Stock-based production of patterned transparent conductive layers

Abstract

The present disclosure provides an electrochemical device and a method for forming the device. The method may include providing a substrate and a stack covering the substrate. The stack may include a first transparent conductive layer above the substrate, a cathode electrochemical layer above the first transparent conductive layer, an anode electrochemical layer above the electrochemical layer, and a second transparent conductive layer covering the anode electrochemical layer. The method may include depositing an insulating layer above the stack and determining a first pattern for the second transparent conductive layer. The first pattern may include a first region and a second region. The first region and the second region may be the same material. The method may include patterning the first region of the second transparent conductive layer without removing the material from the first region. The first region may have a first resistivity and the second region may have a second resistivity.

Description

Technical Field

[0001] The present disclosure relates to electrochemical devices and methods of forming the same. Background Art

[0002] Electrochemical devices may include electrochromic stacks in which transparent conductive layers are used to provide electrical connections for stack operation. Electrochromic (EC) devices utilize materials that are able to reversibly change 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.

[0003] Advances in electrochromic devices seek devices with faster and more uniform switching speeds while maintaining throughput during the manufacturing process.

[0004] Therefore, further improvements are sought in the manufacture of electrochromic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0005] Figure 1 is a schematic cross-sectional view of an electrochromic device according to one embodiment.

[0006] Figures 2A to 2G is a schematic cross-sectional view of an electrochemical process at various stages of fabrication according to an embodiment of the present disclosure.

[0007] Figure 3 is a flow chart depicting a procedure for forming an electrochemical device according to an embodiment of the present disclosure.

[0008] FIG. 4A to FIG. 4B is a schematic diagram of a top view of a transparent conductive layer according to various embodiments.

[0009] Figure 5 is a schematic diagram of an insulated glazing unit according to an embodiment of the present disclosure.

[0010] Figure 6 is a graph of the holding voltage of various samples.

[0011] The skilled person understands that the elements in the drawings are depicted for simplicity and clarity and are not necessarily drawn to scale. For example, the size of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the embodiments of the present invention. DETAILED DESCRIPTION

[0012] The following description is combined with the accompanying drawings to assist in understanding the teachings disclosed herein. The following discussion will focus on specific implementations and implementations of the teachings. The focus is used to assist in describing the teachings and should not be interpreted as limiting the scope or applicability of the teachings disclosed in this application.

[0013] As used herein, the terms "comprises / comprising / includes / including", "has / having" or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to only 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 an exclusive-or. For example, a condition A or B satisfies any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0014] "A" or "an" is used to describe elements and components described herein. This is only for convenience and to give a general sense of the scope of the invention. Unless otherwise clearly intended, this description should be understood to include one or at least one and the singular also includes the plural, or vice versa.

[0015] The use of the words "about", "approximately" or "substantially" means that the numerical value of a parameter is close to the numerical value or position described. However, slight differences may cause the numerical value or position not to be exactly as described.

[0016] Patterned features including busses, holes, apertures, etc. may have a width, a depth or thickness, and a length, wherein the length is greater than the width and the depth or thickness. As used in this specification, the diameter is the width of a circle and the minor axis is the width of an ellipse.

[0017] The "impedance parameter" is a measure of the effective resistance of an electrochemical device (i.e., the combined effect of ohmic resistance and electrochemical reactance) and is measured on a 5 x 5 cm device at 2log(freq / Hz) when a 5 mV to 50 mV DC bias is applied to the device at -20°C. The resultant current is measured and the impedance and phase angle are calculated at each frequency in the range of 100 Hz to 6 MHz.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as understood by one of ordinary skill in the art to which the invention belongs. The materials, methods, and examples are illustrative only and not limiting. To the extent not described herein, many details about specific materials and processing behaviors are conventional and can be found in textbooks and other sources in the field of glass, vapor deposition, and electrochromic.

[0019] According to this disclosure, Figure 1 A cross-sectional view of a partially assembled electrochemical device 100 having an improved film structure is depicted. For purposes of clarity of explanation, the electrochemical device 100 is a variable transmission device. In one embodiment, the electrochemical device 100 may be an electrochromic device. In another embodiment, the electrochemical device 100 may be a thin film battery. However, it should be understood that the present disclosure is equally applicable to other types of scored electroactive devices, electrochemical devices, and other electrochromic devices having different stacks or film structures (e.g., additional layers). In addition, the electroactive device may be incorporated into an automobile, a window, a building facade, a building exterior, a transportation vehicle, a train, or a mirror. About Figure 1 The electrochemical device 100 of the present invention may include a substrate 110 and a stack covering the substrate 110. The stack may include a first transparent conductor layer 120, a cathode electrochemical layer 130, an anode electrochemical layer 140, and a second transparent conductor layer 150. The device 100 may also include an insulating layer 170. In one embodiment, the stack may also include an ion conductive layer between the cathode electrochemical layer 130 and the anode electrochemical layer 140.

[0020] In one embodiment, substrate 110 may include a glass substrate, a sapphire substrate, an aluminum oxynitride substrate or a spinel substrate. In another embodiment, substrate 110 may include a transparent polymer, such as a polyacrylic acid compound, a polyolefin, a polycarbonate, a polyester, a polyether, a polyethylene, a polyimide, a polysulfone, a polysulfide, a polyurethane, a polyvinyl acetate, another suitable transparent polymer, or a copolymer of the foregoing. Substrate 110 may or may not be flexible. In a specific embodiment, substrate 110 may be a float glass or a borosilicate glass, and has a thickness in the range of 0.5mm to 12mm thick. Substrate 110 may have a thickness of not more than 16mm, such as 12mm, not more than 10mm, not more than 8mm, not more than 6mm, not more than 5mm, not more than 3mm, not more than 2mm, not more than 1.5mm, not more than 1mm or not more than 0.01mm. In another specific embodiment, substrate 110 may include ultra-thin glass, which is a mineral glass with a thickness in the range of 50 microns to 300 microns. In a particular embodiment, substrate 110 may be used to form many different electrochemical devices and may be referred to as a motherboard.

[0021] Transparent conductive layers 120 and 150 may include conductive metal oxides or conductive polymers. Examples may include tin oxide or zinc oxide (either of which may be doped with trivalent elements such as Al, Ga, In, etc.), fluorinated tin oxide or sulfonated polymers such as polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene), etc. In another embodiment, transparent conductive layer 120 and transparent conductive layer 150 may include gold, silver, copper, nickel, aluminum, or any combination thereof. Transparent conductive layer 120 and transparent conductive layer 150 may 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. Transparent conductive layer 120 and transparent conductive layer 150 may have the same or different compositions. In one embodiment, transparent conductive layer 150 above anode electrochemical layer 140 may have a first resistivity and a second resistivity without removing material from the active stack. In one embodiment, the transparent conductive layer 150 may have a pattern, wherein a first portion of the pattern 152 corresponds to a first resistivity and a second portion of the pattern 154 corresponds to a second resistivity. The first portion of the pattern 152 and the second portion of the pattern 154 may be the same material. In one embodiment, the first portion of the pattern 152 has been altered by a short pulse laser to increase the resistivity. In one embodiment, the first resistivity is greater than the second resistivity. In another embodiment, the first resistivity is less than the second resistivity. The first portion of the pattern and the second portion of the pattern come from altering the second transparent conductive layer 150, as described in detail below.

[0022] The transparent conductive layer 120 and the transparent conductive layer 150 may have a thickness between 10nm and 600nm. In one embodiment, the transparent conductive layer 120 and the transparent conductive layer 150 may have a thickness between 200nm and 500nm. In one embodiment, the transparent conductive layer 120 and the transparent conductive layer 150 may have a thickness between 320nm and 460nm. In one embodiment, the first transparent conductive layer 120 may have a thickness between 10nm and 600nm. In one embodiment, the second transparent conductive layer 150 may have a thickness between 80nm and 600nm.

[0023] Layer 130 and layer 140 may be electrode layers, wherein one of the layers may be a cathode electrochemical layer and the other of the layers may be an anode electrochromic layer (also referred to as a counter electrode layer). In one embodiment, cathode electrochemical layer 130 is an electrochromic layer. Cathode electrochemical layer 130 may include an inorganic metal oxide material, such as WO 3 、V 2 O 5 、MoO 3 , Nb 2 O5 、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, WV oxide), or any combination thereof, and may have a thickness in the range of 40 nm to 600 nm. In one embodiment, cathode electrochemical layer 130 may have a thickness between 100 nm and 400 nm. In one embodiment, cathode electrochemical layer 130 may have a thickness between 350 nm and 390 nm. Cathode electrochemical layer 130 may include lithium, aluminum, zirconium, phosphorus, nitrogen, fluorine, chlorine, bromine, iodine, astatine, boron; borates with or without lithium; tantalum oxide with or without lithium; lanthanide-based materials with or without lithium; another lithium-based ceramic material; or any combination thereof.

[0024] The anode electrochromic layer 140 may include any of the materials listed for the cathode 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 In some embodiments, the anode electrochromic layer 140 may be anode 130 or anode 140. ...

[0025] In another embodiment, the device 100 may include multiple layers between the substrate 110 and the first transparent conductive layer 120. In one embodiment, an anti-reflective layer may be between the substrate 110 and the first transparent conductive layer 120. The anti-reflective layer may include SiO 2 、NbO 2 , Nb 2 O 5, and may be between 20 nm and 100 nm thick. The device 100 may include at least two bus bars, one of which is electrically connected to the first transparent conductive layer 120 , and the second bus bar is electrically connected to the second transparent conductive layer 150 .

[0026] Figure 3 is a flow chart depicting a process 300 for forming an electrochromic device according to an embodiment of the present disclosure. FIG. 2A to FIG. 2E 2 is a schematic cross-sectional view of an electrochromic device 200 at various stages of manufacture according to an embodiment 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, such as Figure 2A As shown in . The first transparent conductive layer 220 may be similar to the first transparent conductive layer 120 described above. In one embodiment, the deposition of the first transparent conductive layer 220 may be performed by sputtering deposition at a rate between 0.1 m / min and 0.5 m / min in a sputtering gas including oxygen and argon at a power between 5 kW and 20 kW, at a temperature between 200° C. and 400° C. In one embodiment, the sputtering gas includes between 40% and 80% oxygen and between 20% and 60% argon. In one embodiment, the sputtering gas includes 50% oxygen and 50% argon. In one embodiment, the temperature of the sputtering deposition may be between 250° C. and 350° C. In one embodiment, the first transparent conductive layer 220 may be performed by sputtering deposition at a power between 10 kW and 15 kW.

[0027] In one embodiment, the intermediate layer may be deposited between the substrate 210 and the second transparent conductive layer 220. In one embodiment, the intermediate layer may include an insulating layer, such as an anti-reflective layer. The anti-reflective layer may include silicon oxide, niobium oxide, or any combination thereof. In a specific embodiment, the intermediate layer may be an anti-reflective layer that can be used to help reduce reflections. The anti-reflective layer may have a refractive index between the lower layer (the lower layer may have a refractive index of about 2.0) and clean, dry air or an inert gas such as Ar or N 2 The anti-reflection layer may have a refractive index between 1.0 and 2.0 (many gases have a refractive index of about 1.0). In one embodiment, the anti-reflection layer may have a refractive index in the range of 1.4 to 1.6. The anti-reflection layer may include an insulating material with a suitable refractive index. In a specific embodiment, the anti-reflection layer may include silicon dioxide. The thickness of the anti-reflection layer may be selected to be thin and provide sufficient anti-reflection properties. The thickness of the anti-reflection layer may depend at least in part on the refractive index of the electrochromic layer 130 and the opposite electrode layer 140. The thickness of the intermediate layer may be in the range of 20 nm to 100 nm.

[0028] At operation 320 and as Figure 2B As shown, the electrochromic layer 230 can 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 embodiment, the deposition of the electrochromic layer 230 can be performed by sputtering tungsten in a sputtering gas including oxygen and argon at a temperature between 23°C and 400°C. In one embodiment, the sputtering gas includes between 40% and 80% oxygen and between 20% and 60% argon. In one embodiment, the sputtering gas includes 50% oxygen and 50% argon. In one embodiment, the temperature of the sputtering deposition is between 100°C and 350°C. In one embodiment, the temperature of the sputtering deposition is between 200°C and 300°C. The additional deposition of tungsten can be sputtered in a sputtering gas including 100% oxygen.

[0029] At operation 330 and as Figure 2C As shown, the anode electrochemical layer 240 can be deposited on the cathode electrochemical layer 230. In one embodiment, the anode electrochemical layer 240 can be a counter electrode. The anode electrochemical layer 240 can be similar to the anode electrochemical layer 140 described above. In one embodiment, the deposition of the anode electrochemical layer 240 can be performed by sputtering tungsten, nickel and lithium in a sputtering gas including oxygen and argon at a temperature between 20°C and 50°C. In one embodiment, the sputtering gas includes between 60% and 80% oxygen and between 20% and 40% argon. In one embodiment, the temperature of the sputtering deposition is between 22°C and 32°C.

[0030] At operation 340 and as Figure 2D As shown, the second transparent conductive layer 250 can be deposited on the anode electrochemical layer 240. The second transparent conductive layer 250 can be similar to the second transparent conductive layer 150 described above. In one embodiment, the deposition of the second transparent conductive layer 250 can be performed by sputter deposition in a sputtering gas including oxygen and argon at a power between 5 kW and 20 kW, at a temperature between 20° C. and 50° C. In one embodiment, the sputtering gas includes oxygen between 1% and 10% and argon between 90% and 99%. In one embodiment, the sputtering gas includes 8% oxygen and 92% argon. In one embodiment, the temperature of the sputtering deposition is between 22° C. and 32° C. In one embodiment, after the second transparent conductive layer 250 is deposited, the substrate 210, the first transparent conductive layer 220, the cathode electrochemical layer 230, the anode electrochemical layer 240, and the second transparent conductive layer 250 can be heated at a temperature between 300° C. and 500° C. for between 2 min and 10 min.

[0031] At operation 350, an additional layer may be deposited on the second transparent conductive layer 250. In one embodiment, the additional layer 270 may include an insulating layer similar to the insulating layer 170, such as Figure 2E In one embodiment, the insulating layer may include silicon dioxide (SiO 2 In one embodiment, the additional layer 270 may include a high resistance transparent conductive layer and an insulating layer. After depositing the insulating layer, the device 200 may be viewed as a laminated active stack.

[0032] After the stack is deposited as described above, a pattern may be determined. The pattern may 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 360 and as Figure 2F As shown, the second transparent conductive layer 250 can be patterned. In one embodiment, a short pulse laser 260 having a wavelength between 400nm and 700nm is directed through the insulating layer 270 to pattern the second transparent conductive layer 250. In one embodiment, a short pulse laser 260 having a wavelength between 500nm and 550nm is directed through the top of the stack to pattern the second transparent conductive layer 250. The wavelength and duration of the laser 260 are selected to prevent heat accumulation within the device 200. In one embodiment, the insulating layer 270 remains unaffected while the first transparent conductive layer 220 can be patterned. In an embodiment including layers between the insulating layer 270 and the second transparent conductive layer 250, the short pulse laser 260 can be directed through the insulating layer 270 and subsequent layers until reaching and patterning the second transparent conductive layer 250. Patterning the second transparent conductive layer 250 can be accomplished while maintaining the integrity of the insulating layer 270, substrate 210, cathode electrochemical layer 230, anode electrochemical layer 240, and first transparent conductive layer 220. In another embodiment, the laser 260 can be directed to pattern the second transparent conductive layer 250 by directing a laser beam through the substrate 210, first transparent conductive layer 220, cathode electrochemical layer 230, and anode electrochemical layer 240 until reaching the second transparent conductive layer 250 without affecting any other layers.

[0033] In one embodiment, the short pulse laser 260 may have a wavelength between 500nm and 550nm. In one embodiment, the short pulse laser 260 emits for a period 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 second transparent conductive layer 250 compared to the insulating layer 270 or any other layer in the active stack. In one embodiment, the short pulse laser 260 may be moved across the device 200 to form a pattern. In one embodiment, the pattern may include a first resistivity and a second resistivity. The short pulse laser 260 may transform the material of the second transparent conductive layer 250 to change the resistivity without removing any material from the stack. In other words, the short pulse laser 260 targets a first area corresponding to a determined pattern to change the resistivity of the area, while the rest of the first transparent conductive layer remains the same. As in Figure 2G As seen in , the resulting pattern may include a first resistivity and a second resistivity. Before patterning, the second transparent conductive layer 250 may have a uniform resistivity. After patterning, the second transparent conductive layer 250 may have a pattern including a first resistivity and a second resistivity. In one embodiment, the first region 252 may have a first resistivity and the second region 254 may have a second resistivity. In one embodiment, the first region 252 and the second region 254 may have the same material composition. 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 may be between 15Ω / sq and 100Ω / sq. In one embodiment, the second transparent conductive layer 250 may include a first resistivity and a second resistivity, while the first transparent conductive layer 220 may include a single resistivity. Patterning the device after all layers have been deposited on the substrate 210 reduces manufacturing costs. Patterning the transparent conductive layer after all layers have been deposited on the substrate establishes regions of high resistivity and low resistivity in the transparent conductive layer. The laser contacts the region to be patterned of the transparent conductive layer and increases the resistivity of the region. In doing so, the pattern used can help determine the resistance of each point of the device to produce a more uniform transition. Specifically, when the device is switched from a transparent state to a colored state, the patterned device has a more uniform, uniform and fast transition when viewed from the center to the edge of the device. The same patterned transparent conductive layer shows improved retention uniformity as the selective pattern reduces the resistance difference from the center to the edge, as shown in the following example section. As the device becomes larger or the distance between the busses increases, the uniformity of retention becomes more obvious.

[0034] FIG. 4A to FIG. 4Bis a schematic diagram of a top view of the second transparent conductive layer 250 according to various embodiments. The second transparent conductive layer 250 may have a pattern including a first region 422 and a second region 424. In one embodiment, the first region 422 may have a first resistivity and the second region 424 may have a second resistivity. In one embodiment, the pattern may vary across the second transparent conductive layer 250. In one embodiment, the pattern may include a geometric shape. In one embodiment, the pattern may decrease in size toward the center of the second transparent conductive layer 250 and increase in size toward opposite ends of the second transparent conductive layer 250. In one embodiment, the first region 422 may be smaller than the second region 424, such as Figure 4A In another embodiment, the first area 422 may be larger than the second area 424. Figure 2B In one embodiment, the first region 422 may gradually increase from one edge of the first transparent conductive layer 220 to the opposite edge of the second transparent conductive layer 250. The first region 422 may be circular, square, rectangular, linear, hexagonal, polygonal, triangular, or any combination thereof.

[0035] Any electrochemical device can then be processed as part of an insulating glass unit. Figure 5 5 is a schematic diagram of an insulating glass unit 500 according to an embodiment of the present disclosure. The insulating glass unit 500 may 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 the second panel 510. The first panel 505 may be a glass panel, a sapphire panel, an aluminum oxynitride panel, or a spinel panel. In another embodiment, the first panel may include a transparent polymer such as a polyacrylic compound, a polyolefin, a polycarbonate, a polyester, a polyether, a polyethylene, a polyimide, a polysulfone, a polysulfide, a polyurethane, a polyvinyl acetate, another suitable transparent polymer, or a copolymer of the foregoing. The first panel 505 may or may not be flexible. In a specific embodiment, the first panel 505 may be a float glass or a borosilicate glass, and has a thickness in the range of 2 mm to 20 mm thick. The first panel 505 may be a heat-treated, heat-strengthened, or tempered panel. In one embodiment, the electrochemical device 520 is coupled to the first panel 505. In another embodiment, the electrochemical device 520 is on a substrate 525, and the substrate 525 is coupled to the first panel 505. In one embodiment, a laminating interlayer 530 may be disposed between the first panel 505 and the electrochemical device 520. In one embodiment, a laminating 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 laminating interlayer 530 may be coupled to a second side 522 of the substrate. The first side 521 may be parallel and opposite to the second side 522.

[0036] The second panel 510 may be a glass panel, a sapphire panel, an aluminum oxynitride panel or a spinel panel. In another embodiment, the second panel may include a transparent polymer, such as a polyacrylic acid compound, a polyolefin, a polycarbonate, a polyester, a polyether, a polyethylene, a polyimide, a polysulfone, a polysulfide, a polyurethane, a polyvinyl acetate, another suitable transparent polymer, or a copolymer of the foregoing. The second panel may or may not be flexible. In a specific embodiment, the second panel 510 may be a float glass or a borosilicate glass, and has a thickness in the range of 5mm to 30mm thick. The second panel 510 may be a panel that is heat treated, heat strengthened or tempered. In one embodiment, a spacer 515 may 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.

[0037] In another embodiment, the insulating glass unit 500 may further include an additional layer. The insulating glass unit 500 may include a first panel, an electrochemical device 520 coupled to the first panel 505, a second panel 510, a spacer 515 between the first panel 505 and the second panel 510, a third panel, and a second spacer between the first panel 505 and the second panel 510. In one embodiment, the electrochemical device may be on a substrate. A laminated interlayer may be used to couple the substrate to the first panel. The first spacer may be between the substrate and the third panel. In one embodiment, 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. The second spacer may be between the third panel and the second panel. In this embodiment, the third panel is between the first spacer and the second spacer. In other words, the third panel is coupled to the first spacer on the first side and is coupled to the second spacer on the second side opposite to the first side.

[0038] The embodiments described above and illustrated in the accompanying drawings are not limited to rectangular devices. Rather, the description and drawings are intended only to illustrate cross-sectional views of devices and are not intended to limit the shape of such devices in any way. For example, the device may be formed into shapes other than rectangular (e.g., triangular, circular, arcuate structures, etc.). For further examples, the device may be three-dimensionally shaped (e.g., convex, concave, etc.).

[0039] Many different aspects and embodiments are feasible. Some such aspects and embodiments are described below. After reading this specification, the skilled person will understand that such aspects and embodiments are only illustrative and do not limit the scope of the present invention. Exemplary embodiments can be based on any one or more of the following embodiments.

[0040] Embodiment 1. A method of forming an electrochemical device, the method may include providing a substrate and a stack covering the substrate. The stack may include a first transparent conductive layer above the substrate, a cathode electrochemical layer above the first transparent conductive layer, an anode electrochemical layer above the electrochemical layer, and a second transparent conductive layer covering the anode electrochemical layer. The method may also include depositing an insulating layer above the stack and determining a first pattern for the second transparent conductive layer. The first pattern may include a first region and a second region. The first region and the second region may be the same material. The method may also include patterning the first region of the second transparent conductive layer without removing the material from the first region. After patterning, the first region may have a first resistivity and the second region may have a second resistivity.

[0041] Embodiment 2. The method of embodiment 1, wherein patterning the second transparent conductive layer to form the first resistivity and the second resistivity can be patterned through the substrate.

[0042] Embodiment 3. The method of embodiment 1, wherein patterning the second transparent conductive layer to form the first resistivity and the second resistivity can be performed after forming the active stack.

[0043] Embodiment 4. The method of embodiment 1, wherein patterning the second transparent conductive layer includes using a short pulse laser having a wavelength between 400 nm and 700 nm.

[0044] Embodiment 5. The method of embodiment 1, wherein the short pulse laser has a wavelength between 500 nm and 550 nm.

[0045] Embodiment 6. The method of embodiment 1, wherein the short pulse laser emission has a duration between 50 femtoseconds and 1 second.

[0046] Embodiment 7. The method of embodiment 1, wherein the first resistivity is greater than the second resistivity.

[0047] Embodiment 8. The method of embodiment 1, wherein the first resistivity is between 15 Ω / sq and 100 Ω / sq.

[0048] Embodiment 9. A method according to embodiment 1, wherein the substrate comprises glass, sapphire, aluminum oxynitride, spinel, polyacrylic compound, polyolefin, polycarbonate, polyester, polyether, polyethylene, polyimide, polysulfone, polysulfide, polyurethane, polyvinyl acetate, another suitable transparent polymer, copolymers of the foregoing polymers, float glass, borosilicate glass, or any combination thereof.

[0049] Embodiment 10. The method of embodiment 1, wherein the stack further comprises an ion conducting layer between the cathode electrochemical layer and the anode electrochemical layer.

[0050] Embodiment 11. The method of embodiment 1, 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.

[0051] Embodiment 12. The method of embodiment 1, wherein the cathode electrochemical layer comprises an electrochromic material.

[0052] 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, WV oxide), lithium, aluminum, zirconium, phosphorus, nitrogen, fluorine, chlorine, bromine, iodine, astatine, boron, borates with or without lithium, tantalum oxide with or without lithium, lanthanide-based materials with or without lithium, another lithium-based ceramic material, or any combination thereof.

[0053] Embodiment 14. A method according to 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.

[0054] 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.

[0055] Embodiment 16. The method of embodiment 1, wherein the anode electrochemical layer comprises an inorganic metal oxide 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 、 2 O 5 、ZrO 2 , HfO 2 , Sb 2 O 3 , lanthanide-based materials with or without lithium, another lithium-based ceramic material, nickel oxide (NiO, Ni 2 O 3 or a combination of both), and Li, nitrogen, Na, H or another ion, any halogen, or any combination thereof.

[0056] Embodiment 17. The method of embodiment 1, wherein patterning the second transparent conductive layer to form the first resistivity and the second resistivity is patterned through the substrate, the first transparent conductive layer, the cathode electrochemical layer, and the anode electrochemical layer.

[0057] Embodiment 18. An electrochemical device comprising a substrate and a first transparent conductive layer and a second transparent conductive layer over the substrate. The second transparent conductive layer comprises a material, and the material has a first resistivity and a second resistivity. The electrochemical device may also include an anode electrochemical layer between the first transparent conductive layer and the second transparent conductive layer; and a cathode electrochemical layer between the first transparent conductive layer and the second transparent conductive layer.

[0058] Embodiment 19. The electrochemical device of embodiment 18, wherein no material is removed from the second transparent conductive layer.

[0059] Embodiment 20. An insulating glass 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 electrochemical device may also include a cathode electrochemical layer covering the first transparent conductive layer, an anode electrochemical layer covering the cathode electrochemical layer, and a second transparent conductive layer. The second transparent conductive layer includes a material and the material has a first resistivity and a second resistivity. The insulating glass unit may also include a second panel and a spacer frame disposed between the first panel and the second panel.

[0060] Embodiment 21. The electrically insulating glass unit of Embodiment 20, wherein the electrochemical device is between the first panel and the second panel.

[0061] Examples

[0062] Examples are provided to demonstrate the performance of electrochemical devices having patterned transparent conductive layers compared to other electrochemical devices without patterned layers. For the following various examples, Sample 1 (S1) is formed according to the various embodiments described above. Comparative samples, Sample 2 (S2) should be understood as an embodiment without a patterned transparent conductive layer.

[0063] Figure 6 is a graph of the holding voltages of various samples S1 and S2. Figure 6 The plot in shows the sample at a holding voltage as the sample changes from colorless to colored. Figure 6 It can be seen that S1 has a uniform pattern, while S2 has a varying pattern. For the S1 sample, the center-to-edge difference has been reduced by >80% during the hold period. The S2 sample has a varying transmission state. The S1 sample has a uniform transmission state.

[0064] Note that not all of the actions described in the general description or examples above are required, a portion of a specific action may not be required, and one or more further actions in addition to those described may be performed. Further still, the order in which the actions are listed is not necessarily the order in which they are performed.

[0065] For clarity, certain features described herein in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, various features described in the context of a single embodiment for brevity may also be provided individually or in any subcombination. Further, values ​​recited in ranges include each and every value within that range.

[0066] The benefits, other advantages and technical means for solving the problems have been described above for specific embodiments. However, the benefits, advantages, technical means for solving the problems and any features that can make any benefits, advantages, technical means for solving the problems occur or become more significant should not be interpreted as the key, required or essential features of any or all claims.

[0067] The description of the embodiments described in the specification and herein is intended to provide a general understanding of the structure of various embodiments. The specification and description are not intended to be used as a detailed and comprehensive description of all elements and features of the device and system using the structure or method described herein. Individual embodiments may also be provided in combination in a single embodiment, and conversely, for the sake of brevity, the various features described in the context of a single embodiment may also be provided separately or in any combination. Further, the values ​​described in the reference range include each and every value within the range. Only after reading this specification, many other embodiments are clear to those skilled in the art. Other embodiments may be used and derived from the present disclosure, so that structural substitution, logical substitution, or other changes may be made without departing from the scope of the present disclosure. Therefore, the present disclosure should be regarded as illustrative rather than restrictive.

Claims

1. A method of forming an electrochemical device, the method comprising: A substrate and a stack covering the substrate are provided, the stack comprising: a first transparent conductive layer above the substrate; a second transparent conductive layer above the substrate; a cathode electrochemical layer, the cathode electrochemical layer being between the first transparent conductive layer and the second transparent conductive layer; and an anode electrochemical layer, wherein the anode electrochemical layer is between the first transparent conductive layer and the second transparent conductive layer; depositing an insulating layer over the stack; determining a first pattern for the second transparent conductive layer, wherein the first pattern includes a first region and a second region, wherein the first region and the second region comprise the same material; and patterning the first region of the second transparent conductive layer without removing the material from the first region, wherein after patterning the first region, the first region comprises a first resistivity and the second region comprises a second resistivity, The second transparent conductive layer is patterned to form the first resistivity and the second resistivity by patterning through the insulating layer.

2. A method of forming an electrochemical device, the method comprising: A substrate and a stack covering the substrate are provided, the stack comprising: a first transparent conductive layer above the substrate; a second transparent conductive layer above the substrate; a cathode electrochemical layer, the cathode electrochemical layer being between the first transparent conductive layer and the second transparent conductive layer; and an anode electrochemical layer, wherein the anode electrochemical layer is between the first transparent conductive layer and the second transparent conductive layer; depositing an insulating layer over the stack; determining a first pattern for the second transparent conductive layer, wherein the first pattern includes a first region and a second region, wherein the first region and the second region comprise the same material; and patterning the first region of the second transparent conductive layer without removing the material from the first region, wherein after patterning the first region, the first region comprises a first resistivity and the second region comprises a second resistivity, The second transparent conductive layer is patterned to form the first resistivity and the second resistivity through the substrate, the first transparent conductive layer, the cathode electrochemical layer and the anode electrochemical layer. 3 . The method of claim 1 , wherein patterning the second transparent conductive layer comprises using a short pulse laser having a wavelength between 400 nm and 700 nm. The method of claim 3 , wherein the short pulse laser has a wavelength between 500 nm and 550 nm. The method of claim 3 , wherein the short pulse laser emission has a duration between 50 femtoseconds and 1 second. The method of claim 1 , wherein the first resistivity is greater than the second resistivity. The method of claim 1 , wherein the first resistivity is between 15Ω / sq and 100Ω / sq.

8. The method of claim 1, wherein the substrate comprises a material selected from the group consisting of glass, sapphire, aluminum oxynitride, spinel, polyacrylic compounds, polyolefins, polycarbonates, polyesters, polyethers, polyethylene, polyimides, polysulfones, polysulfides, polyurethanes, polyvinyl acetate, float glass, borosilicate glass, and any combination thereof.

9. The method of claim 1, wherein the stack further comprises an ionically conductive layer between the cathode electrochemical layer and the anode electrochemical layer.

10. The method of claim 9, wherein the ion conductive layer comprises a material selected from the group consisting of lithium, sodium, hydrogen, deuterium, potassium, calcium, barium, strontium, magnesium, oxidized lithium, Li2WO4, tungsten, nickel, lithium carbonate, lithium hydroxide, lithium peroxide, and any combination thereof.

11. The method of claim 1 , wherein the cathode electrochemical layer comprises an electrochromic material.

12. The method of claim 11, wherein the electrochromic material comprises a material selected from the group consisting of WO3, V2O5, MoO3, Nb2O5, TiO2, CuO, Ni2O3, NiO, Ir2O3, Cr2O3, Co2O3, Mn2O3, lithium, aluminum, zirconium, phosphorus, nitrogen, fluorine, chlorine, bromine, iodine, astatine, boron, borates with or without lithium, tantalum oxide with or without lithium, lanthanide-based materials with or without lithium, or any combination thereof.

13. The method of claim 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, and any combination thereof.

14. The method of claim 1, wherein patterning the second transparent conductive layer to form the first resistivity and the second resistivity is patterned after forming the stack.

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