Patent Publication Number: US-2020301228-A1

Title: Made-to-stock patterned transparent conductive layer

Description:
CROSS-REFERENCE TO RELATED APPLICATION(S) 
     This application claims priority under 35 U.S.C. § 119(e) to U.S. Patent Application No. 62/821,125, entitled “MADE-TO-STOCK PATTERNED TRANSPARENT CONDUCTIVE LAYER,” by Sebastian Marius Sarrach, filed Mar. 20, 2019, which is assigned to the current assignee hereof and incorporated herein by reference in its entirety. 
    
    
     FIELD OF THE DISCLOSURE 
     The present disclosure is related to electrochemical devices and method of forming the same. 
     BACKGROUND 
     An electrochemical device can include an electrochromic stack where transparent conductive layers are used to provide electrical connections for the operation of the stack. Electrochromic (EC) devices employ materials capable of reversibly altering their optical properties following electrochemical oxidation and reduction in response to an applied potential. The optical modulation is the result of the simultaneous insertion and extraction of electrons and charge compensating ions in the electrochemical material lattice. 
     Advances in electrochromic devices seek the devices have faster and more homogeneous switching speeds while maintaining through-put during manufacturing. 
     As such, further improvements are sought in manufacturing electrochromic devices. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a schematic cross-section of an electrochromic device, according to one embodiment. 
         FIGS. 2A-2F  are schematic cross-sections of an electrochemical at various stages of manufacturing in accordance with an implementation of the present disclosure. 
         FIG. 3  is a flow chart depicting a process for forming an electrochemical device in accordance with an implementation of the current disclosure. 
         FIGS. 4A-4B  are schematic illustrations of a top view of the transparent conductive layer, according to various embodiments. 
         FIG. 5  is a schematic illustration of an insulated glazing unit according to an implementation of the current disclosure. 
         FIG. 6  is a graph of the holding voltages of various samples. 
         FIG. 7  is a schematic cross-section of an electrochromic laminate device, according to another embodiment. 
     
    
    
     Skilled artisans appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of implementations of the invention. 
     DETAILED DESCRIPTION 
     The following description in combination with the figures is provided to assist in understanding the teachings disclosed herein. The following discussion will focus on specific implementations and implementations of the teachings. This focus is provided to assist in describing the teachings and should not be interpreted as a limitation on the scope or applicability of the teachings. 
     As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of features is not necessarily limited only to those features but may include other features not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive-or and not to an exclusive-or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). 
     The use of “a” or “an” is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural, or vice versa, unless it is clear that it is meant otherwise. 
     The use of the word “about”, “approximately”, or “substantially” is intended to mean that a value of a parameter is close to a stated value or position. However, minor differences may prevent the values or positions from being exactly as stated. 
     Patterned features, which include bus bars, holes, holes, etc., can have a width, a depth or a thickness, and a length, wherein the length is greater than the width and the depth or thickness. As used in this specification, a diameter is a width for a circle, and a minor axis is a width for an ellipse. 
     “Impedance parameter” is a measurement the effective resistance—a combined effect of ohmic resistance and electrochemical reactance—of an electrochemical device measured at 2 log (freq/Hz) on a 5×5 cm device with DC bias at −20° C. as 5 mV to 50 mV is applied to the device. The resultant current is measured and impedance and phase angle are computed at each frequency in the range of 100 Hz to 6 MHz. 
     Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The materials, methods, and examples are illustrative only and not intended to be limiting. To the extent not described herein, many details regarding specific materials and processing acts are conventional and may be found in textbooks and other sources within the glass, vapor deposition, and electrochromic arts. 
     In accordance with the present disclosure,  FIG. 1  illustrates a cross-section view of a partially fabricated electrochemical device  100  having an improved film structure. For purposes of illustrative clarity, the electrochemical device  100  is a variable transmission device. In one embodiment, the electrochemical device  100  can be an electrochromic device. In another embodiment, the electrochemical device  100  can be a thin-film battery. However, it will be recognized that the present disclosure is similarly applicable to other types of scribed electroactive devices, electrochemical devices, as well as other electrochromic devices with different stacks or film structures (e.g., additional layers). With regard to the electrochemical device  100  of  FIG. 1 , the device  100  may include a substrate  110  and a stack overlying the substrate  110 . The stack may include a first transparent conductor layer  120 , a cathodic electrochemical layer  130 , an anodic electrochemical layer  140 , and a second transparent conductor layer  150 . In one embodiment, the stack may also include an ion conducting layer between the cathodic electrochemical layer  130  and the anodic electrochemical layer  140 . 
     In an implementation, the substrate  110  can include a glass substrate, a sapphire substrate, an aluminum oxynitride substrate, or a spinel substrate. In another implementation, the substrate  110  can include a transparent polymer, such as a polyacrylic compound, a polyalkene, a polycarbonate, a polyester, a polyether, a polyethylene, a polyimide, a polysulfone, a polysulfide, a polyurethane, a polyvinylacetate, another suitable transparent polymer, or a co-polymer of the foregoing. The substrate  110  may or may not be flexible. In a particular implementation, the substrate  110  can be float glass or a borosilicate glass and have a thickness in a range of 0.5 mm to 12 mm thick. The substrate  110  may have a thickness no greater than 16 mm, such as 12 mm, no greater than 10 mm, no greater than 8 mm, no greater than 6 mm, no greater than 5 mm, no greater than 3 mm, no greater than 2 mm, no greater than 1.5 mm, no greater than 1 mm, or no greater than 0.01 mm. In another particular implementation, the substrate  110  can include ultra-thin glass that is a mineral glass having a thickness in a range of 50 microns to 300 microns. In a particular implementation, the substrate  110  may be used for many different electrochemical devices being formed and may referred to as a motherboard. 
     Transparent conductive layers  120  and  150  can include a conductive metal oxide or a conductive polymer. Examples can include a tin oxide or a zinc oxide, either of which can be doped with a trivalent element, such as Al, Ga, In, or the like, a fluorinated tin oxide, or a sulfonated polymer, such as polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene), or the like. In another implementation, the transparent conductive layers  120  and  150  can include gold, silver, copper, nickel, aluminum, or any combination thereof. The transparent conductive layers  120  and  150  can include indium oxide, indium tin oxide, doped indium oxide, tin oxide, doped tin oxide, zinc oxide, doped zinc oxide, ruthenium oxide, doped ruthenium oxide and any combination thereof. The transparent conductive layers  120  and  150  can have the same or different compositions. In one implementation, the transparent conductive layer  120  over the substrate  110  can have a first resistivity and a second resistivity without removing material from the active stack. In one implementation, the transparent conductive layer  120  can have a pattern wherein a first part of the pattern  122  corresponds to the first resistivity and the second part of the pattern  124  corresponds to the second resistivity. The first part of the pattern  122  and the second part of the pattern  124  can be the same material. In one implementation, the first part of the pattern  122  has been altered by a short pulse laser to increase the resistivity. In one implementation, the first resistivity is greater than the second resistivity. In another implementation, the first resistivity is less than the second resistivity. The first part of the pattern and the second part of the pattern come from altering the first transparent conductive layer  120  as described in more detail below. 
     The transparent conductive layers  120  and  150  can have a thickness between 10 nm and 600 nm. In one implementation, the transparent conductive layers  120  and  150  can have a thickness between 200 nm and 500 nm. In one implementation, the transparent conductive layers  120  and  150  can have a thickness between 320 nm and 460 nm. In one implementation the first transparent conductive layer  120  can have a thickness between 10 nm and 600 nm. In one implementation, the second transparent conductive layer  150  can have a thickness between 80 nm and 600 nm. 
     The layers  130  and  140  can be electrode layers, wherein one of the layers may be a cathodic electrochemical layer, and the other of the layers may be an anodic electrochromic layer (also referred to as a counter electrode layer). In one embodiment, the cathodic electrochemical layer  130  is an electrochromic layer. The cathodic electrochemical layer  130  can include an inorganic metal oxide material, such as WO 3 , V 2 O 5 , MoO 3 , Nb 2 O 5 , TiO 2 , CuO, Ni 2 O 3 , NiO, Ir 2 O 3 , Cr 2 O 3 , Co 2 O 3 , Mn 2 O 3 , mixed oxides (e.g., W—Mo oxide, W—V oxide), or any combination thereof and can have a thickness in a range of 40 nm to 600 nm. In one implementation, the cathodic electrochemical layer  130  can have a thickness between 100 nm to 400 nm. In one implementation, the cathodic electrochemical layer  130  can have a thickness between 350 nm to 390 nm. The cathodic electrochemical layer  130  can include lithium, aluminum, zirconium, phosphorus, nitrogen, fluorine, chlorine, bromine, iodine, astatine, boron; a borate with or without lithium; a tantalum oxide with or without lithium; a lanthanide-based material with or without lithium; another lithium-based ceramic material; or any combination thereof. 
     The anodic electrochromic layer  140  can include any of the materials listed with respect to the cathodic electrochromic layer  130  or Ta 2 O 5 , ZrO 2 , HfO 2 , Sb 2 O 3 , or any combination thereof, and may further include nickel oxide (NiO, Ni 2 O 3 , or combination of the two), and Li, Na, H, or another ion and have a thickness in a range of 40 nm to 500 nm. In one implementation, the anodic electrochromic layer  140  can have a thickness between 150 nm to 300 nm. In one implementation, the anodic electrochromic layer  140  can have a thickness between 250 nm to 290 nm. In some implementations, lithium may be inserted into at least one of the first electrode  130  or second electrode  140 . 
     In another implementation, the device  100  may include a plurality of layers between the substrate  110  and the first transparent conductive layer  120 . In one implementation, an antireflection layer can be between the substrate  110  and the first transparent conductive layer  120 . The antireflection layer can include SiO 2 , NbO 2 , Nb 2 O 5  and can be a thickness between 20 nm to 100 nm. The device  100  may include at least two bus bars with one bus bar electrically connected to the first transparent conductive layer  120  and the second bus bar electrically connected to the second transparent conductive layer  150 . 
       FIG. 3  is a flow chart depicting a process  300  for forming an electrochromic device in accordance with an implementation of the current disclosure.  FIGS. 2A-2F  are schematic cross-sections of an electrochromic device  200  at various stages of manufacturing in accordance with an implementation of the present disclosure. The electrochromic device  200  can be the same as the electrochromic device  100  described above. The process can include providing a substrate  210 . The substrate  210  can be similar to the substrate  110  described above. At operation  310 , a first transparent conductive layer  220  can be deposited on the substrate  210 , as seen in  FIG. 2A . The first transparent conductive layer  220  can be similar to the first transparent conductive layer  120  described above. In one implementation, the deposition of the first transparent conductive layer  220  can be carried out by sputter deposition at a power of between 5 kW and 20 kW, at a temperature between 200° C. and 400° C., in a sputter gas including oxygen and argon at a rate between 0.1 m/min and 0.5 m/min. In one implementation, the sputter gas includes between 40% and 80% oxygen and between 20% and 60% argon. In one implementation, the sputter gas includes 50% oxygen and 50% argon. In one implementation, the temperature of sputter deposition can be between 250° C. and 350° C. In one implementation, the first transparent conductive layer  220  can be carried out by sputter deposition at a power of between 10 kW and 15 kW. 
     In one implementation, an intermediate layer can be deposited between the substrate  210  and the second transparent conductive layer  220 . In an implementation, the intermediate layer can include an insulating layer such as an antireflective layer. The antireflective layer can include a silicon oxide, niobium oxide, or any combination thereof. In a particular implementation, the intermediate layers can be an antireflective layer that can be used to help reduce reflection. The antireflective layer may have an index of refraction between the underlying layers (refractive index of the underlying layers can be approximately 2.0) and clean, dry air or an inert gas, such as Ar or N2 (many gases have refractive indices of approximately 1.0). In an implementation, the antireflective layer may have a refractive index in a range of 1.4 to 1.6. The antireflective layer can include an insulating material having a suitable refractive index. In a particular implementation, the antireflective layer may include silica. The thickness of the antireflective layer can be selected to be thin and provide the sufficient antireflective properties. The thickness for the antireflective layer can depend at least in part on the refractive index of the electrochromic layer  130  and counter electrode layer  140 . The thickness of the intermediate layer can be in a range of 20 nm to 100 nm. 
     At operation  320  and as seen in  FIG. 2B , an electrochromic layer  230  may be deposited on the first transparent conductive layer  220 . The electrochromic layer  230  can be similar to the electrochromic layer  130  described above. In one implementation, the deposition of the electrochromic layer  230  may be carried out by sputter deposition of tungsten, at a temperature between 23° C. and 400° C., in a sputter gas including oxygen and argon. In one implementation, the sputter gas includes between 40% and 80% oxygen and between 20% and 60% argon. In one implementation, the sputter gas includes 50% oxygen and 50% argon. In one implementation, the temperature of sputter deposition is between 100° C. and 350° C. In one implementation, the temperature of sputter deposition is between 200° C. and 300° C. An additionally deposition of tungsten may be sputter deposited in a sputter gas that includes 100% oxygen. 
     At operation  330  and as seen in  FIG. 2C , an anodic electrochemical layer  240  may be deposited on the cathodic electrochemical layer  230 . In one implementation, the anodic electrochemical layer  240  can be a counter electrode. The anodic electrochemical layer  240  can be similar to the anodic electrochemical layer  140  described above. In one implementation, the deposition of the anodic electrochemical layer  240  may be carried out by sputter deposition of tungsten, nickel, and lithium, at a temperature between 20° C. and 50° C., in a sputter gas including oxygen and argon. In one implementation, the sputter gas includes between 60% and 80% oxygen and between 20% and 40% argon. In one implementation, the temperature of sputter deposition is between 22° C. and 32° C. 
     At operation  340  and as seen in  FIG. 2D , a second transparent conductive layer  250  may be deposited on the anodic electrochemical layer  240 . The second transparent conductive layer  250  can be similar to the second transparent conductive layer  150  described above. In one implementation, the deposition of the second transparent conductive layer  250  may be carried out by sputter deposition at a power of between 5 kW and 20 kW, at a temperature between 20° C. and 50° C., in a sputter gas including oxygen and argon. In one implementation, the sputter gas includes between 1% and 10% oxygen and between 90% and 99% argon. In one implementation, the sputter gas includes 8% oxygen and 92% argon. In one implementation, the temperature of sputter deposition is between 22° C. and 32° C. In one implementation, after depositing the second transparent conductive layer  250 , the substrate  210 , first transparent conductive layer  220 , the cathodic electrochemical layer  230 , the anodic electrochemical layer  240 , and the second transparent conductive layer  250  may be heated a at a temperature between 300° C. and 500° C. for between 2 min and 10 min. In one implementation, additional layers may be deposited on the second transparent conductive layer  250 . 
     Following the deposition of the stack above, a pattern may be determined. The pattern can include a first region and a second region. The first region may have a first resistivity and the second region may have a second resistivity. At operation  350  and as seen in  FIG. 2E , the first transparent conductive layer  220  can be patterned. In one embodiment, a short pulse laser  260  having a wavelength between 400 nm and 700 nm is directed through the substrate  110  to pattern the first transparent conductive layer  220 . In one embodiment, the short pulse laser may be directed through the substrate  110  and the support laminate layer  712 , as seen in  FIG. 7 , to pattern the first transparent conductive layer  220 . In one embodiment, the short pulse laser  260  having a wavelength between 500 nm and 550 nm is directed through the substrate  110  to pattern the first transparent conductive layer  220 . The wavelength and duration of the laser  260  are selected to prevent a build up of heat within the device  200 . In one embodiment, the substrate  210  remains unaffected while the first transparent conductive layer  220  can be patterned. In another embodiment, the substrate  210  and the support laminate layer  712  remain unaffected while the first transparent conductive layer  220  can be patterned. In an embodiment including layers between the substrate  210  and the first transparent conductive layer  220 , the short pulse laser  260  can be directed through the substrate  210  and the subsequent layers until reaching and patterning the first transparent conductive layer  220 . Patterning the first transparent conductive layer  220  can be done while maintaining the substrate  210 , the cathodic electrochemical layer  230 , the anodic electrochemical layer  240 , and the second transparent conductive layer  250  intact. In another embodiment, patterning the first transparent conductive layer  220  can be done while maintaining the substrate  210 , the cathodic electrochemical layer  230 , the anodic electrochemical layer  240 , the second transparent conductive layer  250 , the support laminate layer  712 , and the laminate layer  711  intact. In another embodiment, the laser  260  may be directed to pattern the first transparent conductive layer  230  by directing the laser beam through the second transparent conductive layer  250 , the anodic electrochemical layer  240 , and the cathodic electrochemical layer  230  until reaching the first transparent conducive layer  220  without affecting any of the other layers. In yet another embodiment, the laser  260  may be directed to pattern the first transparent conductive layer  230  by directing the laser beam through the laminate layer  711 , the second transparent conductive layer  250 , the anodic electrochemical layer  240 , and the cathodic electrochemical layer  230  until reaching the first transparent conducive layer  220  without affecting any of the other layers. 
     In one embodiment, the short pulse laser  260  may have a wavelength between 500 nm and 550 nm. In one embodiment, the short pulse laser  260  fires for a duration of between 50 femtoseconds and 1 second. The wavelength of the laser  260  may be selected so that the energy of the laser  260  is absorbed by the first transparent conductive layer  220  as compared to the substrate  210 . In one embodiment, the short pulse laser  260  can be moved across the device  200  to form a pattern. In one embodiment, the pattern can include a first resistivity and a second resistivity. The short pulse laser  260  may transform the material of the first transparent conductive layer  220  to change the resistivity without removing any material from the stack. In other words, the short pulse laser  260  targets a first region corresponding to the pattern determined, to change the resistivity of that region while the remainder of the first transparent conductive layer remains the same. The resulting pattern, as seen in  FIG. 2F , then can include a first resistivity and a second resistivity. Before patterning, the first transparent conductive layer  220  can have a uniform resistivity. After patterning, the first transparent conductive layer  220  can have a pattern including a first resistivity and a second resistivity. In one embodiment, the first region can have the first resistivity and the second region can have the second resistivity. In one embodiment, the first region and the second region can have the same composition of materials. In one embodiment, the first resistivity is greater than the second resistivity. In one embodiment, the first resistivity is less than the second resistivity. In one embodiment the first resistivity can be between 15 Ω/sq to 100 Ω/sq. In one embodiment, the first transparent conductive  220  layer can include the first and second festivities while the second transparent conductive layer  250  can include a single resistivity. Patterning the device after all the layers have been deposited on the substrate  210  reduces manufacturing costs. Additionally, the patterned device has a more uniform, homogeneous, and fast transition as seen from center-to-edge of a panel. 
       FIGS. 4A-4B  are schematic illustrations of a top view of the first transparent conductive layer  220 , according to various embodiments. The first transparent conductive layer  220  can have a pattern including a first region  422  and a second  424 . In one embodiment, the first region  422  can have the first resistivity and the second region  424  can have the second resistivity. In one implementation, the pattern varies across the first transparent conductive layer  220 . In one embodiment, the pattern can include geometric shapes. In one embodiment, the pattern can decrease in size towards the center of the first transparent conductive layer  220  and increase in size towards opposite ends of the transparent conductive layer  220 . In one embodiment, the first region  422  may be less than the second region  424 , as seen in  FIG. 4A . In another embodiment, the first region  422  may be greater than the second region  424 , as seen in  FIG. 2B . In one embodiment, the first region  422  may be graduated to increase from one edge of the first transparent conductive layer  220  to the opposite edge of the first transparent conductive layer  220 . 
     Any of the electrochemical devices can be subsequently processed as a part of an insulated glass unit.  FIG. 5  is a schematic illustration of an insulated glazing unit  500  according the implementation of the current disclosure. The insulated glass unit  500  can include a first panel  505 , an electrochemical device  520  coupled to the first panel  505 , a second panel  510 , and a spacer  515  between the first panel  505  and second panel  510 . The first panel  505  can be a glass panel, a sapphire panel, an aluminum oxynitride panel, or a spinel panel. In another implementation, the first panel can include a transparent polymer, such as a polyacrylic compound, a polyalkene, a polycarbonate, a polyester, a polyether, a polyethylene, a polyimide, a polysulfone, a polysulfide, a polyurethane, a polyvinylacetate, another suitable transparent polymer, or a co-polymer of the foregoing. The first panel  505  may or may not be flexible. In a particular implementation, the first panel  505  can be float glass or a borosilicate glass and have a thickness in a range of 2 mm to 20 mm thick. The first panel  505  can be a heat-treated, heat-strengthened, or tempered panel. In one implementation, the electrochemical device  520  is coupled to first panel  505 . In another implementation, the electrochemical device  520  is on a substrate  525  and the substrate  525  is coupled to the first panel  505 . In one implementation, a lamination interlayer  530  may be disposed between the first panel  505  and the electrochemical device  520 . In one implementation, the lamination interlayer  530  may be disposed between the first panel  505  and the substrate  525  containing the electrochemical device  520 . The electrochemical device  520  may be on a first side  521  of the substrate  525  and the lamination interlayer  530  may be coupled to a second side  522  of the substrate. The first side  521  may be parallel to and opposite from the second side  522 . 
     The second panel  510  can be a glass panel, a sapphire panel, an aluminum oxynitride panel, or a spinel panel. In another implementation, the second panel can include a transparent polymer, such as a polyacrylic compound, a polyalkene, a polycarbonate, a polyester, a polyether, a polyethylene, a polyimide, a polysulfone, a polysulfide, a polyurethane, a polyvinylacetate, another suitable transparent polymer, or a co-polymer of the foregoing. The second panel may or may not be flexible. In a particular implementation, the second panel  510  can be float glass or a borosilicate glass and have a thickness in a range of 5 mm to 30 mm thick. The second panel  510  can be a heat-treated, heat-strengthened, or tempered panel. In one embodiment, the spacer  515  can be between the first panel  505  and the second panel  510 . In another embodiment, the spacer  515  is between the substrate  525  and the second panel  510 . In yet another embodiment, the spacer  515  is between the electrochemical device  520  and the second panel  510 . 
     In another implementation, the insulated glass unit  500  can further include additional layers. The insulated glass unit  500  can include the first panel, the electrochemical device  520  coupled to the first panel  505 , the second panel  510 , the spacer  515  between the first panel  505  and second panel  510 , a third panel, and a second spacer between the first panel  505  and the second panel  510 . In one implementation, the electrochemical device may be on a substrate. The substrate may be coupled to the first panel using a lamination interlayer. A first spacer may be between the substrate and the third panel. In one implementation, the substrate is coupled to the first panel on one side and spaced apart from the third panel on the other side. In other words, the first spacer may be between the electrochemical device and the third panel. A second spacer may be between the third panel and the second panel. In such an embodiment, the third panel is between the first spacer and second spacer. In other words, the third panel is couple to the first spacer on a first side and coupled to the second spacer on a second side opposite the first side. 
     The implementations described above and illustrated in the figures are not limited to rectangular shaped devices. Rather, the descriptions and figures are meant only to depict cross-sectional views of a device and are not meant to limit the shape of such a device in any manner. For example, the device may be formed in shapes other than rectangles (e.g., triangles, circles, arcuate structures, etc.). For further example, the device may be shaped three-dimensionally (e.g., convex, concave, etc.). 
       FIG. 7  illustrates a cross-section view of a laminated electrochemical device  700  having an improved film structure. For purposes of illustrative clarity, the electrochemical device  700  is a variable transmission device. The electrochemical device  700  can be similar to the electrochemical device  100 , described in more detail above. The electrochemical device  700  may include a substrate  110  and a stack overlying the substrate  110 . The electrochemical device  700  may also include a laminate layer  711  and a support laminate layer  712 . In one implementation, the electrochemical device  700  may include the laminate layer  711  without the support laminate layer  712 . The stack may include a first transparent conductor layer  120 , a cathodic electrochemical layer  130 , an anodic electrochemical layer  140 , and a second transparent conductor layer  150 . In one embodiment, the stack may also include an ion conducting layer between the cathodic electrochemical layer  130  and the anodic electrochemical layer  140 . 
     In an implementation, the laminate layer  711  and the support laminate layer  712  can include a glass substrate, a sapphire substrate, an aluminum oxynitride substrate, or a spinel substrate. In another implementation, the laminate layer  711  and the support laminate layer  712  can include a transparent polymer, such as a polyacrylic compound, a polyalkene, a polycarbonate, a polyester, a polyether, a polyethylene, a polyimide, a polysulfone, a polysulfide, a polyurethane, a polyvinylacetate, another suitable transparent polymer, or a co-polymer of the foregoing. The laminate layer  711  and the support laminate layer  712  may or may not be flexible. In a particular implementation, laminate layer  711  may have a thickness equal to the support laminate layer  712 . In one implementation, the laminate layer  711  may have a thickness between 0.5 mm and 5 mm. In one implementation, the support laminate layer  712  may have a thickness between 1 mm and 25 mm. 
     Many different aspects and implementations are possible. Some of those aspects and implementations are described below. After reading this specification, skilled artisans will appreciate that those aspects and implementations are only illustrative and do not limit the scope of the present invention. Exemplary implementations may be in accordance with any one or more of the ones as listed below. 
     Embodiment 1 
     A method of forming an electrochemical device, the method can include providing a substrate and a stack overlying the substrate. The stack can include a first transparent conductive layer over the substrate, a cathodic electrochemical layer over the first transparent conductive layer, an anodic electrochemical layer over the electrochromic layer, and a second transparent conductive layer overlying the anodic electrochemical layer. The method can further include determining a first pattern for the first transparent conductive layer. The first pattern can include a first region and a second region. The first region and the second region can include the same material. The method can also include patterning the first region of the first transparent conductive layer without removing the material from the first region. After patterning, the first region can have a first resistivity and the second region can have a second resistivity. 
     Embodiment 2 
     The method of Embodiment 1, wherein patterning the first transparent conductive layer to form the first resistivity and the second resistivity can be patterned through the substrate. 
     Embodiment 3 
     The method of Embodiment 1, wherein patterning the first transparent conductive layer to form the first resistivity and the second resistivity can be patterned after forming the active stack. 
     Embodiment 4 
     The method of Embodiment 1, wherein patterning the first transparent conductive layer comprises using a short pulse laser having a wavelength between 400 nm and 700 nm. 
     Embodiment 5 
     The method of Embodiment 1, wherein the short pulse laser have a wavelength between 500 nm and 550 nm. 
     Embodiment 6 
     The method of Embodiment 1, wherein the short pulse laser fires for a duration of between 50 femtoseconds and 1 second. 
     Embodiment 7 
     The method of Embodiment 1, wherein the first resistivity is greater than the second resistivity. 
     Embodiment 8 
     The method of Embodiment 1, wherein the first resistivity is between 15 Ω/sq to 100 Ω/sq. 
     Embodiment 9 
     The method of Embodiment 1, wherein the substrate comprises glass, sapphire, aluminum oxynitride, spinel, polyacrylic compound, polyalkene, polycarbonate, polyester, polyether, polyethylene, polyimide, polysulfone, polysulfide, polyurethane, polyvinylacetate, another suitable transparent polymer, co-polymer of the foregoing, float glass, borosilicate glass, or any combination thereof. 
     Embodiment 10 
     The method of Embodiment 1, wherein the stack further comprises an ion conducting layer between the cathodic electrochemical layer and the anodic electrochemical layer. 
     Embodiment 11 
     The method of Embodiment 10, wherein the ion-conducting layer comprises lithium, sodium, hydrogen, deuterium, potassium, calcium, barium, strontium, magnesium, oxidized lithium, Li 2 WO 4 , tungsten, nickel, lithium carbonate, lithium hydroxide, lithium peroxide, or any combination thereof. 
     Embodiment 12 
     The method of Embodiment 1, wherein the cathodic electrochemical layer comprises an electrochromic material. 
     Embodiment 13 
     The method of Embodiment 12, wherein the electrochromic material comprises WO 3 , V 2 O 5 , MoO 3 , Nb 2 O 5 , TiO 2 , CuO, Ni 2 O 3 , NiO, Ir 2 O 3 , Cr 2 O 3 , CO 2 O 3 , Mn 2 O 3 , mixed oxides (e.g., W—Mo oxide, W—V oxide), lithium, aluminum, zirconium, phosphorus, nitrogen, fluorine, chlorine, bromine, iodine, astatine, boron, a borate with or without lithium, a tantalum oxide with or without lithium, a lanthanide-based material with or without lithium, another lithium-based ceramic material, or any combination thereof. 
     Embodiment 14 
     The method of Embodiment 1, wherein the first transparent conductive layer comprises indium oxide, indium tin oxide, doped indium oxide, tin oxide, doped tin oxide, zinc oxide, doped zinc oxide, ruthenium oxide, doped ruthenium oxide, silver, gold, copper, aluminum, and any combination thereof. 
     Embodiment 15 
     The method of Embodiment 1, wherein the second transparent conductive layer comprises indium oxide, indium tin oxide, doped indium oxide, tin oxide, doped tin oxide, zinc oxide, doped zinc oxide, ruthenium oxide, doped ruthenium oxide and any combination thereof. 
     Embodiment 16 
     The method of Embodiment 1, wherein the anodic electrochemical layer comprises a an inorganic metal oxide electrochemically active material, such as WO 3 , V 2 O 5 , MoO 3 , Nb 2 O 5 , TiO 2 , CuO, Ir 2 O 3 , Cr 2 O 3 , Co 2 O 3 , Mn 2 O 3 , Ta 2 O 5 , ZrO 2 , HfO 2 , Sb 2 O 3 , a lanthanide-based material with or without lithium, another lithium-based ceramic material, a nickel oxide (NiO, Ni 2 O 3 , or combination of the two), and Li, nitrogen, Na, H, or another ion, any halogen, or any combination thereof. 
     Embodiment 17 
     An electrochemical device including a substrate and a first transparent conductive layer over the substrate. The first transparent conductive layer comprises a material, and the material has a first resistivity and a second resistivity. The electrochemical device can also include a second transparent conductive layer, an anodic electrochemical layer between the first transparent conductive layer and the second transparent conductive layer, and a cathodic electrochemical layer between the first transparent conductive layer and the second transparent conductive layer. 
     Embodiment 18 
     The electrochemical device of Embodiment 17, wherein no material is removed from the first transparent conductive layer. 
     Embodiment 19 
     An insulated glazing unit may include a first panel and an electrochemical device coupled to the first panel. The electrochemical device may include a substrate and a first transparent conductive layer disposed on the substrate. The first transparent conductive layer comprises a material and the material has a first resistivity and a second resistivity. The electrochemical device may also include a cathodic electrochemical layer overlying the first transparent conductive layer, an anodic electrochemical layer overlying the cathodic electrochemical layer, and a second transparent conductive layer. The insulated glazing unit may also include a second panel, and a spacer frame disposed between the first panel and the second panel. 
     Embodiment 20 
     The insulated glazing unit of Embodiment 19, wherein the electrochemical device is between the first panel and the second panel. 
     EXAMPLES 
     An example is provided to demonstrate the performance of an electrochemical device with a patterned ITO layer as compared to other electrochemical devices without patterned layers. For the various examples below, sample  1  (S 1 ) was formed in accordance to the various embodiments described above. Comparative sample, Sample  2  (S 2 ) is understood to be an embodiment without a patterned ITO layer. 
       FIG. 6  is a graph of the holding voltages of various samples S 1  and S 2 . The illustration in  FIG. 6  shows the samples at a held voltage as the sample transitions from clear to tint. As can be seen in  FIG. 5 , S 1  has a homogenous pattern while S 2  has a varying pattern. The center-to-edge difference during holding has been reduced by &gt;80% for the S 1  sample. 
     Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed is not necessarily the order in which they are performed. 
     Certain features that are, for clarity, described herein in the context of separate implementations, may also be provided in combination in a single implementation. Conversely, various features that are, for brevity, described in the context of a single implementation, may also be provided separately or in any subcombination. Further, reference to values stated in ranges includes each and every value within that range. 
     Benefits, other advantages, and solutions to problems have been described above with regard to specific implementations. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims. 
     The specification and illustrations of the implementations described herein are intended to provide a general understanding of the structure of the various implementations. The specification and illustrations are not intended to serve as an exhaustive and comprehensive description of all of the elements and features of apparatus and systems that use the structures or methods described herein. Separate implementations may also be provided in combination in a single implementation, and conversely, various features that are, for brevity, described in the context of a single implementation, may also be provided separately or in any subcombination. Further, reference to values stated in ranges includes each and every value within that range. Many other implementations may be apparent to skilled artisans only after reading this specification. Other implementations may be used and derived from the disclosure, such that a structural substitution, logical substitution, or another change may be made without departing from the scope of the disclosure. Accordingly, the disclosure is to be regarded as illustrative rather than restrictive.