack, the first transparent conductive layer, and / or the second transparent conductive layer in the area not below the bus bar.

[0026] Sensitization may include a treatment selected from the group consisting of: application of heat, irradiation, application of a chemical or composition, and combinations thereof. The stimulus may be selected from the group consisting of: irradiation, heating, exposure to a chemical or composition, and combinations thereof.

[0027] Reducing the conductivity of the first transparent conductive oxide layer and / or the electrochromic layer and / or the counter electrode layer may include applying heat and / or other energy to one or more of these layers. In some embodiments, IR heating may be used to reduce the conductivity of one or more of these layers. The layers may be fused or otherwise altered in morphology by heat to inhibit conductivity and / or ion movement.

[0028] Another aspect relates to a method for making an electrochromic device, the electrochromic device comprising an electrochromic stack between a first transparent conductive layer and a second transparent conductive layer, the transparent conductive layer being configured to transfer a potential on a surface of the electrochromic stack and thereby causing optical switching of the electrochromic device, the method comprising: (a) receiving a substrate; (b) making an electrochromic stack on a first transparent conductive layer disposed on a surface of the substrate, whereby the electrochromic stack comprises an electrochromic layer and a counter electrode layer; (c) forming a second transparent conductive layer on the electrochromic stack; and (d) A bus bar is formed on an area of ​​the second transparent conductive layer, whereby the area is above the first transparent conductive layer; and (e) an operation to reduce short circuits is performed, wherein the operation to reduce short circuits (i) prevents an electrical short circuit from forming between the second transparent conductive layer and the first transparent conductive layer in the area below the bus bar, and / or (ii) removes an electrical short circuit that has formed between the second transparent conductive layer and the first transparent conductive layer in the area below the bus bar, whereby (e) is performed after the electrochromic stack and the second transparent conductive layer are made without substantially deactivating the electrochromic device in the area below the bus bar. In some embodiments, one or more of the bus bars are provided on a visible area of ​​the interior of the electrochromic device or on a surface of the electrochromic device. The bus bar can be transparent. One or more bus bars can also be formed. In some embodiments, one or more of the bus bars can be transparent.

[0029] In some embodiments, the operation of reducing short circuits includes forming the busbars by applying the busbar conductive material in a medium that does not substantially allow the conductive material to migrate, thereby inhibiting or preventing the conductive material from reaching and electrically contacting the second transparent conductive layer. The medium can be a solid, or the medium can be a tape, or the medium can be a gel or a liquid, or the medium can be a polymer solid that inhibits the migration of the conductive material, such as an epoxy resin, a polyimide, a urethane, etc. The medium itself can be conductive, such as a polymer functionalized with a conductive substance, such as a side chain or integrated into a polymer chain. In some embodiments, the conductive material itself is configured so that migration does not occur. In some embodiments, a conductive barrier layer is applied to the second transparent conductive layer, and then a busbar is applied thereon. The conductive barrier layer can be made of a material that is less conductive than the busbar, or is the same as or greater than the busbar.

[0030] The operation of reducing short circuits may include forming the bus bar by applying the bus bar conductive material in a medium that isolates the conductive material, thereby preventing the conductive material from migrating to the second transparent conductive layer.

[0031] The operation of reducing the short circuit may include forming a barrier layer between the bus bar and the second transparent conductive layer. The barrier layer may include materials such as graphite and graphene, titanium oxide, tin oxide, zinc oxide, aluminum oxide, aluminum nitride, titanium nitride, tantalum nitride, chromium, nitride, SiO x N y Compounds, carbon, and combinations thereof.

[0032] The operation of reducing short circuits can be performed during (d) such that forming the bus bar includes forming the bus bar from a composition including a conductive material that resists electromigration into the second transparent conductive layer.

[0033] The operation of reducing the short circuit may include applying a stimulus that restores an existing short circuit between the second transparent conductive layer and the layer of the electrochromic device. Applying the stimulus to restore the existing short circuit may include applying an electric current between the second transparent conductive layer and the layer of the electrochromic device in the area below the bus bar. Applying the stimulus to restore the existing short circuit may include exposing the electrochromic device in the area below the bus bar to high temperature. Applying the stimulus to restore the existing short circuit may include exposing the electrochromic device in the area below the bus bar to laser energy. Applying the stimulus to restore the existing short circuit may include reacting the existing short circuit with a chemical to make the existing short circuit relatively non-conductive. The stimulus may be, for example, alternating current, heat, laser irradiation, and the like.

[0034] The operation of reducing the short circuit may include blocking a path in the second transparent conductive layer at a point where a short circuit may otherwise form. The path may include a defect, depression, or crack in the second transparent conductive layer. Blocking the path in the second transparent conductive layer may include melting or flowing at least a portion of the second transparent conductive layer. Blocking the path in the second transparent conductive layer may include filling the path with a material that prevents material from the bus bar from migrating into the second transparent conductive layer. Blocking the path in the second transparent conductive layer may include covering the second transparent conductive layer with a substantially non-conductive material before forming the bus bar in (d). The material may be, for example, a non-conductive polymer material.

[0035] In various embodiments, the method further comprises depositing a first transparent conductive layer on the substrate in an apparatus for making an electrochromic stack.Some methods may involve performing (e) before performing (d).

[0036] In some embodiments, the method further comprises continuously feeding the substrate from a web of the substrate to an apparatus for coating the electrochromic stack on the substrate.In some implementations, the substrate comprises flexible glass.

[0037] The method may also include forming a first transparent conductive layer on the surface of the substrate. Forming the first transparent conductive layer, making the electrochromic stack and forming the second transparent conductive layer may be sequentially performed in a sputtering device that applies the first transparent conductive layer, the second transparent conductive layer and the electrochromic stack to the surface of the substrate.

[0038] In some embodiments, operations (b) and (c) are sequentially performed in a sputtering apparatus that coats the surface of the substrate with the first and second transparent conductive layers and the electrochromic stack, and operation (d) is performed outside the sputtering apparatus.

[0039] The method may be performed before forming the second transparent conductive layer, without scribing or without isolating the area of ​​the first transparent conductive layer. The method may be performed before forming the second transparent conductive layer, without scribing or without isolating the area of ​​the electrochromic stack. In some embodiments, the method may also include forming one or more additional bus bars on the second transparent conductive layer and / or the first transparent conductive layer. The one or more bus bars may be transparent. In some embodiments, the method may also include cutting the substrate to provide a plurality of electrochromic devices or windows.

[0040] The method may be performed before the electrochromic device and the second transparent conductive layer are completed without predefining where the bus bars of the second transparent conductive layer are to be formed.

[0041] Fabricating the electrochromic stack may include depositing elemental lithium on the counter electrode layer and / or the electrochromic layer.

[0042] On the other hand, it relates to an electrochromic device, which includes: a substrate having a surface; a first transparent conductive layer, which is disposed on the surface of the substrate; an electrochromic stack, which is on the first transparent conductive layer, whereby the electrochromic stack includes an electrochromic layer and a counter electrode layer; a second transparent conductive layer, which is on the electrochromic stack; and a bus bar, which is electrically coupled to a region of the second transparent conductive layer, whereby the region is above the first transparent conductive layer and whereby the electrochromic stack is disposed between the two transparent conductive layers, the transparent conductive layer being configured to transfer an electric potential on the surface of the electrochromic stack and thereby cause optical switching of the electrochromic device, whereby after the electrochromic stack and the second transparent conductive layer are made, the electrochromic stack is inactivated in the region below the bus bar.

[0043] Another aspect relates to an electrochromic device, the electrochromic device comprising: a substrate having a surface; a first transparent conductive layer, the first transparent conductive layer disposed on the substrate surface; an electrochromic stack, the electrochromic stack being on the first transparent conductive layer, whereby the electrochromic stack comprises an electrochromic layer and a counter electrode layer; a second transparent conductive layer, the second transparent conductive layer being on the electrochromic stack; and a bus bar, the bus bar being electrically coupled to a region of the second transparent conductive layer, whereby the region is above the first transparent conductive layer, and whereby the electrochromic stack is disposed between the two transparent conductive layers, the transparent conductive layer being configured to transfer an electrical potential on the surface of the electrochromic stack and thereby cause optical switching of the electrochromic device, whereby the electrochromic stack is active and short circuits and / or potential defects in the region below the bus bar are reduced. In some embodiments, at least one of the potential defects is a potential short circuit.

[0044] Another aspect relates to a system for making an electrochromic device, the electrochromic device including an electrochromic stack between two transparent conductive layers, the transparent conductive layer being configured to transfer an electric potential on a surface of the electrochromic stack and thereby cause optical switching of the electrochromic device, the making apparatus comprising: (a) a coating apparatus configured to receive a substrate optionally having a surface on which a first transparent conductive layer is disposed; to make an electrochromic stack on the first transparent conductive layer, wherein the electrochromic stack includes an electrochromic layer and a counter electrode layer; and to form a second transparent conductive layer on the electrochromic stack; and (b) a post-coating patterning apparatus configured to receive a substrate having an electrochromic stack between two transparent conductive layers; to form one or more bus bars electrically coupled to the second transparent conductive layer and / or the first transparent conductive layer; and to deactivate an underlying device in an area below the one or more bus bars. The post-coating patterning apparatus can be further configured to cut the substrate to provide a plurality of electrochromic devices or windows. The post-coating apparatus may be further configured to form one or more bus bars electrically coupled to the first transparent conductive layer.

[0045] Another aspect relates to a system for making an electrochromic device, the electrochromic device including an electrochromic stack between two transparent conductive layers, the transparent conductive layer being configured to transfer an electric potential on a surface of the electrochromic stack and thereby cause optical switching of the electrochromic device, the making apparatus comprising: (a) a coating apparatus configured to receive a substrate optionally having a surface on which a first transparent conductive layer is disposed; to make an electrochromic stack on the first transparent conductive layer, wherein the electrochromic stack includes an electrochromic layer and a counter electrode layer; and to form a second transparent conductive layer on the electrochromic stack; and (b) a post-coating patterning apparatus configured to receive a substrate having an electrochromic stack between two transparent conductive layers; to form one or more bus bars electrically coupled to the second transparent conductive layer and / or the first transparent conductive layer; and to block penetration of the bus bar material. The post-coating patterning apparatus can be further configured to cut the substrate to provide a plurality of electrochromic devices or windows. The post-coating apparatus may be further configured to form one or more bus bars electrically coupled to the first transparent conductive layer.

[0046] Another aspect relates to a method for manufacturing an electrochromic device, the electrochromic device including an electrochromic stack between a first transparent conductive layer and a second transparent conductive layer, the transparent conductive layer being configured to transfer a potential on the surface of the electrochromic stack and thereby causing optical switching of the electrochromic device, the manufacturing method comprising: (a) making the electrochromic device on a glass substrate without pre-patterning in a first facility; (b) transporting the glass substrate including the electrochromic stack to a second facility; and (c) performing post-processing in the second facility. In various embodiments, (c) includes applying one or more bus bars to the electrochromic stack. In some embodiments, the method further includes deactivating the electrochromic stack below at least one of the one or more bus bars applied to the substrate during post-processing. Deactivation can be performed before or after applying the one or more bus bars. Certain methods include applying a hermetic sealing layer to the electrochromic device before (b). The hermetic sealing layer is applied to the exposed (top) transparent conductive oxide layer and can be permanent or temporary, for example, in the latter case a strippable coating or layer that can be etched away or otherwise removed. In some embodiments, (c) can include cutting the glass substrate including the electrochromic stack into a plurality of electrochromic windows. In some embodiments, (c) can include patterning the electrochromic device with a laser.

[0047] In some embodiments, deactivation includes sensitizing the electrochromic stack, the first transparent conductive layer, and / or the second transparent conductive layer by performing a treatment selected from the group consisting of applying heat, irradiating, applying a chemical or composition, and combinations thereof.

[0048] In various embodiments, (c) includes performing a short circuit reduction operation, wherein the short circuit reduction operation (i) prevents an electrical short circuit from forming between the second transparent conductive layer and the first transparent conductive layer in the region below the bus bar, and / or (ii) removes an electrical short circuit that has formed between the second transparent conductive layer and the first transparent conductive layer in the region below the bus bar, and wherein the short circuit reduction operation is performed after the electrochromic stack and the second transparent conductive layer are fabricated without substantially deactivating the electrochromic device in the region below the bus bar.

[0049] In some embodiments, the method further comprises, prior to (b), providing hermetic protection to the electrochromic stack.

[0050] In some embodiments, providing hermetic protection includes forming a hermetic top coating on the electrochromic stack. In some embodiments, the hermetic top coating is made of materials such as parylene, silicon-based sealants, epoxy-based sealants, oxide-polymer multilayers, and combinations thereof.

[0051] In some embodiments, the method further comprises removing the sealing top coating at the second facility.

[0052] In some embodiments, a glass substrate including an electrochromic stack has a roughness of less than about 30 nm.

[0053] In some embodiments, the method further comprises providing the glass substrate comprising the electrochromic stack in an environment that is not affected by atmospheric humidity. In some embodiments, the environment is an argon environment.

[0054] In some embodiments, the method further includes providing a glass substrate including the electrochromic stack, and at least one other glass substrate has the electrochromic stack interwoven with a protective material.

[0055] In various embodiments, the protective material comprises a powder and / or an interwoven sheet. In some embodiments, the interwoven sheet is rice paper.

[0056] In some embodiments, the transported glass substrate including the electrochromic stack is not tempered. In some embodiments, the method further comprises annealing the glass substrate including the electrochromic stack after cutting at a second facility during post-processing. In some embodiments, the transported glass substrate including the electrochromic stack comprises an electrochromic precursor. In some embodiments, the method further comprises tempering the glass substrate including the electrochromic stack after cutting at a second facility during post-processing.

[0057] On the other hand, a method for making an electrochromic device is provided, the method comprising: a. depositing a first electrochromic stack comprising a first electrochromic layer and a first counter electrode layer on a first transparent conductive layer; b. depositing a second electrochromic stack comprising a second electrochromic layer and a second counter electrode layer on the first electrochromic stack, wherein at least one of the electrochromic stacks comprises a superstoichiometric amount of oxygen at the interface between the electrochromic layer and the counter electrode layer; c. depositing lithium on the second electrochromic stack; d. depositing a second transparent conductive layer on the second electrochromic stack to form an electrochromic device precursor; and e. selectively activating the electrochromic device precursor in areas other than areas where a bus bar is to be present, the bus bar being configured to power the second transparent conductive layer.

[0058] In some embodiments, the bus bar is a non-penetrating bus bar.

[0059] When the bus bar is made in the area where the bus bar will be present, the area can be configured to extend about 0.5 mm to about 5 mm beyond any edge of the bus bar. When the bus bar is made in the area where the bus bar will be present, the area can be configured to extend about 0.5 mm to about 2 mm beyond any edge of the bus bar. When the bus bar is made in the area where the bus bar will be present, the area can be configured to extend about 0.5 mm to about 1 mm beyond any edge of the bus bar.

[0060] The method may further include deactivating the region to inhibit electrical conduction between the first transparent conductive layer and the second transparent conductive layer.

[0061] In some embodiments, the bus bar includes a bus bar conductive material in a dielectric that insulates the conductive material, thereby preventing the conductive material from migrating to the second transparent conductive layer.

[0062] These and other aspects are further described below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figures 1A-1C is a schematic representation of an example of an electrochromic device.

[0064] Figure 1D is a schematic representation of an insulating glass unit.

[0065] Figure 2 is a schematic representation of an example of silver deposition in an electrochromic device.

[0066] Figure 3 is a process flow diagram of operations performed in accordance with the disclosed embodiments.

[0067] Figure 4Ais a schematic representation of an example of a bus bar applied to an electrochromic device.

[0068] Figure 4B , Figure 5 and Figure 6 is a process flow diagram of operations performed in accordance with the disclosed embodiments.

[0069] Figure 7 is a process flow diagram illustrating a method of making an electrochromic window according to the disclosed embodiments.

[0070] Figure 8 is a schematic representation showing roll-to-roll processing of an electrochromic device. DETAILED DESCRIPTION

[0071] The following description includes certain details for providing context and / or complete description of the referenced embodiments, however the referenced embodiments may be practiced without some or all of these details. Thus, although some disclosed embodiments are described with specific operations and / or features, the applicant does not intend to limit the embodiments to these operations and / or features. In some cases, well-known operations and / or features are not described in order to clarify the disclosed embodiments.

[0072] Preface

[0073] For the sake of brevity, embodiments are described with respect to electrochromic (EC) devices; however, the scope of the present disclosure is not limited thereto. One of ordinary skill in the art will appreciate that the methods and devices described are applicable to other thin film devices in which one or more layers are sandwiched between two thin film conductor layers. Certain embodiments relate to optical devices, i.e., thin film devices having at least one transparent conductor layer. In the simplest form, the optical device comprises a substrate and one or more material layers, the material layers being sandwiched between two conductor layers, one of the conductor layers being transparent. In one embodiment, the optical device comprises a transparent substrate and two transparent conductor layers. In another embodiment, the optical device comprises a transparent substrate, a lower transparent conductor layer disposed thereon, and an opaque upper conductor layer. In another embodiment, the substrate is opaque, and one or both of the conductor layers are transparent. Some examples of optical devices include electrochromic devices, electroluminescent devices, photovoltaic devices, suspended particle devices (SPDs), and the like. For context, a description of an electrochromic device is presented below. For convenience, all solid-state and inorganic electrochromic devices are described; however, the embodiments are not limited in this manner.

[0074] Examples of electrochromic device structure and fabrication will be presented. Figures 1A-1C1 is a schematic cross-sectional view of an electrochromic device 100, which shows a structural model of such a device. The electrochromic device 100 includes a glass substrate 102, a diffusion barrier layer 103, a conductive layer (CL) layer 104, an EC stack 106, and another conductive layer (CL) 112. The substrate can be made of glass material and in particular architectural glass or other shatter-resistant glass materials, such as silicon oxide (SO x ) glass material. As a more specific example, the substrate can be a soda-lime glass substrate or a float glass substrate. Such glass substrates can be composed of, for example, approximately 75% silicon dioxide (SiO2) and Na2O, CaO, and a number of small amounts of additives. However, the substrate can be formed of any material with suitable optical, electrical, thermal, and mechanical properties. For example, other suitable substrates can include other glass materials and plastic, semi-plastic, and thermoplastic materials (e.g., poly(methyl methacrylate), polystyrene, polycarbonate, allyl diglycol carbonate, SAN (styrene acrylonitrile copolymer), poly(4-methyl-1-pentene), polyester, polyamide), or mirror materials. In some implementations, each of the first window panel and the second window panel (not shown) can be strengthened, for example, by tempering, heating, or chemical strengthening. Glass substrates can be combined so that one or more substrates can be used to form an insulating glass unit (IGU).

[0075] The EC stack 106 includes an electrochromic layer (not shown) and an ion conductive (electronic resistance) layer (IC) (not shown). The EC stack may also include an opposing counter electrode layer, also known as an ion storage layer. This layer may or may not be electrochromic. Generally speaking, such devices are constructed so that the electrochromic layer is cathode colored and the counter electrode layer is anodically colored. Although this is not limiting, this has the advantage that the coloring layers are complimentary, that is, they are colored or bleached at the same time and therefore darker coloring and more neutral coloring can be achieved.

[0076] Conductive layers 104 and 112 typically include transparent conductive materials, such as metal layers, metal oxides, alloy oxides, and doped versions thereof, and are often referred to as "TCO" layers because they are sometimes made of transparent conductive oxides or transparent metal oxides. The term "TCO" is conventionally used to refer to a wide range of transparent conductive materials that can be formed into a conductive layer that is used to transfer an electrical potential across the surface of an electrochromic device to drive or maintain an optical transition. Although such materials are referred to as TCOs in this document, the term encompasses transparent and conductive non-oxides and oxides, such as certain extremely thin metals and certain non-metallic materials. Transparent conductive materials typically have a conductivity significantly greater than that of electrochromic materials or counter electrode materials. For example, a transparent conductive material may have a resistivity of at least about 100 μOhm-cm to about 600 μOhm-cm. In addition, a transparent conductive material may have a sheet resistance of at most about 10 ohms / square to about 20 ohms / square. Example transparent layers include indium tin oxide (ITO), fluorinated tin oxide (FTO), and aluminum zinc oxide (AZO). The term "TCO" as described herein may also include multilayer structures. For example, a TCO may include a first ITO layer, a metal layer, and a second ITO layer, wherein the metal layer is between the two ITO layers. A TCO may also refer to a multilayer structure having one or more layers of transparent conductive material. Some TCOs may also include a metal top or bottom conductive layer.

[0077] As described herein, conductive layer 104 may be referred to as a "first TCO," "bottom TCO," or "TCO 1." Conductive layer 112 may be referred to as a "second TCO," "top TCO," or "TCO2." In general, however, the transparent layer may be made of any transparent conductive material that is compatible with the device stack. Some glass substrates are provided with a thin transparent conductive oxide layer, such as fluorinated tin oxide (sometimes referred to as "FTO"). In some embodiments, the second TCO is substantially transparent. A substantially transparent component of a device is one whereby at least about 80% or at least about 90% of light is transmitted through the device.

[0078] The bottom TCO 104 is the first of two conductive layers used to form an electrode of the electrochromic device 100 fabricated on a glass substrate or glass sheet 102. In some examples, the glass substrate 102 can be pre-fabricated with a diffusion barrier layer 103 formed on the underlying glass 102. Thus, in some embodiments, the diffusion barrier layer 103 is deposited prior to depositing the bottom TCO 104, the EC stack 106 (e.g., a stack having an electrochromic layer, an ion conductor layer, and a counter electrode layer), and the top TCO 112. In some embodiments, the glass substrate 102 can be pre-fabricated with both the diffusion barrier layer 103 and the bottom TCO 104 formed on the underlying glass 102.

[0079] A non-penetrating bus bar (such as bus bar 1 or "top bus bar" as used herein) is applied to the top TCO 112. A non-penetrating bus bar (such as bus bar 2 or "bottom bus bar" as used herein) is applied to an area on the bottom TCO 104 where the EC stack 106 and the top TCO 112 are not deposited or have been removed (e.g., removed from a mask that protects the bottom TCO 104 from device deposition; or removed by using a mechanical abrasion process or by using a laser ablation process). Bus bars are typically used to provide electrical connections for providing current and voltage to conductive layers, often to drive or maintain optical states. Bus bars can be penetrating or non-penetrating. A penetrating bus bar is a bus bar that is typically pressed (or welded) through one or more layers to contact a lower conductor (e.g., a TCO located at the bottom of the EC stack or below one or more layers thereof). Conventionally, bus bars 1 and 2 can be made of ink applied as a liquid. In some embodiments, bus bar 1 is aligned so that it is deposited on the edge of the top TCO 112. In various embodiments, the bus bar is applied as part of a post-patterning process. The bus bar material can include liquid silver ink. In some embodiments, bus bar 2 can be a through bus bar. In some embodiments, bus bar 2 can be applied on top of the entire EC stack, penetrating down to contact the first TCO layer. For example, an ultrasonically welded bus bar can be used in this manner. In this configuration, an isolation line can be applied so that it passes through at least the top TCO 112, but not through the bottom TCO 104.

[0080] TCO layers 104 and 112 can be electrically connected using bus bars, which can be fabricated using screen and photolithographic patterning methods. Electrical connectivity between the TCO layers of the device is established by screen printing of a conductive ink (or using another patterning method), followed by thermal curing or sintering of the ink.

[0081] Figure 1B1 is a schematic representation of the operation of an electrochromic device 100, which includes a substrate 102, a bottom TCO 104, an EC electrode layer 106a, an optional ion conductive (electronic resistance) layer (IC) 106b, a counter electrode layer (CE) 106c, and a top TCO 112. Elements 106a, 106b, and 106c are collectively referred to as an electrochromic stack 106. A voltage source operable to apply an electric potential to the entire electrochromic stack 106 achieves a transition of the electrochromic device from, for example, a transparent state to a colored state. In various embodiments, the EC stack is made by forming a counter electrode layer in direct contact with the EC electrode layer. The resulting structure has no IC layer or has an IC layer that is formed in situ after or during the deposition of the EC electrode and / or counter electrode layer. Such devices are described in U.S. Patent Nos. 12 / 772,055, filed April 30, 2010 (now U.S. Patent No. 8,300,298); and 12 / 814,279, filed June 11, 2010 (now U.S. Patent No. 8,764,952), both of which are incorporated herein by reference in their entirety.

[0082] like Figure 1B As shown, a voltage source 116 operable to apply an electric potential across the EC stack 106 enables the electrochromic device 100 to change from, for example, a transparent state (referring to Figure 1B ) to the shaded state (referring to Figure 1C )’s transformation.

[0083] During normal operation, an electrochromic device such as device 100 reversibly cycles between a transparent state and a colored state. Figure 1A Busbar 1 (or "top busbar" as used herein) and busbar 2 (or "bottom busbar" as used herein) are shown to be energized so as to facilitate Figure 1B A potential is applied across the electrochromic device as shown; for example, the bottom TCO 104 has a negative charge and the top TCO 112 has a positive charge or vice versa. Figure 1B As shown, in the transparent state, a potential is applied across the electrodes (TCO layers 104 and 112) of the EC stack 106 so that the available ions (e.g., lithium ions) in the stack are primarily present in the counter electrode 106c. If the electrochromic layer 106a includes a cathode coloring material, the device is in the transparent state. In some electrochromic devices, the counter electrode layer 106c can be considered an ion storage layer when loaded with available ions.

[0084] To understand the context of the embodiments described herein, Figures 1A-1CThe device 100 shown is intended for illustrative purposes. The methods and apparatus described herein are used to identify and reduce defects in electrochromic devices, regardless of the structural arrangement of the electrochromic device.

[0085] The order of the layers may be reversed with respect to the substrate 102. That is, the layers may be in the following order: substrate, conductive layer, counter electrode layer, ion conductive layer, EC layer, and conductive layer. The counter electrode layer may include electrochromic or non-electrochromic materials. If both the electrochromic layer and the counter electrode layer use electrochromic materials, one of them should be a cathode coloring material and the other should be an anode coloring material. For example, the EC layer may use a cathode coloring material and the counter electrode layer may use an anode coloring material. This is also the case when the electrochromic layer is tungsten oxide and the counter electrode layer is nickel tungstate.

[0086] refer to Figure 1C , when the potential on the EC stack 106 is reversed, ions are transported through the ion conductive layer 106b to the electrochromic layer 106a and the material enters a colored state. Again, this assumes that the optically reversible material in the electrochromic device is a cathode coloring type electrochromic material. In certain embodiments, the depletion of ions in the counter electrode material may cause the counter electrode material to be colored as shown. In other words, the counter electrode material is an anode coloring type electrochromic material. Therefore, layers 106a and 106c are combined to synergistically reduce the amount of light transmitted through the stack. When a reverse voltage is applied to the device 100, ions travel from the EC layer 106a through the ion conductive layer 106b and back to the counter electrode layer 106c. Therefore, the device becomes transparent.

[0087] Some examples of suitable electrochromic devices are presented in the following U.S. patent applications, each of which is incorporated by reference in its entirety: U.S. patent application Ser. No. 12 / 645,111, filed Dec. 22, 2009; U.S. patent application Ser. No. 12 / 772,055, filed Apr. 30, 2010 (now U.S. Pat. No. 8,300,298); U.S. patent application Ser. No. 12 / 645,159, filed Dec. 22, 2009 (now U.S. Pat. No. 8,4 32,603); U.S. patent application No. 12 / 814,279 filed on June 11, 2010 (now U.S. Patent No. 8,764,951); U.S. patent application No. 13 / 462,725 filed on May 2, 2012; U.S. Provisional Patent Application No. 61 / 988,107 filed on May 2, 2014; U.S. patent application No. 13 / 763,505 filed on February 8, 2013 (now U.S. Patent No. 9,007,674).

[0088] Electrochromic devices, such as relative to Figure 1A–Those described in 1C are used, for example, in electrochromic windows. An electrochromic window is a window that includes an electrochromic window sheet that is a transparent window panel, and the optical properties of the electrochromic window sheet, such as color or degree of tinting, change when a driving potential is applied to the window sheet. For example, the electrochromic window sheet can be tinted to filter out 50% of the light that passes through the window panel, or filter out about 70% of the light. Electrochromic windows can be deployed in buildings, such as commercial skyscrapers or family homes, to help save energy used in central heating or air conditioning systems. For example, the electrochromic window sheet can be tinted in warm weather to reduce the amount of light entering the room, thereby reducing the energy used to power the air conditioner in the room. For example, substrate 102 can be architectural glass on which the electrochromic device is made. Architectural glass is glass used as a building material. Architectural glass is commonly used in commercial buildings, but can also be used in residential buildings, and usually (but not necessarily) separates the indoor environment from the outdoor environment. In certain embodiments, the architectural glass is at least 20 inches by 20 inches, and can be larger, for example, up to about 72 inches by 120 inches, or up to about 72 inches by 144 inches.

[0089] In some embodiments, the electrochromic glass is integrated into an insulating glass unit (IGU). An IGU includes multiple glass panes assembled into a unit, and the intent is generally to maximize the insulating properties of the gas contained in the space formed by the unit while providing clear vision throughout the unit. Insulating glass units incorporating electrochromic glass are similar to IGUs currently known in the art, except for electrical terminals for connecting the electrochromic glass to a voltage source.

[0090] In general, the substrate and the IGU as a whole are rectangular parallelepipeds. However, in some other implementations, other shapes (e.g., circular, elliptical, triangular, curved, convex, concave) are possible and may be desirable. In some implementations, the length "L" of the substrate may be in the range of approximately 20 inches to approximately 12 feet, the width "W" of each substrate may be in the range of approximately 20 inches to approximately 12 feet, and the thickness "T" of each substrate may be in the range of approximately 1 mm to approximately 10 mm (but based on the needs of a particular user, manager, administrator, builder, architect, or owner, smaller and larger other lengths, widths, or thicknesses are possible and may be desirable). In addition, the IGU may include two window panels (not shown), or in some other implementations, the IGU may include three or more window panels. Each window panel may be a glass substrate as described above. In addition, in some implementations, one or more of the window panels themselves may be a laminated structure of two, three, or more layers or sub-window panels.

[0091] The window panels or substrates of the IGU are separated from each other by spacers to form an interior volume. Figure 1D An example of an IGU 190 is shown in which a spacer 195 is interposed between both window panes of glass 191 and between primary seal 192 and secondary seal 193, respectively. The spacer 195 in this example is a hollow metal structure with a desiccant 194 inside. In some implementations, the internal volume or void 196 is filled with argon (Ar), but in some other implementations, the internal volume or void 196 can be filled with another gas, such as another rare gas (e.g., krypton (Kr) or xenon (Xe)), another (non-rare) gas, a gas mixture (e.g., air). Filling the internal volume or void 196 with a gas such as Ar, Kr, or Xe can reduce conductive heat transfer in the IGU due to the low thermal conductivity of these gases; and improve sound insulation due to their increased atomic weight. In some other implementations, the air or other gas of the internal volume or void 196 can be evacuated. The spacer 195 generally determines the thickness of the internal volume; that is, the spacing between the substrates. In some implementations, the spacing between the substrates is in the range of approximately 0.375" to approximately 1". The width of the spacer 195 can be in the range of approximately 0.25" to approximately 1". Although shown in a cross-sectional view, the spacer 195 can be formed around all sides of the IGU (e.g., the top side, bottom side, left side, and right side of the IGU). For example, the spacer 195 can be formed of a foam or plastic material. However, in some other implementations, the spacer 195 can be formed of a metal or other conductive material, such as a metal tube structure. The first primary seal 192 adheres to and hermetically seals each of the spacer 195 and the second surface of the first window panel or window sheet. The second primary seal 192 adheres to and hermetically seals each of the spacer 195 and the first surface of the second window panel or window sheet. In some implementations, each of the primary seals 192 can be formed of an adhesive sealant, such as PIB (polyisobutylene). The moisture vapor barrier layer and the seal form a sealed gap. The material acts as a soft, sticky o-ring around the perimeter of the spacer 195 to form a seal between the spacer 195 and the glass surface. In some embodiments, the IGU also includes a secondary seal 193 that hermetically seals the border around the entire IGU outside the spacer 195. The secondary seal 193 is used for structural integrity. If filled in the gap around the entire perimeter of the IGU, the depth relative to the edge is generally about 3mm to about 9mm. They have the consistency of tar when applied and then cure and harden to a rubber-like consistency before shipping. To this end, the spacer 195 can be embedded at a certain distance relative to the edges of the first and second window panels or windows. In some embodiments, the secondary seal 193 can be formed by an adhesive sealant, such as silicone or polysulfide.

[0092] Electrochromic devices, such as Figure 1A The electrochromic device shown may have certain types of defects (sometimes shown as "halos"), notably small shorts. As used herein, the term "defect" refers to a defective point or area of ​​the electrochromic device. Typically, the defect is an electrical short or pinhole. A short is a localized conductive path across an ion-conducting layer (e.g., a conductive path between two transparent conductive layers). A halo is a relatively large, perceptible area in the device where no coloring occurs. A short prevents the area surrounding the electrochromic device from coloring, resulting in a small circle of material that cannot withstand coloring and decolorization as described above.

[0093] In addition, defects can be characterized as being visible or invisible. Generally speaking, defects in electrochromic devices and sometimes areas surrounding defects do not change optical state (e.g., color) in response to an applied potential that is sufficient to cause non-defective areas of the electrochromic device to color or otherwise change optical state. Defects tend to appear as visually discernible anomalies in electrochromic windows or other devices. Such defects are referred to herein as "visible" defects. Other defects are so small that they are not visually noticeable to an observer during normal use (e.g., such defects do not produce perceptible light spots or "pinholes" when the device is in a tinted state during daylight hours).

[0094] A short circuit is a localized conductive path across an ion-conducting layer (e.g., a conductive path between two transparent conductive layers). A short circuit may form between a second transparent conductive layer and another layer of the EC stack. For example, a short circuit may form between the second transparent conductive layer and the first transparent conductive layer. Typically, defects that cause visible shorts will have a physical size of about tens of microns, sometimes smaller, which is a relatively small defect from a visual perspective. However, these relatively small defects can produce visual anomalies in the tinted electrochromic window film, i.e., "halos" with a diameter of, for example, about 1 cm, sometimes larger.

[0095] Pinholes are areas where one or more layers of an electrochromic device are damaged or inactivated so that they cannot exhibit electrochromic changes. Pinholes are not electrical shorts, and as described above, they may be the result of reducing electrical shorts in the device. In certain embodiments, pinholes have a defect size between about 25 microns and about 300 microns, typically between about 50 microns and about 150 microns, so visually discerning the pinholes is much more difficult than halos. Typically, in order to reduce the visual perception of pinholes due to reduced halos, people limit the size of intentionally created pinholes to about 100 microns or less.

[0096] In some cases, the electrical short circuit is created by conductive particles being buried in the ionically conductive layer and / or throughout the ionically conductive layer, thereby creating an electron path between the counter electrode layer and the electrochromic layer or a transparent conductive layer associated with either.

[0097] Shorts may be inherently formed during the fabrication of electrochromic devices. As described above, in the case of a visible short, the defect appears as a central lighted area with diffuse boundaries (when the device is in the colored state), such that the device gradually darkens with distance from the center of the short. If a large number of electrical shorts (visible or not) are concentrated in a region of an electrochromic device, they may collectively affect a wide area of ​​the device, whereby the device cannot switch in such an area. This is because the potential difference between the EC layer and the CE layer in such an area cannot reach the threshold level required to drive ions through the ion-conducting layer.

[0098] Visible shorts can create halos when the device is darkened. Halos are areas in the device where an electrical short on the electrochromic stack causes the area around the short to drain current into the short and therefore the area around the short does not darken. As mentioned, these areas can be up to about 1 cm in diameter and therefore present a problem of making the electrochromic window sheet unsightly to the observer when tinted. This defeats the purpose of having a window sheet that can operate in a tinted mode. Halos can also form around the edges of the busbars when multiple micro-shorts occur between the busbars and the bottom TCO. The busbars can be the source of the shorts, so that the micro-shorts together form a large defect below the busbars. The defect then causes halos to form around the edges of the busbars.

[0099] Since the electrochromic device does not work at the short circuit, the material remains transparent, thereby forming a halo when the rest of the electrochromic device is colored. Historically, halos often appear in the visible area of ​​the electrochromic window. The visible area can be defined as the area in the electrochromic window where light may pass. In some embodiments, the visible area can be within the perimeter of the IGU or other "window" arrangement in which an opaque spacer or frame element is positioned. Improvements in device design and manufacturing technology pioneered by View, Inc. of Milpitas, CA have greatly reduced this problem. However, some new EC technologies may produce halos at or near the location where the top bus bar exists. Although the spacers used in the IGU can normally cover the area in the window where the top bus bar is applied, the halo may extend beyond the inner edge of the spacer position and be visible to the user. Without being limited by a particular theory, it is believed that the migration of the busbar material into the underlying electrochromic device will cause a short circuit, thereby producing an effect that radiates the uncolored area into the visible area. One form of this migration is busbar material, such as silver-based liquid ink, filling cracks and depressions within the electrochromic device, creating a short circuit situation. The width of such cracks and depressions can be in the size range of about 5μm to about 100μm, and they can extend partially into the electrochromic device, or in some embodiments, extend down to the first TCO layer. In some embodiments, these depressions are caused by foreign debris that contaminates the edge of the glass before the EC coating is applied and then moves away over time. Short circuits or potential defects can be reduced by operations to reduce short circuits as described herein. In some embodiments, potential short circuits are potential defects reduced by the manufacturing methods in the disclosed embodiments.

[0100] Some observations indicate that the top TCO 115 may have small pinholes with a diameter of less than about 100 μm. The process used to deposit the top TCO during electrochromic device fabrication may cause the formation of such cracks or defects. Defects tend to show up as visually discernible anomalies in the electrochromic window or other device. Such defects are referred to herein as "visible" defects. Other defects are so small that they are not visually noticeable to an observer during normal use (e.g., such defects do not produce noticeable spots of light or "pinholes" when the device is in a tinted state during daylight hours).

[0101] Pinholes occur where one or more layers of an electrochromic device are missing or damaged such that it cannot exhibit electrochromism. Alternatively or in addition, intrinsic TCO properties resulting from its composition or morphology may cause such defects. In some electrochromic devices where haloing was observed, silver was found in cracks or defects in the top TCO, and cross-sections of these defects showed that silver was not only accumulated in these cracks, but also may be embedded near the glass substrate, indicating that the silver may have migrated toward the bottom TCO, thereby attacking portions of the EC stack and the bottom TCO.

[0102] Figure 2 is a diagram showing an example of a cross section of the electrochromic device 100 in which halo is observed. Figure 2 In the example of, the electrochromic device 100 is made with multiple layers, such as Figure 1A Those shown, where the silver ink bus bar 1 is applied on the second TCO 130 and above the activated device area of ​​the electrochromic device 100, that is, the area (from a top view or plan view perspective) or area (the volume of the aforementioned area) that actively switches. The expanded portion of the figure shows the problem overcome by certain disclosed embodiments. The expanded portion shows the accumulation of silver 155 on the top of the second TCO 130. The layer surrounding the silver 155 is provided to facilitate imaging and is not part of the device 100. The silver 155 has migrated to the extent that the second TCO 130 is fully eroded at the interface with the EC stack 125. Similarly, the EC stack 125 has been eroded where the silver 155 accumulates, and the first TCO 115 has been partially eroded at the top surface. In normal operation, the unwanted physical connection between the second TCO 130, the silver 155 and the first TCO 115 may form an electrical short circuit. These short circuit problems can cause the formation of halos. The bus bars are conventionally deposited using liquid-based inks, such as silver ink. Without being bound by a particular theory, it is believed that the silver or other conductive bus bar material migrates through defects or cracks in the second TCO 130 and through the EC stack 125, thereby corroding or even etching the bottom TCO 115. The bus bar conductive material may penetrate the second TCO 130 due to electromigration. Electromigration is the transport of materials caused by the gradual movement of ions in a conductor due to momentum transfer between conductive electrons and diffusing metal atoms. Regardless of the actual mechanism, the conductive material may corrode and / or migrate into certain activated device areas under the bus bar, causing an electrical short.

[0103] Some electrochromic devices avoid these short circuit problems by deactivating materials that would otherwise be active electrochromic device materials under the top bus bar, or excluding the activated electrochromic device under the top bus bar. For example, the area under the top bus bar may be free of electrochromic layers and / or counter electrode layers. Alternatively, in some cases, the electrochromic device is made so that the first TCO and optionally the diffusion barrier layer in the area directly below the top bus bar are removed before the EC stack and the top TCO are coated. In another approach, the manufacturing process applies a scribe to the bottom TCO before coating. This electrically isolates the lower TCO in the upper bus bar area and prevents the negative effects of the short circuit from affecting the upper bus bar. Regardless of how deactivation is achieved, the electrochromic device under the top bus bar will not be subjected to coloring. This is beneficial, but requires knowledge of the expected location of the bus bars before depositing the EC stack. Only with this knowledge can the process be customized to exclude or remove the first TCO or EC layer under the top bus bar. These methods are referred to as "pre-patterning" methods because the pattern of the bus bars is known before the electrochromic device is made. This is good for some applications, but not for applications where the manufacturer needs to retain flexibility in the location of the optically switchable windows made on large sheets or rolls of coated electrochromic glass. Some patterning methods are described in U.S. Patent Application No. 14 / 362,863, filed on June 4, 2014, entitled "THIN-FILM DEVICES AND FABRICATION," which is incorporated herein by reference in its entirety.

[0104] Patterning is defined as a process used to change, modify, manipulate, deposit material on, remove material from, or otherwise define and / or define areas of an electrochromic device. Patterning can be performed in conjunction with determining the dimensions of an electrochromic device or window sheet (sometimes referred to as a "window sheet") to be cut in subsequent processing. Patterning includes locally modifying an overall deposited EC device, which can include any one or more of the following: (1) applying bus bars, (2) locally removing material, (3) locally deactivating areas of an electrochromic device, (4) locally reducing shorts, and (5) locally activating areas of an electrochromic device while deactivating other areas.

[0105] Other methods for avoiding this problem involve depositing the bottom TCO on the substrate; moving the substrate from the deposition chamber to a separate patterning chamber to pattern the bottom TCO so as to remove the portion of the bottom TCO where the busbars will be applied; and moving the substrate with the patterned bottom TCO back into the deposition apparatus to continue coating the rest of the apparatus. However, these methods use breaks in the deposition apparatus, thereby reducing throughput and increasing processing complexity. These methods also require that the glass be patterned in advance, so they lose considerable flexibility.

[0106] Some of the fabrication techniques are referred to as "cut before coating" techniques because the glass substrate is cut to a predetermined size prior to coating. Unfortunately, coating equipment, which is typically sputtering equipment, may not be optimized for all glass sizes, and processes that employ only large glass substrates of a single size are used to improve processing. Various embodiments disclosed herein allow EC stacks to be fabricated on large glass substrates and bus bar patterns to be subsequently defined for windows or other structures of any size and shape, whether large or slightly smaller. Certain embodiments relate to "coat first, ship then cut," where electrochromic devices are coated on large sheets in one facility, which are packaged and shipped to another facility for post-processing and / or patterning.

[0107] Some conventional electrochromic device fabrication techniques employ glass substrates pre-coated with a bottom TCO layer and optionally a diffusion layer. Such substrates limit design and fabrication flexibility by limiting the chemistry of the bottom TCO to that of the layer as deposited by the manufacturer. Various embodiments disclosed herein allow EC stacks to be fabricated with TCO layers selected by and / or deposited by the electrochromic device manufacturer.

[0108] Provided herein is a method for reducing defects below the top bus bar in the production of an electrochromic device. Some of the production methods described herein form EC coatings that do not require pre-patterning and do not need to be troubled by the problem of short circuits below the bus bar. In these methods, no matter where the top bus bar may be applied after coating, the resulting electrochromic device will not form a short circuit. In certain embodiments, the bus bar can be applied to any position on the entire electrochromic device during post-patterning. Post-patterning is defined as a process performed after the layers of the electrochromic device are deposited. In various embodiments, post-patterning is the first time to define the boundaries of the electrochromic device or window and apply the bus bar. It may be the first time that local processing occurs, such as when heating is applied in a local area where the bus bar is applied or to be applied. The coating equipment may only allow processes that affect the entire area or almost the entire area of ​​the substrate. In some embodiments, post-patterning includes determining where the bus bar will be applied. Post-patterning can be performed by a dealer at a location different from the location where the electrochromic device is coated. The method described herein also provides flexibility for the manufacturing process. That is, in some embodiments, one facility may make an electrochromic stack on a glass substrate without pre-patterning, the substrate with the EC stack may be shipped to a second facility, and post-processing and / or post-patterning may be performed in the second facility. Post-processing operations may include applying bus bars, cutting, laminating, and / or making IGUs (an IGU may have a laminate as its inner and / or outer panes, and the laminate may be used as glazing in place of an IGU).

[0109] Post-patterning operations may also include deactivating areas of the electrochromic device, such as by sensitizing the stack via: performing treatments such as applying heat, irradiation, applying chemicals or compositions, and combinations thereof. Deactivation may be performed before or after applying one or more bus bars. In some embodiments, post-patterning includes performing short circuit reduction operations such as preventing short circuits or removing short circuits by applying bus bars made of a material that resists electromigration, or performing other operations described herein. Other examples of short circuit reduction operations that may be performed in post-patterning include depositing an insulating cap layer on the second TCO before applying the bus bars on the second TCO.

[0110] In some embodiments, the deactivation or reduction is performed after the electrochromic device is made. The deactivation method or reduction method can be performed after the IGU is made, without performing the deactivation or reduction operation during the IGU production. In this type of method, conventional chemical processes and techniques can be used to apply the cover coating to the electrochromic device, and conventional techniques can be used to make the IGU before deactivating the area where the bus bar is applied. For example, in some embodiments, the IGU produced can be treated with a laser to deactivate the area of ​​the IGU where the bus bar is applied. In some embodiments, these processes can be performed before or after the bus bar is applied.

[0111] In certain methods described herein, layers of an electrochromic device coating are first deposited in, for example, a vacuum integrated reactor, the coating comprising a bottom TCO, an EC stack (comprising an EC layer, an optional IC layer, and a CE layer), and a top TCO. Subsequently, in some embodiments, the substrate is cut into smaller windows during post-patterning. Regardless of whether the substrate is subsequently cut, bus bars and co-located device features as described herein can be formed after the coating is applied. As used herein, the term "position" or "region" is defined as an area on an electrochromic device, and may refer to any one or more of the electrochromic device layers in the area. They can be defined by the area of ​​a feature on the electrochromic device, such as a bus bar, and in such cases, they include not only the portion of the electrochromic device that is directly below the feature, but also the portion that extends from the perimeter for a distance, such as on the order of a few millimeters, for example, up to about 5 mm or 10 mm, but typically between about 0.5 mm and about 5 mm, or between about 0.5 mm and about 2 mm, or between about 0.5 mm and about 1 mm, or between about 0.1 mm and about 3 mm, or between about 0.1 mm and about 2 mm, or between about 0.1 mm and about 1 mm. The location where the top bus bar is applied is a location that can be specified during post-patterning, and the electrochromic device layer below this location can be specified as the area where the top bus bar will be applied; that is, the area below or in line with the top bus bar. In the following discussion, the phrase "below the bus bar" or "below the top bus bar" can be used to refer to such a location.

[0112] The methods disclosed herein provide the flexibility of coating first and applying the busbars later and may be referred to as a "coat first, cut later" technique. Certain methods described herein may be performed so that coated glass may be manufactured in large quantities at one location and patterned at different locations, possibly by different entities, such as an end user or a downstream glass supplier. Certain aspects of coating first and cutting later are described in U.S. Patent Application No. 13 / 456,056, filed on April 25, 2012 and entitled "ELECTROCHROMIC WINDOWFABRICATION METHODS," which is incorporated herein by reference in its entirety.

[0113] Many of the processes provided in the present disclosure fall into one of two general categories: (1) processes for deactivating an electrochromic device in a region below where a top bus bar is to be or has been applied; and (2) processes for preventing shorts in an electrochromic device while maintaining activation of the electrochromic device below the top bus bar. Falling into the first category are processes that produce devices that are partially deactivated, but to some extent, sometimes tinted and detinted in a manner that is not noticeable to an occupant. For example, a method may deactivate an area of ​​a device by reducing the conductivity of the lower TCO below the top bus bar, but otherwise leaving the EC stack unchanged. If the deactivated region of the lower TCO is thin enough, then the device stack atop the region may be tinted or detinted when exposed to a sufficiently large potential from the lower TCO surrounding the deactivated region. As explained below, in the second category, methods for preventing shorts without pre-patterning include device-based solutions, material-based solutions, and process-based solutions.

[0114] Deactivation device under busbar

[0115] Certain embodiments of reducing short circuits in electrochromic devices involve a process of deactivating locations in the region below the top bus bar in the electrochromic device. This deactivation can be performed on any one or more of the layers below the top bus bar except the top TCO, since the top TCO is used to promote the coloring and decoloring of the electrochromic device when an electric potential is applied. The deactivation methods described herein can allow post-patterning so that the coating on the electrochromic device can be made without determining where the top bus bar will be applied on the electrochromic device.

[0116] Once deactivated, the deactivated portion may not undergo coloration. Therefore, when a voltage is applied to the electrochromic device, the deactivated area will be transparent. It should be noted that in some embodiments, the area very close to the deactivated area may still be colored when a potential is applied. The deactivated area will not form a short circuit, thereby eliminating the formation of halos. In some embodiments, the deactivated area will not be visible to the user because the area where the busbar is applied is masked by a spacer on the window or IGU.

[0117] The deactivation method can be performed during and / or after deposition of the layers of the electrochromic device. In some embodiments, deactivation is performed during post-patterning, which includes applying bus bars and cutting the electrochromic device into smaller units after the EC device is fully fabricated.

[0118] In some embodiments, the method is performed during deposition so that the treatment is applied to the entire portion and the subsequent deactivation step is applied to a local portion of the electrochromic device during post-patterning. For example, in some embodiments, the area below the bus bar in the electrochromic device can be exposed to a flash lamp anneal (FLA), which uses a pulse of high-energy light to rapidly anneal the surface of the substrate and any coating on the substrate. This annealing method is different from conventional oven annealing, which heats the entire substrate. In some embodiments, a mask can be used on the area to be kept deactivated to prevent such area from being exposed to a flash lamp. In certain embodiments, a laser can be used to achieve the same or similar results.

[0119] Some of the deactivation mechanisms will be described. The corresponding techniques for inducing these mechanisms will be described later.

[0120] Deactivate the device

[0121] The area of ​​the device can be deactivated by "poisoning" the area, or destroying the area using a mechanical, optical or thermal process. Poisoning is defined as chemically treating the layer of the electrochromic device or chemically modifying the layer, thereby rendering the device inoperable or inactivated. In some embodiments, poisoning the area of ​​the electrochromic device involves reacting or diffusing one or more chemicals to deactivate the area. For example, poisoning can be performed when applying the upper bus bar. In some embodiments, the poisoning method does not interfere with the deposition technology used to deposit the TCO layer or EC stack. Instead, poisoning is performed after the electrochromic device is made. The electrochromic device can also be made using conventional techniques in such cases. In some embodiments, the electrochromic device can be made in the following special way: prepare one or more layers of the electrochromic device so that they can be poisoned in a later step, such as post-patterning. It should be noted that such preparation techniques are applied during the coating process, and since many coating tools cannot locally change the coating conditions with sufficient accuracy to affect only the small area where the bus bar will be applied, the process of preparing the layer to poison the entire electrochromic device as a whole will be applied. Poisoning is performed later, typically during post-patterning only where the bus bars will be applied.

[0122] In some embodiments, the electrochromic device includes one or more layers that are inactivated when formed, but are activated during subsequent post-patterning at locations where the top bus bar is not or will not be applied to the electrochromic device. In some embodiments, an electrochromic device without an ion conductive layer is made so that an ion conductive layer can be inherently formed when an area other than below the bus bar is activated. In one example, the device layer is deposited as an electrochromic device precursor. Electrochromic device precursors are described in U.S. Patent No. 8,300,298, entitled "ELECTROCHROMIC DEVICES," issued on October 30, 2012, which is incorporated herein by reference for all purposes. Such electrochromic device precursors include layers and materials that form functional electrochromic devices when an appropriate driving force is applied. In one example, the electrochromic device precursor is heated to form an ion conductive electrical insulating layer in situ between the electrochromic layer and the counter electrode layer. This technique uses a superstoichiometric oxygenated electrode material that can be electrically insulating in itself, but the device precursor is not a functional electrochromic device. When heat is applied, for example, at the interface between adjacent electrode layers, an ion-conducting electronic insulating material is formed. Therefore, by selectively applying a driving force, such as heat, to the device precursor stack, a functional electrochromic device is formed, except for the location where the top transparent conductor bus bar will be made. For example, an IR heating element or a thermal probe can be used on the entire electrochromic device precursor, such as by using an XY plotter system, where the user can enter the coordinates of the device layout and apply heat in an area outside the location where the top transparent conductor layer bus bar will be applied. In some embodiments, heat can be applied to a temperature greater than about 500°C within a few milliseconds. In another example, flash lamp annealing can be used to anneal the coating on the surface of the substrate without fully heating the substrate to activate the area outside the bus bar. The resulting device may be functionally the same as the following: in the area where the top TCO bus bar will pass or the existing top TCO bus bar, the activated electrochromic device is selectively deactivated. Thus, discussion herein of selectively deactivating regions beneath bus bars may be viewed in the appropriate context as producing electrochromic devices equivalent to those produced by selectively activating regions other than the region on the top transparent conductor where the bus bars are or will be made.

[0123] In some embodiments, the electrochromic device may be substantially deactivated. Substantially deactivating an electrochromic device generally results in a reduction or elimination of the electrochromic function or capability of the device to such an extent that upon application of an electrical potential sufficient to change the state of a functional electrochromic device, substantially deactivated regions of the device do not change optical state. Electrochromic capability is the ability of a device or material to respond to changes in an applied electrical potential by changing an optical property, such as color or degree of tint.

[0124] As examples, a layer or device can be deactivated by disrupting or inhibiting: (1) the mechanical properties of the device, (2) the ionic and / or electrical conductivity of the device, or (3) the electrochromic functionality of the device.

[0125] The mechanical properties of the area in the electrochromic device where the busbar is to be applied can be degraded or destroyed by physically preventing the area of ​​the electrochromic device from functioning. Examples of mechanical methods include applying pressure or grinding the area. In this mechanism, the structure below the busbar in the electrochromic device is destroyed. If the area on the bottom TCO below the busbar is mechanically degraded, even in the case of silver migration from the top busbar toward the bottom TCO, no short circuit will be formed. In some embodiments, mechanical degradation is performed locally so that pressure is applied in a direction perpendicular to the device layer or the pressure is applied by shearing action or grinding to inactivate the device in a local area. In some embodiments, the properties of the top TCO can be tailored to be suitable for mechanical stress, that is, when the underlying layer is broken or otherwise degraded, the top TCO will not be so. Examples can include the use of pyrolytic FTO, which is much harder than the underlying electrochromic device; or a very flexible top TCO, while the underlying EC stack remains brittle or compressive. In other embodiments, mechanical degradation is performed by selective absorption of light or heat energy by the device layer below the upper TCO. For example, a device layer may absorb laser or other energy of a specific wavelength, and / or such energy may be selectively focused in one or more of the underlying layers and not in the top TCO. In some implementations, mechanical degradation is performed by selectively heating the EC stack layers without degrading the upper TCO, which should be preserved in order to transfer the electrical potential and current from the upper bus bar to the entire surface of the device.

[0126] In one embodiment, an alternating current is applied or induced in a localized region of the device to deactivate the device below the bus bar. Inductive coupling can be used selectively in a region of the device. For example, a TCO can be inductively coupled to receive an alternating current and provide heating in the region to deactivate the EC stack therebetween. A magnetic field can be applied in a localized region to enhance the inductive effect. Inductive coupling can be achieved locally / selectively using a probe approaching the coating on one or both sides of the substrate where the coating is located. This can be done in a high throughput manner.

[0127] Various mechanisms may limit or reduce the ions and / or conductivity of the area where the busbar is to be applied in the electrochromic device. In some embodiments, the conductivity can be suppressed by chemically reacting a conductive material, such as a bottom TCO material, to produce a material with a sufficiently high resistance that poisons the electrochromic device. Examples of mechanisms and materials for chemically modifying conductive materials include oxidation, halogenation, ozonation, hydration (applying water, such as steam, optionally followed by dehydration (drying) of the area to remove unwanted or excess moisture), and the like. For example, an electrochromic device can be locally deactivated by replacing the fluorine in the TCO with oxygen. In another example, different halides, such as chlorides, bromides, or iodides can be used to replace the fluoride in a tin fluoride-based TCO. The replacement of fluorine can be performed by depositing an oxygen-containing layer, such as a titanium oxide layer, which is used as an oxygen source to diffuse into the TCO when thermally activated, thereby locally deactivating the position on the electrochromic device. Halogenation other than fluoride (or over-fluorination for killing activity) can be performed under appropriate conditions with a halogen gas or compound that is a halide source (for example, phosgene is a powerful chlorinating agent). In some embodiments, the high oxygen content layer at the glass-TCO interface can be treated to locally inactivate the location on the electrochromic device. In some embodiments, a high concentration of oxygen is provided in the bottom TCO to poison the bottom TCO by suppressing its conductivity. Local poisoning (below the top bus bar) by high oxygen (or other contaminants or oxygen sources, such as perchlorates, ozone, phosphates, sulfonates, etc.) concentration can be performed by transferring oxygen from a source outside the EC stack—usually during post-patterning—or from within the EC stack, followed by local activation to increase the oxygen concentration below the top bus bar. Various oxygen sources or donors can be used. In some embodiments, oxygen is provided by the underlying substrate itself or a layer formed during coating. In one example, the bottom TCO includes a fluorinated tin oxide material that is locally altered during post-processing after thermal treatment to increase oxygen concentration in a region of the electrochromic device, thereby inhibiting conductivity. The oxygen source includes layers of the device itself (whether provided by its native composition or by an oxygen-enriched form produced by providing excess oxygen during deposition), bus bar materials, or other sources.

[0128] Oxygen can reduce conductivity by various mechanisms. In one case, oxygen forms a passivation layer on or within the lower TCO. In some embodiments, the passivation layer can be on a different layer of the electrochromic device. The passivation layer can be produced by a reaction between the TCO material and some external material, such as a bus bar material. In some cases, TCO conductivity is reduced by internal chemical or morphological modifications (e.g., reduced crystallinity or more grain boundaries) caused by changing substrate temperature or other processes.

[0129] Embodiments where high concentrations of oxygen deactivate the bottom TCO by reducing conductivity can be practiced in conjunction with the local post-treatment methods described below. For example, during processing of a fabricated electrochromic device, high concentrations of oxygen are provided in locations where bus bars have been or will be applied by performing the local post-treatment methods described below.

[0130] In various embodiments, the source of 'poisons' such as oxygen and sodium comes from some layers within the EC stack and / or the substrate itself. For example, the WB layer used in the EC stack is superstoichiometric, with a chemical formula of about WO 3.3 Without being bound by a particular theory, it is believed that excess oxygen is present within the structure and is not limited to W atoms. It is possible to use a laser to "activate" this excess oxygen to poison the electrochromic device in a localized portion so that the electrochromic device under the area where the top bus bar will be applied has about WO 2.8 To a composition below about WO 3. A similar process can be used to change the stoichiometry of sodium or other alkali metals present in a sodium-lime glass substrate to deactivate the bottom TCO or reduce its conductivity.

[0131] The electrochromic activity of a region of an electrochromic device can be suppressed or eliminated by reacting interstitial oxygen in the tungsten oxide matrix of the EC stack to produce an oxygen-rich form of tungsten oxide that is not electrochromically active and thereby inactivates the electrochromic device. For example, an electrochromic tungsten oxide can have a substoichiometric formula of WO 2.8 , while WO3 is non-electrochromic. This reaction can be performed in conjunction with post-treatment so that the location in the electrochromic device where the top bus bar will be applied is exposed to excess oxygen and locally heated. In some embodiments, local heating of the electrochromic device in the zone is sufficient to convert the electrochromic tungsten oxide in the zone into non-electrochromic WO3 to inhibit or eliminate electrochromic activity without exposing the device to excess oxygen.

[0132] In some embodiments, the lithiation of one or more layers of the electrochromic device is altered or modified in the location, thereby inhibiting the conductivity of the electrochromic device. For example, lithium can be consumed to deactivate the area under the bus bar, or a structure can be formed in a location during post-patterning so that the structure cannot support lithium transport, such as a thicker IC layer formed by local chemical modification in the area.

[0133] Deactivation method

[0134] This section describes methods for locally deactivating an electrochromic device below the top bus bar. These methods may cause any one or more of the results described above (e.g., mechanical damage, reduced TCO conductivity, or loss of electrochromic function). In various embodiments, the deactivation method is completed during coating to form the electrochromic device and / or during post-coating processing. Figure 3 is a flow chart showing a method of making an electrochromic device, wherein the method includes deactivating a region below a top bus bar. In operation 302, a first TCO layer or bottom TCO is deposited on a glass substrate. In some embodiments, a substrate is provided on which a bottom TCO layer has been deposited. For example, float glass is sometimes provided with a thin layer of fluorinated tin oxide, sometimes referred to as an FTO layer. In operation 304, an EC stack is deposited on the bottom TCO layer. The EC stack may include the above-described Figures 1A-1C The layers described herein. Variations of the stack fabrication process may be employed, such as described in U.S. Patent Application No. 13 / 763,505 filed on February 8, 2013, which is incorporated herein by reference in its entirety. In operation 308, a second TCO layer or top TCO may be deposited on the EC stack. Performing operations 302, 304, and 308 forms an electrochromic device, and such coatings may be performed in a single apparatus.

[0135] In some embodiments, during operations 302, 304, or both, a material may be delivered to a partially fabricated electrochromic device, which may sensitize the layer before local deactivation is achieved in a subsequent operation, such as a post-patterning operation. Additionally or alternatively, a partially fabricated electrochromic device may be treated to sensitize one or more layers. Regardless of the sensitization mode, the entire surface of the device is typically treated because sensitization typically occurs in an electrochromic device fabrication facility where a majority of the substrate is coated by sputtering or other processes. The term "sensitization" is typically used to describe a process in which some or all of the electrochromic device is susceptible to deactivation during post-processing after a stimulus is applied locally, such as delivering a chemical or other material to the electrochromic device, applying radiation or heat, laser energy, and applying force. In some implementations, the sensitization operation is performed during a coating operation, which may coat all or nearly all of the areas on the substrate. In such implementations, the sensitization operation may affect areas of the electrochromic device other than those near the busbars, where post-processing modifications may occur. Post-treatment may deactivate or otherwise modify the sensitized electrochromic device in only the region below the bus bar. Thus, sensitization represents one stage in a two-stage process in which sensitization occurs globally and a local post-treatment deactivation step converts the sensitized device into a locally deactivated device. Examples of sensitization processes include depositing a layer containing a poison precursor or encapsulating a poison; exposing the region to an oxidant, a reductant, a halide, water vapor, or other liquid or gaseous material to deactivate the region or prepare the region for deactivation; exposing the region to electromagnetic radiation, lasers, microwaves, and the like (ultrasound or hypersonic energy may also be used); and combinations thereof.

[0136] Operations 378a and 378b are sometimes referred to as post-patterning processes. In some embodiments, operation 378a may be performed before or after operation 378b. In operation 378a, one or more locations of the electrochromic device are locally deactivated. Depending on the deactivation mechanism, this local deactivation is performed on a sensitized or unsensitized electrochromic device. In many embodiments, operation 378a includes processing the device area to which the top bus bar will be applied, is being applied, or has been applied. In some embodiments, the local deactivation process is performed as a part of normal electrochromic device production. Example processing includes heating, applying radiation, mechanical treatment, chemical treatment, or any combination thereof. In operation 378b, the bus bar is applied in one or more locations. The top bus bar is applied in the location of the local deactivation in operation 378a, thereby forming a device with a bus bar, wherein the device is deactivated below the top bus bar. In some embodiments, operations 378a and 378b are performed together as a single operation. In other words, forming the top bus bar in 378b deactivates the underlying device in 378a. One example of this dual purpose operation involves applying the bus bar as a liquid containing a material that diffuses or flows to the underlying electrochromic device and locally deactivates the device there. In another example, the bus bar is applied with a mechanical pressure that locally deactivates the underlying electrochromic device. The mechanical pressure may be accompanied by heating or additional application of electromagnetic radiation and / or application of one or more poisons as described.

[0137] Local heating methods for deactivating the electrochromic device in operation 378a may include contacting a region of the electrochromic device with (1) laser irradiation or another focused incoherent radiation (such as, UV, visible light, or IR source), (2) a solid heating element, or (3) flash lamp annealing (FLA). In flash lamp annealing, a high frequency Xe lamp can, for example, anneal a film in a few microseconds, which otherwise may take several minutes in conventional methods. One advantage is that flash lamp annealing locally heats the film stack without heating the substrate. These methods can be performed before, during, or after applying the top bus bar. Local heating methods can use thermal energy to deactivate the electrochromic device. Such heating can make the heated region have a greater resistance, thereby reducing or eliminating the possibility of a short circuit forming in the region of the electrochromic device. For example, a region of the substrate can be heated to a high temperature, such as in excess of about 200°C or in excess of about 600°C.

[0138] Suitable equipment for heating electrochromic devices can be a laser scribing tool. Examples of laser scribing can be found in the following: U.S. Patent Application No. 12 / 645,111, filed on December 22, 2009, entitled "FABRICATION OF LOW DEFECTIVITY ELECTROCHROMIC DEVICES"; U.S. Patent Application No. 13 / 456,056, filed on April 25, 2012, entitled "ELECTROCHROMIC WINDOW FABRICATION METHODS"; and PCT Patent Application No. PCT / US2012 / 068817, filed on December 10, 2012, entitled "THIN-FILM DEVICES AND FABRICATION", which are incorporated herein by reference in their entirety. Flash lamps, infrared heaters, quartz lamps, induction coils, microwave generators, ultraviolet lamps, etc. may also be used.

[0139] When implementing laser modes, various elements are relevant. First, there may be differences between laser tools and scanners. Scanners are usually part of laser tools. The scanner can emit light and guide the laser beam according to the mode provided to the scanner. The scanner itself is not aware of its position relative to the workpiece at a given time. Programming codes are usually used to provide instructions that guide the laser tool to position the scanner relative to the workpiece. In various embodiments, this code is used to reposition the scanner after the mode has been executed and guide the scanner to perform the next mode, thereby ensuring that the scanner performs the next mode at the correct part of the workpiece. The scanner receives instructions (usually in the form of programming code) that define one or more modes, and the scanner will use the instructions to emit light and guide the laser beam according to the one or more modes. The laser tool receives instructions that detail where to position the scanner relative to the workpiece. These instructions can contain information about the timing and positioning of each process / component.

[0140] The one or more lasers used in the laser scribing process are typically (but not necessarily) pulsed lasers, such as diode-pumped solid-state lasers. For example, the laser scribing process can be performed using a suitable laser. Some examples of suppliers that can provide suitable lasers include IPG Photonics (Oxford, Massachusetts); Ekspla (Vilnius, Lithuania); TRUMPF (Farmington, Connecticut); SPI Lasers LLC (Santa Clara, California); Spectra-Physics (Santa Clara, California); nLIGHT (Vancouver, Washington); and Fianium (Eugene, Oregon).

[0141] Exemplary electromagnetic radiation includes UV, laser, and the like. The laser wavelength can vary, such as from about 532 nm to about 10 μm, or from about 1064 nm to about 10 μm. The wavelength used for heating is different from the wavelength used when removing material from the substrate. The laser irradiation is delivered to the substrate using, for example, an optical fiber or an open optical path. Heating can be performed from the substrate side or the EC film side, depending on the choice of substrate processing equipment and configuration parameters. The energy density required to heat the film can be achieved by passing the laser beam through an optical lens. The lens focuses the laser beam to heat a specific area on the substrate according to the desired shape and size. In one embodiment, a "flat top" beam configuration is used, which, for example, has a wavelength between about 0.005 mm 2 To about 2mm 2 In one embodiment, the focusing level of the beam is used to achieve the desired energy density to heat the EC film stack. In one embodiment, the energy density used in heating is between about 2 J / cm 2 About 6J / cm 2 between.

[0142] In some embodiments, the substrate can receive local irradiation in one or more positions on the electrochromic device, typically below the top bus bar, so that the light can deactivate the electrochromic device. Local irradiation can be delivered by a laser with an appropriate wavelength, such as a UV, visible light or IR laser. Non-laser sources such as incandescent lamps or arc lamps can be used together with focusing elements to deliver radiation to the precise position of the device. In another example, a positive or negative mask is used during post-patterning, and then the exposed area is irradiated by a laser or UV source. The exposed area can be a position where a bus bar will be applied, or a position where a bus bar will not be applied (for example, the electrochromic device will be active). Various deactivation mechanisms can occur after local exposure to radiation. In one example, UV radiation decomposes the cross-linked polymer present in the electrochromic device and / or deactivates or destroys the chromophore responsible for the electrochromic activity in the device.

[0143] Another technique for locally deactivating an electrochromic device involves chemical post-treatment of one or more locations on the electrochromic device. Chemicals may be delivered locally during post-treatment, or delivered as a whole during electrochromic device fabrication in a coating device (as a precursor or contained material). In some embodiments, chemical post-treatment includes applying a busbar using a material that inactivates the contact area when in contact with the EC stack or bottom TCO. In some embodiments, the chemical may be delivered via a medium other than the busbar. Examples include applying chemicals directly via spraying liquids; screen printing; bubble jet printing; applying gaseous chemicals such as those in contact with the electrochromic device coating and forming a temporary closed volume via a local nozzle or manifold or plenum. The closed volume is filled with gaseous chemicals, and then evacuated or rinsed after achieving appropriate exposure. After this or in order to discharge the volume, the manifold or plenum may be removed from the device. In some embodiments, post-treatment is performed on a stack of materials deposited as a whole during electrochromic device coating, such as in operation 302 or 304. For example, a sodium-based paste is deposited and then treated in the area where the busbars will be deposited so that the sodium contacts the area of ​​the device and inactivates it. Other examples of post-deposition chemical poisons include halogenating agents, sulfates, oxides, peroxides, phosphates, water, sulfides, hydroxides, amines, hydrazines, ammonia, acids, and bases. It is known that tungsten oxide expands significantly when hydrated or otherwise reacts with water-based materials, so in embodiments where deactivation is achieved by this means, the stoichiometry of the applied material should be carefully considered. For example, if water vapor is used, the transfer mechanism is precise, otherwise the expansion will not only destroy the activity of the electrochromic device, but also the top TCO. In some implementations, the overall sensitized device is locally treated with a laser to release chemicals or convert their precursors into "poisons". These "poison" methods can suppress the conductivity of the electrochromic device as described above in some implementations.

[0144] In some implementations, a combination of the post-treatment and / or coating methods described above can be used to deactivate regions of an electrochromic device. For example, a chemical "poison" or precursor can be applied overall before or during coating of the electrochromic device, while a thermal post-treatment can be applied selectively at the location of the busbars after coating and before the busbars are applied. In this example, a combination of heating and chemical poisoning is used to deactivate the device.

[0145] Inactivation Example 1

[0146] Electrochromic devices can be made by exposing the bottom TCO or another layer of the EC stack to a chemical "poison", such as oxygen, when depositing the layer. For example, a sensitized bottom TCO can be made by exposing a glass substrate to a reactant to form fluorinated tin oxide or indium tin oxide while intermittently exposing the substrate to, for example, multiple doses of excess oxygen or ozone. During post-patterning, a common stimulus, such as heat generated by laser irradiation, can be applied to one or more locations to deactivate the electrochromic device in the one or more locations. In this example, the combination of the presence of a high concentration of oxygen and heating in a region of the electrochromic device deactivates the device. Although an oxygen dose may have been applied to the entire electrochromic device as a whole during fabrication (coating), only the region where the common stimulus is applied is deactivated.

[0147] Inactivation Example 2

[0148] A glass substrate is provided to a processing device, wherein a bottom TCO is deposited on the glass substrate. In some embodiments, the bottom TCO material is fluorinated tin oxide or indium tin oxide. After the bottom TCO is deposited, the bottom TCO can be exposed to a sodium compound to sensitize the surface of the substrate. Subsequently, an EC stack is made on the sodium-containing layer. For example, tungsten oxide can be formed on the sodium-containing layer. The top TCO is then deposited to form an electrochromic device. During post-patterning, the device is heated to a temperature of up to, for example, 800° C. with a laser to locally deactivate the area where the busbar is to be applied, activating the sodium compound, thereby poisoning the fluorinated tin oxide and deactivating the area. In some instances, exposing the area to a laser may also penetrate the sodium diffusion barrier to further poison the fluorinated tin oxide. Local heat is used to set conditions so that the amount of sodium from the glass substrate can penetrate the barrier between the glass substrate and the first TCO and enter the electrochromic device to deactivate the electrochromic device.

[0149] Inactivation Example 3

[0150] The electrochromic device can be made by exposing the bottom TCO or another layer of the EC stack to a light or heat source, such as a laser or UV, while the layer is being deposited. For example, a sensitized bottom TCO can be made by exposing a glass substrate to a reactant to form fluorinated tin oxide while intermittently exposing the substrate to multiple doses of UV exposure. After the rest of the electrochromic device is made, one or more locations on the electrochromic device can be determined as where the busbars will be applied. During post-patterning, a common stimulus, such as a chemical poison, can then be applied to the one or more locations to deactivate the electrochromic device in the one or more locations.

[0151] Inactivation Example 4

[0152] The electrochromic device coating can be made on a large glass sheet as usual, for example without pre-patterning. The glass coated with the electrochromic device can be post-processed at the same facility, or transported to another facility for post-processing. Before or after cutting the electrochromic window from the large sheet, one or more layers in the coating below the top TCO are deactivated by selectively applying electromagnetic radiation to the area where the top bus bar is to be applied. For example, laser irradiation selectively deactivates one or more underlying layers in the selected area. Post-processing can also include laser edge removal, (lower) bus bar pad exposure and laser isolation scribing (if permitted) - these further post-processing steps can be performed individually or collectively before or after cutting the window from the mother sheet.

[0153] Activation device under the bus bar

[0154] This section describes methods for making electrochromic devices that reduce local shorts between the top bus bar and the bottom TCO without deactivating the electrochromic device below the top bus bar. Associated devices are also described. In these methods, the device area below the top bus bar can be subjected to coloring without producing the problematic halo described above. The operation of reducing shorts can be used to prevent the formation of shorts and / or eliminate or reduce the negative effects of existing shorts. In various embodiments, the method can be performed in a coating-before-cutting procedure, so some or all of the production is performed before taking the steps required to specify the bus bar position. Therefore, after coating, the bus bar position can be first defined during the post-patterning stage. The process provides the flexibility to position the bus bar on any window and to position it anywhere within a given device (including in the visible or internal area of ​​the device, such as the middle area of ​​the window). Figure 4AAn example of a top view of an electrochromic device with busbar 1 placed in the interior of a viewable area of ​​a window unit 400 is shown. Busbar 1 is applied to the top TCO layer 475 in the interior area of ​​the device, and busbar 2 is applied to the bottom TCO 440. In some embodiments, it may be desirable to place the busbars in the interior area of ​​the window to facilitate faster, more efficient and / or more uniform optical switching. Where the busbars are placed in the interior area, the busbars may preferably be transparent and / or extremely thin, such as having a width of about 0.5 mm to about 2 mm and a thickness in microns. In some embodiments, the busbars may be transparent. Transparent busbars are further described in PCT International Patent Application No. PCT / US2014 / 72362, entitled “OBSCURING BUS BARS INELECTROCHROMIC GLASS STRUCTURES,” filed on December 24, 2014, which is incorporated herein by reference in its entirety. The bus bars may be placed anywhere from out of sight beneath the septum to the visible or interior area of ​​the electrochromic window.

[0155] Methods for reducing shorts in electrochromic devices tinted below the top busbar can be accomplished by any one or more of at least three categories of processes: (1) modifying the deposition of the top busbar to reduce the physical propensity for electromigration or other short formation mechanisms; (2) restoring the short as it is formed, or shortly after it is formed, or "self-healing" techniques as described herein; and (3) filling or blocking cracks in the top TCO that would otherwise become a path for the short to form. It should be noted that in addition to cracks in the top TCO, the conductive busbar material may also contact the bottom TCO through depressions, or missing segments in the EC film stack caused by, for example, foreign particles on the substrate. These foreign particles may land on the substrate or become incorporated into the substrate during the coating process.

[0156] Busbar design and application

[0157] This section presents examples of bus bar designs that reduce or eliminate shorts due to electromigration or related phenomena where conductive material from the bus bar leaves the bus bar and passes through the upper TCO to ultimately contact the lower TCO. Figure 2and the associated description. Examples of suitable designs include those in which the bus bar material is not susceptible to electromigration during normal operation; the bus bar conductive material is provided in a vehicle or substrate that prevents it from entering defects or cracks in the underlying TCO or EC stack; and / or the bus bar has sufficiently viscous properties to be substantially solid, so that the bus bar cannot fill cracks or depressions in areas of the bus bar. In embodiments in which the bus bar structure is modified as described herein, pinholes or cracks may still exist in the top TCO, but the bus bar material does not migrate into the pinholes or cracks of the top TCO, thereby reducing the formation of shorts.

[0158] Figure 4B 4 is a flow chart of general operations that can be employed to make an electrochromic device with a modified top bus bar. In operation 402, a bottom TCO is first deposited on a substrate. In operation 404, an EC stack is deposited on the bottom TCO. In operation 408, a second or top TCO is deposited on the EC stack. It should be noted that these operations can be performed using any technique for depositing TCO and EC stack materials to form an electrochromic device as described herein and in the documents incorporated by reference. In operation 478, a bus bar (or multiple bus bars in certain embodiments) is applied to a location on the electrochromic device. This is performed during the post-patterning stage. Operation 478 is the focus of this section; this represents a difference from conventional bus bar design and fabrication methods.

[0159] Conventionally, busbars are provided as ink or liquid media that dries or hardens on the surface of the electrochromic device. During application, the liquid can penetrate into the underlying device through cracks or defects, carrying the conductive material with it. To address this problem, "non-liquid" busbar materials can be used during manufacturing. The concept of non-liquid busbars includes a variety of non-removable busbar materials, including solids, gels, high-viscosity liquids, glasses, and the like. The material in such a non-removable busbar will essentially not flow into any cracks on the top TCO; in other words, the material rarely, if ever, forms a short circuit.

[0160] The viscous liquid can be, for example, a polymer-containing silver ink. Drying processes, sintering, and the like can be used, in which powder or other solid phase busbar materials are attached to the top TCO layer. Drying processing techniques can use a solid mixture of conductive busbar materials and adhesives, such as polymer materials similar to PVDF and similar materials. In some implementations, the solid top busbar is applied to the top TCO by adhesion, pressure from a covering structure such as a spacer, diffusion bonding, solder bonding, epoxy resin, cold metal flow under high initial contact pressure, or another technique. In some embodiments, the solid busbar is a wire or a conductive strip or foil that can be held in place by pressure from a covering structure or by adhesion to the top TCO. In some embodiments, non-removable busbar materials are used for both the top busbar and the bottom busbar, and in some embodiments, the materials used for the top busbar and the bottom busbar are different.

[0161] In certain embodiments, the bottom bus bar material deposited on the electrochromic device includes a medium, carrier, or form that physically prevents conductive material from penetrating into the device. The bottom bus bar material is a sublayer of a multilayer bus bar deposited on the top TCO. In some embodiments, a material that prevents conductive material from penetrating into the device is deposited on the top TCO before the bus bar material is applied to the top TCO. In some embodiments, the material that prevents conductive material from penetrating into the device is the bus bar material applied to the top TCO. Examples of such materials include: carbon materials including graphite and graphene, titanium oxide, tin oxide, zinc oxide, aluminum oxide, aluminum nitride, titanium nitride, tantalum nitride, chromium, nitride, SiO x N y Compounds and combinations thereof. These materials can be deposited as diffusion barriers on conductive materials (e.g., silver), or between the top TCO and the busbar if conductive. That is, the conductive diffusion barrier material is applied to the selected area, and then the busbar is applied to the conductive diffusion barrier. Examples of busbars containing blocking media include conductive tapes that adhere to the device and prevent conductive materials from moving into the device during the cycle or operation of the electrochromic device. The width of the example busbar can be between about 0.5 mm and about 4 mm, or between about 0.5 and about 5 mm. The width of the busbar can be about 100 microns. In some embodiments, the busbar can have a length of up to about 144 inches.

[0162] In another method, the conductive busbar material can have a limited tendency to electromigration. Examples of such materials include copper, palladium, gold, nickel, iron, tin, graphite, graphene, indium, aluminum, zinc, other compounds and mixtures of these materials. In some embodiments, the busbar can be treated with an electromigration inhibitor. A non-limiting example can be to treat a copper busbar with phosphorus to inhibit electromigration and thereby reduce the formation of a short circuit. In another example, the plastic pre-strain of the busbar is used to introduce internal voids and / or dislocations into the busbar material. It has been found that such voids and / or dislocations are used as internal reservoirs of migrating substances, and therefore effectively inhibit the electromigration of such substances in certain solders, such as SnBi solders.

[0163] In some examples, one or both of the top busbar and the bottom busbar are non-penetrating busbars. A penetrating busbar is a busbar that is typically pressed, welded, or sintered (e.g., a glass frit busbar) through one or more layers to contact the lower conductor (e.g., a TCO located at the bottom of the EC stack or below one or more layers thereof). A non-penetrating busbar is a busbar that does not penetrate into the layer, but instead makes electrical and physical contact on the surface of the conductive layer (e.g., TCO). Being a solid or viscous busbar that is non-penetrating or penetrating may prevent or reduce the reduction caused by the form of the busbar material.

[0164] Self-recovery method

[0165] This section describes procedures and materials for "recovering" small shorts in electrochromic devices. Shorts that occur during or shortly after device fabrication may occur during the coating process and / or during top busbar application. Recovery is performed by applying a stimulus to the electrochromic device to cause a transformation that "recovers" the physical conditions that would otherwise form a short. The transformation may occur in the top TCO and / or one or more other layers in the electrochromic device; it may transform the conductive material that constitutes the short or the material surrounding the conductive material. Examples of transformations include melting or fusing, oxidizing or reducing, or otherwise chemically degrading; mechanically cutting or otherwise structurally degrading; in some cases, each is applied to either or both of the conductive material and the surrounding material. Another example includes activating impurities in the lattice by exposure to radiation, such as electron beams, x-rays, lasers, or other radiation. The recovery mechanism can utilize thermal, electrical, chemical, radiation, and other stimuli. The stimulus can be, for example, alternating current, heat, laser irradiation, and the like. Alternating current for electrochromic devices is further described in U.S. Patent Application No. 12 / 336,466, filed on December 16, 2008, entitled "METHOD FOR REMEDYING SHORT CIRCUITS INELECTROCHROMIC DEVICES," which is incorporated herein by reference in its entirety.

[0166] For context, Figure 5 A process flow for making an electrochromic device with bus bars is shown in which a short circuit in a region below a top bus bar is restored. In operation 502, a first or bottom TCO is first deposited on a glass substrate. In operation 504, an EC stack is deposited on the bottom TCO. In operation 508, a second or top TCO is deposited on the EC stack. Operations 502, 504, and 508 form an electrochromic device. In some embodiments, the bottom TCO, the top TCO, the EC stack, or a combination thereof contains self-recovery features. For example, the bottom TCO or the top TCO or both may contain features that allow the layer to self-recover when the bus bar material penetrates therein. In operation 578, the bus bars may be deposited at one or more locations on the electrochromic device during post-patterning.

[0167] As explained, busbar conductive materials such as silver ink can penetrate into depressions on the top TCO, such as defects. The material can penetrate by electromigration, capillary action, pressure-driven flow, gravity, or another mechanism. This effectively creates a small short circuit between the top TCO and the bottom TCO in the area below the top busbar. In some self-recovery methods, the short circuit is "recovered" by applying a stimulus to convert the conductive busbar material within the short circuit into a non-conductive or other inactive state. Relatively non-conductive areas in the electrochromic device may include small recovery shorts or other small areas with non-conductive materials, but the areas may still be colored in response to an applied potential. Substantially non-conductive or substantially non-conductive areas in the electrochromic device resist conduction and may not support electrochromic activity and / or may not support unfavorable short circuits (e.g., short circuits that produce halos or significantly increase leakage current). Substantially non-conductive areas can be areas in the electrochromic device that are not colored after applying a potential. Such a stimulus or event may include physical contact with the conductive busbar material, high current density in the short circuit, high temperature, or another condition. In some self-recovery methods, the short circuit is "recovered" by causing a transformation of the material surrounding the conductive material in the short circuit so that the short circuit is no longer conductive. Examples of self-recovery methods for preventing or reducing short circuits are provided below.

[0168] The self-recovery mechanism may be performed by a chemical reaction that inactivates the short circuit. Recovery may include contacting the shorted conductive material or surrounding material with one or more chemicals. In various implementations, the bottom TCO restores the short circuit after contacting the bus bar material in the defect. That is, once the bus bar material reaches and contacts the bottom TCO due to electromigration or another mechanism, the bottom TCO "recovers" the short circuit by converting the bus bar material to a less conductive material or otherwise inactivating the bus bar material. For example, electrical energy transmitted via the short circuit provides a stimulus, such as self-recovery via resistive heating in the short circuit. In various embodiments, because the bus bar material that penetrates into the bottom TCO occupies a small area (e.g., on the order of about 5 μm to about 100 um or less in diameter), the small inactivated portion of the bottom TCO may appear invisible to someone viewing the device, particularly where the top bus bar is opaque or partially opaque.

[0169] Examples of chemical reactions that drive recovery include chemical reactions that convert the conductive material of the busbar into an insulating material. These reactions can be catalyzed using heat, UV, laser, flash lamp annealing, electrical energy flowing in the short circuit itself, such as via resistive heating, etc. Examples include converting silver into chlorides or nitrates with poor conductivity. For example, the busbar can be made of silver, wherein a halogen or nitrate is present in the busbar. During normal operation of the electrochromic device, the busbar material will not experience a current peak of the level experienced in the electrical short circuit. Therefore, if an electrical short circuit is formed due to the electromigration of silver particles into cracks in the device and thus across the TCO, the current flowing in the short circuit will provide enough energy, such as heat, to convert silver into halides or nitrates, which have poor conductivity, and therefore the short circuit will disappear by itself, that is, self-recovery. This is completely different from the common sense that requires laser ablation to cut off / electrically isolate such short circuits. In various embodiments, a busbar material with potential chemical reactivity is selected, wherein the driving force for the chemical reaction is selectively applied by the short circuit. The chemical reactants may be separate, such as co-reactants in the conductive particles and busbar material, or, for example, the conductive particles may be chemically modified with potential co-reactants chemically bound thereto. When a short circuit occurs, the conductive particles self-react, self-destruct in a sense, because they lose or weaken their previous conductivity properties. Thus, the chemical reaction that occurs is precisely designed to destroy or inhibit the conductivity of the material that would otherwise form a short circuit across the entire electrochromic device.

[0170] In some embodiments, a self-recovery mechanism can be stimulated when a short circuit below the top bus bar experiences a high current density, which can melt the conductive material in the short circuit, break it, or otherwise degrade the conductive material. This deactivation can produce a non-conductive bus bar material that does not participate in the short circuit and thus reduces the presence of the halo on the electrochromic device. In some implementations, when a moderate current flows from the top bus bar, the short circuit will naturally experience a suitably high current density. For example, since the distance between the top bus bar and the position of the bottom TCO directly below the top bus bar position is the shortest distance between the top bus bar and another conductive material that is not the top TCO, a small short circuit in the area below the top bus bar will experience a particularly high current density. This is especially true when the short circuit has a small diameter. The material can be selected for the top bus bar so that if or when the material from the top bus bar experiences a high current density, the bus bar material is deactivated. Examples of such materials include materials with sufficient resistance, such as polymer-based conductors. The resistance of polymer-based conductors can increase with high local current density, thereby serving to deactivate conductive pathways below high local current density.

[0171] In some embodiments, the self-recovery mechanism is triggered by high temperatures, which can be induced by various mechanisms, including contacting or locally exposing a bus bar area to a heating element; placing the device in an oven or other high temperature environment; irradiating an area of ​​the bus bar with radiation absorbed by the device or a portion thereof; passing an electric current through the short circuit, etc. As an example, passing an electric current under the top bus bar will resistively heat the short circuit or the area around it. The high temperature may cause the conductive material in the short circuit to melt, crack, chemically react to produce a non-conductive material, etc. In certain embodiments, the local temperature employed to restore the short circuit is in a range between about 50°C and about 500°C, or between about 100°C and 350°C.

[0172] In many self-recovery methods, the conductive material from the busbar penetrates into the active layer below the busbar in the electrochromic device, but does not form a halo. In some embodiments, the self-recovery method may involve depositing a specific type of busbar material; or depositing a specific combination of busbars and electrochromic device layers (such as, a specific busbar and a specific bottom TCO); or treating the busbar or the electrochromic device; or a combination thereof. For example, the self-recovery method can be performed by depositing a busbar material that becomes non-conductive due to a chemical reaction with the bottom TCO after migrating into the bottom TCO. In another example, the self-recovery method can be used in the following manner: make an electrochromic device, apply a busbar, and treat the busbar so that the treated busbar will recover when in contact with the bottom TCO, or at high current density and / or high temperature. In some embodiments, the self-recovery method may involve incorporating additional materials into the busbar, or incorporating materials into the top TCO so that when the busbar material migrates through the top TCO, the material forms a non-conductive compound. In some embodiments, recovery does not interrupt the short circuit, but rather locally deactivates the electrochromic material or other components of the electrochromic device around the short circuit so that no halo is produced when current may pass through the short circuit.

[0173] Transparent Conductive Layer Modification

[0174] The top TCO layer can be repaired or strengthened in some embodiments to prevent or reduce the formation of short circuits. As explained, cracks or other defects in the deposited top TCO layer can become potential paths for busbar conductive material to migrate through it and thus form short circuits in the electrochromic device. In the embodiments of this part, the top TCO is modified so that the busbar material is prevented from entering the defects and may not migrate through the defects. A material that does not migrate substantially is a material that does not significantly leave the initial deposition location. A material that does not migrate substantially does not generally form a short circuit. In some embodiments, a material that significantly leaves its initial location will produce a short circuit and / or degrade adjacent materials. In this context, migration is the net movement of atoms in a component, not just the movement of ions or other charge carriers within the component. Migration can be driven by diffusion, convection, electric fields, and the like.

[0175] Figure 6 is a process flow diagram of operations for making an electrochromic device with a modified top TCO. In operation 602, a first or bottom TCO is deposited on a glass substrate. In operation 604, an EC stack is deposited on the bottom TCO. In operation 608, a modified second or top TCO is deposited on the EC stack. The modifications can be performed after depositing the top TCO, or the modifications can be performed during the TCO deposition process. It should be noted that operations 602 and 604 can be performed using any suitable technique for depositing TCO and EC stack materials to form an electrochromic device. In operation 678, bus bars are applied to one or more locations on the electrochromic device during post patterning.

[0176] One technique for repairing the top TCO to eliminate defects involves flowing material in the top TCO to seal the defects. The material used in this technique can be the same as or different from the TCO material. In some implementations, the TCO material is reflowed by exposure to radiation (e.g., from a laser or UV lamp); or direct heat generated during or after the coating process; or flash lamp annealing. In some embodiments, the TCO material can be reflowed without heat, such as by using a low temperature epoxy. The process can completely or partially melt the top surface of the TCO. In certain embodiments, reflow does not cause the TCO to become less conductive, and in some cases, it can produce a more conductive TCO, such as by sealing pre-existing voids in the TCO.

[0177] In some embodiments, the cracks can be repaired by filling with materials other than the TCO material. Example materials include conductive or non-conductive materials, such as non-conductive organic polymers. The material can be applied, for example, by screen printing, inkjet printing (e.g., bubble jet), spraying, etc., with or without a mask. In some embodiments, the material is applied as a sol-gel. The repair process can involve coating the top TCO with the repair material to fill in the cracks, after which the overload or excess filling material is removed, leaving only the material in the cracks. For example, excess material can be removed by mechanical scraping and / or grinding; polishing; and / or plasma etching. Busbars are applied after filling the cracks. Although the cracks are filled with insulating material and may not be colored (i.e., they remain transparent), the holes are in small areas and therefore may not be visible to the user. The insulating material can be applied as a whole or only partially in the area where the busbars are applied / to be applied.

[0178] Alternatively, the cracks may be covered with an insulating or non-conductive material before the busbars are applied. In such embodiments, the cracks or fissures still exist, but the busbar material cannot penetrate into these cracks due to the presence of the capping layer. When this layer is an insulating layer, the device switching relies on capacitive coupling. For example, a thin layer containing silicon oxide can be deposited as a capping layer. In other embodiments, the capping layer is conductive, but blocks the diffusion and electromigration of the busbar conductive material. In some embodiments, the cover is a flowable (optionally conformable) cover formed after the EC stack is applied. The cover can also prevent the busbar material from entering cracks or depressions caused by defects, such as the case where particles in the glass pop out after the EC stack is deposited; and the cover is not deposited by physical vapor deposition in some embodiments. The cover can be etched back or ground or polished back to facilitate filling (covering) the top of the crack, while exposing the rest of the TCO area to make it directly contact the busbar.

[0179] Production

[0180] Electrochromic device manufacturing method

[0181] Figure 7Various aspects of a process flow 700 for making an insulating glass unit (IGU) related to an optical electrochromic device are described. Exposed portions of bus bars, device edges, and / or a first conductor layer may be sealed in a primary seal of the IGU. Dual electrochromic device IGUs are described in U.S. Patent Application No. 12 / 851,514 (now U.S. Patent No. 8,270,059), filed on August 5, 2010, entitled "Multi-pane Electrochromic Windows," which is incorporated herein by reference in its entirety. One embodiment is a multi-pane window as described in the application, the multi-pane window having one or more electrochromic devices as described herein. One embodiment is any optical device described herein that does not include a deactivated portion of an optical device.

[0182] In operation 770, a substrate is provided. In some embodiments, this substrate is a glass substrate. In some embodiments, the substrate is tempered or untempered float glass. The substrate can be a thin, flexible, low-sodium glass.

[0183] Process flow 700 is described in terms of thin, flexible, low-sodium glass. Although not limited in this manner, these embodiments are particularly suitable for applying sputtered inorganic electrochromic devices to flexible substrates. Because flexible glass substrates can be both extremely low defect surfaces and low in sodium, the glass substrates can be excellent substrates on which to fabricate low-defect electrochromic devices. Example flexible substrates include thin, durable glass materials such as those commercially available from Corning, Incorporated of Corning, New York. Glass (eg, having a thickness between about 0.5 mm and about 2.0 mm) and Willow TM Glass. In one embodiment, the thickness of the flexible substrate is less than 0.3 mm; in another embodiment, the thickness of the flexible substrate is less than 0.2 mm; and in another embodiment, the thickness of the flexible substrate is about 0.1 mm. In certain embodiments, the thickness of the thin flexible low sodium substrate can be less than 0.1 mm.

[0184] In certain embodiments, some or all of the device manufacturing operations are performed under vacuum or other controlled environmental conditions. For example, the flow manufacturing process can involve passing the substrate through a series of interconnected chambers or stations, each of which is associated with a specific process operation and each of which is integrated with a vacuum system or other pressure control system. In some embodiments, the integrated deposition system includes a substrate holder and a transmission mechanism, which are operable to hold architectural glass or other substrates in a vertical orientation when located at multiple deposition stations. In some cases, the integrated deposition system includes one or more load lock chambers for passing the substrate between the external environment and the integrated deposition system. In another embodiment, multiple deposition stations include one or more stations for depositing any one or more of an electrochromic layer, an ion conductive layer, a defect reduction insulating layer, and a counter electrode layer. Sputtering or other physical vapor deposition systems can be used to deposit any one or more of the individual layers constituting the electrochromic device. The sputtering system can also be used to deposit lithium on the device.

[0185] Referring to operations 702-708, an electrochromic device is fabricated on a thin flexible glass substrate. Exemplary methods for fabricating an electrochromic device are described herein. An electrochromic device is fabricated on the flexible substrate as in process flow 700 described herein, but including fabricating a first transparent conductor on a thin flexible substrate. One embodiment is a method of fabricating an electrochromic device as described below. It should be noted that in some embodiments, Figure 3 , Figure 4B , Figure 5 and Figure 6 Some operations in Figure 7 For example, operations 302, 402, 502, and 602 may be performed during some or all of the operations. Figure 7 304, 404, 504 and 604 may be performed in operations 704-707; operations 308, 408, 508 and 608 may be performed in operation 708; and operations 378a, 378b, 478, 578 and 678 may be performed in operation 778.

[0186] The first and second conductor layers (e.g., bottom and top TCO) and one or more material layers of the optical devices described herein may all be solid and inorganic. In certain embodiments, the first transparent conductor (first TCO or bottom TCO layer) is applied in operation 702 as part of the manufacturing process flow without a pre-applied transparent conductor on the flexible glass substrate. If the provided substrate includes this layer, then the operation may not need to be performed.

[0187] The bottom TCO deposited in operation 702 includes tin oxide, for example, fluorinated tin oxide. The bottom TCO can be deposited by various methods. In some embodiments, the bottom TCO can be deposited according to the above description with respect to Figure 5 Operation 502 is described for deposition to form a self-healing bottom TCO.

[0188] Regardless of how the bottom TCO is formed, the EC stack can be deposited on the bottom TCO in operations 704-707. In operation 704, a first electrochromic layer is deposited on the bottom TCO, in operation 704. In some embodiments, the first electrochromic layer includes a cathode electrochromic material. In other embodiments, the first electrochromic layer includes an anode electrochromic material.

[0189] In some cases, the substrate is heated prior to depositing the first electrochromic material. The first electrochromic material layer is typically deposited by a process involving physical or chemical vapor deposition under vacuum or other controlled pressures. In a typical embodiment, the process involves sputtering a target containing the elements contained in the electrochromic layer. However, in an alternative embodiment, the electrochromic layer is deposited by a solution phase reaction at ambient pressure.

[0190] In one implementation, the first electrochromic layer contains a cathodically coloring electrochromic material deposited in two operations, one operation providing a sublayer of a base material of a first stoichiometry and another operation providing another sublayer of a base material of a second stoichiometry. As an example, the cathodically coloring electrochromic material is tungsten oxide, which has a nominal composition WO x The first deposited sublayer may have a tungsten oxide composition where the x value is about 2.7 to 2.8, and the second deposited sublayer may have a tungsten oxide composition where x is about 2.85 to 3.5. In one example, the first sublayer is thicker; for example, the first sublayer has a thickness of about 400 nm, while the second sublayer has a thickness of about 100 nm.

[0191] After depositing the first electrochromic layer, the partially fabricated device is optionally lithiated as indicated by operation 705. The lithiation operation involves transferring lithium metal or lithium ions into the first electrochromic layer. The lithium can be provided by sputtering or other suitable processes. Certain aspects of lithium deposition and targets used in lithium deposition processes are described in International Application No. PCT / US2012 / 034556 filed on April 20, 2012 (designating the United States) and International Application No. PCT / US2012 / 042514 filed on June 14, 2012 (designating the United States), both of which are incorporated herein by reference in their entirety.

[0192] The next operation in fabrication process 700 involves depositing the second electrochromic layer (an example of the counter electrode layer generally described above) in operation 706. As with the deposition of the first electrochromic layer, this deposition process can be completed using, for example, physical or chemical vapor deposition. If the first electrochromic layer contains a cathode coloring type electrochromic material, the second electrochromic layer can contain an anode coloring type electrochromic material. The opposite is also true. If the first electrochromic layer contains an anode coloring type electrochromic material, the second electrochromic layer can contain a cathode coloring type electrochromic material. In certain embodiments, the second electrochromic layer contains an anode coloring type electrochromic material, such as nickel oxide or tungsten-doped nickel oxide (sometimes referred to as NiWO). In some instances, when nickel tungstate serves as the second electrochromic layer, the second electrochromic layer is formed to have a thickness between about 200 and 300nm. In some cases, only one electrochromic layer is used. Ions are shuttled from the non-electrochromic counter electrode into the single electrochromic layer and out of the single electrochromic layer to the non-electrochromic counter electrode. Figure 7 In the example of FIG. 5 , an ion conductive layer is not separately deposited between the first electrochromic layer and the second electrochromic layer.

[0193] After depositing the second electrochromic layer, the device including the first electrochromic layer and the second electrochromic layer is lithiated as indicated in operation 707. The lithiation may be accomplished as described in the context of operation 705. As mentioned, the lithiation operation may facilitate the ejection of particles previously embedded in the partially fabricated electrochromic device stack. Figure 7 The process flow of is not shown, but the insulating protective layer can be deposited after any step that facilitates particle ejection. Therefore, in some embodiments, the deposition of the protective insulating layer can be performed after the lithiation operation 705 or the lithiation operation 707.

[0194] return Figure 7 10. In the process flow shown in FIG. 10, after lithiation of the device in 707, the next process operation is to deposit a second or top TCO layer as shown in operation 708. At this point, all of the structures required for the basic electrochromic device have been created. In some embodiments, in this operation, the device is deposited as described above with respect to the electrochromic device. Figure 5 The self-healing top TCO is deposited in operation 508 as described above. Figure 6 Operation 608 is described to deposit the modified top TCO layer deposited in operation 708 .

[0195] In certain embodiments, one or more coatings as described can be formed on a substrate (e.g., a glass sheet) in an integrated deposition system, wherein the substrate does not leave the integrated deposition system at any time during the layer fabrication. In one embodiment, an electrochromic device including an EC stack and a top TCO can be fabricated in an integrated deposition system, wherein the glass sheet does not leave the integrated deposition system at any time during the layer fabrication. In one case, the bottom TCO layer can also be formed using an integrated deposition system, wherein the glass sheet does not leave the integrated deposition system during deposition of the EC stack and TCO layers. In one embodiment, all layers (e.g., diffusion barrier layer, bottom TCO, EC stack, and top TCO) are deposited in an integrated deposition system, wherein the glass sheet does not leave the integrated deposition system during deposition.

[0196] In operation 776, a top coating is optionally applied to the electrochromic device to protect the electrochromic device. The top coating can be used as a sealant, for example, as a hermetic seal to add to protect the laminate from environmental influences. In certain embodiments, the sealant is also used as an edge adhesive as described herein. For example, in one embodiment, the sealant is polyparaxylene, for example, polyparaxylene AF-4 (p-xylene derivative, which is also a Teflon derivative). In another embodiment, the top coating is a silicone or epoxy-based sealant, such as those commercially available from, for example, Polysciences, Warrington, Pennsylvania, or those commercially available from Dow Corning, Midland, Michigan. These sealants can also be adhesives, so in certain embodiments, the top coating procedure also protects the edge of the annealed thin glass, and can therefore be used to replace edge treatment, or in addition to edge treatment, the top coating procedure can also be used. Edge treatment can be similar to the edge treatment described above relative to operation 774. In one embodiment, process flow 700 does not include edge treatments, but rather top coating application 776 is all that is required to protect the edges of the thin annealed glass substrate (and the electrochromic device as a whole). In other embodiments, one or more edge treatments as described herein are combined with a top coating to achieve a more robust laminate that can withstand temperature changes as well as environmental exposure and impact.

[0197] In operation 778, after coating the substrate, the substrate may be post-patterned, which includes applying bus bars, cutting the coated substrate, and making IGUs. Examples of suitable post-processing include thermal and / or chemical conditioning operations. Such operations are described in U.S. Patent No. 12 / 645,111, which is incorporated herein by reference. In some embodiments, post-patterning may include the above-described Figure 3In some embodiments, post-patterning may include locally deactivating a region of the electrochromic device as described in operation 378a of FIG. 1 and applying a bus bar as in operation 378b. Figure 4B Operation 478 is used to apply the non-liquid bus bar.

[0198] Fabricating the bus bars on the second or first TCO layer can be performed before cutting the substrate. In some embodiments, a single glass unit is fabricated where multiple transparent bus bars can be applied on the second TCO to enable fast switching. By placing the bus bars in the interior area of ​​the window (which may be the area visible to the building occupants), the distance between the bus bars is reduced, thereby minimizing the ohmic potential drop in the area between the outer bus bars.

[0199] The electrochromic device can have two bus bars, one for each transparent conductive layer. However, the methods herein also include making devices with more than one bus bar per transparent conductive layer, specifically having bus bars on opposite sides of each of the first and second conductor layers. This can be particularly useful in making large electrochromic devices that would otherwise use longer switching times due to sheet resistance and devices with large areas.

[0200] The bottom bus bar can be applied by first exposing a portion of the first conductor or bottom TCO layer (bus bar pad exposure, or "BPE"). The BPE does not need to extend the entire length of the side, it only needs to be long enough to accommodate the bus bar and leave some space between the bus bar and the second conductor layer in order not to short on the second conductor layer. In one embodiment, the BPE spans the length of the bottom TCO layer on the side.

[0201] As described above, in various embodiments, the BPE is the following location: a portion of the material layer is removed downward until the lower electrode or other conductive layer (e.g., a transparent conductive oxide layer) is reached, so as to create a surface for the busbar to be applied, and thus make electrical contact with the electrode. The applied busbar can be a welded busbar, an ink busbar, a solid busbar, a sticky busbar, and the like. The BPE typically has a rectangular area, but this is not required; the BPE can be any geometric or irregular shape. For example, the BPE can be circular, triangular, elliptical, trapezoidal, and other polygonal shapes, depending on demand. The shape can depend on the configuration of the electrochromic device, the substrate carrying the electrochromic device (e.g., an irregularly shaped window), or even a more effective laser ablation mode (e.g., material removal, time, etc.) for producing the shape. In one embodiment, the BPE spans at least about 50% of the length of one side of the electrochromic device. In one embodiment, the BPE spans at least about 80% of the length of one side of the electrochromic device. In one embodiment, the BPE is substantially rectangular, with a length approaching one side of the electrochromic device, and a width between about 5 mm and about 15 mm, between about 5 mm and about 10 mm in another embodiment, and between about 7 mm and about 9 mm in yet another embodiment. As mentioned, the width of the busbar can be between about 1 mm and about 5 mm, with a width of about 3 mm being typical.

[0202] As mentioned, in some embodiments, the BPE is made with any suitable width or at any desired location, since the busbars can be deposited on the active material. The busbar width can exceed the width of the BPE (and therefore there is busbar material contacting both the lower conductor and the glass (and / or diffusion barrier)). In embodiments where the BPE fully accommodates the busbar width (that is, the busbar is entirely on top of the lower conductor), the outer edge of the busbar along the length is aligned with the outer edge of the BPE, or is embedded therein by about 1 mm to about 3 mm. Similarly, the space between the busbar and the electrochromic device is between about 1 mm and about 3 mm, between about 1 mm and 2 mm in another embodiment, and about 1.5 mm in another embodiment. The formation of the BPE is described in more detail below with respect to an electrochromic device having a lower electrode that is a TCO. The electrode can be any suitable electrode, transparent or opaque, for optical devices, just for convenience.

[0203] To make a BPE, a region of the bottom TCO is cleared of deposited material so that a bus bar can be made on the bottom TCO. In one embodiment, this is achieved by laser processing that selectively removes the deposited film layer while exposing the bottom TCO in a defined region at a defined location. In one embodiment, the absorption characteristics of the bottom electrode and the deposited layer are exploited to achieve selectivity during laser ablation, that is, so that the EC material on the TCO is selectively removed while the TCO material remains intact. In certain embodiments, the upper portion (depth) of the TCO layer is also removed, for example by removing any mixture of TCO and EC material that may have been present during deposition, in order to ensure good electrical contact for the bus bar.

[0204] In certain embodiments, the electromagnetic radiation used to make the BPE is the same as the electromagnetic radiation used to perform edge removal. The (laser) radiation is delivered to the substrate using an optical fiber or an open optical path. Ablation can be performed from the glass side or the film side, depending on the choice of the wavelength of the electromagnetic radiation. The energy density used to ablate the film thickness is achieved by passing the laser beam through an optical lens. The lens focuses the laser beam into the desired shape and size, for example, a "flat top" has the dimensions described above, and in one embodiment has a wavelength between about 0.5 J / cm 2 About 4J / cm 2 In one embodiment, laser scan overlap for BPE is accomplished as described above for laser edge removal. In certain embodiments, variable depth ablation is used for BPE fabrication. This is described in more detail below.

[0205] In certain embodiments, laser treatment at the focal plane results in a certain amount (between about 10 nm and about 100 nm) of residue, e.g., tungsten oxide, being left on the exposed area of ​​the lower conductor, e.g., due to the selective nature of absorption in the EC film. Since many EC materials are not as conductive as the underlying conductor layer, the busbars fabricated on this residue do not fully contact the underlying conductor, resulting in a voltage drop at the busbar to lower conductor interface. The voltage drop not only affects the coloration of the device, but also affects the adhesion of the busbar to the lower conductor. One way to overcome this problem is to increase the amount of energy used for film removal, however, this approach results in the formation of grooves where the spots overlap, thereby unacceptably consuming the lower conductor. To overcome this problem, laser ablation is performed above the focal plane, i.e., the laser beam is defocused. In one embodiment, the defocus profile of the laser beam is a modified flat top, or "quasi-flat top." By using a defocused laser profile, the fluence delivered to the surface can be increased without damaging the underlying TCO at the spot overlap area. This approach minimizes the amount of residue left on the exposed lower conductor layer and thus allows for better contact of the bus bar with the lower conductor layer.

[0206] After forming the BPE, busbars are applied to the device, one busbar applied to the exposed area BPE of the bottom TCO layer (e.g., the first TCO), and one busbar applied to the opposite side of the device, i.e., the top TCO layer (e.g., the second TCO), on a portion of the second conductor layer that is not above the first conductor layer. In some embodiments, the busbar applied to the top TCO is made with the width of the zone where the electrochromic device is deactivated after the electrochromic device coating is completed and at the location of the zone. The busbar deposited on the top TCO can have a size such that the length is between about 10" and about 144", the width is between about 0.5mm and about 5mm, and the thickness is between about 10um and 1000um.

[0207] After the busbars are fabricated or otherwise applied to one or more conductive layers, the electrochromic window sheet, laminated or not laminated to another window sheet, can be integrated into an IGU, which includes, for example, wiring for the busbars, etc. In some embodiments, one or both of the busbars are within the finished IGU. In a particular embodiment, both busbars are configured between the spacer and the glass of the IGU (commonly referred to as the primary seal of the IGU); that is, the busbars are aligned with the spacers used to separate the window sheets of the IGU. The area in the device that has been patterned to remove the device layer can be used at least in part to make the seal contact one face of the spacer used to form the IGU. Therefore, the wires or other connections to the busbars extend between the spacer and the glass. Since many spacers are made of conductive metals such as stainless steel, it is desirable to take steps to avoid short circuits caused by electrical connectivity between the busbars and the connectors connected to the busbars and the metal spacers. Specific methods and apparatus for accomplishing this are described in U.S. Patent Application No. 13 / 312,057 (now U.S. Patent No. 8,711,465), filed December 6, 2011, and entitled "IMPROVED SPACERS FOR INSULATED GLASS UNITS," which is incorporated herein by reference in its entirety. In certain embodiments described herein, the methods and resulting IGUs include having the perimeter edge of the electrochromic device, the bus bars, and any isolation scribes within the primary seal of the IGU.

[0208] refer to Figure 7In operation 772, the substrate may be laminated to a support window, such as a tempered or heat-strengthened window, having a thickness between about 3 mm and about 25 mm, in another embodiment between about 3 mm and about 12 mm, and in yet another embodiment between about 3 mm and about 6 mm. Glass may be laminated to a tempered glass or heat-strengthened glass window; however, this is only one embodiment of the lamination portion of the process flow. For example, a thin flexible glass may be laminated to a plastic substrate. In certain embodiments, a thin flexible substrate is laminated to an unannealed glass window, such as a tempered or heat-strengthened glass window or another thin flexible glass.

[0209] The laminate formed in operation 772 should have a uniform surface, for example, the laminating adhesive should be evenly distributed between the tempered window and the flexible annealed glass substrate in terms of thickness and the absence of bubbles. Having a uniform (e.g., substantially planar) surface on a flexible substrate allows the layers to be more uniform when subsequently deposited. For an absorbing device, for example, the laminating adhesive should have high clarity, low haze, and sufficient light transmittance for the specifications of the final optical device. Depending on the requirements, the laminating layer can be colored or not. The colored laminating layer can be used to offset the unwanted color in another part of the optical device, or to enhance the existing color. If the laminating adhesive turns yellow during processing, the color of the supporting window can be selected to make the color space of the final product meet the specifications. The dye that can be used in the laminating layer is preferably highly stable to heat and ultraviolet (UV) radiation. If an inorganic pigment is selected, the inorganic pigment should not catalyze the decomposition of the laminating adhesive under heat or UV. In one embodiment, the laminating adhesive is formulated to have lateral give so that the difference in coefficient of thermal expansion between the support pane and the thin flexible pane can be accommodated without cracking due to thermal shock.

[0210] Reference again Figure 7In process flow 700, edge treatment is optionally applied to the laminate, see 774. The edge treatment may include a grinding and / or polishing procedure that is used to increase edge strength or more adequately protect and / or guard the edge of the thin flexible substrate. In one embodiment, the edge of the thin flexible glass partner is heated to a high temperature to melt the glass around the perimeter, thereby removing microcracks and inducing stress in the edge to increase strength. In one embodiment, after lamination, the edge of the flexible thin annealed glass is ground and / or polished, for example, the laminate is a "rough cut" laminate, for example, a mechanically cut laminate, which is subjected to an edge grinding and polishing process to strengthen the edge of the thin annealed window sheet (the tempered window sheet typically already has a ground and polished edge). In the resulting structure, although the area ("coverage area") of the tempered support window sheet and the thin flexible window sheet is the same, the outermost edge of the thin glass is inclined, for example, approaching the curvature of the ground (and optionally polished) edge of the tempered window sheet.

[0211] Lamination is performed in a clean, low-particle environment. However, since optical device fabrication occurs after lamination, the laminate may optionally be cleaned prior to, for example, electrochromic device fabrication, see 774. Cleaning is performed, for example, using commercially available glass cleaning equipment.

[0212] The laminate is optionally integrated into the IGU. Since the methods described herein can produce a strong laminate, integration into the IGU is optional. The laminate can be further strengthened by laminating another tempered heat-strengthened or polymer window to the electrochromic device to protect the flexible annealed window and / or the electrochromic device from the impact of impact.

[0213] In one embodiment, the laminate is integrated into the IGU, wherein the optical device such as the electrochromic device is within the internal volume of the IGU. This can be done before or after cutting the laminate from a large sheet. In such embodiments, the electrochromic device may or may not have a top coating and / or an additional window laminated to one side of the electrochromic device, because the internal volume protects the electrochromic device. In one embodiment, the laminate not only includes a top coating, but is also integrated into the IGU, wherein the electrochromic device is within the internal volume of the IGU. This construction is useful, for example, in the case of failure of the window panel and / or primary and secondary seals close to the interior of the IGU, the electrochromic device will be protected from the impact of the environment by the top coating. The IGU can have only a single laminate as described herein, for example, a double-layer window panel IGU, wherein the mating window of the IGU is a single glass window. In other embodiments, the IGU is a double-layer window panel structure with two laminates serving as two window panels of the IGU as described herein. Triple pane IGUs having one, two, or three laminates as described herein are also within the scope of the embodiments described herein.

[0214] The "coat first, cut later" approach allows for high-throughput manufacturing because not only can multiple electrochromic devices be made on a single large-area substrate, but the electrochromic devices can also be tested and their defects reduced before the large glass sheet is cut into individual window sheets. In one embodiment, the large glass window panel is laminated with individual reinforced window panels that are aligned with the individual electrochromic devices before cutting the large thin sheet. Prior to lamination, bus bars may or may not be attached; for example, the mating window sheet may extend with the area that implements some exposed portions of the top and bottom TCOs for subsequent bus bar attachment. In another example, the mating window sheet is a thin flexible material, such as a thin flexible glass, that is substantially coextensive with the electrochromic device or the entire large thin sheet. The thin flexible mating window sheet (and the laminating adhesive, if present in these areas) is ablated downwardly until the first conductor layer and the second conductor layer, so that the bus bars can be attached to the conductor layers as described herein. In yet another embodiment, the thin flexible mating window, whether coextensive with the entire large sheet or with individual electrochromic devices, is configured with apertures that align with the top conductor layer and BPE during lamination. The busbars are attached before or after lamination of the mating window, as the apertures allow for either order of operations. Lamination and busbar attachment can be performed separately before or after cutting the large sheet.

[0215] In certain embodiments, at lamination, the busbars may be applied prior to lamination, where the busbars are applied to the BPE and upper TCO and then squeezed out from between these areas at lamination, such as into the aperture of the mating window or extending around the edge of the laminate to allow wire attachment at points outside the lamination area. In another embodiment, a flat foil tape is applied to the top conductor and BPE, extending across the lamination area so that wires can be soldered to the tape after lamination. In these embodiments, cutting must precede lamination (e.g., as described with respect to the roll-to-roll embodiments herein), unless, for example, the laminated mating window does not cover the entire surface of a large substrate.

[0216] Laminated or unlaminated windows can be integrated into an IGU. In one embodiment, individual EC windows are integrated into an IGU, and one or more of the EC windows of the IGU are then laminated with a reinforcing window plate (mating window) as described herein or in U.S. Patent No. 8,164,818. In other embodiments, for example, as described herein, the lamination can include a flexible substrate, for example, the aforementioned lamination of an IGU, wherein the mating window is a flexible substrate; or for example, the EC window is laminated directly to a flexible substrate. In addition, relative to Figure 8 Such embodiments are described.

[0217] Equipment for electrochromic device fabrication

[0218] Figure 8 Roll-to-roll processing 872 of laminates forming electrochromic devices is shown, where the lamination uses mating windows, which can be tempered windows or flexible thin glass or even IGUs for added support. Substrate 876 is fed into a lamination line, which in this example includes a conveyor 877. Substrate 876 can be an IGU incorporating at least one EC window, or substrate 876 can be a monolithic electrochromic device such as described herein, or substrate 876 can be a large substrate with multiple EC windows fabricated thereon. In some embodiments, substrate 876 can be a laminate according to Figure 7 In some embodiments, substrate 876 is an IGU to be fabricated by process 700. Figure 7 The glass substrate laminated in operation 772. As shown here relative to Figure 8 The term "substrate" as used in the discussion of the present invention includes optically coated electrochromic devices. Such substrates can be used in a roll-to-roll process. During lamination, a flexible, thin, durable glass material such as that commercially available from Corning, Incorporated of Corning, New York, can be used. Glass (eg, having a thickness between about 0.5 mm and about 2.0 mm) and Willow TM Glass.

[0219] In this example, a thin and flexible substrate 878, such as a glass substrate, is fed from a coil into a lamination line. In one embodiment, one or more coils are applied in parallel to a large glass sheet including a plurality of electrochromic devices (the substrate 876 itself can be a thin flexible glass in the form of a coil, i.e., the thin flexible glass has been coated with an electrochromic device coating and has been post-patterned and processed as described herein). For example, three separate and parallel rolls of flexible substrates are fed into a lamination line, which laminates a large glass substrate longitudinally or transversely, so that three columns or rows of electrochromic devices are each laminated with a flexible substrate. Therefore, using a roll-to-roll process, a large glass sheet can be laminated with a flexible mating window material and the large glass sheet can be cut into individual EC windows. Large glass sheets can be cut when laminating each row or after laminating the entire sheet. In certain embodiments, individual EC windows or IGUs containing them are laminated with a roll-to-roll process.

[0220] Adhesive is applied to substrate 876, flexible substrate 878, or both. Roller 879 applies sufficient pressure to ensure good bonding between substrate 876 and flexible substrate 878. For example, laser 880 is used to cut flexible substrate 878 to match its lamination partner 876. The final laminated structure 881 is produced. Using this roll-to-roll method, a single electrochromic device, IGU, or a large glass sheet carrying multiple EC windows can be reinforced with a thin flexible reinforced window plate, or, for example, a thin flexible EC window can be reinforced with another thin flexible glass lamination partner. These methods are applicable to any EC substrate described herein or otherwise. In one embodiment, a single EC window sheet, for example, cut from a large area substrate, is fed into a lamination production line to be laminated with a flexible substrate. In another embodiment, a large area substrate on which multiple electrochromic devices are made is laminated with a flexible substrate of corresponding width, and after lamination, for example, at the end of lamination or after laminating the entire large sheet, the individual electrochromic devices that are now laminated are cut from the large area laminate in rows. In another embodiment, a large area substrate having multiple electrochromic devices fabricated thereon is laminated with multiple flexible substrates having widths or lengths corresponding to individual EC windows, and after lamination, the now-laminated electrochromic devices are cut from the large area laminate, for example individually or in rows (or columns).

[0221] In certain embodiments, an electrochromic device coating is applied to a large annealed glass such as a thin flexible glass in one facility, such as described herein, and then post-processing is performed in another facility. For example, the embodiments described herein provide an example in which patterning of individual electrochromic devices can be completed after deposition to solve any short circuit problems below the top bus bar. Therefore, a large glass sheet can be coated with a device coating, which is stored and / or transported to another facility for post-processing into a sub-window sheet. In this way, for example, a manufacturer can produce large glass coated with a single electrochromic device coating as its product. The coated glass can be a large sheet or a large roll of flexible glass. Coated glass can be produced in large quantities and stored or transported to customers who can post-process the coated glass according to their needs. In some embodiments, the method described herein is used to post-process the coated glass into a plurality of electrochromic devices or windows, which can then be made into laminates and / or IGUs. The coated glass can have a sealing protective layer as described herein. The method described herein provides great flexibility for post-processing of the device without pre-patterning.

[0222] The embodiments described herein that do not require pre-patterning of electrochromic devices on large glass, for example, provide great flexibility in how such large-scale coated glass is post-processed. For example, busbar placement and EC device configuration are determined at downstream stages after the electrochromic coating process.

[0223] The "coat first, ship then cut" approach provides additional advantages to the manufacturing process. For example, annealed glass coated with electrochromic devices can be loaded into, for example, large shipping racks, rather than having to manufacture and load finished IGUs and / or laminates. Significant financial savings are achieved due to the significant reduction in factory complexity and the reduction in costs (freight) in terms of shipping volume and weight. In addition, since post-processing can be completed locally at downstream factories, the diversity of post-processing is accommodated. Therefore, a single product of glass coated with electrochromic devices can be shipped to multiple locations for a variety of customized post-processing. Having a centralized coating facility and satellite post-processing facilities improves the quality and consistency of the product and downstream products because the electrochromic device coating process is highly centralized and uses a highly skilled workforce relative to downstream post-processing. Downstream customers such as IGU manufacturers have more control over product manufacturing, and this allows the end customer (window purchaser) to have more choices in customized design and quality. Additionally, decentralizing the manufacturing process allows the most important parts of the window to be made at a large-scale coater with reliable power, thereby avoiding power outages, and proximity to large-scale shipping hubs may not be as critical (because shipping is lighter and the shipped devices take up less volume per square foot).

[0224] In certain embodiments, a top coating, such as a hermetic sealing layer for providing hermetic protection, is applied to the electrochromic device coating. The coating provides a hermetic seal to protect the coating during transportation, such as in the "coating first, cutting after transportation" embodiment. This top coating can be applied by various techniques, such as spraying, dipping, etc. This top coating protects the device coating from moisture, which otherwise may damage the device function if there are cracks in, for example, the top TCO, or the top TCO itself does not provide a moisture barrier between the environment and the EC stack. This top coating can be applied, for example, immediately after the electrochromic device coating is applied or shortly thereafter. For example, a large piece of coated glass or a continuous glass sheet coated with an electrochromic device can pass through the front, below, or above a spraying device and a drying station such as an oven. In this way, the device coating without moisture is immediately sealed and protected from the influence of the environment. This can be free from the influence of pinhole formation in some cases. In addition, the electrochromic device coating may often be easily scratched, which may damage the function and / or aesthetics, such as switching uniformity. The top coating protects the coating. Furthermore, shielding the coating from the environment allows for greater flexibility in handling, thereby providing more time to inspect, package, store and ship the product, i.e. extending waiting time control and making the control more flexible. The sealing top coating may be permanent or temporary, e.g. a film that is removed at a downstream stage, e.g. at a separate post-processing facility.

[0225] In an alternative to or in addition to the topcoat, the glass sheets or rolls coated with the electrochromic device can be handled, processed and / or transported in an atmosphere controlled environment, such as a dry environment and / or an inert gas environment. In addition, the sheets or rolls coated with the electrochromic device can be protected with, for example, interlaced sheets, powders, or similar temporary protectors as known in the glass industry. Suitable interlaced sheets can be highly polished papers, such as rice paper. Example interlaced powders, such as those commercially available from Chemetall Group of New Providence, NJ, can also be used, and the interlaced powders also include those of G. LASS D IGEST Those described above by Duffer, Paul F. in "How to Prevent Glass Corrosion". A wide range of interwoven sheets can be used, and the interwoven sheets range from kraft paper to high-tech pH balanced materials. The powder can include a type of bead, such as acrylate or ultra-high molecular weight (UHMW) beads; and an acidic component to prevent staining, such as adipic acid.

[0226] In certain embodiments, the "coat first, ship then cut" method can be enhanced by using a temperable electrochromic device coating and / or providing the coating as a device precursor that is converted into a functional EC device as part of a post-processing. Temperable electrochromic devices are described in U.S. Patent Application No. 13 / 137,750, entitled "TEMPERABLE ELECTROCHROMIC DEVICES," filed on December 20, 2013, which is incorporated herein by reference for all purposes. Electrochromic device precursors are described in U.S. Patent No. 8,300,298, entitled "ELECTROCHROMIC DEVICES," issued on October 30, 2012, which is incorporated herein by reference for all purposes. Both technologies allow a series of layers to be applied to glass, wherein the layers are not used as electrochromic devices. These layers are later heated or other energy sources are applied to the layers, which convert the layers into functional electrochromic device coatings. The temperable electrochromic device coating may or may not be a functional device prior to heat treatment (in this case tempering the annealed glass).

[0227] For example, an electrochromic device precursor coating or a temperable electrochromic device coating is applied to annealed glass. The glass can then be transported to various facilities for post-processing. In one embodiment, the coated glass includes an electrochromic device precursor coating. As part of post-processing, the coating is exposed to energy, such as heat, so that the device precursor coating is converted into a functional electrochromic device coating. This has the advantage of further flexibility in post-processing, for example, individual post-processing personnel can determine the optimal conditions for the conversion of the electrochromic device. In the case where the electrochromic device precursor coating is converted into a functional electrochromic device coating, the glass can be cut into sub-windows or devices before or after the heating process. In another example, a temperable electrochromic device coating is applied to annealed glass (thickness sufficient for tempering). As part of post-processing, the coating is exposed to energy, such as heat, so that the glass substrate is tempered and optionally the device precursor coating is converted into a functional electrochromic device coating (unless the coating is already a functional device coating that can withstand the tempering process). This has the advantage of further flexibility in post-processing, for example the individual post-processor can decide on the optimal conditions for tempering and / or electrochromic device conversion.In the case of a temperable EC coating, the glass is cut into sub-panes or devices prior to tempering.

[0228] In some embodiments, the glass substrate including the first transparent conductive layer can be made planar by polishing the substrate. Examples of polished substrates are further described in: U.S. Patent No. 9,007,674, entitled "DEFECT-MITIGATION LAYERS IN ELECTROCHROMIC DEVICES," issued on April 14, 2015; PCT International Application No. PCT / US2015 / 26150, entitled "PARTICLE REMOVAL DURING FABRICATION OF ELECTROCHROMIC DEVICES," filed on April 16, 2015; and PCT International Application No. PCT / US2012 / 57606, entitled "OPTICAL DEVICE FABRICATION," filed on September 27, 2012, all of which are incorporated herein by reference in their entirety. The planar electrochromic device coating can extend the duration that the electrochromic device coating can withstand atmospheric humidity exposure.

[0229] In some embodiments, the first transparent conductive layer can be deposited as a planar layer. For example, in some embodiments, the transparent conductive layer can be deposited by a method such as PVD. Such films deposited by PVD can be deposited as amorphous, and then the film is catalyzed so that the resulting film tends to be smoother than a film deposited in a crystalline form. This is primarily due to the deposition temperature.

[0230] Planar glass substrates including electrochromic stacks may be able to withstand longer duration exposure to atmospheric humidity. Planar may be defined as having a peak-to-peak roughness of less than about 30 nm, or less than about 15 nm, or less than about 10 nm.

[0231] in conclusion

[0232] Although the foregoing embodiments have been described in some detail for the purpose of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative forms of processes, systems and equipment for implementing embodiments of the present invention. Therefore, the embodiments of the present invention should be considered illustrative rather than restrictive, and the embodiments are not limited to the details given herein.

Claims

1. A method of manufacturing an electrochromic device, the electrochromic device comprising an electrochromic stack between a first transparent conductive layer and a second transparent conductive layer, the first transparent conductive layer and the second transparent conductive layer being configured to deliver an electrical potential on a surface of the electrochromic stack and thereby cause optical switching of the electrochromic device, the manufacturing method comprising: (a) fabricating the electrochromic stack on a glass substrate without pre-patterning in a first facility; (b) transporting the glass substrate including the electrochromic stack to a second facility; as well as (c) performing post-processing in said second facility, Wherein (c) comprises cutting the glass substrate into a plurality of electrochromic windows, and Wherein (c) further comprises performing an operation to reduce short circuits, wherein the operation to reduce short circuits is: (i) preventing an electrical short from forming between the second transparent conductive layer and a layer of the electrochromic device in the region below the bus bar, and / or (ii) removing an electrical short that has formed between the second transparent conductive layer and another layer of the electrochromic device, and Wherein the short reducing operation is performed after fabricating the electrochromic stack and the second transparent conductive layer without substantially deactivating the electrochromic device in the region below the bus bar.

2. The method of claim 1, further comprising deactivating the electrochromic stack beneath at least one of the one or more bus bars applied to the substrate during post-processing.

3. The method of claim 2, wherein the deactivation is performed before or after applying the one or more bus bars.

4. The method of claim 2, wherein said cutting is performed prior to applying said one or more bus bars to said electrochromic stack.

5. The method of claim 2, wherein said cutting is performed after applying said one or more bus bars to said electrochromic stack.

6. The method of claim 2, wherein the deactivation comprises sensitizing the electrochromic stack, the first transparent conductive layer, and / or the second transparent conductive layer by performing a treatment selected from the group consisting of: applying heat, irradiation, applying chemicals, and combinations thereof.

7. The method of claim 1, wherein (c) comprises patterning the electrochromic stack with a laser.

8. The method of claim 1, wherein (c) comprises applying one or more bus bars to the electrochromic stack.

9. The method of claim 1, further comprising, before (b), providing hermetic protection to the electrochromic stack.

10. The method of claim 9, wherein providing the hermetic protection comprises forming a hermetic top coating over the electrochromic stack.

11. The method of claim 10, wherein the hermetic top coating is made of a material selected from the group consisting of parylene, silicon-based sealants, epoxy-based sealants, oxide-polymer multilayers, and combinations thereof.

12. The method of claim 10, further comprising removing the sealing top coating at the second facility.

13. The method of claim 1, wherein the glass substrate comprising the electrochromic stack has a roughness of less than 30 nm.

14. The method of claim 1, further comprising providing the glass substrate including the electrochromic stack in an environment that is not affected by atmospheric humidity. The method of claim 14 , wherein the environment is an argon environment.

16. The method of claim 1, further comprising providing the glass substrate including the electrochromic stack with at least one other glass substrate having the electrochromic stack interwoven with a protective material.

17. The method of claim 16, wherein the protective material comprises a powder and / or interwoven flakes.

18. The method of claim 17, wherein the interwoven web is rice paper.

19. The method of claim 1, wherein the shipped glass substrate including the electrochromic stack is not tempered.

20. The method of claim 19, wherein the shipped glass substrate including the electrochromic stack comprises an electrochromic precursor.

21. The method of claim 19, further comprising tempering the glass substrate including the electrochromic stack after dicing at the second facility during the post-processing.

22. The method of claim 20, further comprising annealing the glass substrate including the electrochromic stack after dicing at the second facility during the post-processing.

23. An electrochromic device comprising: a substrate having a surface; A first transparent conductive layer disposed on the surface of the substrate; an electrochromic stack disposed on the first transparent conductive layer, wherein the electrochromic stack comprises an electrochromic layer and a counter electrode layer; a second transparent conductive layer disposed on the electrochromic stack; as well as a bus bar electrically coupled to a region of the second transparent conductive layer, wherein the region is located above the first transparent conductive layer, wherein the electrochromic stack is disposed between the two transparent conductive layers, the two transparent conductive layers being configured to transfer an electrical potential across a surface of the electrochromic stack and thereby cause optical switching of the electrochromic device, and Wherein after fabricating the electrochromic stack and the second transparent conductive layer, the electrochromic stack is deactivated in the region below the bus bar.

24. An electrochromic device, comprising: a substrate having a surface; A first transparent conductive layer disposed on the surface of the substrate; an electrochromic stack disposed on the first transparent conductive layer, wherein the electrochromic stack comprises an electrochromic layer and a counter electrode layer; a second transparent conductive layer disposed on the electrochromic stack; as well as a bus bar electrically coupled to a region of the second transparent conductive layer, wherein the region is located above the first transparent conductive layer, wherein the electrochromic stack is disposed between the two transparent conductive layers, the two transparent conductive layers being configured to transfer an electrical potential across a surface of the electrochromic stack and thereby cause optical switching of the electrochromic device, and Wherein the electrochromic stack is active to allow for short circuit and / or latent defect reduction operations to be performed in the region below the bus bar.

25. The electrochromic device of claim 24, wherein at least one of the potential defects is a potential short circuit.

26. A system for making an electrochromic device, the electrochromic device comprising an electrochromic stack between two transparent conductive layers, the two transparent conductive layers being configured to pass an electrical potential across a surface of the electrochromic stack and thereby cause optical switching of the electrochromic device, the making system comprising: (a) A coating apparatus configured to: receiving a substrate optionally having a surface with a first transparent conductive layer disposed thereon, fabricating the electrochromic stack on the first transparent conductive layer, wherein the electrochromic stack comprises an electrochromic layer and a counter electrode layer, and forming a second transparent conductive layer on the electrochromic stack; as well as (b) a post-coating patterning apparatus configured to: receiving the substrate having the electrochromic stack between the two transparent conductive layers, forming one or more bus bars electrically coupled to the second transparent conductive layer, and Portions of the electrochromic device are deactivated in an area beneath the one or more bus bars.

27. The system of claim 26, wherein the post-coating patterning device is further configured to form one or more bus bars electrically coupled to the first transparent conductive layer.

28. The system of claim 26, wherein the post-coating patterning apparatus is further configured to cut the substrate to provide a plurality of electrochromic windows.

29. A system for making an electrochromic device, the electrochromic device comprising an electrochromic stack between two transparent conductive layers, the two transparent conductive layers being configured to pass an electrical potential across a surface of the electrochromic stack and thereby cause optical switching of the electrochromic device, the making system comprising: (a) A coating apparatus configured to: receiving a substrate optionally having a surface with a first transparent conductive layer disposed thereon, fabricating the electrochromic stack on the first transparent conductive layer, wherein the electrochromic stack comprises an electrochromic layer and a counter electrode layer, and forming a second transparent conductive layer on the electrochromic stack; as well as (b) a post-coating patterning apparatus configured to: receiving the substrate having the electrochromic stack between the two transparent conductive layers, forming one or more bus bars electrically coupled to the second transparent conductive layer, deactivating the electrochromic stack in an area beneath the one or more bus bars, and The penetration of the bus bar material is blocked.

30. The system of claim 29, wherein the post-coating patterning apparatus is further configured to cut the substrate to provide a plurality of electrochromic windows.

31. A method for making an electrochromic device, the method comprising: a. depositing a first electrochromic stack comprising a first electrochromic layer and a first counter electrode layer on the first transparent conductive layer; b. depositing a second electrochromic stack comprising a second electrochromic layer and a second counter electrode layer on the first electrochromic stack, wherein at least one of the electrochromic stacks comprises superstoichiometric oxygen at an interface between the electrochromic layer and the counter electrode layer; c. depositing lithium on the second electrochromic stack; d. depositing a second transparent conductive layer on the second electrochromic stack to form an electrochromic device precursor; as well as e. Selectively activating the electrochromic device precursor in areas other than the first area where a bus bar will be present, the bus bar configured to power the second transparent conductive layer.

32. The method of claim 31, wherein the bus bar is a non-penetrating bus bar.

33. The method of claim 31, wherein when the bus bar is fabricated within the first region, the first region is configured to extend 0.5 mm to 5 mm beyond any edge of the bus bar.

34. The method of claim 31, wherein when the bus bar is fabricated within the first region, the first region is configured to extend 0.5 mm to 2 mm beyond any edge of the bus bar.

35. The method of claim 31, wherein when the bus bar is fabricated within the first region, the first region is configured to extend 0.5 mm to 1 mm beyond any edge of the bus bar.

36. The method of claim 31, further comprising deactivating the first region to inhibit electrical conduction between the first transparent conductive layer and the second transparent conductive layer.

37. The method of claim 31, wherein the bus bar comprises a bus bar conductive material in a dielectric, the dielectric isolating the conductive material to prevent migration of the conductive material to the second transparent conductive layer.

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