Low Sheet Resistance Coating

Abstract

The coated article comprises a substrate, a first dielectric layer on at least a portion of the substrate, a first metal layer on at least a portion of the first dielectric layer, a first primer layer on at least a portion of the first metal layer, and a second dielectric layer on at least a portion of the first primer layer, wherein the first primer layer is selected from the group consisting of zinc, aluminum doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, zinc tin, indium zinc, silver zinc, gallium zinc, indium tin, mixtures thereof, combinations thereof, and alloys thereof.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates generally to vehicle transparencies such as vehicle windshields, and in one particular embodiment to heatable vehicle windshields. [Background technology]

[0002] Passing an electric current through the conductors in a laminated automobile windshield increases the temperature of the windshield, which is particularly beneficial in cold climates for defrosting and melting ice and / or snow on the windshield.

[0003] In a wire heated windshield, a thin conductive wire is placed between the windshield layers. The wire is connected to a power source, such as a conventional 14-volt vehicle alternator. The resistance of the wire is low enough that it can deliver 5 to 7 watts per decimeter squared (W / dm 2 ) power density.

[0004] The problem with wire-heated windshields is that the wires are visible to vehicle occupants, which is aesthetically undesirable and can obstruct visibility through the windshield. Reducing the wire diameter to reduce wire visibility requires increasing the number of wires to maintain the desired power density, which in turn reduces the total solar energy transmitted by the windshield (TSET). Increasing the windshield height requires longer wires to maintain the required power density. Longer wires are undesirable in terms of aesthetics and / or transmittance.

[0005] Some heated windshields use a transparent conductive coating instead of wire. However, these coatings have their own drawbacks. For example, conventional heated windshield coatings typically have a sheet resistance of 2 ohms per square (Ω / □) or higher. A conventional 14V (80 amp, 1,120 watt) alternator does not provide enough voltage to power a conventional heated windshield coating to a temperature sufficient for de-icing. Therefore, for vehicles with these coatings, the vehicle must be modified to increase the available voltage. For example, the alternator can be replaced with a 42V alternator, or a DC / DC converter can be added to boost the voltage from a 14V alternator. However, these solutions increase the cost and complexity of the vehicle's electrical system. Summary of the Invention [Problem to be solved by the invention]

[0006] It would therefore be desirable to provide a transparency that reduces or eliminates at least some of the problems associated with conventional heatable transparencies. [Means for solving the problem]

[0007] The present invention is directed to reducing the sheet resistance of coated transparencies by adding a metallic silver layer to the coating stack. Specifically, the silver layer can range from a single stack to a quadruple stack of silver layers. However, if the silver thickness is too thick, the transmittance drops below 70%, which is unacceptable. Also, if the silver thickness is too thick, the glass appears red, which is also undesirable. Therefore, the present invention is directed to a coating stack in which the total silver thickness is sufficiently thick to provide a sheet resistance that allows de-icing on a 14v alternator, and which has a light transmittance greater than 70%, preferably greater than 70.5%, and more preferably greater than 71%.

[0008] The present invention relates to a coated article comprising a substrate coated with at least one dielectric layer, at least one metal layer, and at least one primer layer, the at least one metal layer having a total thickness of 30 to 65 nm, 35 to 52 nm, 35 to 48 nm, or 40 to 52 nm.

[0009] In one embodiment, the present invention relates to a coated article. The coated article includes a substrate. A first dielectric layer is disposed on at least a portion of the substrate. A first metal layer is disposed on at least a portion of the first dielectric layer. A first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first primer layer. The combined metal layers have a total thickness of at least 30 nm and at most 65 nm.

[0010] In another embodiment, the present invention relates to a coated article. The coated article includes a substrate. A first dielectric layer is disposed on at least a portion of the substrate. A first metal layer is disposed on at least a portion of the first dielectric layer. A first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first primer layer. A second metal layer is disposed on at least a portion of the second dielectric layer. A second primer layer is disposed on at least a portion of the second metal layer. A third dielectric layer is disposed on at least a portion of the second primer layer.

[0011] In another embodiment, the present invention relates to a coated article. The coated article includes a substrate. A first dielectric layer is disposed on at least a portion of the substrate. A first metal layer is disposed on at least a portion of the first dielectric layer. A first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first primer layer. A second metal layer is disposed on at least a portion of the second dielectric layer. The second primer layer is disposed on at least a portion of the second metal layer. A third dielectric layer is disposed on at least a portion of the second primer layer. A third metal layer is disposed on at least a portion of the third dielectric layer. The third primer layer is disposed on at least a portion of the third metal layer. A fourth dielectric layer is disposed on at least a portion of the third primer layer.

[0012] In another embodiment, the present invention relates to a coated article. The coated article includes a substrate. A first dielectric layer is disposed on at least a portion of the substrate. A first metal layer is disposed on at least a portion of the first dielectric layer. A first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first primer layer. A second metal layer is disposed on at least a portion of the second dielectric layer. A second primer layer is disposed on at least a portion of the second metal layer. A third dielectric layer is disposed on at least a portion of the second primer layer. A third metal layer is disposed on at least a portion of the third dielectric layer. A third primer layer is disposed on at least a portion of the third metal layer. A fourth dielectric layer is disposed on at least a portion of the third primer layer. A fourth metal layer is disposed on at least a portion of the fourth dielectric layer. A fourth primer layer is disposed on at least a portion of the fourth metal layer. A fourth primer layer is disposed on at least a portion of the fourth metal layer. A fifth dielectric layer is disposed on at least a portion of the fourth primer layer.

[0013] The present invention relates to a coated article. The coated article includes a substrate. A first dielectric layer is disposed on at least a portion of the substrate. A first metal layer is disposed on at least a portion of the first dielectric layer. A first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first primer layer. The article has a sheet resistance of 0.7 ohms / square or less.

[0014] The present invention relates to a coated article. The coated article includes a substrate. A first dielectric layer is disposed on at least a portion of the substrate. A first metal layer is disposed on at least a portion of the first dielectric layer. A first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first primer layer. A second metal layer is disposed on at least a portion of the second dielectric layer. A second primer layer is disposed on at least a portion of the second metal layer. A third dielectric layer is disposed on at least a portion of the second primer layer. The article has a sheet resistance of 0.7 ohms / square or less.

[0015] In another embodiment, the present invention relates to a coated article. The coated article includes a substrate. A first dielectric layer is disposed on at least a portion of the substrate. A first metal layer is disposed on at least a portion of the first dielectric layer. A first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first primer layer. A second metal layer is disposed on at least a portion of the second dielectric layer. The second primer layer is disposed on at least a portion of the second metal layer. A third dielectric layer is disposed on at least a portion of the second primer layer. A third metal layer is disposed on at least a portion of the third dielectric layer. The third primer layer is disposed on at least a portion of the third metal layer. A fourth dielectric layer is disposed on at least a portion of the third primer layer. The article has a sheet resistance of 0.7 ohms / square or less.

[0016] In another embodiment, the present invention relates to a coated article. The coated article includes a substrate. A first dielectric layer is disposed on at least a portion of the substrate. A first metal layer is disposed on at least a portion of the first dielectric layer. A first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first primer layer. A second metal layer is disposed on at least a portion of the second dielectric layer. A second primer layer is disposed on at least a portion of the second metal layer. A third dielectric layer is disposed on at least a portion of the second primer layer. A third metal layer is disposed on at least a portion of the third dielectric layer. A third primer layer is disposed on at least a portion of the third metal layer. A fourth dielectric layer is disposed on at least a portion of the third primer layer. A fourth metal layer is disposed on at least a portion of the fourth dielectric layer. A fourth primer layer is disposed on at least a portion of the fourth metal layer. A fifth primer layer is disposed on at least a portion of the fourth primer layer. The article has a sheet resistance of 0.7 ohms / square or less.

[0017] In another embodiment, the present invention relates to a coated article. The coated article includes a first substrate having a first surface and a second surface. A second substrate is disposed on at least a portion of the first substrate and includes a third surface and a fourth surface. A coating is disposed on either the second surface or the third surface. The coating has a first dielectric layer disposed on at least a portion of the second surface or the third surface. A first metal layer is disposed on at least a portion of the first dielectric layer. A first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first primer layer. The coated substrate has a visible light transmittance of at least 70%. The total thickness, including the metal layers, is 30 nm or more and 65 nm or less.

[0018] A seed film can be deposited between a metal layer and a dielectric layer. The seed film can be between one or more of various combinations of metal layers and dielectric layers. The seed film can be between a first metal layer and a first dielectric layer. The seed film can be between a second metal layer and a second dielectric layer. The seed film can be between a third metal layer and a third dielectric layer. The seed film can be between a fourth metal layer and a fourth dielectric layer. The seed film can be adjacent to and in direct contact with any metal layer. In one particular embodiment, the seed film is present between all metal layers and dielectric layers (i.e., between the first metal layer and the first dielectric layer, the second metal layer and the second dielectric layer, the third metal layer and the third dielectric layer, and the fourth metal layer and the fourth dielectric layer) and is adjacent to and in direct contact with the metal layers.

[0019] The seed film promotes two-dimensional growth and helps to densify the metal layer (most often silver) with its high surface energy. The high surface energy (high Gibbs free energy, high surface tension) prevents aggregation of the silver in the metal layer during the growth and heating process. The most suitable materials for reducing aggregation of the silver in the metal layer are metals with high cohesive energy and oxides with high Gibbs free energy of oxide formation. These particular materials prevent the migration of silver within the metal layer during the heating process.

[0020] The present invention is described with reference to the following drawings, in which like reference numerals identify like parts throughout. [Brief explanation of the drawings]

[0021] [Figure 1a] 1 is a cross-sectional view (not to scale) of a non-limiting coating according to the present invention. [Figure 1b] 1 is a cross-sectional view (not to scale) of a non-limiting coating according to the present invention. [Figure 2a] 1 is a cross-sectional view (not to scale) of a non-limiting coating according to the present invention. [Figure 2b] 1 is a cross-sectional view (not to scale) of a non-limiting coating according to the present invention. [Figure 3a] 1 is a cross-sectional view (not to scale) of a non-limiting coating according to the present invention. [Figure 3b] 1 is a cross-sectional view (not to scale) of a non-limiting coating according to the present invention. [Figure 4a] 1 is a cross-sectional view (not to scale) of a non-limiting coating according to the present invention. [Figure 4b] 1 is a cross-sectional view (not to scale) of a non-limiting coating according to the present invention. [Figure 5a] 1 is a cross-sectional view (not to scale) of a non-limiting embodiment of a first dielectric layer according to the present invention. [Figure 5b] 1 is a cross-sectional view (not to scale) of a non-limiting embodiment of a first dielectric layer according to the present invention. [Figure 6a] 2 is a cross-sectional view (not to scale) of a non-limiting embodiment of a second dielectric layer according to the present invention. [Figure 6b] 2 is a cross-sectional view (not to scale) of a non-limiting embodiment of a second dielectric layer according to the present invention. [Figure 6c] 2 is a cross-sectional view (not to scale) of a non-limiting embodiment of a second dielectric layer according to the present invention. [Figure 6d] 2 is a cross-sectional view (not to scale) of a non-limiting embodiment of a second dielectric layer according to the present invention. [Figure 7a] 3 is a cross-sectional view (not to scale) of a non-limiting embodiment of a third dielectric layer according to the present invention. [Figure 7b] 3 is a cross-sectional view (not to scale) of a non-limiting embodiment of a third dielectric layer according to the present invention. [Figure 7c] 3 is a cross-sectional view (not to scale) of a non-limiting embodiment of a third dielectric layer according to the present invention. [Figure 7d] 3 is a cross-sectional view (not to scale) of a non-limiting embodiment of a third dielectric layer according to the present invention. [Figure 8a] FIG. 2 is a cross-sectional view (not to scale) of a non-limiting fourth dielectric layer embodiment according to the present invention. [Figure 8b] FIG. 2 is a cross-sectional view (not to scale) of a non-limiting fourth dielectric layer embodiment according to the present invention. [Figure 8c] FIG. 2 is a cross-sectional view (not to scale) of a non-limiting fourth dielectric layer embodiment according to the present invention. [Figure 8d] FIG. 2 is a cross-sectional view (not to scale) of a non-limiting fourth dielectric layer embodiment according to the present invention. [Figure 9a] FIG. 2 is a cross-sectional view (not to scale) of a non-limiting embodiment of a fifth dielectric layer according to the present invention. [Figure 9b] FIG. 2 is a cross-sectional view (not to scale) of a non-limiting embodiment of a fifth dielectric layer according to the present invention. [Figure 10] 1 is a schematic diagram (not to scale) of a windshield incorporating features of the present invention; [Figure 11] 11 is an enlarged view (not to scale) of the windshield taken along line II-II of FIG. 10. [Figure 12] 1 is a schematic diagram (not to scale) of another windshield incorporating features of the present invention; [Figure 13] FIG. 1 illustrates the initial nucleation of film growth on a surface. DETAILED DESCRIPTION OF THE INVENTION

[0022] As used herein, spatial or directional terms such as "left," "right," "inside," "outside," "top," and "bottom" refer to the present invention as shown in the drawings. However, it should be understood that the present invention can assume various alternative orientations, and therefore, such terms should not be considered limiting. Furthermore, as used herein, all numbers expressing dimensions, physical properties, processing parameters, quantities of ingredients, reaction conditions, and the like, used in the specification and claims, should be understood to be modified in all instances by the term "about." Thus, unless indicated to the contrary, the numerical values set forth in the following specification and claims may vary depending on the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should be construed at least in light of the number of reported significant digits and by applying ordinary rounding techniques. Furthermore, all ranges disclosed herein should be understood to encompass the beginning and ending values of the range, as well as any and all subranges subsumed therein. For example, a specified range of "1 to 10" is deemed to include any and all subranges between the minimum value of 1 and the maximum value of 10 (inclusive) (i.e., all subranges beginning with a minimum value of 1 or greater and ending with a maximum value of 10 or less (e.g., 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc.)). Furthermore, as used herein, the terms "formed on," "deposited on," or "provided on" mean formed on, deposited on, or provided on, but not necessarily in contact with, a surface. For example, a coating layer "formed on" a substrate does not exclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate. As used herein, the terms "polymer" or "polymeric" include oligomers, homopolymers, copolymers, and terpolymers, e.g., polymers formed from two or more types of monomers or polymers. The terms "visible region" or "visible light" refer to electromagnetic radiation having wavelengths ranging from 380 nm to 800 nm.The terms "infrared region" or "infrared radiation" refer to electromagnetic radiation having wavelengths ranging from greater than 800 nm to 100,000 nm. The terms "ultraviolet region" or "ultraviolet radiation" refer to electromagnetic energy having wavelengths ranging from 300 nm to less than 380 nm. Additionally, all documents referenced herein, including but not limited to published patents and patent applications, are to be deemed "incorporated by reference" in their entirety. As used herein, the term "film" refers to a coating region of a desired or selected coating composition. A "layer" can include one or more "films," and a "coating" or "coating stack" can include one or more "layers." The terms "metal" and "metal oxide" include silicon and silica, as well as conventionally recognized metals and metal oxides, respectively, although silicon may not traditionally be considered a metal. Thickness values are geometric thickness values unless otherwise specified.

[0023] The discussion of the present invention may describe certain configurations as "particularly" or "preferably" within certain constraints (e.g., "preferably," "more preferably," or "most preferably" within certain constraints). It should be understood that the present invention is not limited to these particular or preferred constraints, but encompasses the full scope of the disclosure.

[0024] Coating 10 is a coating deposited on at least a portion of a major surface of one of glass plies 12, 112, such as on the No. 2 surface 16 of first glass ply 12 (FIG. 11) or the No. 3 surface 114 of second glass ply 110. Coating 10 can include up to four metal layers disposed between dielectric layers sequentially deposited on at least a portion of one of glass plies 12, 112. Coating 10 can be a heat and / or radiation reflective coating and can have one or more coating layers or films of the same or different composition and / or functionality. As used herein, the term "film" refers to a coating region of a desired or selected coating composition. A "layer" can include one or more "films," and a "coating" or "coating stack" can include one or more "layers." Coating 10 can be a multilayer coating including up to four metal layers.

[0025] Non-limiting examples of suitable coatings include one or more antireflective coating films, typically comprising a dielectric or antireflective material, such as a metal oxide or an oxide of a metal alloy, that is transparent to visible light. Coating 10 can also include up to four metal layers, including a reflective metal (e.g., a noble metal such as gold, copper, or silver) or a combination or alloy thereof, and can further include a primer layer or barrier film, such as titanium or a titanium-aluminum alloy, located above and / or optionally below the metal reflective layer, as known in the art. Coating 10 can have up to four metal layers, or can have at least one metal layer. For example, coating 10 can consist of four metal layers, three metal layers, two metal layers, or one metal layer. In one non-limiting embodiment, one or more of the metal layers can include silver and / or aluminum-doped silver.

[0026] In certain embodiments, the coating can include up to four primer layers. Non-limiting examples of materials suitable for the primer layer include zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, germanium, magnesium, molybdenum, silver, silicon carbide, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, zinc tin, indium zinc, silver zinc, gallium zinc, indium tin, mixtures thereof, combinations thereof, and alloys thereof. The primer layer material can take the form of a metal, oxide, suboxide, nitride, subnitride, oxynitride, and / or suboxynitride of any of the materials that can be used as a primer layer, as listed above. At least a portion of the primer layer can be an oxide or nitride. In certain embodiments, a portion of the primer layer is a nitride.

[0027] For a particular material composition, the lower limit for one of the materials may be "greater than 0." When a lower limit is "greater than 0," this means that the weight percent of that material is not equal to zero, but can be any weight percent greater than 0 up to the upper weight percent. Depending on the material composition, the composition may change before and after heating the layer. This is due to the material's reaction with atmospheric species, which changes the weight percent distributed among the present species. Therefore, a particular material composition may have a pre-heat ("BH") and post-heat ("AH") weight percent measurement to account for this change. Some materials may only have a pre-heat or post-heat measurement, as the pre-heat or post-heat measurement is more important.

[0028] In certain embodiments, the primer layer comprises Al x Zn 1-x(wherein x is greater than 0 to 30 wt %, preferably greater than 0 to 20 wt %, more preferably greater than 0 to 15 wt %, and most preferably in the range of 1 to 12 wt %). In another embodiment, the primer layer may be x Zn 1-x (wherein x is greater than 0 to 20 wt %, preferably greater than 0 to 15 wt %, more preferably greater than 0 to 10 wt %, and most preferably in the range of 1 to 5 wt %). In another embodiment, the primer layer comprises In x Zn 1-x (wherein x is greater than 0 wt % to 40 wt %, preferably greater than 0 wt % to 18 wt %, more preferably greater than 0 wt % to 15 wt %, and most preferably in the range of 1 to 10 wt %). In another embodiment, the primer layer comprises V x Zn 1-x (wherein x is greater than 0 wt % to 20 wt %, preferably greater than 0 wt % to 15 wt %, more preferably greater than 0 wt % to 10 wt %, and most preferably in the range of 1 to 5 wt %). In another embodiment, the primer layer comprises Ag x Zn 1-x (wherein x is greater than 0 wt % and less than 50 wt %, preferably greater than 0 wt % and less than 40 wt %, more preferably greater than 0 wt % and less than 30 wt %, and most preferably in the range of 5 to 30 wt %).

[0029] In another embodiment, the primer layer comprises Al x Ti 1-x (where x can be 2 to 75 wt % before heating (hereinafter "BH") and 1 to 100 wt % after heating (hereinafter "AH"), preferably 2 to 60 wt % BH and 1 to 98 wt % AH, more preferably 2 to 50 wt % BH and 2 to 95 wt % AH, and most preferably 2 to 40 wt % BH and 2 to 15 wt % AH or 20 to 95 wt % AH). In another embodiment, the primer layer comprises Al x Nb 1-x(wherein x is within the range of 2 to 40 wt% BH and 2 to 95 wt% AH, preferably 2 to 30 wt% BH and 2 to 80 wt% AH, more preferably 2 to 19 wt% BH and 3 to 60 wt% AH, and most preferably 2 to 13 wt% BH and 4 to 45 wt% AH). In another embodiment, the primer layer comprises Al x Nb 1-x nitride (where x is in the range of 1-100 wt. % BH and 1-100 wt. % AH, preferably 1-98 wt. % BH and 2-75 wt. % AH, more preferably 1-95 wt. % BH and 3-50 wt. % AH, and most preferably 2-93 wt. % BH and 4-40 wt. % AH), and there is an 80% nitrogen gas flow rate for nitride deposition. In another embodiment, the primer layer is W x Ti 1-x (wherein x is within the range of 55-100 wt. % BH (containing 7% O2 during deposition) and 30-95 wt. % AH (containing 3% O2 during deposition), preferably 65-100 wt. % BH (containing 7% O2 during deposition) and 40-95 wt. % AH (containing 3% O2 during deposition), more preferably 75-100 wt. % BH (containing 7% O2 during deposition) and 50-95 wt. % AH (containing 3% O2 during deposition), and most preferably 80-100 wt. % BH (containing 7% O2 during deposition) and 55-95 wt. % AH (containing 3% O2 during deposition). In another embodiment, the primer layer comprises a Ti x Ta 1-x (wherein x is within the range of 2 to 80 wt % BH and 2 to 40 wt % AH, preferably 2 to 60 wt % BH and 2 to 40 wt % AH, more preferably 2 to 35 wt % BH and 2 to 25 wt % AH, and most preferably 1 to 20 wt % BH and 1 to 20 wt % AH). In another embodiment, the primer layer comprises Ti x Nb 1-x (wherein x is in the range of 2 to 95 wt% AH, preferably 2 to 93 wt% AH, more preferably 3 to 92 wt% AH, and most preferably 5 to 90 wt% AH). In another embodiment, the primer layer comprises Ti x Nb1-x In another embodiment, the primer layer may be a nitride (where x is in the range of 1 to 65 wt%, preferably 1 to 50 wt%, more preferably 1 to 40 wt%, and most preferably 1 to 30 wt%), and there is an 80% nitrogen gas flow rate for nitride deposition. In another embodiment, the primer layer may be Nb x Zr 1-x (wherein x is within the range of 1 to 80% by weight BH and 60 to 100% by weight AH, preferably 1 to 70% by weight BH and 70 to 100% by weight AH, more preferably 1 to 60% by weight BH and 80 to 100% by weight AH, and most preferably 1 to 50% by weight BH and 85 to 100% by weight AH). In another embodiment, the primer layer may be x W 1-x (wherein x is in the range of 2 to 95 wt% BH, preferably 2 to 80 wt% BH, more preferably 3 to 60 wt% BH, and most preferably 5 to 50 wt% BH). In another embodiment, the primer layer is x Nb 1-x (wherein x is within the range of 5 to 100 wt % BH and 2 to 50 wt % AH, preferably 6 to 90 wt % BH and 2 to 45 wt % AH, more preferably 8 to 80 wt % BH and 2 to 40 wt % AH, and most preferably 10 to 70 wt % BH and 2 to 30 wt % AH). In another embodiment, the primer layer is x Nb 1-x nitride (where x is in the range of 2-90 wt. % BH and 2-70 wt. % AH, preferably 5-80 wt. % BH and 10-70 wt. % AH, more preferably 7-75 wt. % BH and 20-70 wt. % AH, and most preferably 10-70 wt. % BH and 30-70 wt. % AH), and there is an 80% nitrogen gas flow rate for nitride deposition. In another embodiment, the primer layer is Zn x Ti 1-x(where x is within the range of 10 to 100 wt% BH and 20 to 100 wt% AH, preferably 10 to 80 wt% BH and 40 to 97 wt% AH, more preferably 10 to 70 wt% BH and 50 to 94 wt% AH, and most preferably 10 to 60 wt% BH and 60 to 90 wt% AH).

[0030] Coating 10 can be deposited by any conventional method, such as, but not limited to, conventional chemical vapor deposition (CVD) and / or physical vapor deposition (PVD) processes. Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam evaporation and vacuum sputtering (e.g., magnetron sputter deposition (MSVD)). Other coating methods, such as, but not limited to, sol-gel deposition, can also be used. In one non-limiting embodiment, coating 10 can be deposited by MSVD. Examples of MSVD coating equipment and methods are well understood by those skilled in the art and are described, for example, in U.S. Patent Nos. 4,379,040, 4,861,669, 4,898,789, 4,898,790, 4,900,633, 4,920,006, 4,938,857, 5,328,768, and 5,492,750.

[0031] A non-limiting coating suitable for the present invention is shown in Figures 1a and 1b. This coating includes a metal layer and a primer layer disposed between two dielectric layers. It includes a base layer or first dielectric layer 20 disposed on or in direct contact with at least a portion of a major surface of the substrate (e.g., the No. 2 surface 16 of the first ply 12 or the No. 3 surface 114 of the second ply 110). A first metal layer 28 is disposed on or in direct contact with at least a portion of the first dielectric layer 20. A first primer layer 30 can be disposed on or in direct contact with at least a portion of the first metal layer 28. A second dielectric layer 32 is disposed on or in direct contact with the first primer layer 30. A protective layer 84 can be disposed on or in direct contact with the second dielectric layer 32. A stress layer 82 can be disposed between the second dielectric layer 32 and the protective layer 84.

[0032] Another non-limiting coating suitable for the present invention is shown in Figures 2a and 2b. This coating includes two metal layers and two primer layers disposed between the dielectric layers. It includes a base layer or first dielectric layer 20 disposed on or in direct contact with at least a portion of a major surface of the substrate (e.g., the No. 2 surface 16 of the first ply 12 or the No. 3 surface 114 of the second ply 110). A first metal layer 28 is disposed on or in direct contact with at least a portion of the first dielectric layer 20. A first primer layer 30 can be disposed on or in direct contact with at least a portion of the first metal layer 28. A second dielectric layer 32 is disposed on or in direct contact with the first primer layer 30. A second metal layer 42 is disposed on or in direct contact with at least a portion of the second dielectric layer 32. A second primer layer 44 can be disposed on or in direct contact with the second metal layer 42. The third dielectric layer 46 is disposed on or in direct contact with the second primer layer 44. The protective layer 84 can be disposed on or in direct contact with the third dielectric layer 46. The stress layer 82 can be disposed between the third dielectric layer 46 and the protective layer 84.

[0033] A non-limiting coating suitable for the present invention is shown in Figures 3a and 3b. This exemplary coating includes three metal layers and three primer layers disposed between the dielectric layers. It includes a base layer or first dielectric layer 20 disposed on or in direct contact with at least a portion of a major surface of the substrate (e.g., the No. 2 surface 16 of the first ply 12 or the No. 3 surface 114 of the second ply 110). A first metal layer 28 is disposed on or in direct contact with at least a portion of the first dielectric layer 20. A first primer layer 30 can be disposed on or in direct contact with at least a portion of the first metal layer 28. A second dielectric layer 32 is disposed on or in direct contact with at least a portion of the first primer layer 30. A second metal layer 42 is disposed on or in direct contact with at least a portion of the second dielectric layer 32. The second primer layer 44 may be disposed on or in direct contact with at least a portion of the second metal layer 42. The third dielectric layer 46 may be disposed on or in direct contact with at least a portion of the second primer layer 44. The third metal layer 56 may be disposed on or in direct contact with at least a portion of the third dielectric layer 46. The third primer layer 58 may be disposed on or in direct contact with at least a portion of the third metal layer 56. The fourth dielectric layer 60 may be disposed on or in direct contact with at least a portion of the third primer layer 58. The protective layer 84 may be disposed on or in direct contact with at least a portion of the fourth dielectric layer 60. The stress layer 82 may be disposed between the second dielectric layer 32 and the protective layer 84.

[0034] The first dielectric layer 20 can include one or more films of antireflective and / or dielectric materials, including, but not limited to, metal oxides, metal alloy oxides, nitrides, oxynitrides, or mixtures thereof. The first dielectric layer 20 can be transparent to visible light. Examples of metal oxides suitable for the first dielectric layer 20 include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum, silicon, and mixtures thereof. These metal oxides can contain small amounts of other materials, such as manganese in bismuth oxide or tin in indium oxide. Alternatively, oxides containing zinc and tin (e.g., zinc stannate), oxides of metal alloys or mixtures of metals, such as oxides of indium-tin alloys, silicon nitride, aluminum silicon nitride, or aluminum nitride can be used. Additionally, doped metal oxides, such as antimony- or indium-doped tin oxide, or nickel- or boron-doped silicon oxide, can be used. As shown in Figures 5a and 5b, the first dielectric layer 20 can include a first film 22 and a second film 24. In one non-limiting embodiment, the first film 22 can be zinc tin oxide. Zinc tin oxide can be obtained by magnetron sputter vacuum deposition from a zinc and tin cathode, which can contain zinc and tin in proportions of 10% to 90% zinc and 90% to 10% tin by weight. One suitable metal alloy oxide that can be present in the first film 22 includes zinc stannate. "Zinc stannate" refers to Zn x Sn 1-x O 2-x (Chemical Formula 1) (where "x" varies from greater than 0 to less than 1). For example, "x" can be greater than 0 and can be any fraction or decimal number greater than 0 but less than 1. For example, when x=2 / 3, Chemical Formula 1 is Zn 2 / 3 Sn 1 / 3 O 4 / 3 and is more commonly described as Zn2SnO4. Zinc stannate-containing films have one or more of the forms of Formula 1 predominate in the film.

[0035] The second film 24 can be a zinc-containing film, such as zinc oxide. A zinc oxide film can be deposited from a zinc cathode that includes other materials to improve the sputtering characteristics of the cathode. For example, the zinc cathode can include a small amount of tin (e.g., less than 10% by weight, e.g., greater than 0% and up to 5% by weight) to improve sputtering. In that case, the resulting zinc oxide film contains a small percentage of tin oxide (e.g., 0-10% by weight or less tin oxide, e.g., 0-5% by weight tin oxide). An oxide layer sputtered from a zinc / tin cathode having 95 percent zinc and 5 percent tin is referred to herein as Zn. 0.95 Sn 0.5 O 1.05 and referred to as a zinc oxide film. It is believed that a small amount of tin (e.g., less than 10% by weight) in the cathode forms a small amount of tin oxide in the second film 24, which contains primarily zinc oxide. In one non-limiting embodiment, the first film 22 comprises zinc stannate and the second film 24 contains zinc oxide (Zn 0.95 Sn 0.5 O 1.05 ) is included.

[0036] In one exemplary, non-limiting embodiment, the second film 24 is a film composed of at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide. The aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide film is deposited from a zinc cathode containing other materials to improve the sputtering characteristics of the cathode. For example, the aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide film can include a small amount of additional tin (e.g., less than 10% by weight, e.g., greater than 0% to 5% by weight) to improve sputtering. It is believed that a small amount of tin (e.g., less than 10% by weight) in the cathode forms a small amount of tin oxide in the second film 24. In one non-limiting embodiment, first film 22 comprises zinc stannate, and second film 24 comprises zinc aluminum oxide, zinc gallium oxide, zinc indium oxide, indium tin oxide, or zinc vanadium oxide. In one non-limiting embodiment, the first or second dielectric layer comprises a silicon nitride film. In some embodiments, such as FIG. 5b, first dielectric layer 20 includes only first film 22 and second film 24.

[0037] The first dielectric layer 20 can have a total thickness of 1,000 Å or less (e.g., 800 Å or less, e.g., 200 Å to 800 Å, 300 Å to 600 Å, e.g., 400 Å to 550 Å, e.g., 410 Å to 500 Å, or e.g., 420 Å to 470 Å, e.g., 422 Å, and 463 Å).

[0038] 5a, the first seed film 26 can be disposed on or in direct contact with at least a portion of the second film of the first dielectric layer 20. The first seed film 26 can be adjacent to or in direct contact with the first metal layer 28, and can be between the first dielectric layer 20 and the first metal layer 28. The first seed film 26 is a film composed of at least one of the following: aluminum, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, mixtures thereof, metals thereof, alloys thereof, combinations thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, oxynitrides thereof, suboxynitrides thereof, oxycarbides thereof, carbonitrides thereof, or oxycarbonitrides thereof. In one embodiment, first seed film 26 includes aluminum zinc, vanadium zinc, zinc, silver zinc, a metal thereof, an alloy thereof, an oxide thereof, or a suboxide thereof, while in another embodiment, first seed film 26 includes gallium zinc, indium zinc, indium tin, a metal thereof, an alloy thereof, an oxide thereof, a nitride thereof, a subnitride thereof, or a suboxide thereof.

[0039] In another embodiment, the first seed film 26 is V x Zn 1-x In another embodiment, the first seed film 26 comprises an Al oxide (where x is in the range of 1 to 25 wt %, preferably 1 to 15 wt %, more preferably 1 to 10 wt %, and most preferably 1 to 8 wt %). x Zn 1-x In another embodiment, the first seed film 26 comprises a Ga oxide (where x is in the range of 1 to 25 wt %, preferably 1 to 15 wt %, more preferably 1 to 12 wt %, and most preferably 1 to 10 wt %). x Zn 1-xIn another embodiment, the first seed film 26 comprises an In oxide (where x is in the range of 1 to 20 wt %, preferably 1 to 15 wt %, more preferably 1 to 10 wt %, and most preferably 1 to 5 wt %). x Zn 1-x In another embodiment, the first seed film 26 comprises an oxide of Sn, where x is in the range of 1 to 40 wt %, preferably 1 to 18 wt %, more preferably 1 to 15 wt %, and most preferably 1 to 10 wt %. x In 1-x In another embodiment, the first seed film 26 comprises Ag deposited in an oxygen / argon gas environment, with an oxygen flow rate of 1-70%, preferably 1-50%, more preferably 10-40%, and most preferably 20-40%. In another embodiment, the first seed film 26 comprises Al x Ag 1-x (wherein x is in the range of 1 to 35 wt % (BH and AH), preferably 1 to 20 wt % (BH and AH), more preferably 1 to 18 wt % (BH and AH), and most preferably 1 to 15 wt % (BH and AH).) In some embodiments, such as FIG. 5a, first dielectric layer 20 includes first film 22, second film 24, and first seed film 26.

[0040] A first metal layer 28 can be deposited on the first dielectric layer 20. The first metal layer 28 can comprise a reflective metal such as, but not limited to, metallic gold, copper, silver, aluminum, or mixtures, alloys, or combinations thereof. In one embodiment, the first metal layer 28 comprises a metallic silver layer. In another embodiment, the first metal layer 28 comprises a metallic aluminum-doped silver layer. In another non-limiting embodiment, the first metal layer 28 comprises silver and / or copper. The first metal layer 28 can have a thickness ranging from 50 Å to 200 Å, preferably from 75 Å to 150 Å, more preferably from 80 Å to 120 Å, and most preferably from 90 Å to 110 Å.

[0041] A first primer layer 30 can be deposited over the first metal layer 28. The first primer layer 30 can be an oxygen-scavenging material, such as titanium, which can be sacrificed during the deposition process to prevent degradation or oxidation of the first metal layer 28 during the sputtering process or subsequent heating process. The oxygen-scavenging material can be selected to oxidize before the material of the first metal layer 28. Examples of materials suitable for the primer layer include zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, gallium, indium, germanium, magnesium, molybdenum, silver, silicon carbide, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, zinc tin, indium zinc, silver zinc, gallium zinc, indium tin, mixtures thereof, and alloys thereof, and the primer can be deposited as a metal and subsequently oxidized. At least a portion of the primer layer is a nitride or oxide. The first primer layer can include an oxide, nitride, suboxide, subnitride, oxynitride, or suboxynitride of any of the materials that can be used as the first primer layer. When silver zinc, zinc, silver zinc oxide, aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, or vanadium zinc oxide is used as the first primer layer 30, it will preferentially oxidize before the oxidation of the underlying silver layer.

[0042] In one embodiment, the first primer layer 30 comprises zinc. In another embodiment, the first primer layer 30 comprises Ag. x Zn 1-x In another embodiment, the first primer layer 30 comprises an Ag oxide. x Zn 1-x In another embodiment, the first primer layer 30 comprises Al x Zn 1-x In another embodiment, the first primer layer 30 comprises an In oxide. x Zn 1-xIn another embodiment, the first primer layer 30 comprises a Ga oxide. x Zn 1-x In another embodiment, the first primer layer 30 comprises a V oxide. x Zn 1-x In another embodiment, the first primer layer 30 comprises an Al oxide. x Ti 1-x In another embodiment, the first primer layer 30 comprises an Al oxide. x Nb 1-x In another embodiment, the first primer layer 30 comprises an Al oxide. x Nb 1-x In another embodiment, the first primer layer 30 comprises W x Nb 1-x In another embodiment, the first primer layer 30 comprises W x Ti 1-x In another embodiment, the first primer layer 30 comprises a Ti oxide. x Ta 1-x In another embodiment, the first primer layer 30 comprises a Ti oxide. x Nb 1-x In another embodiment, the first primer layer 30 comprises a Ti oxide. x Nb 1-x In another embodiment, the first primer layer 30 comprises Nb x Zr 1-x In another embodiment, the first primer layer 30 comprises a Ta oxide. x W 1-x In another embodiment, the first primer layer 30 comprises a W oxide. x Nb 1-x In another embodiment, the first primer layer 30 comprises a Zn oxide. x Ti 1-x The first primer layer 30 has a thickness in the range of 5 Å to 50 Å, for example, 10 Å to 35 Å, for example, 15 Å to 35 Å, for example, 10 Å to 20 Å, for example, 10 Å to 30 Å, for example, 20 Å to 30 Å, or for example, 30 Å to 40 Å.

[0043] A second dielectric layer 32 can be deposited over the first primer layer 30. In the illustrated non-limiting embodiment of FIGS. 6a-6d, the second dielectric layer 32 includes a first film 34 and a second film 36. The first film 34 can be composed of an oxide, nitride, oxynitride, or mixture of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, vanadium, and mixtures thereof. In one embodiment, the first film 34 includes zinc oxide. In another embodiment, the first film 34 includes aluminum zinc oxide. In another embodiment, the first film 34 includes indium zinc oxide. In another embodiment, the first film 34 includes gallium zinc oxide. In another embodiment, the first film 34 includes indium tin oxide. In another embodiment, the first film 34 includes vanadium zinc oxide.

[0044] A second film 36 can be deposited on the first film 34. The second film 36 can be composed of an oxide, nitride, oxynitride, or mixture of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, vanadium, and mixtures thereof. In one embodiment, the second film 36 comprises zinc stannate. In some embodiments, similar to that of FIG. 6b, the first film 34 and the second film 36 are the only films of the second dielectric layer 32.

[0045] An optional third film 38 can be deposited on the second film 36 to form the multilayer second dielectric layer 32. The third film 38 can be composed of an oxide, nitride, oxynitride, or mixture of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, and vanadium. In one embodiment, the third film 38 comprises zinc oxide. In another embodiment, the third film 38 comprises indium zinc oxide. In another embodiment, the third film 38 comprises aluminum zinc oxide. In another embodiment, the third film 38 comprises gallium zinc oxide. In another embodiment, the third film 38 comprises indium tin oxide. In another embodiment, the third film 38 comprises vanadium zinc oxide. In a non-limiting embodiment, the first dielectric layer 20 or the second dielectric layer 32 comprises a silicon nitride film. 6a and 6c, the second dielectric layer 32 includes a first film 34, a second film 36, and a third film 38. In some embodiments, such as in FIG. 6a, the second dielectric layer 32 has only a first film 34, a second film 36, and a third film 38.

[0046] In certain embodiments, the second dielectric layer 32 is the top dielectric layer. The second dielectric layer 32 can have a thickness of 1,500 Å or less, such as 1,200 Å or less, such as between 400 Å and 1,200 Å, between 500 Å and 1,100 Å, such as between 600 Å and 1,000 Å, such as between 700 Å and 900 Å, or such as between 775 Å and 850 Å.

[0047] The second seed film 40 may be adjacent to or in direct contact with the second metal layer 42 and may be between the second dielectric layer 32 and the second metal layer 42. The second seed film 40 is a film including at least one of the following: aluminum, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, mixtures thereof, metals thereof, alloys thereof, combinations thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, oxynitrides thereof, suboxynitrides thereof, oxycarbides thereof, carbonitrides thereof, or oxycarbonitrides thereof. In one embodiment, the second seed film 40 includes aluminum zinc, vanadium zinc, zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another embodiment, the second seed film 40 is gallium zinc, indium zinc, indium tin, silver, aluminum doped silver, metals thereof, alloys thereof, oxides thereof, or suboxides thereof.

[0048] In one embodiment, the second seed film 40 is V x Zn 1-x In another embodiment, the second seed film 40 comprises an Al oxide (where x is in the range of 1 to 25 wt %, preferably 1 to 15 wt %, more preferably 1 to 10 wt %, and most preferably 1 to 8 wt %). x Zn 1-x In another embodiment, the second seed film 40 comprises a Ga oxide (where x is in the range of 1 to 25 wt %, preferably 1 to 15 wt %, more preferably 1 to 12 wt %, and most preferably 1 to 10 wt %). x Zn 1-x In another embodiment, the second seed film 40 comprises an In oxide (where x is in the range of 1 to 20 wt %, preferably 1 to 15 wt %, more preferably 1 to 10 wt %, and most preferably 1 to 5 wt %). x Zn 1-xIn another embodiment, the second seed film 40 comprises Sn oxide (where x is in the range of 1 to 40 wt %, preferably 1 to 18 wt %, more preferably 1 to 15 wt %, and most preferably 1 to 10 wt %). x In 1-x In another embodiment, the second seed film 40 comprises Ag deposited in an oxygen / argon gas environment, with an oxygen flow rate of 1-70%, preferably 1-50%, more preferably 10-40%, and most preferably 20-40%. In another embodiment, the second seed film 40 comprises Al x Ag 1-x (where x is in the range of 1 to 35 wt % (BH and AH), preferably 1 to 20 wt % (BH and AH), more preferably 1 to 18 wt % (BH and AH), and most preferably 1 to 15 wt % (BH and AH). In some embodiments, such as FIGS. 6c and 6d, the second dielectric layer 32 includes a first film 34, a second film 36, and a second seed film 40. In some embodiments, such as FIG. 6d, the second dielectric layer 32 has only the first film 34, the second film 36, and the second seed film 40. In some embodiments, such as FIG. 6c, the second dielectric layer 32 includes a first film 34, a second film 36, a third film 38, and a second seed film 40.

[0049] A second metal layer 42 can be deposited on the second dielectric layer 32. The second metal layer 42 can include any one or more of the reflective materials described above for the first metal layer 28. In one non-limiting embodiment, the second metal layer 42 includes silver. In another non-limiting embodiment, the second metal layer 42 includes aluminum-doped silver. In another non-limiting embodiment, the second metal layer 42 includes silver and / or copper. The second metal layer 42 can have a thickness ranging from 75 Å to 175 Å, preferably from 100 Å to 150 Å, more preferably from 110 Å to 130 Å, and most preferably from 119 Å to 129 Å. In another non-limiting embodiment, the second metal layer 42 can be thicker than the first and / or third metal layers.

[0050] A second primer layer 44 can be deposited on the second metal layer 42. The second primer layer 44 can be any of the materials described above for the first primer layer 30. Examples of materials suitable for the primer layer include zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, gallium, indium, germanium, magnesium, molybdenum, silver, silicon carbide, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, zinc tin, indium zinc, silver zinc, gallium zinc, indium tin, mixtures thereof, and alloys thereof. The primer can be deposited as a metal and subsequently oxidized. At least a portion of the primer layer is a nitride or oxide. The second primer layer can comprise an oxide, nitride, suboxide, subnitride, oxynitride, or suboxynitride of any of the materials that can be used as a second primer layer. When silver zinc, zinc, silver zinc oxide, aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, or vanadium zinc oxide is used as the first primer layer 30, it will preferentially oxidize before the oxidation of the underlying silver layer.

[0051] In one embodiment, the second primer layer 44 comprises zinc. In another embodiment, the second primer layer 44 comprises Ag. x Zn 1-x In another embodiment, the second primer layer 44 comprises an Ag oxide. x Zn 1-x In another embodiment, the second primer layer 44 comprises Al x Zn 1-x In another embodiment, the second primer layer 44 is an In oxide. x Zn 1-x In another embodiment, the second primer layer 44 comprises a Ga oxide. x Zn 1-x In another embodiment, the second primer layer 44 comprises a V x Zn 1-x In another embodiment, the second primer layer 44 comprises an Al oxide. x Ti 1-x In another embodiment, the second primer layer 44 comprises an Al oxide. x Nb 1-x In another embodiment, the second primer layer 44 comprises an Al oxide. x Nb 1-x In another embodiment, the second primer layer 44 comprises W. x Nb 1-x In another embodiment, the second primer layer 44 comprises W. x Ti 1-x In another embodiment, the second primer layer 44 comprises a Ti oxide. x Ta 1-x In another embodiment, the second primer layer 44 comprises a Ti oxide. x Nb 1-x In another embodiment, the second primer layer 44 comprises a Ti oxide. x Nb 1-x In another embodiment, the second primer layer 44 comprises Nb x Zr 1-x In another embodiment, the second primer layer 44 comprises a Ta oxide. x W 1-xIn another embodiment, the second primer layer 44 comprises a W oxide. x Nb 1-x In another embodiment, the second primer layer 44 comprises a Zn oxide. x Ti 1-x The second primer layer 44 may have a thickness in the range of about 5 Å to 50 Å, such as 10 Å to 35 Å, for example, 15 Å to 35 Å, for example, 10 Å to 20 Å, for example, 10 Å to 30 Å, for example, 20 Å to 30 Å, or for example, 30 Å to 40 Å.

[0052] A third dielectric layer 46 can be deposited over the second metal layer 42. The third dielectric layer 46 can also include one or more materials discussed above with respect to the first and second dielectric layers 20, 32. In one non-limiting embodiment, the third dielectric layer 46 can include a first film 48. The first film 48 can be composed of an oxide, nitride, oxynitride, or mixture of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, vanadium, and mixtures thereof. In one embodiment, the first film 48 includes zinc oxide. In another embodiment, the first film 48 includes aluminum zinc oxide. In another embodiment, the first film 48 includes indium zinc oxide. In another embodiment, the first film 48 includes gallium zinc oxide. In another embodiment, the first film 48 includes indium tin oxide. In another embodiment, the first film 48 comprises zinc vanadium oxide.

[0053] The third dielectric layer 46 can include a second film 50 deposited on the first film 48. In one embodiment, the second film 50 can be composed of an oxide, nitride, oxynitride, or mixture of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, vanadium, and mixtures thereof. In one embodiment, the second film 50 comprises zinc stannate. In some embodiments, the first film 48 and the second film 50 are the only films of the third dielectric layer 46, similar to that of FIG. 7b.

[0054] The third dielectric layer 46 can include an optional third film 52. The third film 52 can be composed of an oxide, nitride, oxynitride, or mixture of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, vanadium, and mixtures thereof. In one embodiment, the third film 52 includes zinc oxide. In another embodiment, the third film 52 includes aluminum zinc oxide. In another embodiment, the third film 52 includes indium zinc oxide. In another embodiment, the third film 52 includes gallium zinc oxide. In another embodiment, the third film 52 includes indium tin oxide. In another embodiment, the third film 52 includes vanadium zinc oxide. In some embodiments, such as those shown in FIGS. 7a and 7c, the third dielectric layer 46 includes a first film 48, a second film 50, and a third film 52. In some embodiments, such as FIG. 7 a , the third dielectric layer 46 has only a first film 48 , a second film 50 , and a third film 52 .

[0055] In certain embodiments, the third dielectric layer 46 is the top dielectric layer. In one non-limiting aspect of the present invention, the second dielectric layer 32 and the third dielectric layer 46 have thicknesses that are within 15% of each other, e.g., within 10%, e.g., within 5% of each other. The third dielectric layer 46 can have a thickness in the range of 1,500 Å or less, e.g., 1,200 Å or less, e.g., between 300 Å and 1,200 Å, between 400 Å and 1,100 Å, e.g., between 500 Å and 1,000 Å, e.g., between 600 Å and 900 Å, e.g., between 700 Å and 825 Å, or between 730 Å and 760 Å.

[0056] The third seed film 54 may be adjacent to and / or in direct contact with the third metal layer 56, and may be between the third dielectric layer 46 and the third metal layer 56. The third seed film 54 is a film composed of at least one of the following: aluminum, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, mixtures thereof, metals thereof, alloys thereof, combinations thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, oxynitrides thereof, suboxynitrides thereof, oxycarbides thereof, carbonitrides thereof, or oxycarbonitrides thereof. In one embodiment, the third seed film 54 includes aluminum zinc, vanadium zinc, zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another embodiment, the third seed film 54 is gallium zinc, indium zinc, indium tin, a metal thereof, an alloy thereof, an oxide thereof, a nitride thereof, a subnitride thereof, or a suboxide thereof.

[0057] In another embodiment, the third seed film 54 is V x Zn 1-x In another embodiment, the third seed film 54 comprises an Al oxide (where x is in the range of 1 to 25 wt %, preferably 1 to 15 wt %, more preferably 1 to 10 wt %, and most preferably 1 to 8 wt %).x Zn 1-x In another embodiment, the third seed film 54 comprises a Ga oxide (where x is in the range of 1 to 25 wt %, preferably 1 to 15 wt %, more preferably 1 to 12 wt %, and most preferably 1 to 10 wt %). x Zn 1-x In another embodiment, the third seed film 54 comprises an In oxide (where x is in the range of 1 to 20 wt %, preferably 1 to 15 wt %, more preferably 1 to 10 wt %, and most preferably 1 to 5 wt %). x Zn 1-x In another embodiment, the third seed film 54 comprises an oxide of Sn, where x is in the range of 1 to 40 wt %, preferably 1 to 18 wt %, more preferably 1 to 15 wt %, and most preferably 1 to 10 wt %. x In 1-x In another embodiment, the third seed film 54 comprises Ag deposited in an oxygen / argon gas environment, with an oxygen flow rate of 1-70%, preferably 1-50%, more preferably 10-40%, and most preferably 20-40%. In another embodiment, the third seed film 54 comprises Al x Ag 1-x (where x is in the range of 1 to 35 wt % (BH and AH), preferably 1 to 20 wt % (BH and AH), more preferably 1 to 18 wt % (BH and AH), and most preferably 1 to 15 wt % (BH and AH). In some embodiments, such as Figures 7c and 7d, the third dielectric layer 46 includes a first film 48, a second film 50, and a third seed film 54. In some embodiments, such as Figure 7d, the third dielectric layer 46 has only the first film 48, the second film 50, and the third seed film 54. In some embodiments, such as Figure 7c, the third dielectric layer 46 includes the first film 48, the second film 50, the third film 52, and the third seed film 54.

[0058] The coating 10 can further include a third metal layer 56 deposited on the third dielectric layer 46. The third metal layer 56 can be any of the materials discussed above with respect to the first and second metal layers 28, 42. In one non-limiting embodiment, the third metal layer 56 includes silver. In another non-limiting embodiment, the third metal layer 56 includes aluminum-doped silver. In another non-limiting embodiment, the third metal layer 56 includes silver and / or copper. The third metal layer 56 can have a thickness ranging from 75 Å to 175 Å, preferably from 100 Å to 150 Å, more preferably from 110 Å to 130 Å, and most preferably from 118 Å to 127 Å. In one non-limiting aspect of the invention, the first metal layer 28 is thinner than the third metal layer 56. In another non-limiting aspect of the invention, the second metal layer 42 is thinner than the third metal layer 56.

[0059] In one non-limiting embodiment, the coated article includes only the first, second, and third metal layers 28, 42, 56. The coated article may not have additional metal layers. The metal layers may include only silver, aluminum-doped silver, or silver and copper, or may include greater than 80% by weight of silver, aluminum-doped silver, or silver and copper.

[0060] A third primer layer 58 can be deposited on the third metal layer 56. The third primer layer 58 can be any of the primer materials described above for the first or second primer layer 30, 44. Examples of materials suitable for the primer layer include zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, gallium, indium, germanium, magnesium, molybdenum, silver, silicon carbide, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, zinc tin, indium zinc, silver zinc, gallium zinc, indium tin, mixtures thereof, and alloys thereof. The primer can be deposited as a metal and subsequently oxidized. At least a portion of the primer layer is a nitride or oxide. The third primer layer can comprise an oxide, nitride, suboxide, subnitride, oxynitride, or suboxynitride of any of the materials that can be used as a third primer layer. When silver zinc, zinc, silver zinc oxide, aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, or vanadium zinc oxide is used as the third primer layer 58, it will preferentially oxidize before the oxidation of the underlying silver layer.

[0061] In one embodiment, the third primer layer 58 comprises zinc. In another embodiment, the third primer layer 58 comprises Ag. x Zn 1-x In another embodiment, the third primer layer 58 comprises an Ag oxide. x Zn 1-x In another embodiment, the third primer layer 58 comprises Al x Zn 1-x In another embodiment, the third primer layer 58 comprises an In oxide. x Zn 1-x In another embodiment, the third primer layer 58 comprises a Ga oxide. x Zn 1-x In another embodiment, the third primer layer 58 comprises a Vx Zn 1-x In another embodiment, the third primer layer 58 comprises an Al oxide. x Ti 1-x In another embodiment, the third primer layer 58 comprises an Al oxide. x Nb 1-x In another embodiment, the third primer layer 58 comprises an Al oxide. x Nb 1-x In another embodiment, the third primer layer 58 comprises W. x Nb 1-x In another embodiment, the third primer layer 58 comprises W. x Ti 1-x In another embodiment, the third primer layer 58 comprises a Ti oxide. x Ta 1-x In another embodiment, the third primer layer 58 comprises a Ti oxide. x Nb 1-x In another embodiment, the third primer layer 58 comprises a Ti oxide. x Nb 1-x In another embodiment, the third primer layer 58 comprises Nb x Zr 1-x In another embodiment, the third primer layer 58 comprises a Ta oxide. x W 1-x In another embodiment, the third primer layer 58 comprises a W oxide. x Nb 1-x In another embodiment, the third primer layer 58 comprises a Zn oxide. x Ti 1-x The third primer layer 58 has a thickness in the range of 5 Å to 50 Å, for example, 10 Å to 35 Å, for example, 15 Å to 35 Å, for example, 10 Å to 20 Å, for example, 10 Å to 30 Å, for example, 20 Å to 30 Å, or for example, 30 Å to 40 Å.

[0062] A fourth dielectric layer 60 can be deposited on the third primer layer 58. The fourth dielectric layer 60 can be composed of one or more metal oxide or metal alloy oxide-containing layers, such as those discussed above with respect to the first, second, or third dielectric layers 20, 32, 46. Alternatively, the fourth dielectric layer can include silicon nitride or silicon oxynitride. In one non-limiting embodiment, the fourth dielectric layer 60 includes a first film 62 deposited on the third primer layer 58, a second film 64 deposited on the first film 62, and an optional third film 66 on the second film 64. The first film 62 can be composed of an oxide, nitride, oxynitride, or mixture of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, gallium, vanadium, and mixtures thereof. In one embodiment, the first film 62 comprises zinc oxide or zinc stannate. In another embodiment, the first film 62 comprises zinc aluminum oxide. In another embodiment, the first film 62 comprises zinc indium oxide. In another embodiment, the first film 62 comprises zinc gallium oxide. In another embodiment, the first film 62 comprises indium tin oxide. In another embodiment, the first film 62 comprises zinc vanadium oxide.

[0063] The fourth dielectric layer 60 can include a second film 64 deposited on the first film 62. In one embodiment, the second film 64 can be composed of an oxide, nitride, oxynitride, or mixture of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, vanadium, and mixtures thereof. In one embodiment, the second film 64 includes zinc stannate, silicon nitride, or silicon oxynitride. In some embodiments, similar to that of FIG. 8b, the first film 62 and the second film 64 are the only films of the fourth dielectric layer 60.

[0064] The fourth dielectric layer 60 may include an optional third film 66 deposited on the second film 64. The third film 66 may be composed of an oxide, nitride, oxynitride, or mixture of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, vanadium, and mixtures thereof. In one embodiment, the third film 66 includes zinc oxide, silicon oxynitride, or silicon nitride. In another embodiment, the third film 66 includes zinc oxide. In another embodiment, the third film 66 includes aluminum zinc oxide. In another embodiment, the third film 66 includes indium zinc oxide. In another embodiment, the third film 66 includes gallium zinc oxide. In another embodiment, the third film 66 includes indium tin oxide. In another embodiment, the third film 66 includes vanadium zinc oxide. In some embodiments, such as those shown in Figures 8a and 8c, the fourth dielectric layer 60 includes a first film 62, a second film 64, and a third film 66. In some embodiments, such as Figure 8b, the fourth dielectric layer 60 has only a first film 62, a second film 64, and a third film 66.

[0065] In one non-limiting embodiment, the first and third films 62, 66 of the fourth dielectric layer 60 can each have a thickness in the range of about 50 Å to 200 Å, such as 75 Å to 150 Å (e.g., 100 Å). The second film 64 can have a thickness in the range of 250 Å to 900 Å, such as 275 Å to 800 Å, such as 300 Å to 775 Å, such as 350 Å to 710 Å.

[0066] In embodiments in which the fourth dielectric layer 60 is the top dielectric layer, the fourth dielectric layer 60 can have a thickness in the range of 1,000 Å or less, such as 600 Å or less, such as between 200 Å and 600 Å, between 250 Å and 550 Å, such as between 300 Å and 500 Å, such as between 325 Å and 475 Å, or such as between 360 Å and 390 Å. In embodiments in which the fourth dielectric layer 60 is the top dielectric layer, both the first dielectric layer 20 and the fourth dielectric layer 60 can be thinner than the second dielectric layer 32 and the third dielectric layer 46.

[0067] The fourth seed film 68 may be adjacent to or in direct contact with the fourth metal layer 70 and may be between the fourth dielectric layer 60 and the fourth metal layer 70. The fourth seed film 68 is a film composed of at least one of the following: aluminum, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, mixtures thereof, metals thereof, alloys thereof, combinations thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, oxynitrides thereof, suboxynitrides thereof, oxycarbides thereof, carbonitrides thereof, or oxycarbonitrides thereof. In one embodiment, the fourth seed film 68 includes aluminum zinc, vanadium zinc, zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another embodiment, the fourth seed film 68 comprises gallium zinc, indium zinc, indium tin, a metal thereof, an alloy thereof, an oxide thereof, a nitride thereof, a subnitride thereof, or a suboxide thereof.

[0068] In another embodiment, the fourth seed film 68 is V x Zn 1-x In another embodiment, the fourth seed film 68 comprises an Al oxide (where x is in the range of 1 to 25 wt %, preferably 1 to 15 wt %, more preferably 1 to 10 wt %, and most preferably 1 to 8 wt %). xZn 1-x In another embodiment, the fourth seed film 68 comprises a Ga oxide (where x is in the range of 1 to 25 wt %, preferably 1 to 15 wt %, more preferably 1 to 12 wt %, and most preferably 1 to 10 wt %). x Zn 1-x In another embodiment, the fourth seed film 68 comprises an In oxide (where x is in the range of 1 to 20 wt %, preferably 1 to 15 wt %, more preferably 1 to 10 wt %, and most preferably 1 to 5 wt %). x Zn 1-x In another embodiment, the fourth seed film 68 comprises an oxide of Sn, where x is in the range of 1 to 40 wt %, preferably 1 to 18 wt %, more preferably 1 to 15 wt %, and most preferably 1 to 10 wt %. x In 1-x In another embodiment, the fourth seed film 68 comprises Ag deposited in an oxygen / argon gas environment, with an oxygen flow rate of 1-70%, preferably 1-50%, more preferably 10-40%, and most preferably 20-40%. In another embodiment, the fourth seed film 68 comprises Al x Ag 1-x (where x is in the range of 1 to 35 wt % (BH and AH), preferably 1 to 20 wt % (BH and AH), more preferably 1 to 18 wt % (BH and AH), and most preferably 1 to 15 wt % (BH and AH). In some embodiments, such as FIGS. 8c and 8d, the fourth dielectric layer 60 includes a first film 62, a second film 64, and a fourth seed film 68. In some embodiments, such as FIG. 8d, the fourth dielectric layer 60 has only the first film 62, the second film 64, and the fourth seed film 68. In some embodiments, such as FIG. 8c, the fourth dielectric layer 60 includes the first film 62, the second film 64, the third film 66, and the fourth seed film 68.

[0069] Another exemplary, non-limiting coating 10 suitable for the present invention is shown in Figures 4a and 4b. The coating 10 can further include a fourth metal layer 70 deposited on or in direct contact with at least a portion of the fourth dielectric layer 60. The fourth metal layer 70 can be any of the materials discussed above with respect to the first, second, or third metal layers 28, 42, 56. In one non-limiting embodiment, the fourth metal layer 70 comprises silver and / or copper. In another non-limiting embodiment, the fourth metal layer 70 comprises aluminum-doped silver. The fourth metal layer 70 can have a thickness ranging from 50 Å to 175 Å, preferably from 75 Å to 150 Å, more preferably from 80 Å to 120 Å, and most preferably from 90 Å to 110 Å. In one non-limiting embodiment of the present invention, the first metal layer 28 and the fourth metal layer 70 have thicknesses that are within 20% of each other, such as within 15%, for example within 5% to 10% of each other.

[0070] In one non-limiting embodiment, the coated article includes only the first, second, third, and fourth metal layers 28, 42, 56, and 70. The coated article may not have additional metal layers. The metal layers may include only silver, aluminum-doped silver, or silver and copper, or may include greater than 80% by weight of silver, aluminum-doped silver, or silver and copper.

[0071] Each metal layer has a thickness. The sum of the thicknesses of all metal layers is at least 30 nm and at most 65 nm (e.g., at least 35 nm, at most 52 nm). In one non-limiting embodiment, the total combined thickness of the metal layers is 55 nanometers or less (e.g., 52 nm or less, e.g., 48 nanometers or less). In another non-limiting embodiment, the total combined thickness of the metal layers is at least 30 nm, at least 32 nm, at least 34 nm, at least 35 nm, at least 38 nm, or at least 40 nm.

[0072] A fourth primer layer 72 can be deposited over or in direct contact with at least a portion of the fourth metal layer 70. The fourth primer layer 72 can be any of the primer materials described above with respect to the first, second, or third primer layers 30, 44, 58. Examples of materials suitable for the primer layer include zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, gallium, indium, germanium, magnesium, molybdenum, silver, silicon carbide, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, zinc tin, indium zinc, silver zinc, gallium zinc, indium tin, mixtures thereof, and alloys thereof, and the primer can be deposited as a metal and subsequently oxidized. The fourth primer layer can comprise an oxide, nitride, suboxide, subnitride, oxynitride, or suboxynitride of any of the materials that can be used as the fourth primer layer. At least a portion of the primer layer is a nitride or oxide. When silver zinc, zinc, silver zinc oxide, aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, or vanadium zinc oxide is used as the first primer layer 30, it oxidizes preferentially before the oxidation of the underlying silver layer.

[0073] In one embodiment, the fourth primer layer 72 comprises zinc. In another embodiment, the fourth primer layer 72 comprises Ag. x Zn 1-x In another embodiment, the fourth primer layer 72 comprises an oxide of Ag. x Zn 1-x In another embodiment, the fourth primer layer 72 comprises Al x Zn 1-x In another embodiment, the fourth primer layer 72 is an In oxide. x Zn 1-x In another embodiment, the fourth primer layer 72 comprises a Ga oxide. x Zn 1-xIn another embodiment, the fourth primer layer 72 comprises a V oxide. x Zn 1-x In another embodiment, the fourth primer layer 72 comprises an Al oxide. x Ti 1-x In another embodiment, the fourth primer layer 72 comprises an Al oxide. x Nb 1-x In another embodiment, the fourth primer layer 72 comprises an Al oxide. x Nb 1-x In another embodiment, the fourth primer layer 72 comprises W. x Nb 1-x In another embodiment, the fourth primer layer 72 comprises W. x Ti 1-x In another embodiment, the fourth primer layer 72 comprises a Ti oxide. x Ta 1-x In another embodiment, the fourth primer layer 72 comprises a Ti oxide. x Nb 1-x In another embodiment, the fourth primer layer 72 comprises a Ti oxide. x Nb 1-x In another embodiment, the fourth primer layer 72 comprises Nb x Zr 1-x In another embodiment, the fourth primer layer 72 comprises a Ta oxide. x W 1-x In another embodiment, the fourth primer layer 72 comprises a W oxide. x Nb 1-x In another embodiment, the fourth primer layer 72 comprises a Zn oxide. x Ti 1-x The fourth primer layer 72 has a thickness in the range of 5 Å to 50 Å, for example, 10 Å to 35 Å, for example, 15 Å to 35 Å, for example, 10 Å to 20 Å, for example, 10 Å to 30 Å, for example, 20 Å to 30 Å, or for example, 30 Å to 40 Å.

[0074] The fifth dielectric layer 74 can be deposited on or in direct contact with the fourth primer layer 72. The fifth dielectric layer 74 can be composed of one or more metal oxide or metal alloy oxide-containing layers, such as those discussed above with respect to the first, second, third, or fourth dielectric layers 20, 32, 46, 60. In one non-limiting embodiment, the fifth dielectric layer 74 includes a first film 76 deposited on or in direct contact with the fourth primer layer 72. The first film 76 can be composed of an oxide, nitride, oxynitride, or mixtures thereof of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, vanadium, and mixtures thereof. In one embodiment, the first film 76 includes zinc oxide or zinc stannate. In another embodiment, the first film 76 includes zinc aluminum oxide. In another embodiment, the first film 76 comprises indium zinc oxide. In another embodiment, the first film 76 comprises gallium zinc oxide. In another embodiment, the first film 76 comprises indium tin oxide. In another embodiment, the first film 76 comprises vanadium zinc oxide.

[0075] The fifth dielectric layer 74 can include a second film 78 deposited on or in direct contact with at least a portion of the first film 76. In one embodiment, the second film 78 comprises an oxide, nitride, oxynitride, or mixture thereof of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, vanadium, and mixtures thereof. In one embodiment, the second film 78 comprises zinc stannate, silicon nitride, or silicon oxynitride. In some embodiments, such as FIG. 9b, the first film 76 and the second film 78 are the only films of the fifth dielectric layer 74.

[0076] The fifth dielectric layer 74 may include an optional third film 80 deposited on the second film 78. The third film 80 includes an oxide, nitride, oxynitride, or mixtures thereof of one or more metals selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, aluminum, gallium, vanadium, and mixtures thereof. In one embodiment, the third film 80 includes zinc oxide, silicon oxynitride, or silicon nitride. In another embodiment, the third film 80 includes silicon nitride. In another embodiment, the third film 80 includes zinc oxide. In another embodiment, the third film 80 includes aluminum zinc oxide. In another embodiment, the third film 80 includes indium zinc oxide. In another embodiment, the third film 80 includes gallium zinc oxide. In another embodiment, the third film 80 includes indium tin oxide. In another embodiment, the third film 80 comprises vanadium zinc oxide. In some embodiments, such as in Figure 9a, the fifth dielectric layer 74 comprises a first film 76, a second film 78, and a third film 80.

[0077] The fifth dielectric layer 74 may have a thickness in the range of 1,000 Å or less, such as 800 Å or less, such as between 200 Å and 700 Å, between 275 Å and 600 Å, such as between 300 Å and 500 Å, such as between 325 Å and 475 Å, or such as between 350 Å and 460 Å.

[0078] In embodiments in which the article includes a fifth dielectric layer 74, the fourth dielectric layer 60 can have a thickness in the range of 1,400 Å or less, such as 1,200 Å or less, such as between 400 Å and 1,200 Å, between 500 Å and 1,000 Å, such as between 600 Å and 800 Å, such as between 675 Å and 725 Å, or such as between 690 Å and 710 Å. In embodiments in which the fifth dielectric layer 74 is the topmost dielectric layer, both the first dielectric layer 20 and the fifth dielectric layer 74 can be thinner than the second dielectric layer 32, the third dielectric layer 46, and the fourth dielectric layer 60.

[0079] The coating 10 can include an outermost protective layer 84, which, for example, in the non-limiting embodiment shown in FIGS. 1a-4b, is deposited on the topmost dielectric layer to help protect underlying layers, such as metal layers, from mechanical and chemical attack during processing. In one non-limiting embodiment, the protective layer 84 can be deposited on the second dielectric layer 32, the third dielectric layer 46, the fourth dielectric layer 60, or the fifth dielectric layer 74. In another non-limiting embodiment, the protective layer 84 can be disposed on, and optionally in direct contact with, the metal layer 32, 56, or 70, or the primer layer 44, 58, or 72. The protective layer 84 can be an oxygen barrier coating layer to prevent or reduce the passage of ambient oxygen to underlying layers of the coating 10, such as during heating or bending. The protective layer 84 can be any desired material or mixture of materials. In one exemplary embodiment, the protective layer 84 may include a layer having one or more metal oxide or nitride materials, such as, but not limited to, oxides and / or nitrides of aluminum, silicon, or mixtures thereof.For example, the protective coating 84 may be 0% to 100% by weight alumina and / or 100% to 0% by weight silica, for example 5% to 95% by weight alumina and 95% to 5% by weight silica, for example 10% to 90% by weight alumina and 90% to 10% by weight silica, for example 15% to 90% by weight alumina and 85% to 10% by weight silica, for example 50% to 75% by weight alumina and 50% to 25% by weight silica, for example 50% to 70% by weight alumina and 50% to 30% by weight silica, for example 35% to 100% by weight The protective layer 84 may be a single coating layer containing alumina and 65% to 0% silica by weight, e.g., 70% to 90% alumina and 30% to 10% silica by weight, e.g., 75% to 85% alumina and 25% to 15% silica by weight, e.g., 88% alumina and 12% silica by weight, e.g., 65% to 75% alumina and 35% to 25% silica by weight, e.g., 70% alumina and 30% silica by weight, e.g., 60% to less than 75% alumina and more than 25% to 40% silica by weight. Other materials, such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium, and / or their oxides, may also be present to adjust the refractive index of the protective layer 84. In one non-limiting embodiment, the refractive index of the protective layer 84 can range from 1 to 3, such as from 1 to 2, such as from 1.4 to 2, such as from 1.4 to 1.8.

[0080] In one non-limiting embodiment, the protective layer 84 comprises a combination coating of silica and alumina. The protective coating 84 can be sputtered from two cathodes (e.g., one silicon and one aluminum) or from a single cathode containing both silicon and aluminum. This silicon oxide / aluminum protective layer 84 can be sputtered from Si x Al [2(1-x)] O (3-x) (where x can vary from greater than 0 to less than 1).

[0081] In another non-limiting embodiment, protective layer 84 comprises a combination of titania and alumina.

[0082] In one non-limiting embodiment, the protective layer 84 can be composed of silicon nitride (Si3N4), silicon oxynitride (SiON), silicon aluminum nitride (SiAlN), silicon aluminum oxynitride (SiAlON), mixtures thereof, and / or alloys thereof, which can increase the durability of the metal layer 42, 56, or 70. The protective layer 84 can be formed from silicon nitride deposited with other materials having good electrical conductivity to improve sputtering of silicon. For example, during deposition, the silicon cathode can include a small amount of aluminum (e.g., up to 20 wt%, up to 15 wt%, up to 10 wt%, or up to 5 wt%) to improve sputtering. In that case, the resulting silicon nitride protective layer includes a small amount of aluminum, e.g., up to 15 wt% aluminum, e.g., up to 10 wt% aluminum, e.g., up to 5 wt% aluminum. Coating layers deposited from silicon cathodes having up to 10% aluminum by weight (added to increase the cathode's conductivity) are referred to herein as "silicon nitride" layers, although small amounts of aluminum may be present. Small amounts of aluminum (e.g., 15% by weight or less, e.g., 10% by weight or less, e.g., 5% by weight or less) in the cathode are believed to form primarily aluminum nitride in the silicon nitride protective layer 84. The protective layer 84 may be formed in a nitrogen atmosphere, although it should be understood that other gases, such as oxygen, argon, or air, may be present in the atmosphere during deposition of the protective layer 84. For example, silicon nitride may be deposited in a nitrogen atmosphere. In one non-limiting embodiment, the outermost protective layer 84 may be composed of SiAlN, SiON, SiAlON, titania, alumina, silica, zirconia, alloys thereof, or mixtures thereof.

[0083] The protective layer 84 can be of any desired thickness. The protective layer 84 can be of any desired thickness, for example, 10 Å to 100,000 Å, for example, 10 Å to 90,000 Å, for example, 10 Å to 80,000 Å, for example, 10 Å to 70,000 Å, for example, 10 Å to 60,000 Å, for example, 10 Å to 50,000 Å, for example, 10 Å to 40,000 Å, for example, 10 Å to 30,000 Å, for example, 10 Å to 20,000 Å, for example, 10 Å to 10,000 Å, for example, 10 Å to 9,000 Å, for example, 10 Å to 8,000 Å, for example, 10 Å to 7,000 Å, for example, 10 Å to 6,000 Å. The thickness may be in the range of 10 Å to 5,000 Å, for example, 10 Å to 4,000 Å, for example, 10 Å to 3,000 Å, for example, 10 Å to 2,000 Å, for example, 10 Å to 1,000 Å, for example, 10 Å to 900 Å, for example, 10 Å to 800 Å, for example, 10 Å to 700 Å, for example, 10 Å to 600 Å, for example, 10 Å to 500 Å, for example, 10 Å to 400 Å, for example, 10 Å to 300 Å, for example, 10 Å to 200 Å, for example, 10 Å to 100 Å, for example, 10 Å to 50 Å. In one non-limiting embodiment, the protective coating 84 has a thickness of 10 Å to 100,000 Å, such as 10 Å to 90,000 Å, for example, 10 Å to 80,000 Å, for example, 10 Å to 70,000 Å, for example, 10 Å to 60,000 Å, for example, 10 Å to 50,000 Å, for example, 10 Å to 40,000 Å, for example, 10 Å to 30,000 Å, for example, 10 Å to 20,000 Å, for example, 10 Å to 10,000 Å, for example, 10 Å to 9,000 Å, for example, 10 Å to 8,000 Å, for example, 10 Å to 7,000 Å, for example, 10 Å to 6,000 Å. a silicon oxide / aluminium coating (SixAl) having a thickness in the range of 100 Å, for example 10 Å to 5,000 Å, for example 10 Å to 4,000 Å, for example 10 Å to 3,000 Å, such as 10 Å to 2,000 Å, for example 10 Å to 1,000 Å, for example 10 Å to 900 Å, for example 10 Å to 800 Å, for example 10 Å to 700 Å, such as 10 Å to 600 Å, for example 10 Å to 500 Å, for example 10 Å to 400 Å, for example 10 Å to 300 Å, such as 10 Å to 200 Å, for example 10 Å to 100 Å, for example 10 Å to 50 Å [2(1-x)] O (3-x)). Protective layer 84 is the outermost layer of the coated article. Furthermore, protective layer 84 can be of non-uniform thickness. By "non-uniform thickness" it is meant that the thickness of protective layer 84 can vary over a given unit area; for example, protective layer 84 can have high or low spots or areas.

[0084] In another non-limiting embodiment, the protective coating 84 can be a multi-layer coating including a first film and a second film formed on the first film. The first film can include alumina, silica, titania, zirconia, tin oxide, or a mixture thereof. In a specific non-limiting embodiment, the first film can include alumina or a mixture or alloy including alumina and silica. For example, the first film can include more than 5 wt.% alumina, e.g., more than 10 wt.% alumina, e.g., more than 15 wt.% alumina, e.g., more than 30 wt.% alumina, e.g., more than 40 wt.% alumina, e.g., 50 wt.%-70 wt.% alumina, e.g., 60 wt.%-100 wt.% alumina and 40 wt.%-0 wt.% silica, e.g., a silica / alumina mixture having 60 wt.% alumina and 40 wt.% silica. In another example, the first film can include zinc stannate. In another example, the first film can include zirconia. In one non-limiting embodiment, the first film has a thickness of from greater than 0 Å to 50,000 Å, such as greater than 0 Å to 45,000 Å, for example greater than 0 Å to 40,000 Å, for example greater than 0 Å to 35,000 Å, for example greater than 0 Å to 30,000 Å, for example greater than 0 Å to 25,000 Å, for example greater than 0 Å to 20,000 Å, for example greater than 0 Å to 15,000 Å, for example greater than 0 Å to 10,000 Å, for example greater than 0 Å to 5,000 Å, for example greater than 0 Å to 4,500 Å, for example greater than 0 Å to 4,000 Å, for example greater than 0 Å to 3,500 Å, for example 0 Å to 3 The thickness may range from 0 to 2,000 Å, for example from 0 to 2,500 Å, for example from 0 to 2,000 Å, for example from 0 to 1,500 Å, for example from 0 to 1,000 Å, for example from 0 to 500 Å, for example from 0 to 450 Å, for example from 0 to 400 Å, for example from 0 to 350 Å, for example from 0 to 300 Å, for example from 0 to 250 Å, for example from 0 to 200 Å, for example from 0 to 150 Å, for example from 0 to 100 Å, for example from 0 to 50 Å, for example from 0 to 25 Å.

[0085] The second film of the protective layer 84 can include, for example, a metal oxide or a metal nitride. The second film can be titania, alumina, silica, zirconia, tin oxide, a mixture thereof, or an alloy thereof. For example, the second film can include a mixture of titania and alumina, a mixture of titania and silica, or zirconia. Examples of the second film include a titania / alumina mixture having 40-60 wt% alumina and 60-40 wt% titania, 45-55 wt% alumina and 45-55 wt% titania, 48-52 wt% alumina and 52-48 wt% titania, 49-51 wt% alumina and 51-49 wt% titania, or 50 wt% alumina and 50 wt% titania. An example of the second film includes titanium aluminum oxide (TiAlO). Another example of the second membrane comprises a silica / alumina mixture having more than 40 wt% silica, such as more than 50 wt% silica, for example more than 60 wt% silica, for example more than 70 wt% silica, for example more than 80 wt% silica, for example 80 wt% to 90 wt% silica and 10 wt% to 20 wt% alumina, for example 85 wt% silica and 15 wt% alumina.In one non-limiting embodiment, the second film has a thickness of from greater than 0 Å to 50,000 Å, such as greater than 0 Å to 45,000 Å, for example greater than 0 Å to 40,000 Å, for example greater than 0 Å to 35,000 Å, for example greater than 0 Å to 30,000 Å, for example greater than 0 Å to 25,000 Å, for example greater than 0 Å to 20,000 Å, for example greater than 0 Å to 15,000 Å, for example greater than 0 Å to 10,000 Å, for example greater than 0 Å to 5,000 Å, for example greater than 0 Å to 4,500 Å, for example greater than 0 Å to 4,000 Å, for example greater than 0 Å to 3,500 Å, for example greater than 0 Å to 3 The thickness may range from 0 to 2,000 Å, for example from 0 to 2,500 Å, for example from 0 to 2,000 Å, for example from 0 to 1,500 Å, for example from 0 to 1,000 Å, for example from 0 to 500 Å, for example from 0 to 450 Å, for example from 0 to 400 Å, for example from 0 to 350 Å, for example from 0 to 300 Å, for example from 0 to 250 Å, for example from 0 to 200 Å, for example from 0 to 150 Å, for example from 0 to 100 Å, for example from 0 to 50 Å, for example from 0 to 25 Å. Non-limiting examples of suitable protective layers are described, for example, in U.S. Patent Application Nos. 10 / 007,382, 10 / 133,805, 10 / 397,001, 10 / 422,094, 10 / 422,095, and 10 / 422,096.

[0086] In a non-limiting example, the protective layer 84 can include an additional third film formed on the second film. This third film can be any of the materials used to form the first or second film. The third film can include, for example, alumina, silica, titania, zirconia, tin oxide, or a mixture thereof. For example, the third film can include a mixture of silica and alumina. In another example, the third film includes zirconia.

[0087] A stress layer 82 may be present between the upper dielectric layer and the protective layer 84, and on at least a portion of the upper dielectric layer, or in direct contact with the upper dielectric layer. The stress layer 82 is added below the protective layer 84 to reduce the sheet resistance of the coating. The stress layer 82 may have a thickness of 0.5 to 30 nm, preferably 1 to 25 nm, more preferably 1 to 20 nm, or most preferably 1 to 18 nm. In certain embodiments, the stress layer 82 may comprise silicon, cobalt, titanium, niobium, zirconium, tantalum, oxygen, and / or titanium. In one embodiment, the stress layer 82 comprises silicon cobalt. In one embodiment, the stress layer 82 comprises Ti x Nb 1-x In another embodiment, the stress layer 82 comprises a Nb suboxide or oxide, where x is in the range of 1 to 100 wt. % (BH and AH). x Zr 1-x In another embodiment, the stress layer 82 comprises a suboxide or oxide, where x is in the range of 1-12 wt. % AH, preferably 1-11 wt. % AH, more preferably 1-11 wt. % AH, and most preferably 1-10 wt. % AH. x Ta 1-x In another embodiment, the stress layer 82 comprises a suboxide or oxide, where x is in the range of 1-100 wt% AH, preferably 1-20 wt% AH or 30-100 wt% AH, more preferably 1-10 wt% AH or 500 wt% AH, and most preferably 1-4 wt% AH or 60-100 wt% AH. In another embodiment, the stress layer 82 comprises a Si x Co 1-x It comprises a suboxide or oxide, where x is in the range of 10 to 90 wt% AH, preferably 15 to 90 wt% AH, more preferably 18 to 90 wt% AH, and most preferably 20 to 90 wt% AH.

[0088] A non-limiting heatable transparency 100 (e.g., an automobile windshield) incorporating features of the present invention is shown in Figures 10 and 11. The transparency 100 can have any desired transmission and reflection of visible light, infrared radiation, or ultraviolet radiation. For example, the transparency 100 can have any desired amount of visible light transmittance (e.g., greater than 0% to 100%, e.g., greater than 70%). In the windshield and front sidelight areas in the United States, visible light transmittance is typically 70% or greater. In privacy areas such as rear seat sidelights and rear windows, visible light transmittance can be lower than that of the windshield, e.g., less than 70%.

[0089] As seen in FIG. 11 , transparency 100 includes a first ply or first substrate 12 having a first major surface facing the exterior of the vehicle (i.e., outer major surface 14 (No. 1 surface) and an opposite second or inner major surface 16 (No. 2 surface)). Transparency 100 also includes a second ply or second substrate 110 having an outer (first) major surface 112 (No. 4 surface) and an inner (second) major surface 114 (No. 3 surface). This numbering of the ply surfaces is consistent with conventional practice in the automotive industry. The first and second plies 12, 110 can be bonded together in any suitable manner, for example, by a conventional interlayer 108. Although not required, a conventional edge sealant can be applied around the perimeter of laminated transparency 100 in any desired manner during and / or after lamination. A decorative band, such as an opaque, translucent, or colored shade band 102 (shown in FIG. 11 ), e.g., a ceramic band, may be provided on at least one surface of the plies 12, 110, e.g., around the periphery of the inner major surface 16 of the first ply 12. A coating 10 is formed on at least a portion of one of the plies 12, 110 (e.g., on the No. 2 surface 16 or the No. 3 surface 114). A busbar assembly 120 ( FIG. 10 ) is in electrical contact with the coating 10. The busbar assembly 120 is also connected to a power source 122 ( FIG. 10 ), which will be described in more detail below. In one non-limiting aspect of the present invention, the power source 122 may be, for example, a conventional vehicle alternator configured to provide approximately 14 volts. Thus, in the implementation of one non-limiting embodiment of the present invention, a DC-DC power converter is not present. In one non-limiting embodiment, power supply 122 can be a 42 volt DC alternator, or a DC-DC converter can be added to step up the voltage from a 14 volt alternator to a sufficient level (e.g., 42 volts DC). In another embodiment, power supply 122 can be a 14 volt vehicle alternator.

[0090] In the broad implementation of the present invention, the plies 12, 110 of the transparency 100 can be the same or different materials. The plies 12, 110 can include any desired material having any desired properties. For example, one or more of the plies 12, 110 can be transparent or translucent to visible light. "Transparent" means having a visible light transmittance greater than 0% and up to 100%. Alternatively, one or more of the plies 12, 110 can be translucent. "Translucent" means allowing electromagnetic energy (e.g., visible light) to pass through but diffusing this energy to prevent a viewer from clearly seeing objects on the other side. Examples of suitable materials include, but are not limited to, plastic substrates (e.g., acrylic polymers (e.g., polyacrylates), polyalkyl methacrylates (e.g., polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, etc.), polyurethanes, polycarbonates, polyalkyl terephthalates (e.g., polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, etc.), polysiloxane-containing polymers, or copolymers of any monomers therefor, or any mixtures thereof), ceramic substrates, glass substrates, or mixtures or combinations of any of the above. For example, one or more of the plies 12, 110 can comprise conventional soda-lime silicate glass, borosilicate glass, or lead glass. The glass can be clear glass. "Clear glass" means untinted or colorless glass. Alternatively, the glass can be colored glass or otherwise tinted glass. The glass can be annealed or heat-treated glass. As used herein, the term "heat-treated" means tempered or at least partially tempered. The glass can be of any type, such as conventional float glass, and can be of any composition with any optical properties (e.g., any values of visible transmittance, ultraviolet transmittance, infrared transmittance, and / or total solar energy transmittance)."Float glass" refers to glass formed by the conventional float process, in which molten glass is deposited onto a molten metal bath and controllably cooled to form a float glass ribbon. The ribbon is then cut and / or shaped and / or heat treated as needed. Examples of float glass processes are disclosed in U.S. Patent Nos. 4,466,562 and 4,671,155. The first and second plies 12, 110 can each be, for example, clear float glass, or tinted or colored glass, or one ply 12, 110 can be clear glass and the other ply 12, 110 can be colored glass. Although not limiting to the present invention, examples of glass suitable for the first ply 12 and / or second ply 110 are described in U.S. Patent Nos. 4,746,347, 4,792,536, 5,030,593, 5,030,594, 5,240,886, 5,385,872, and 5,393,593. The first and second plies 12, 110 can be of any desired dimensions (e.g., length, width, shape, or thickness). In one exemplary automotive transparency, the first and second plies can each be 1 mm to 10 mm thick, e.g., 1 mm to 5 mm thick, or 1.5 mm to 2.5 mm, or 1.8 mm to 2.3 mm. In one non-limiting embodiment, the first ply 12 and / or the second ply 110 can have a visible light transmittance of greater than 90% (e.g., greater than 91%) at a reference wavelength of 550 nm. The glass composition of the first ply 12 and / or the second ply 110 can have a total iron content ranging from greater than 0% to 0.2% by weight and / or a redox ratio ranging from 0.3 to 0.6.

[0091] In one non-limiting embodiment, one or both of the plies 12, 110 can have high visible light transmittance at a reference wavelength of 550 nanometers (nm). By "high visible light transmittance" is meant that the visible light transmittance at 550 nm is 85% or greater, e.g., 87% or greater, e.g., 90% or greater, e.g., 91% or greater, e.g., 92% or greater, for glass thicknesses of 2 mm to 25 mm and an equivalent thickness of 5.5 mm. Glasses particularly useful in practicing the present invention are disclosed in U.S. Patent Nos. 5,030,593 and 5,030,594.

[0092] The interlayer 108 can be any desired material and can include one or more layers or plies. The interlayer 108 can be a polymeric or plastic material, such as a multilayer thermoplastic material including, for example, polyvinyl butyral, plasticized polyvinyl chloride, or polyethylene terephthalate. Suitable interlayers are disclosed, for example, in U.S. Patent Nos. 4,287,107 and 3,762,988, but should not be considered limiting. The interlayer 108 secures the first and second plies 12, 110 together, provides energy absorption, reduces sound, and increases the strength of the laminate structure. The interlayer 108 can also be an acoustic or damping material, as described, for example, in U.S. Patent No. 5,796,055. The interlayer 108 can have a solar control coating disposed thereon or incorporated therein, or can include a colored material to reduce solar energy transmission.

[0093] In the non-limiting embodiment shown in FIGS. 10 and 11 , a busbar assembly 120 includes a first or lower busbar 104 and a second or upper busbar 106 formed on the inner surface 16 of the outer ply 12 and separated by a busbar-to-busbar distance D. The busbars 104, 106 are in electrical contact with the coating 10. The busbar assembly 120 also includes a first conductive lead or strip 116 connected to the first busbar 104 and a second conductive lead or strip 118 connected to the second busbar 106. Each of the leads 116, 118 is connected to a power source 122. The busbars 104, 106 and / or the conductive strips 116, 118 can be formed from a conductive metal foil or strip (such as, but not limited to, copper foil or tinned copper foil), or can be formed with a conductive coating (e.g., a ceramic coating), or a combination thereof. In one non-limiting embodiment of the present invention, bus bars 104 and 106 can be at least partially or completely disposed on decorative band 102 (as shown in FIG. 11).

[0094] Power source 122 can be any conventional power source, however, in one non-limiting embodiment, power source 122 can be a conventional vehicle alternator configured to provide a voltage in the range of 13 to 15 volts, such as approximately 14 volts.

[0095] A further transparency 130 incorporating features of the present invention is shown in FIG. 12. The configuration of transparency 130 is similar to transparency 100, except that coating 10 includes one or more "cut-out" regions, such as cut-outs 132 and 134. Cut-outs 132 and 134 divide coating 10 into first main portion 136, second main portion 138, and central portion 140. Busbar assembly 142 in this non-limiting embodiment is a quad-feed assembly, i.e., has four connectors 144, 146, 148, and 150 connected to four busbars 152, 154, 156, and 158, respectively. Busbars 152 and 154 primarily supply power to first main portion 136, while busbars 156 and 158 primarily supply power to second main region 138.

[0096] In one non-limiting embodiment of the present invention, when the coating is in electrical contact with a conventional vehicle alternator (e.g., a conventional alternator producing 80 amps and 14 volts), the coating 10 provides a busbar-to-busbar distance D (see FIG. 10) of 2 to 10 watts per decimeter (W / dm 2 ) power density (e.g., 4~8W / dm 2 , for example, 5-6W / dm 2). Such a power density is believed to be sufficient to melt ice in contact with the exterior surface 14 of the substrate 12. For visibility panels (e.g., windshields) in the United States, the transparency must also have a visible light transmittance of 70% or greater (e.g., 71% or greater). As those skilled in the art will appreciate, providing a coating with sufficient conductivity and sufficient transmittance requires balancing several different competing factors. For example, as the distance D between the busbars increases (i.e., the transparency becomes wider from top to bottom), the resistance between the busbars increases. Increasing resistance between the busbars reduces the power density. To maintain power density as the distance between the busbars increases, the resistivity of the coating must be reduced. One way to reduce resistivity is by increasing the thickness of one or more silver layers and / or by increasing the number of silver layers. In one non-limiting embodiment of the present invention, the thickness and / or number of silver layers are configured to provide a total resistivity of the coating of 0.6 to 1.5 ohms per square (Ω / □), e.g., 0.6 to 1.0 ohms per square (Ω / □), e.g., 0.6 to 0.9 ohms per square (Ω / □). In one non-limiting embodiment of the present invention, the thickness and / or number of silver layers are configured to provide a total resistivity of 0.850 ohms per square (Ω / □), e.g., 0.800 ohms per square (Ω / □), e.g., 0.700 ohms per square (Ω / □), e.g., 0.695 ohms per square (Ω / □). However, as will also be understood by those skilled in the art, as the number or thickness of silver layers increases, visible light transmittance decreases. In the forward viewing area of a vehicle, such as a windshield, the thickness and / or number of silver layers should not be increased to the point where the visible light transmittance of the viewing area falls below about 70%.

[0097] In one non-limiting implementation of the present invention, the coating provides a visible light reflectance of 25% or less, such as 20% or less, such as 10% or less, such as 8% or less.

[0098] In one non-limiting implementation of the present invention, coating 10 provides an external reflectance a* (Rg8a*) at an angle of 8 degrees in the range of 0 to -10, e.g., -1 to -8, preferably -1.2 to -7.0, more preferably -1.5 to -6.8, and most preferably -1.7 to -6.5.

[0099] In one non-limiting implementation of the present invention, coating 10 provides an external reflectance b* at an angle of 8 degrees (Rg8b*) in the range of 2 to -8, e.g., 2.5 to -8.0, preferably 2.0 to -7.5, more preferably 1.8 to -7.3, and most preferably 1.5 to -7.0.

[0100] One embodiment of the present invention is a vehicle transparency having only three metal layers sandwiched between dielectric layers. Each metal layer has a thickness. The combined thickness of all three metal layers is between 30 nm and 65 nm, preferably between 32 nm and 52 nm, more preferably between 34 nm and 50 nm, and most preferably between 35 nm and 48 nm. This vehicle transparency can have a coating as shown in Table 1. [Table 1-1] [Table 1-2]

[0101] One embodiment of the present invention is a vehicle transparency having only four metal layers sandwiched between dielectric layers. Each metal layer has a thickness. The combined thickness of all four metal layers is between 30 nm and 65 nm, preferably between 35 nm and 55 nm, more preferably between 39 nm and 53 nm, and most preferably between 40 nm and 52 nm. This vehicle transparency can have a coating as shown in Table 2. [Table 2-1] [Table 2-2]

[0102] Figure 13 shows a diagram of the initial nucleation of film growth on a surface. Nucleation leads to a change in the Gibbs free energy of the system, including the volume and surface Gibbs free energies. To grow a 2D layer, the growth surface must have a high surface energy (i.e., high surface tension) for 2D growth, and the change in Gibbs free energy must be large enough to produce a denser film. Therefore, the material on which silver grows (i.e., the seed film) and the material beneath which silver is coated (i.e., the primer layer) must have a high Gibbs free energy to promote dense 2D silver growth and avoid agglomeration of silver. Some elements with higher cohesive energy and Gibbs free energy compared to silver are listed in Table 3 below. These elements are some of the materials that may reduce silver agglomeration when used as either a seed film or a primer layer. [Table 3]

[0103] The present invention also includes a method of producing these various embodiments of a coated article, comprising providing a substrate and depositing a coating over the substrate, the coating including a first dielectric layer deposited over at least a portion of the substrate, an optional first seed film deposited over at least a portion of the first dielectric layer, a first metal layer deposited over at least a portion of the first dielectric layer or the optional first seed film, a first primer layer deposited over at least a portion of the first metal layer, and a second dielectric layer deposited over at least a portion of the first primer layer. The coating provided by the above method can also optionally include a second seed film deposited on at least a portion of the second dielectric layer, a second metal layer deposited on at least a portion of the second dielectric layer or the second seed film, a second primer layer deposited on at least a portion of the second metal layer, a third dielectric layer deposited on at least a portion of the second primer layer, a third seed film deposited on at least a portion of the third dielectric layer, a third metal layer deposited on at least a portion of the third dielectric layer or the third seed film, a third primer layer deposited on at least a portion of the third metal layer, a fourth dielectric layer deposited on at least a portion of the third primer layer, a fourth seed film deposited on at least a portion of the fourth dielectric layer, a fourth metal layer deposited on at least a portion of the fourth dielectric layer or the fourth seed film, a fourth primer layer deposited on at least a portion of the fourth metal layer, and / or a fifth dielectric layer deposited on at least a portion of the fourth primer layer. The coating of the above method may also optionally include a protective layer over at least a portion of the top dielectric layer, and / or a stress layer deposited over at least a portion of the top dielectric layer, between the top dielectric layer and the protective layer.

[0104] The present invention also includes methods of producing these various embodiments of coated articles, comprising the steps of providing a substrate, depositing a coating on the substrate, heating the substrate including the coating, and bending the substrate including the coating into a desired shape, the coating comprising a first dielectric layer deposited on at least a portion of the substrate, an optional first seed film deposited on at least a portion of the first dielectric layer, a first metal layer deposited on at least a portion of the first dielectric layer or the optional first seed film, a first primer layer deposited on at least a portion of the first metal layer, and a second dielectric layer deposited on at least a portion of the first primer layer. The coating provided by the above method can also optionally include a second seed film deposited on at least a portion of the second dielectric layer, a second metal layer deposited on at least a portion of the second dielectric layer or the second seed film, a second primer layer deposited on at least a portion of the second metal layer, a third dielectric layer deposited on at least a portion of the second primer layer, a third seed film deposited on at least a portion of the third dielectric layer, a third metal layer deposited on at least a portion of the third dielectric layer or the third seed film, a third primer layer deposited on at least a portion of the third metal layer, a fourth dielectric layer deposited on at least a portion of the third primer layer, a fourth seed film deposited on at least a portion of the fourth dielectric layer, a fourth metal layer deposited on at least a portion of the fourth dielectric layer or the fourth seed film, a fourth primer layer deposited on at least a portion of the fourth metal layer, and / or a fifth dielectric layer deposited on at least a portion of the fourth primer layer. The coating of the above method may also optionally include a protective layer over at least a portion of the top dielectric layer, and / or a stress layer deposited over at least a portion of the top dielectric layer, between the top dielectric layer and the protective layer. [Example]

[0105] As mentioned previously, the sheet resistance of a coating can be reduced by using new materials in individual layers. Adding new layers altogether is expected to reduce the sheet resistance as well. In Table 4, instead of a Ti primer layer, a Ti 78 Nb 22 were integrated into the stack. Under the silver metal layer, Ag with oxygen deposition was also included as a seed film. The substrate was a transparent glass substrate. ZT stands for zinc tin, also known as zinc stannate. Zn90 is tin-doped zinc oxide (i.e., ZnO 90 / 10), deposited from a cathode containing 10% tin and 90% zinc by weight in the presence of oxygen. Ag stands for silver. PPO is the protective layer or coating described above. Before integrating these layers, each layer was optimized to have the lowest sheet resistance. The following table shows the best samples for various combinations. [Table 4]

[0106] The Ti layer under the protective layer acts as the stress layer. 78 Nb 22 O x An additional coating stack was also tested, inserting a layer. A total of three layers were changed from the baseline to the final coating stack, and the sheet resistance values can be seen in Table 5. [Table 5]

[0107] Table 6 shows the Ti primer layer or Ti 78 Nb 22 Primer layer is Ti3Nb 97 N x Or it is replaced with titanium niobium nitride. [Table 6]

[0108] Table 7 shows coating stack experiments using aluminum zinc primer and aluminum zinc oxide above and below the silver layer as part of the dielectric layer. For the single silver stack, the sheet resistance is reduced from 3.75 to 3.21 Ω / □. [Table 7]

[0109] Table 8 shows the coating stack experiments using aluminum zinc primer and aluminum zinc oxide above and below the silver layer. 90 Sn 10 For triple silver stacks using Ag oxygen deposited seed films between O, the sheet resistance is reduced from 1 to 0.73 Ω / □. [Table 8]

[0110] The addition of a stress layer below the protective layer may further reduce the sheet resistance of the coating stack. A variety of additional materials have been tested for use as stress layers. Some of these materials are listed in Table 9, which demonstrate that their inclusion as a stress layer reduces the sheet resistance. [Table 9]

[0111] Experiments were conducted to replace the dielectric layer film surrounding the metal layer with VZnO (vanadium zinc oxide). The top dielectric layer film directly below the metal layer was replaced, and the bottom dielectric layer film directly above the metal layer was replaced. These were paired with both a Ti primer layer and a zinc metal primer layer. The results of these experiments are shown in Table 10 below. [Table 10]

[0112] (Clause 1) A coated article comprising: a substrate; a first dielectric layer on at least a portion of the substrate; a first metal layer on at least a portion of the first dielectric layer; a first primer layer on at least a portion of the first metal layer; and a second dielectric layer on at least a portion of the first primer layer, wherein the primer layer is selected from the group consisting of zinc, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, zinc tin, indium zinc, silver zinc, gallium zinc, indium tin, combinations thereof, mixtures thereof, or alloys thereof.

[0113] (Clause 2) The article of clause 1, wherein at least a portion of the primer layer is an oxide or a nitride.

[0114] (Clause 3) The article of clause 1 or 2, including a seed film adjacent to and in direct contact with the first metal layer and between the first dielectric layer and the first metal layer.

[0115] (Clause 4) The article of any one of clauses 1 to 3, wherein the primer layer is selected from the group consisting of silver zinc, zinc, silver zinc oxide, aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, vanadium zinc oxide, mixtures thereof, combinations thereof, or alloys thereof.

[0116] (Clause 5) The article of any one of clauses 1 to 4, wherein the primer layer is a metal, oxide, nitride, suboxide, subnitride, oxynitride, and / or suboxynitride.

[0117] (Clause 6) The article of any one of clauses 3-5, wherein the seed film is comprised of aluminum, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum doped silver, silver, silver zinc, titanium aluminum, mixtures thereof, metals thereof, alloys thereof, combinations thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, oxynitrides thereof, suboxynitrides thereof, oxycarbides thereof, carbonitrides thereof, or oxycarbonitrides thereof.

[0118] (Clause 7) The article of any one of clauses 3 to 6, wherein the seed film comprises aluminum zinc, vanadium zinc, zinc, or silver zinc.

[0119] (Clause 8) The article of clause 7, wherein the seed film is a metal, oxide, or suboxide.

[0120] (Clause 9) The article of any one of clauses 3 to 6, wherein the seed film comprises gallium zinc, indium zinc, or indium tin.

[0121] 10. The article of claim 9, wherein the seed film is a metal, oxide, nitride, suboxide, or subnitride.

[0122] (Clause 11) The article of any one of clauses 1 to 10, further comprising a second metal layer on at least a portion of the second dielectric layer, a second primer layer on at least a portion of the second metal layer, and a third dielectric layer on at least a portion of the second primer layer.

[0123] (Clause 12) The article described in Clause 11, further comprising a third metal layer on at least a portion of the third dielectric layer, a third primer layer on at least a portion of the third metal layer, and a fourth dielectric layer on at least a portion of the third primer layer.

[0124] (Clause 13) The article described in Clause 12, further comprising a fourth metal layer on at least a portion of the fourth dielectric layer, a fourth primer layer on at least a portion of the fourth metal layer, and a fifth dielectric layer on at least a portion of the fourth primer layer.

[0125] (Clause 14) The article of any one of clauses 1 to 13, wherein the one or more metal layers comprise silver or aluminum-doped silver.

[0126] (Clause 15) The article of any one of clauses 1 to 14, wherein the first dielectric layer comprises a zinc stannate film and a second film comprising at least one of zinc oxide, zinc aluminum oxide, indium zinc oxide, zinc gallium oxide, indium tin oxide, or zinc vanadium oxide on at least a portion of the zinc stannate film.

[0127] (Clause 16) The article of any one of clauses 1 to 15, wherein the first dielectric layer comprises a zinc stannate film and a second film comprising at least one of aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the zinc stannate film.

[0128] (Clause 17) An article described in any one of clauses 11 to 16, wherein the second dielectric layer and the third dielectric layer include a first film comprising zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, a second film comprising zinc stannate on at least a portion of the first film, and a third film comprising at least one of zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the second film.

[0129] (Clause 18) An article described in any one of clauses 11 to 16, wherein the second dielectric layer and the third dielectric layer include a first film comprising aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, a second film comprising zinc stannate on at least a portion of the first film, and a third film comprising at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the second film.

[0130] (Clause 19) An article described in any one of clauses 12 to 18, wherein the fourth dielectric layer comprises a first film comprising at least one of zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, and zinc stannate on at least a portion of the first film.

[0131] (Clause 20) An article described in any one of clauses 12 to 19, wherein the fourth dielectric layer comprises a first film comprising at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, and a zinc stannate film on at least a portion of the first film.

[0132] (Clause 21) The article of any one of clauses 1 to 20, wherein the first dielectric layer or the second dielectric layer comprises a silicon nitride film.

[0133] (Clause 22) The article of any one of clauses 1 to 21, further comprising an outermost protective layer comprising SiAlN, SiON, SiAlON, titania, alumina, silica, zirconia, alloys thereof, or mixtures thereof.

[0134] (Clause 23) The article of clause 22, further comprising a stress layer beneath the outermost protective layer.

[0135] (Clause 24) The article of clause 23, wherein the stress layer comprises silicon cobalt, titanium niobium, zirconium niobium, tantalum titanium, an oxide thereof, or a suboxide thereof.

[0136] (Article 25) The primer layer is Al x Zn 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of greater than 0% to 30% by weight.

[0137] (Clause 26) The primer layer is Ga x Zn 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of greater than 0% to 20% by weight.

[0138] (Article 27) The primer layer is In x Zn 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of greater than 0% to 40% by weight.

[0139] (Article 28) The primer layer is V x Zn 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of greater than 0% to 20% by weight.

[0140] (Article 29) The primer layer is made of Ag x Zn 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of greater than 0% to 50% by weight.

[0141] (Article 30) The primer layer is Al x Ti 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of 2 to 75% by weight before heating.

[0142] (Article 31) The primer layer is Al x Ti 1-x25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of 1 to 100% by weight after heating.

[0143] (Article 32) The primer layer is Al x Nb 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of 2 to 40% by weight before heating.

[0144] (Article 33) The primer layer is Al x Nb 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of 2 to 95% by weight after heating.

[0145] (Article 34) The primer layer is W x Ti 1-x 25. The article of any one of clauses 1 to 24, comprising: (wherein x is in the range of 55 to 100 wt. % before heating with 7% O2 during deposition).

[0146] (Article 35) The primer layer is W x Ti 1-x 25. The article of any one of clauses 1-24, comprising: wherein x is in the range of 30-95 wt% after heating with 3% O2 during deposition.

[0147] (Article 36) The primer layer is made of Ti x Ta 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of 2 to 80% by weight before heating.

[0148] (Article 37) The primer layer is made of Ti x Ta 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of 2 to 40 wt % after heating.

[0149] (Article 38) The primer layer is made of Ti x Nb 1-x25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of 2 to 95% by weight after heating.

[0150] (Article 39) The primer layer is made of Nb x Zr 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of 1 to 80% by weight before heating.

[0151] (Article 40) The primer layer is made of Nb x Zr 1-x 25. The article of any one of clauses 1 to 24, comprising: (wherein x is in the range of 60 to 100 wt % after heating).

[0152] (Article 41) The primer layer is Ta x W 1-x 25. The article of any one of clauses 1 to 24, comprising: (wherein x is in the range of 2 to 95% by weight before heating).

[0153] (Article 42) The primer layer is W x Nb 1-x 25. The article of any one of clauses 1 to 24, comprising: (wherein x is in the range of 5 to 100% by weight before heating).

[0154] (Article 43) The primer layer is W x Nb 1-x 25. The article of any one of clauses 1 to 24, comprising: wherein x is in the range of 2 to 50 wt % after heating.

[0155] (Article 44) The primer layer is Zn x Ti 1-x 25. The article of any one of clauses 1 to 24, comprising: (wherein x is in the range of 10 to 100% by weight before heating).

[0156] (Article 45) The primer layer is Zn x Ti 1-x 25. The article of any one of clauses 1 to 24, comprising: (wherein x is in the range of 20 to 100 wt % after heating).

[0157] (Clause 46) The article of any one of clauses 1 to 45, wherein at least a portion of one or more primer layers is a nitride.

[0158] (Article 47) The primer layer is Al x Nb 1-x 47. The article of claim 46, comprising a nitride, wherein x is in the range of 1 to 100 wt % before heating.

[0159] (Article 48) The primer layer is Al x Nb 1-x 47. The article of claim 46, comprising a nitride, wherein x is in the range of 1 to 100 wt % after heating.

[0160] (Article 49) The primer layer is made of Ti x Nb 1-x 47. The article of claim 46, comprising a nitride, wherein x is in the range of 1 to 65 wt.%.

[0161] (Article 50) The primer layer is W x Nb 1-x 47. The article of claim 46, comprising a nitride, wherein x is in the range of 2 to 90 wt % before heating.

[0162] (Article 51) The primer layer is W x Nb 1-x 47. The article of claim 46, comprising a nitride, wherein x is in the range of 2 to 70 wt % after heating.

[0163] (Article 52) The seed film is V x Zn 1-x 52. The article of any one of clauses 3 to 51, comprising an oxide, wherein x is in the range of 1 to 25 wt.%.

[0164] (Article 53) The seed film is Al x Zn 1-x 52. The article of any one of clauses 3 to 51, comprising an oxide, wherein x is in the range of 1 to 25 wt.%.

[0165] (Article 54) The seed film is Ga x Zn 1-x 52. The article of any one of clauses 3 to 51, comprising an oxide, wherein x is in the range of 1 to 20 wt.%.

[0166] (Article 55) The seed film is In x Zn 1-x 52. The article of any one of clauses 3 to 51, comprising an oxide, wherein x is in the range of 1 to 40 wt.%.

[0167] (Article 56) The seed film is Sn x In 1-x 52. The article of any one of clauses 3 to 51, comprising an oxide, wherein x is in the range of 1 to 20 wt.%.

[0168] (Clause 57) The article of any one of clauses 3 to 51, wherein the seed film comprises Ag, and the Ag is deposited in an oxygen and argon gas environment having an oxygen gas flow rate of 1 to 70%.

[0169] (Article 58) The seed film is Al x Ag 1-x wherein x is in the range of 1 to 35% by weight before and after heating.

[0170] (Article 59) The stress layer is made of Ti x Nb 1-x 59. The article of any one of clauses 23 to 58, comprising a suboxide or oxide, where x is in the range of 1 to 100% by weight before and after heating.

[0171] (Article 60) The stress layer is made of Nb x Zr 1-x 59. The article of any one of clauses 23 to 58, comprising a suboxide or oxide, wherein x is in the range of 1 to 12% by weight after heating.

[0172] (Article 61) The stress layer is made of Ti x Ta1-x 59. The article of any one of clauses 23 to 58, comprising a suboxide or oxide, wherein x is in the range of 1 to 100% by weight after heating.

[0173] (Article 62) The stress layer is made of Si x Co 1-x 59. The article of any one of clauses 23 to 58, comprising a suboxide or oxide, wherein x is in the range of 10 to 90% by weight after heating.

[0174] (Clause 63) The article of any one of Clauses 1 to 62, wherein the article has a visible light transmittance of at least 70%.

[0175] (Clause 64) The article of any one of Clauses 1 to 63, wherein the article has a sheet resistance of 0.7 ohms / square or less.

[0176] (Clause 65) A coated article comprising a substrate, a first dielectric layer on at least a portion of the substrate, a first metal layer on at least a portion of the first dielectric layer, a first primer layer on at least a portion of the first metal layer, a second dielectric layer on at least a portion of the first primer layer, and an outermost protective layer, wherein a stress layer is added between the protective outer layer and the upper dielectric layer and comprises one or a combination of silicon cobalt, titanium niobium, zirconium niobium, tantalum titanium, oxides thereof, or suboxides thereof.

[0177] (Clause 66) The article according to Clause 65, wherein at least a portion of the primer layer is an oxide or a nitride.

[0178] (Clause 67) The article of clause 65 or 66, including a seed film adjacent to and in direct contact with the first metal layer and between the first dielectric layer and the first metal layer.

[0179] (Clause 68) The article of any one of Clauses 65 to 67, wherein the primer layer is selected from the group consisting of silver zinc, zinc, silver zinc oxide, aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, vanadium zinc oxide, mixtures thereof, combinations thereof, and alloys thereof.

[0180] (Clause 69) The article according to any one of Clauses 65 to 67, wherein the primer layer is a metal, an oxide, a nitride, a suboxide, a subnitride, an oxynitride, or a suboxynitride.

[0181] (Clause 70) The article of any one of clauses 67-69, wherein the seed film is comprised of aluminum, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum doped silver, silver, silver zinc, titanium aluminum, mixtures thereof, metals thereof, alloys thereof, combinations thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, oxynitrides thereof, suboxynitrides thereof, oxycarbides thereof, carbonitrides thereof, or oxycarbonitrides thereof.

[0182] (Clause 71) The article of clause 70, wherein the seed film comprises aluminum zinc, vanadium zinc, zinc, or silver zinc.

[0183] 72. The article of claim 71, wherein the seed film is a metal, oxide, or suboxide.

[0184] (Clause 73) The article of clause 70, wherein the seed film comprises gallium zinc, indium zinc, or indium tin.

[0185] 74. The article of claim 73, wherein the seed film is a metal, oxide, nitride, suboxide, or subnitride.

[0186] (Clause 75) An article described in any one of clauses 65 to 74, further comprising a second metal layer on at least a portion of the second dielectric layer, a second primer layer on at least a portion of the second metal layer, and a third dielectric layer on at least a portion of the second primer layer.

[0187] (Clause 76) The article described in Clause 75, further comprising a third metal layer on at least a portion of the third dielectric layer, a third primer layer on at least a portion of the third metal layer, and a fourth dielectric layer on at least a portion of the third primer layer.

[0188] (Clause 77) The article described in Clause 76, further comprising a fourth metal layer on at least a portion of the fourth dielectric layer, a fourth primer layer on at least a portion of the fourth metal layer, and a fifth dielectric layer on at least a portion of the fourth primer layer.

[0189] (Clause 78) An article according to any one of clauses 65 to 77, wherein the one or more metal layers comprise silver or aluminum-doped silver.

[0190] (Clause 79) An article described in any one of clauses 65 to 78, wherein the first dielectric layer comprises a zinc stannate film and the second film comprises zinc oxide, zinc aluminum oxide, zinc indium oxide, zinc gallium oxide, indium tin oxide, or zinc vanadium oxide on at least a portion of the zinc stannate film.

[0191] (Clause 80) An article described in any one of clauses 65 to 78, wherein the first dielectric layer comprises a zinc stannate film and a second film comprising at least one of aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the zinc stannate film.

[0192] (Clause 81) An article described in any one of clauses 75 to 80, wherein the second dielectric layer and the third dielectric layer include a first film comprising zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, a second film comprising zinc stannate on at least a portion of the first film, and a third film comprising at least one of zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the second film.

[0193] (Clause 82) An article described in any one of clauses 75 to 81, wherein the second dielectric layer and the third dielectric layer include a first film comprising aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, a second film comprising zinc stannate on at least a portion of the first film, and a third film comprising at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the second film.

[0194] (Clause 83) An article described in any one of clauses 76 to 82, wherein the fourth dielectric layer comprises a first film comprising at least one of zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, and zinc stannate on at least a portion of the first film.

[0195] (Clause 84) An article described in any one of clauses 76 to 83, wherein the fourth dielectric layer comprises a first film comprising at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, and a zinc stannate film on at least a portion of the first film.

[0196] (Clause 85) The article of any one of Clauses 65 to 84, wherein the first dielectric layer or the second dielectric layer comprises a silicon nitride film.

[0197] (Clause 86) The article of any one of Clauses 65 to 85, wherein the outermost protective layer comprises SiAlN, SiON, SiAlON, titania, alumina, silica, zirconia, an alloy thereof, or a mixture thereof.

[0198] (Clause 87) The article of any one of clauses 65 to 86, wherein the stress layer comprises silicon cobalt, titanium niobium, zirconium niobium, tantalum titanium, an oxide thereof, or a suboxide thereof.

[0199] (Article 88) The primer layer is Al x Zn 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range from greater than 0 to 30% by weight).

[0200] (Article 89) The primer layer is Ga x Zn 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range from greater than 0% to 20% by weight).

[0201] (Article 90) The primer layer shall be In x Zn 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range from greater than 0 to 40% by weight).

[0202] (Article 91) The primer layer shall be V x Zn 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range from greater than 0% to 20% by weight).

[0203] (Article 92) The primer layer is made of Ag x Zn 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range from greater than 0 to 50% by weight).

[0204] (Article 93) The primer layer shall be Al x Ti1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 2 to 75% by weight before heating).

[0205] (Article 94) The primer layer is Al x Ti 1-x 88. The article of any one of clauses 65 to 87, comprising: wherein x is in the range of 1 to 100% by weight after heating.

[0206] (Article 95) The primer layer is Al x Nb 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 2 to 40% by weight before heating).

[0207] (Article 96) The primer layer shall be Al x Nb 1-x 88. The article of any one of clauses 65 to 87, comprising: wherein x is in the range of 2 to 95% by weight after heating.

[0208] (Article 97) The primer layer is W x Ti 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 55 to 100 wt. % before heating with 7% O2 during deposition).

[0209] (Article 98) The primer layer is W x Ti 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 30 to 95 wt. % after heating with 3% O2 during deposition).

[0210] (Article 99) The primer layer is made of Ti x Ta 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 2 to 80% by weight before heating).

[0211] (Article 100) The primer layer is made of Ti x Ta 1-x88. The article of any one of clauses 65 to 87, comprising: wherein x is in the range of 2 to 40% by weight after heating.

[0212] (Article 101) The primer layer is made of Ti x Nb 1-x 88. The article of any one of clauses 65 to 87, comprising: wherein x is in the range of 2 to 95% by weight after heating.

[0213] (Article 102) The primer layer is made of Nb x Zr 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 1 to 80% by weight before heating).

[0214] (Article 103) The primer layer is made of Nb x Zr 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 60 to 100% by weight after heating).

[0215] (Article 104) The primer layer is Ta x W 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 2 to 95% by weight before heating).

[0216] (Article 105) The primer layer is W x Nb 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 5 to 100% by weight before heating).

[0217] (Article 106) The primer layer is W x Nb 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 2 to 50% by weight after heating).

[0218] (Article 107) The primer layer is Zn x Ti 1-x88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 10 to 100% by weight before heating).

[0219] (Article 108) The primer layer is Zn x Ti 1-x 88. The article of any one of clauses 65 to 87, comprising: (wherein x is in the range of 20 to 100% by weight after heating).

[0220] (Clause 109) An article described in any one of clauses 65 to 108, wherein at least a portion of one or more primer layers is a nitride.

[0221] (Article 110) The primer layer is Al x Nb 1-x 109. The article of claim 109, comprising a nitride, wherein x is in the range of 1 to 100 wt % before heating.

[0222] (Article 111) The primer layer is Al x Nb 1-x 109. The article of claim 109, comprising a nitride, wherein x is in the range of 1 to 100 wt % after heating.

[0223] (Article 112) The primer layer is made of Ti x Nb 1-x 109. The article of claim 109, comprising a nitride, wherein x is in the range of 1 to 65 wt.%.

[0224] (Article 113) The primer layer is W x Nb 1-x 109. The article of claim 109, comprising a nitride, wherein x is in the range of 2 to 90 wt. % before heating.

[0225] (Article 114) The primer layer is W x Nb 1-x 109. The article of claim 109, comprising a nitride, wherein x is in the range of 2 to 70 wt. % after heating.

[0226] (Article 115) The seed film is Vx Zn 1-x 115. The article of any one of clauses 67 to 114, comprising an oxide, wherein x is in the range of 1 to 25% by weight.

[0227] (Article 116) The seed film is Al x Zn 1-x 115. The article of any one of clauses 67 to 114, comprising an oxide, wherein x is in the range of 1 to 25% by weight.

[0228] (Article 117) The seed film is Ga x Zn 1-x 115. The article of any one of clauses 67 to 114, comprising an oxide, wherein x is in the range of 1 to 20% by weight.

[0229] (Article 118) The seed film is In x Zn 1-x 115. The article of any one of clauses 67 to 114, comprising an oxide, wherein x is in the range of 1 to 40% by weight.

[0230] (Article 119) The seed film is Sn x In 1-x 115. The article of any one of clauses 67 to 114, comprising an oxide, wherein x is in the range of 1 to 20% by weight.

[0231] (Clause 120) An article described in any one of clauses 67 to 114, wherein the seed film comprises Ag, and the Ag is deposited in an oxygen and argon gas environment having a gas flow rate of 0 to 70%.

[0232] (Article 121) The seed film is Al x Ag 1-x wherein x is in the range of 1 to 35% by weight before and after heating.

[0233] (Article 122) The stress layer is made of Ti x Nb 1-x122. An article according to any one of clauses 65 to 121, comprising a suboxide or oxide, where x is in the range of 1 to 100% by weight before and after heating.

[0234] (Article 123) The stress layer is made of Nb x Zr 1-x 122. The article of any one of clauses 65 to 121, comprising a suboxide or oxide, wherein x is in the range of 1 to 12% by weight after heating.

[0235] (Article 124) The stress layer is made of Ti x Ta 1-x 122. The article of any one of clauses 65 to 121, comprising a suboxide or oxide, wherein x is in the range of 1 to 100% by weight after heating.

[0236] (Article 125) The stress layer is made of Si x Co 1-x 122. An article according to any one of clauses 65 to 121, comprising a suboxide or oxide, wherein x is in the range of 10 to 90% by weight after heating.

[0237] (Clause 126) The article of any one of Clauses 65 to 125, wherein the article has a visible light transmittance of at least 70%.

[0238] (Clause 127) The article of any one of clauses 65 to 126, wherein the article has a sheet resistance of 0.7 ohms / square or less.

[0239] (Clause 128) A method for producing a coated article, the method comprising: providing a substrate; and depositing a coating on the substrate, the coating comprising a first dielectric layer on at least a portion of the substrate, a first metal layer on at least a portion of the first dielectric layer, a first primer layer on at least a portion of the first metal layer, and a second dielectric layer on at least a portion of the first primer layer, wherein the primer layer is selected from the group consisting of zinc, aluminum doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, zinc tin, indium zinc, silver zinc, gallium zinc, indium tin, mixtures thereof, or alloys thereof.

[0240] (Clause 129) A method for producing a coated article, the method comprising: providing a substrate; depositing a coating on the substrate, the coating comprising a first dielectric layer on at least a portion of the substrate, a first metal layer on at least a portion of the first dielectric layer, a first primer layer on at least a portion of the first metal layer, and a second dielectric layer on at least a portion of the first primer layer, wherein the primer layer is selected from the group consisting of zinc, aluminum doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, zinc tin, indium zinc, silver zinc, gallium zinc, indium tin, mixtures thereof, or alloys thereof; heating the substrate including the coating; and bending the substrate including the coating into a desired shape.

[0241] (Clause 130) The method of clause 128 or 129, wherein at least a portion of the primer layer is an oxide or nitride.

[0242] (Clause 131) A method according to any one of clauses 128 to 130, wherein the article includes a seed film adjacent to and in direct contact with the first metal layer and between the first dielectric layer and the first metal layer.

[0243] (Clause 132) The method of any one of Clauses 128 to 131, wherein the primer layer is selected from the group consisting of silver zinc, zinc, silver zinc oxide, aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, vanadium zinc oxide, mixtures thereof, combinations thereof, and alloys thereof.

[0244] (Clause 133) The method of any one of Clauses 128 to 132, wherein the primer layer is a metal, oxide, nitride, suboxide, subnitride, oxynitride, or suboxynitride.

[0245] (Clause 134) The method of any one of Clauses 131 to 133, wherein the seed film is composed of aluminum, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum doped silver, silver, silver zinc, titanium aluminum, mixtures thereof, metals thereof, alloys thereof, combinations thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, oxynitrides thereof, suboxynitrides thereof, oxycarbides thereof, carbonitrides thereof, or oxycarbonitrides thereof.

[0246] (Clause 135) The method of any one of Clauses 131 to 134, wherein the seed film comprises aluminum zinc, vanadium zinc, zinc, or silver zinc.

[0247] (Clause 136) The method of Clause 135, wherein the seed film is a metal, oxide, or suboxide.

[0248] (Clause 137) The method of any one of Clauses 131 to 134, wherein the seed film comprises gallium zinc, indium zinc, or indium tin.

[0249] 138. The method of claim 137, wherein the seed film is a metal, oxide, nitride, suboxide, or subnitride.

[0250] (Clause 139) The method of any one of Clauses 128 to 138, wherein the article further comprises a second metal layer on at least a portion of the second dielectric layer, a second primer layer on at least a portion of the second metal layer, and a third dielectric layer on at least a portion of the second primer layer.

[0251] (Clause 140) The method described in Clause 139, wherein the article further comprises a third metal layer on at least a portion of the third dielectric layer, a third primer layer on at least a portion of the third metal layer, and a fourth dielectric layer on at least a portion of the third primer layer.

[0252] (Clause 141) The method described in Clause 140, wherein the article further comprises a fourth metal layer on at least a portion of the fourth dielectric layer, a fourth primer layer on at least a portion of the fourth metal layer, and a fifth dielectric layer on at least a portion of the fourth primer layer.

[0253] (Clause 142) The method of any one of clauses 128 to 141, wherein the one or more metal layers comprise silver or aluminum-doped silver.

[0254] (Clause 143) A method according to any one of clauses 128 to 142, wherein the first dielectric layer comprises a zinc stannate film and the second film comprises zinc oxide, zinc aluminum oxide, zinc indium oxide, zinc gallium oxide, indium tin oxide, or zinc vanadium oxide on at least a portion of the zinc stannate film.

[0255] (Clause 144) A method according to any one of clauses 128 to 143, wherein the first dielectric layer comprises a zinc stannate film and a second film comprising at least one of aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the zinc stannate film.

[0256] (Clause 145) A method according to any one of clauses 139 to 144, wherein the second dielectric layer and the third dielectric layer comprise a first film comprising zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, a second film comprising zinc stannate on at least a portion of the first film, and a third film comprising at least one of zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the second film.

[0257] (Clause 146) A method according to any one of clauses 139 to 145, wherein the second dielectric layer and the third dielectric layer comprise a first film comprising aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, a second film comprising zinc stannate on at least a portion of the first film, and a third film comprising at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the second film.

[0258] (Clause 147) A method according to any one of clauses 140 to 146, wherein the fourth dielectric layer comprises a first film comprising at least one of zinc oxide, zinc aluminum oxide, zinc gallium oxide, zinc indium oxide, indium tin oxide, or zinc vanadium oxide, and zinc stannate on at least a portion of the first film.

[0259] (Clause 148) A method according to any one of clauses 140 to 147, wherein the fourth dielectric layer comprises a first film comprising at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, and a zinc stannate film on at least a portion of the first film.

[0260] (Clause 149) The method of any one of Clauses 128 to 148, wherein the first dielectric layer or the second dielectric layer comprises a silicon nitride film.

[0261] (Clause 150) The method of any one of clauses 128 to 149, wherein the article further comprises an outermost protective layer comprising SiAlN, SiON, SiAlON, titania, alumina, silica, zirconia, alloys thereof, or mixtures thereof.

[0262] (Clause 151) The method of clause 150, wherein the article further comprises a stress layer beneath the outermost protective layer.

[0263] 152. The method of claim 151, wherein the stress layer comprises silicon cobalt, titanium niobium, zirconium niobium, tantalum titanium, an oxide thereof, or a suboxide thereof.

[0264] (Article 153) The primer layer is Al x Zn 1-x 153. The method of any one of clauses 128 to 152, comprising: wherein x is in the range of greater than 0% to 30% by weight.

[0265] (Article 154) The primer layer is Ga x Zn 1-x 153. The method of any one of clauses 128 to 152, comprising: wherein x is in the range of greater than 0% to 20% by weight.

[0266] (Article 155) The primer layer is In x Zn 1-x153. The method of any one of clauses 128 to 152, comprising: wherein x is in the range of greater than 0% to 40% by weight.

[0267] (Article 156) The primer layer is V x Zn 1-x 153. The method of any one of clauses 128 to 152, comprising: wherein x is in the range of greater than 0% to 20% by weight.

[0268] (Article 157) The primer layer is made of Ag x Zn 1-x 153. The method of any one of clauses 128 to 152, comprising: wherein x is in the range of greater than 0% to 50% by weight.

[0269] (Article 158) The primer layer is Al x Ti 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 2 to 75% by weight before heating).

[0270] (Article 159) The primer layer is Al x Ti 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 1 to 100% by weight after heating).

[0271] (Article 160) The primer layer is Al x Nb 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 2 to 40% by weight before heating).

[0272] (Article 161) The primer layer is Al x Nb 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 2 to 95% by weight after heating).

[0273] (Article 162) The primer layer is W x Ti 1-x153. The method of any one of clauses 128-152, comprising: (wherein x is in the range of 55-100 wt % before heating with 7% O2 during deposition).

[0274] (Article 163) The primer layer is W x Ti 1-x 153. The method of any one of clauses 128-152, comprising: (wherein x is in the range of 30-95 wt % after heating with 3% O2 during deposition).

[0275] (Article 164) The primer layer is made of Ti x Ta 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 2 to 80% by weight before heating).

[0276] (Article 165) The primer layer is made of Ti x Ta 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 2 to 40 wt % after heating).

[0277] (Article 166) The primer layer is made of Ti x Nb 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 2 to 95% by weight after heating).

[0278] (Article 167) The primer layer is made of Nb x Zr 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 1 to 80% by weight before heating).

[0279] (Article 168) The primer layer is made of Nb x Zr 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 60 to 100 wt % after heating).

[0280] (Article 169) The primer layer is Ta x W 1-x(wherein x is in the range of 2 to 95% by weight before heating).

[0281] (Article 170) The primer layer is W x Nb 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 5 to 100% by weight before heating).

[0282] (Article 171) The primer layer is W x Nb 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 2 to 50 wt % after heating).

[0283] (Article 172) The primer layer is Zn x Ti 1-x (wherein x is in the range of 10 to 100% by weight before heating).

[0284] (Article 173) The primer layer is Zn x Ti 1-x 153. The method of any one of clauses 128 to 152, comprising: (wherein x is in the range of 20 to 100 wt % after heating).

[0285] (Clause 174) The method of any one of clauses 128 to 173, wherein at least a portion of the one or more primer layers is a nitride.

[0286] (Article 175) The primer layer is Al x Nb 1-x 175. The method of claim 174, comprising a nitride, wherein x is in the range of 1 to 100 wt % before heating.

[0287] (Article 176) The primer layer is Al x Nb 1-x 175. The method of claim 174, comprising a nitride, wherein x is in the range of 1 to 100 wt % after heating.

[0288] (Article 177) The primer layer is made of Ti x Nb 1-x 175. The method of claim 174, comprising a nitride, wherein x is in the range of 1 to 65 wt. %.

[0289] (Article 178) The primer layer is W x Nb 1-x 175. The method of claim 174, comprising a nitride, wherein x is in the range of 2 to 90 wt % before heating.

[0290] (Article 179) The primer layer is W x Nb 1-x 175. The method of claim 174, comprising a nitride, wherein x is in the range of 2 to 70 wt % after heating.

[0291] (Article 180) The seed film is V x Zn 1-x 179. The method of any one of clauses 131 to 179, comprising an oxide, wherein x is in the range of 1 to 25 wt.%.

[0292] (Article 181) The seed film is Al x Zn 1-x 179. The method of any one of clauses 131 to 179, comprising an oxide, wherein x is in the range of 1 to 25 wt.%.

[0293] (Article 182) The seed film is Ga x Zn 1-x 179. The method of any one of clauses 131 to 179, comprising an oxide, wherein x is in the range of 1 to 20 wt.%.

[0294] (Article 183) The seed film is In x Zn 1-x 179. The method of any one of clauses 131 to 179, comprising an oxide, wherein x is in the range of 1 to 40 wt.%.

[0295] (Article 184) The seed film is Sn x In 1-x179. The method of any one of clauses 131 to 179, comprising an oxide, wherein x is in the range of 1 to 20 wt.%.

[0296] (Clause 185) A method according to any one of clauses 131 to 179, wherein the seed film comprises Ag, and the Ag is deposited in an oxygen and argon gas environment having an oxygen gas flow rate of 1 to 70%.

[0297] (Article 186) The seed film is Al x Ag 1-x 179. The method of any one of clauses 131 to 179, comprising: (wherein x is in the range of 1 to 35% by weight before and after heating).

[0298] (Article 187) The stress layer is made of Ti x Nb 1-x 187. The method of any one of clauses 151 to 186, comprising a suboxide or oxide, where x is in the range of 1 to 100% by weight before and after heating.

[0299] (Article 188) The stress layer is made of Nb x Zr 1-x 187. The method of any one of clauses 151 to 186, comprising a suboxide or oxide, wherein x is in the range of 1 to 12 wt% after heating.

[0300] (Article 189) The stress layer is made of Ti x Ta 1-x 187. The method of any one of clauses 151 to 186, comprising a suboxide or oxide, wherein x is in the range of 1 to 100% by weight after heating.

[0301] (Article 190) The stress layer is made of Si x Co 1-x 187. The method of any one of clauses 151 to 186, comprising a suboxide or oxide, wherein x is in the range of 10 to 90 wt% after heating.

[0302] (Clause 191) The method of any one of Clauses 128 to 190, wherein the article has a visible light transmittance of at least 70%.

[0303] (Clause 192) The method of any one of clauses 128 to 191, wherein the article has a sheet resistance of 0.7 ohms / square or less.

[0304] (Clause 193) A method for producing a coated article, the method comprising: providing a substrate; and depositing a coating on the substrate, the coating comprising a first dielectric layer on at least a portion of the substrate, a first metal layer on at least a portion of the first dielectric layer, a first primer layer on at least a portion of the first metal layer, and a second dielectric layer on at least a portion of the first primer layer; and a stress layer is added between the protective outer layer and the upper dielectric layer, the stress layer comprising silicon cobalt, titanium niobium, zirconium niobium, tantalum titanium, an oxide thereof, or a suboxide thereof.

[0305] (Clause 194) A method for producing a coated article, the method comprising: providing a substrate; depositing a coating on the substrate, the coating comprising a first dielectric layer on at least a portion of the substrate, a first metal layer on at least a portion of the first dielectric layer, a first primer layer on at least a portion of the first metal layer, and a second dielectric layer on at least a portion of the first primer layer; and adding a stress layer between the protective outer layer and the upper dielectric layer, the stress layer comprising silicon cobalt, titanium niobium, zirconium niobium, tantalum titanium, an oxide thereof, or a suboxide thereof; heating the substrate including the coating; and bending the substrate including the coating into a desired shape.

[0306] (Clause 195) The method of clause 193 or 194, wherein at least a portion of the primer layer is an oxide or a nitride.

[0307] (Clause 196) A method according to any one of clauses 193 to 195, wherein the article includes a seed film adjacent to and in direct contact with the first metal layer and between the first dielectric layer and the first metal layer.

[0308] (Clause 197) The method of any one of Clauses 193 to 196, wherein the primer layer is selected from the group consisting of silver zinc, zinc, silver zinc oxide, aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, vanadium zinc oxide, mixtures thereof, combinations thereof, and alloys thereof.

[0309] (Clause 198) The method of any one of Clauses 193 to 197, wherein the primer layer is a metal, oxide, nitride, suboxide, subnitride, oxynitride, or suboxynitride.

[0310] (Clause 199) The method of any one of clauses 196 to 198, wherein the seed film is composed of aluminum, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum doped silver, silver, silver zinc, titanium aluminum, mixtures thereof, metals thereof, alloys thereof, combinations thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, oxynitrides thereof, suboxynitrides thereof, oxycarbides thereof, carbonitrides thereof, or oxycarbonitrides thereof.

[0311] (Clause 200) The method of any one of Clauses 196 to 199, wherein the seed film comprises aluminum zinc, vanadium zinc, zinc, or silver zinc.

[0312] (Claim 201) The method of Clause 200, wherein the seed film is a metal, oxide, or suboxide.

[0313] (Clause 202) The method of any one of Clauses 196 to 199, wherein the seed film comprises gallium zinc, indium zinc, or indium tin.

[0314] (Claim 203) The method of Clause 202, wherein the seed film is a metal, oxide, nitride, suboxide, or subnitride.

[0315] (Clause 204) The method of any one of Clauses 193 to 203, wherein the article further comprises a second metal layer on at least a portion of the second dielectric layer, a second primer layer on at least a portion of the second metal layer, and a third dielectric layer on at least a portion of the second primer layer.

[0316] (Clause 205) The method described in Clause 204, wherein the article further comprises a third metal layer on at least a portion of the third dielectric layer, a third primer layer on at least a portion of the third metal layer, and a fourth dielectric layer on at least a portion of the third primer layer.

[0317] (Clause 206) The method of Clause 205, wherein the article further comprises a fourth metal layer over at least a portion of the fourth dielectric layer, a fourth primer layer over at least a portion of the fourth metal layer, and a fifth dielectric layer over at least a portion of the fourth primer layer.

[0318] (Clause 207) The method of any one of clauses 193 to 206, wherein the one or more metal layers comprise silver or aluminum-doped silver.

[0319] (Clause 208) The method of any one of Clauses 193 to 207, wherein the first dielectric layer comprises a zinc stannate film and the second film comprises zinc oxide, zinc aluminum oxide, zinc indium oxide, zinc gallium oxide, indium tin oxide, or zinc vanadium oxide on at least a portion of the zinc stannate film.

[0320] (Clause 209) A method according to any one of clauses 193 to 208, wherein the first dielectric layer comprises a zinc stannate film and a second film comprising at least one of aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the zinc stannate film.

[0321] (Clause 210) The method of any one of clauses 204 to 209, wherein the second dielectric layer and the third dielectric layer include a first film comprising zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, a second film comprising zinc stannate on at least a portion of the first film, and a third film comprising at least one of zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the second film.

[0322] (Clause 211) The method of any one of clauses 204 to 210, wherein the second dielectric layer and the third dielectric layer include a first film comprising aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, a second film comprising zinc stannate on at least a portion of the first film, and a third film comprising at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the second film.

[0323] (Clause 212) The method of any one of clauses 205 to 211, wherein the fourth dielectric layer comprises a first film comprising at least one of zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, and zinc stannate on at least a portion of the first film.

[0324] (Clause 213) The method of any one of Clauses 205 to 212, wherein the fourth dielectric layer comprises a first film comprising at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, and a zinc stannate film on at least a portion of the first film.

[0325] (Clause 214) The method of any one of Clauses 193 to 213, wherein the first dielectric layer or the second dielectric layer comprises a silicon nitride film.

[0326] (Clause 215) The method of any one of Clauses 193 to 214, wherein the outermost protective layer comprises SiAlN, SiON, SiAlON, titania, alumina, silica, zirconia, alloys thereof, or mixtures thereof.

[0327] (Clause 216) The method of any one of clauses 193 to 215, wherein the stress layer comprises silicon cobalt, titanium niobium, zirconium niobium, tantalum titanium, an oxide thereof, or a suboxide thereof.

[0328] (Article 217) The primer layer is Al x Zn 1-x 217. The method of any one of clauses 193 to 216, comprising: wherein x is in the range of greater than 0% to 30% by weight.

[0329] (Article 218) The primer layer is Ga x Zn 1-x 217. The method of any one of clauses 193 to 216, comprising: wherein x is in the range of greater than 0% to 20% by weight.

[0330] (Article 219) The primer layer shall be In x Zn 1-x 217. The method of any one of clauses 193 to 216, comprising: wherein x is in the range of greater than 0% to 40% by weight.

[0331] (Article 220) The primer layer is V x Zn 1-x 217. The method of any one of clauses 193 to 216, comprising: wherein x is in the range of greater than 0% to 20% by weight.

[0332] (Article 221) The primer layer is made of Ag x Zn 1-x 217. The method of any one of clauses 193 to 216, comprising: wherein x is in the range of greater than 0% to 50% by weight.

[0333] (Article 222) The primer layer is Al x Ti 1-x (wherein x is in the range of 2 to 75% by weight before heating).

[0334] (Article 223) The primer layer is Al x Ti 1-x wherein x is in the range of 1 to 100% by weight after heating.

[0335] (Article 224) The primer layer is Al x Nb 1-x (wherein x is in the range of 2 to 40% by weight before heating).

[0336] (Article 225) The primer layer is Al x Nb 1-x wherein x is in the range of 2 to 95% by weight after heating.

[0337] (Article 226) The primer layer is W x Ti 1-x 217. The method of any one of clauses 193-216, comprising: (wherein x is in the range of 55-100 wt. % before heating with 7% O2 during deposition).

[0338] (Article 227) The primer layer is W x Ti 1-x 217. The method of any one of clauses 193-216, comprising: (wherein x is in the range of 30-95 wt. % after heating with 3% O2 during deposition).

[0339] (Article 228) The primer layer is made of Ti x Ta 1-x (wherein x is in the range of 2 to 80% by weight before heating).

[0340] (Article 229) The primer layer is made of Ti x Ta 1-x (wherein x is in the range of 2 to 40 wt. % after heating).

[0341] (Article 230) The primer layer is made of Ti x Nb 1-x wherein x is in the range of 2 to 95% by weight after heating.

[0342] (Article 231) The primer layer is made of Nb x Zr 1-x (wherein x is in the range of 1 to 80% by weight before heating).

[0343] (Article 232) The primer layer is made of Nb x Zr 1-x (wherein x is in the range of 60 to 100 wt % after heating).

[0344] (Article 233) The primer layer is Ta x W 1-x (wherein x is in the range of 2 to 95% by weight before heating).

[0345] (Article 234) The primer layer is W x Nb 1-x (wherein x is in the range of 5 to 100% by weight before heating).

[0346] (Article 235) The primer layer is W x Nb 1-x (wherein x is in the range of 2 to 50 wt. % after heating).

[0347] (Article 236) The primer layer is Znx Ti 1-x (wherein x is in the range of 10 to 100% by weight before heating).

[0348] (Article 237) The primer layer is Zn x Ti 1-x (wherein x is in the range of 20 to 100 wt % after heating).

[0349] (Clause 238) A method according to any one of clauses 193 to 237, wherein at least a portion of one or more primer layers is a nitride.

[0350] (Article 239) The primer layer is Al x Nb 1-x 239. The method of claim 238, comprising a nitride, wherein x is in the range of 1 to 100 wt % before heating.

[0351] (Article 240) The primer layer is Al x Nb 1-x 239. The method of claim 238, comprising a nitride, wherein x is in the range of 1 to 100 wt % after heating.

[0352] (Article 241) The primer layer is made of Ti x Nb 1-x 239. The method of claim 238, comprising a nitride, wherein x is in the range of 1 to 65 wt. %.

[0353] (Article 242) The primer layer is W x Nb 1-x 239. The method of claim 238, comprising a nitride, wherein x is in the range of 2 to 90 wt % before heating.

[0354] (Article 243) The primer layer is W x Nb 1-x 239. The method of claim 238, comprising: a nitride, wherein x is in the range of 2 to 70 wt. % after heating.

[0355] (Article 244) The seed film is V x Zn 1-x 244. The method of any one of clauses 196 to 243, comprising an oxide, wherein x is in the range of 1 to 25 wt.%.

[0356] (Article 245) The seed film is Al x Zn 1-x 244. The method of any one of clauses 196 to 243, comprising an oxide, wherein x is in the range of 1 to 25 wt.%.

[0357] (Article 246) The seed film is Ga x Zn 1-x 244. The method of any one of clauses 196 to 243, comprising an oxide, wherein x is in the range of 1 to 20 wt.%.

[0358] (Article 247) The seed film is In x Zn 1-x 244. The method of any one of clauses 196 to 243, comprising an oxide, wherein x is in the range of 1 to 40 wt.%.

[0359] (Article 248) The seed film is Sn x In 1-x 244. The method of any one of clauses 196 to 243, comprising an oxide, wherein x is in the range of 1 to 20 wt.%.

[0360] (Clause 249) A method according to any one of clauses 196 to 243, wherein the seed film comprises Ag, and the Ag is deposited in an oxygen and argon gas environment having a gas flow rate of 0 to 70%.

[0361] (Article 250) The seed film is Al x Ag 1-x (wherein x is in the range of 1 to 35% by weight before and after heating).

[0362] (Article 251) The stress layer is made of Ti x Nb 1-x251. The method of any one of clauses 193 to 250, comprising a suboxide or oxide, wherein x is in the range of 1 to 100% by weight before and after heating.

[0363] (Article 252) The stress layer is made of Nb x Zr 1-x 251. The method of any one of clauses 193 to 250, comprising a suboxide or oxide, wherein x is in the range of 1 to 12 wt% after heating.

[0364] (Article 253) The stress layer is made of Ti x Ta 1-x 251. The method of any one of clauses 193 to 250, comprising a suboxide or oxide, wherein x is in the range of 1 to 100% by weight after heating.

[0365] (Article 254) The stress layer is made of Si x Co 1-x 251. The method of any one of clauses 193 to 250, comprising a suboxide or oxide, wherein x is in the range of 10 to 90% by weight after heating.

[0366] (Clause 255) The method of any one of Clauses 193 to 254, wherein the article has a visible light transmittance of at least 70%.

[0367] (Clause 256) The method of any one of clauses 193 to 255, wherein the article has a sheet resistance of 0.7 ohms / square or less.

[0368] (Clause 257) A coated article comprising: a substrate; a first dielectric layer on at least a portion of the substrate; a first metal layer on at least a portion of the first dielectric layer; a first primer layer on at least a portion of the first metal layer; and a second dielectric layer on at least a portion of the first primer layer, wherein the first metal layer is composed of aluminum-doped silver.

[0369] (Clause 258) The article of clause 257, wherein at least a portion of the primer layer is an oxide or nitride.

[0370] (Clause 259) An article according to clause 257 or 258, comprising a seed film adjacent to and in direct contact with the first metal layer and between the first dielectric layer and the first metal layer.

[0371] (Clause 260) The article of any one of clauses 257 to 259, wherein the primer layer is selected from the group consisting of silver zinc, zinc, silver zinc oxide, aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, vanadium zinc oxide, mixtures thereof, combinations thereof, and alloys thereof.

[0372] (Clause 261) The article of any one of Clauses 257 to 260, wherein the primer layer is a metal, oxide, nitride, suboxide, subnitride, oxynitride, or suboxynitride.

[0373] (Clause 262) The article of any one of clauses 259-261, wherein the seed film is comprised of aluminum, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum doped silver, silver, silver zinc, titanium aluminum, mixtures thereof, metals thereof, alloys thereof, combinations thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, oxynitrides thereof, suboxynitrides thereof, oxycarbides thereof, carbonitrides thereof, or oxycarbonitrides thereof.

[0374] (Clause 263) The article of any one of clauses 259 to 262, wherein the seed film comprises aluminum zinc, vanadium zinc, zinc, or silver zinc.

[0375] (Clause 264) The article of clause 263, wherein the seed film is a metal, oxide, or suboxide.

[0376] (Clause 265) The article of any one of clauses 259 to 262, wherein the seed film comprises gallium zinc, indium zinc, or indium tin.

[0377] 266. The article of claim 265, wherein the seed film is a metal, oxide, nitride, suboxide, or subnitride.

[0378] (Clause 267) An article described in any one of clauses 257 to 266, further comprising a second metal layer on at least a portion of the second dielectric layer, a second primer layer on at least a portion of the second metal layer, and a third dielectric layer on at least a portion of the second primer layer.

[0379] (Clause 268) The article described in Clause 267, further comprising a third metal layer on at least a portion of the third dielectric layer, a third primer layer on at least a portion of the third metal layer, and a fourth dielectric layer on at least a portion of the third primer layer.

[0380] (Clause 269) The article described in Clause 268, further comprising a fourth metal layer on at least a portion of the fourth dielectric layer, a fourth primer layer on at least a portion of the fourth metal layer, and a fifth dielectric layer on at least a portion of the fourth primer layer.

[0381] (Clause 270) An article according to any one of clauses 257 to 269, wherein the metal layer comprises silver or aluminum-doped silver.

[0382] (Clause 271) An article described in any one of clauses 257 to 270, wherein the first dielectric layer comprises a zinc stannate film and the second film comprises zinc oxide, zinc aluminum oxide, zinc indium oxide, zinc gallium oxide, indium tin oxide, or zinc vanadium oxide on at least a portion of the zinc stannate film.

[0383] (Clause 272) An article described in any one of clauses 257 to 271, wherein the first dielectric layer comprises a zinc stannate film and a second film comprising at least one of aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the zinc stannate film.

[0384] (Clause 273) An article described in any one of clauses 267 to 272, wherein the second dielectric layer and the third dielectric layer include a first film comprising zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, a second film comprising zinc stannate on at least a portion of the first film, and a third film comprising at least one of zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the second film.

[0385] (Clause 274) An article described in any one of clauses 267 to 273, wherein the second dielectric layer and the third dielectric layer include a first film comprising aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, a second film comprising zinc stannate on at least a portion of the first film, and a third film comprising at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide on at least a portion of the second film.

[0386] (Clause 275) An article described in any one of clauses 268 to 274, wherein the fourth dielectric layer comprises a first film comprising at least one of zinc oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, and zinc stannate on at least a portion of the first film.

[0387] (Clause 276) An article described in any one of clauses 268 to 275, wherein the fourth dielectric layer comprises a first film comprising at least one of aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, indium tin oxide, or vanadium zinc oxide, and a zinc stannate film on at least a portion of the first film.

[0388] (Clause 277) An article described in any one of Clauses 257 to 276, wherein the first dielectric layer or the second dielectric layer comprises a silicon nitride film.

[0389] (Clause 278) The article of any one of clauses 257 to 277, further comprising an outermost protective layer comprising SiAlN, SiON, SiAlON, titania, alumina, silica, zirconia, alloys thereof, or mixtures thereof.

[0390] (Clause 279) The article of clause 278, further comprising a stress layer beneath the outermost protective layer.

[0391] (Clause 280) The article of clause 279, wherein the stress layer comprises silicon cobalt, titanium niobium, zirconium niobium, tantalum titanium, an oxide thereof, or a suboxide thereof.

[0392] (Article 281) The primer layer is Al x Zn 1-x 281. The article of any one of clauses 257 to 280, comprising: (wherein x is in the range of greater than 0% to 30% by weight).

[0393] (Article 282) The primer layer is Ga x Zn 1-x 281. The article of any one of clauses 257 to 280, comprising: (wherein x is in the range of greater than 0% to 20% by weight).

[0394] (Article 283) The primer layer shall be In x Zn 1-x281. The article of any one of clauses 257 to 280, comprising: (wherein x is in the range of greater than 0% to 40% by weight).

[0395] (Article 284) The primer layer is V x Zn 1-x 281. The article of any one of clauses 257 to 280, comprising: (wherein x is in the range of greater than 0% to 20% by weight).

[0396] (Article 285) The primer layer is made of Ag x Zn 1-x 281. The article of any one of clauses 257 to 280, comprising: (wherein x is in the range of greater than 0% to 50% by weight).

[0397] (Article 286) The primer layer is Al x Ti 1-x wherein x is in the range of 2 to 75% by weight before heating.

[0398] (Article 287) The primer layer is Al x Ti 1-x wherein x is in the range of 1 to 100% by weight after heating.

[0399] (Article 288) The primer layer is Al x Nb 1-x 281. The article of any one of clauses 257 to 280, comprising: (wherein x is in the range of 2 to 40% by weight before heating).

[0400] (Article 289) The primer layer is Al x Nb 1-x wherein x is in the range of 2 to 95% by weight after heating.

[0401] (Article 290) The primer layer is W x Ti 1-x281. The article of any one of clauses 257 to 280, comprising: (where x is in the range of 55 to 100 wt. % before heating with 7% O2 during deposition).

[0402] (Article 291) The primer layer is W x Ti 1-x 281. The article of any one of clauses 257 to 280, comprising: (wherein x is in the range of 30 to 95 wt. % after heating with 3% O2 during deposition).

[0403] (Article 292) The primer layer is made of Ti x Ta 1-x wherein x is in the range of 2 to 80% by weight before heating.

[0404] (Article 293) The primer layer is made of Ti x Ta 1-x wherein x is in the range of 2 to 40% by weight after heating.

[0405] (Article 294) The primer layer is made of Ti x Nb 1-x wherein x is in the range of 2 to 95% by weight after heating.

[0406] (Article 295) The primer layer is made of Nb x Zr 1-x wherein x is in the range of 1 to 80% by weight before heating.

[0407] (Article 296) The primer layer is made of Nb x Zr 1-x wherein x is in the range of 60 to 100% by weight after heating.

[0408] (Article 297) The primer layer is Ta x W 1-xwherein x is in the range of 2 to 95% by weight before heating.

[0409] (Article 298) The primer layer is W x Nb 1-x wherein x is in the range of 5 to 100% by weight before heating.

[0410] (Article 299) The primer layer is W x Nb 1-x wherein x is in the range of 2 to 50% by weight after heating.

[0411] (Article 300) The primer layer is Zn x Ti 1-x wherein x is in the range of 10 to 100% by weight before heating.

[0412] (Article 301) The primer layer is Zn x Ti 1-x wherein x is in the range of 20 to 100% by weight after heating.

[0413] (Clause 302) An article described in any one of clauses 257 to 301, wherein at least a portion of one or more primer layers is a nitride.

[0414] (Article 303) The primer layer is Al x Nb 1-x 303. The article of claim 302, comprising a nitride, wherein x is in the range of 1 to 100 wt. % before heating.

[0415] (Article 304) The primer layer is Al x Nb 1-x 303. The article of claim 302, comprising a nitride, wherein x is in the range of 1 to 100 wt. % after heating.

[0416] (Article 305) The primer layer is made of Ti x Nb 1-x 303. The article of claim 302, comprising a nitride, wherein x is in the range of 1 to 65 wt.%.

[0417] (Article 306) The primer layer is W x Nb 1-x 303. The article of claim 302, comprising a nitride, wherein x is in the range of 2 to 90 wt. % before heating.

[0418] (Article 307) The primer layer is W x Nb 1-x 303. The article of claim 302, comprising a nitride, wherein x is in the range of 2 to 70 wt. % after heating.

[0419] (Article 308) The seed film is V x Zn 1-x 8. The article of any one of clauses 259 to 307, comprising an oxide, wherein x is in the range of 1 to 25% by weight.

[0420] (Article 309) The seed film is Al x Zn 1-x 8. The article of any one of clauses 259 to 307, comprising an oxide, wherein x is in the range of 1 to 25% by weight.

[0421] (Article 310) The seed film is Ga x Zn 1-x 8. The article of any one of clauses 259 to 307, comprising an oxide, wherein x is in the range of 1 to 20 wt.%.

[0422] (Article 311) The seed film is In x Zn 1-x 8. The article of any one of clauses 259 to 307, comprising an oxide, wherein x is in the range of 1 to 40 wt.%.

[0423] (Article 312) The seed film is Sn x In 1-x8. The article of any one of clauses 259 to 307, comprising an oxide, wherein x is in the range of 1 to 20 wt.%.

[0424] (Clause 313) An article described in any one of clauses 259 to 307, wherein the seed film comprises Ag, and the Ag is deposited in an oxygen and argon gas environment having an oxygen gas flow rate of 1 to 70%.

[0425] (Article 314) The seed film is Al x Ag 1-x wherein x is in the range of 1 to 35% by weight before and after heating.

[0426] (Article 315) The stress layer is made of Ti x Nb 1-x 10. The article of any one of clauses 279 to 314, comprising a suboxide or oxide, where x is in the range of 1 to 100% by weight before and after heating.

[0427] (Article 316) The stress layer is made of Nb x Zr 1-x 10. The article of any one of clauses 279 to 314, comprising a suboxide or oxide, wherein x is in the range of 1 to 12% by weight after heating.

[0428] (Article 317) The stress layer is made of Ti x Ta 1-x 315. The article of any one of clauses 279 to 314, comprising a suboxide or oxide, wherein x is in the range of 1 to 100% by weight after heating.

[0429] (Article 318) The stress layer is made of Si x Co 1-x An article according to any one of clauses 279 to 314, comprising a suboxide or oxide, wherein x is in the range of 10 to 90% by weight after heating.

[0430] (Clause 319) An article according to any one of clauses 257 to 318, wherein the article has a visible light transmittance of at least 70%.

[0431] (Clause 320) An article described in any one of clauses 257 to 319, wherein the article has a sheet resistance of 0.7 ohms / square or less.

Claims

1. A coated article, comprising: A substrate; a first dielectric layer in direct contact with at least a portion of the substrate, the first dielectric layer including a first film in direct contact with the substrate and a second film in direct contact with the first film; a first metal layer in direct contact with at least a portion of the first dielectric layer; a first primer layer in direct contact with at least a portion of the first metal layer, the first primer layer comprising Al x Zn 1-x , where x is in the range of greater than 0 to 30 wt %; a second dielectric layer in direct contact with at least a portion of the first primer layer, the second dielectric layer including a first film in direct contact with the first primer layer, a second film in direct contact with the first film, and a third film in direct contact with the second film; a second metal layer in direct contact with at least a portion of the second dielectric layer; a second primer layer in direct contact with at least a portion of the second metal layer, the second primer layer comprising Al x Zn 1-x , where x is in the range of greater than 0 to 30 wt %; a third dielectric layer in direct contact with at least a portion of the second primer layer; a third metal layer in direct contact with at least a portion of the third dielectric layer; a third primer layer in direct contact with at least a portion of the third metal layer, the third primer layer comprising Al x Zn 1-x , where x is in the range of greater than 0 to 30 wt %; a fourth dielectric layer in direct contact with at least a portion of the third primer layer; Including, The coated article has a sheet resistance of 0.85 ohms / square or less and a visible light transmittance of at least 70%.

2. The article of claim 1 , wherein the first primer layer has a thickness in the range of 5 Å to 50 Å.

3. 10. The article of claim 1, wherein a first film of the first dielectric layer comprises zinc stannate and a second film of the first dielectric layer comprises at least one of aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, indium tin oxide, or vanadium zinc oxide over at least a portion of the first film of the first dielectric layer.

4. The article of claim 1 , wherein the second primer layer has a thickness in the range of 5 Å to 50 Å.

5. The article of claim 1 , wherein the third primer layer has a thickness in the range of 5 Å to 50 Å.

6. a fourth metal layer directly contacting at least a portion of the fourth dielectric layer; a fourth primer layer in direct contact with at least a portion of the fourth metal layer, the fourth primer layer comprising Al x Zn 1-x , where x is in the range of greater than 0 to 30 wt %; a fifth dielectric layer directly contacting at least a portion of the fourth primer layer; The article of claim 1 further comprising:

7. The article of claim 6, wherein the fourth primer layer has a thickness in the range of 5 Å to 50 Å.

8. 1. A method for producing a coated article, comprising: providing a substrate; depositing a coating on the substrate, the coating comprising: a first dielectric layer in direct contact with at least a portion of the substrate, the first dielectric layer including a first film in direct contact with the substrate and a second film in direct contact with the first film; a first metal layer in direct contact with at least a portion of the first dielectric layer; a first primer layer in direct contact with at least a portion of the first metal layer, the first primer layer comprising Al x Zn 1-x , where x is in the range of greater than 0 to 30 wt %; a second dielectric layer in direct contact with at least a portion of the first primer layer, the second dielectric layer including a first film in direct contact with the first primer layer, a second film in direct contact with the first film, and a third film in direct contact with the second film; a second metal layer in direct contact with at least a portion of the second dielectric layer; a second primer layer in direct contact with at least a portion of the second metal layer, the second primer layer comprising Al x Zn 1-x , where x is in the range of greater than 0 to 30 wt %; a third dielectric layer in direct contact with at least a portion of the second primer layer; a third metal layer in direct contact with at least a portion of the third dielectric layer; a third primer layer in direct contact with at least a portion of the third metal layer, the third primer layer comprising Al x Zn 1-x , where x is in the range of greater than 0 to 30 wt %; a fourth dielectric layer in direct contact with at least a portion of the third primer layer; Including, at least a portion of the first primer layer, the second primer layer, and the third primer layer is oxidized after deposition of the first primer layer, the second primer layer, and the third primer layer; The method wherein the coated article has a sheet resistance of 0.85 ohms / square or less and a visible light transmittance of at least 70%.

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