Coated Article Having a Protective Coating Comprising Silicon Nitride and / or Silicon Oxynitride

Abstract

To reduce or avoid these defects in a coating stack.SOLUTION: A coated article includes a substrate, a functional layer over at least a portion of the substrate, and a protective coating over at least a portion of the functional layer, where an uppermost layer of the functional layer is a metal oxide layer, and where the protective coating comprises a metal nitride layer and a metal oxynitride layer that is disposed between, and in contact with at least part of, the metal nitride layer and the metal oxide layer of the functional layer.SELECTED DRAWING: None

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 62 / 631,283, filed February 15, 2018, U.S. Provisional Patent Application No. 62 / 631,588, filed February 16, 2018, and U.S. Provisional Patent Application No. 62 / 734,656, filed September 21, 2018, each of which is incorporated by reference in its entirety.

[0002] The invention according to the present disclosure generally relates to solar control coatings having a metal nitride layer and / or a topcoat comprising a metal oxynitride disposed on a metal oxide layer. [Background technology]

[0003] The coating stack(s) of the coated article may corrode over time. To prevent this, a protective coating can be applied to the coating stack. For example, titanium dioxide films, as disclosed in US Pat. Nos. 4,716,086 and 4,786,563, are protective films that provide chemical resistance to the coating. Silicon oxide, as disclosed in Canadian Patent No. 2,156,571, aluminum oxide and silicon nitride, as disclosed in US Pat. Nos. 5,425,861, 5,344,718, 5,376,455, 5,584,902 and 5,532,180 and PCT International Patent Publication No. 95 / 29883, are also protective films that provide chemical resistance to the coating. This technology could be advanced by more chemically and / or mechanically durable coatings.

[0004] An additional known problem with coating stacks including protective coatings occurs in silver-based coating stacks. In certain coated articles, the top layer of the functional coating includes a metal oxide layer, such as a zinc oxide layer, disposed over the terminal metal-primer layer of the functional coating. This can cause corrosion or photoluminescence defects in the stack when exposed to condensed, humid environments for extended periods of time. Thus, a further need exists to reduce or avoid these defects in coating stacks. Summary of the Invention

[0005] According to one aspect of the invention, a coated article is provided, the coated article comprising a substrate, a first functional layer over at least a portion of the substrate, and a protective coating over at least a portion of the functional layer, where a top layer of the functional layer is a metal oxide film, and the protective coating comprises one or more layers of a metal nitride, a metal oxynitride, or a combination thereof.

[0006] In one embodiment, the coated article comprises a glass substrate, a first layer of zinc stannate on at least a portion of the glass substrate, a layer of zinc oxide on at least a portion of the zinc stannate layer, a layer of silver on at least a portion of the zinc oxide layer, a primer layer comprising Ti, TiAl and / or an oxide thereof on at least a portion of the silver layer, a second zinc stannate layer on at least a portion of the primer layer, a metal oxynitride layer comprising silicon oxynitride directly on at least a portion of the second zinc stannate layer, a metal nitride layer comprising silicon directly on at least a portion of the metal oxynitride layer, and a second protective layer comprising Ti, TiAl, and / or an oxide of any of the foregoing on at least a portion of the metal nitride layer.

[0007] In another aspect, a coated article is provided that includes a substrate, a functional layer having a top layer on at least a portion of the substrate, and a protective coating on at least a portion of the functional layer, where the top layer of the functional layer is a dielectric layer having a refractive index of at least 1.5 and no greater than 2.1.

[0008] In another aspect, a coated article is provided that includes a substrate, a functional layer on at least a portion of the substrate, and a protective coating on at least a portion of the functional layer, wherein the functional layer includes at least one metal layer and a primer layer disposed at least partially in contact with at least a portion of the at least one metal layer, and a top layer of the functional layer is disposed in contact with at least a portion of the primer layer, and the top layer of the functional layer does not include zinc oxide.

[0009] The present invention is described with reference to the following drawings, in which like reference numbers identify like parts throughout. [Brief description of the drawings]

[0010] [Figure 1A] 1 is a side view (not to scale) of an insulated glass unit ("IGU") having a coating of the present invention.

[0011] [Figure 1B] 1 is a cross-sectional view of a transparency having a coating of the present invention.

[0012] [Figure 2A] 1 is a cross-sectional view (not to scale) of a coating of the present invention. [Figure 2B] 1 is a cross-sectional view (not to scale) of a coating of the present invention.

[0013] [Diagram 3] 1 is a cross-sectional view (not to scale) of a coating according to an example of the present invention.

[0014] [Figure 4A] 1 is a cross-sectional view (not to scale) of a coating according to an example of the present invention. [Figure 4B] 1 is a cross-sectional view (not to scale) of a coating according to an example of the present invention.

[0015] [Diagram 5]1 is a cross-sectional view (not to scale) of a coating according to an example of the present invention.

[0016] [Figure 6] 1 is a cross-sectional view (not to scale) of a coating according to an example of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] As used herein, spatial or directional terms such as "left", "right", "inside", "outside", "top", "bottom" and the like relate to the present invention as depicted 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, amounts 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 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 range values, as well as any and all subranges subsumed therein. For example, a specified range of "1 to 10" should be considered to include any and all subranges between (and including) a minimum value of 1 and a maximum value of 10, i.e., all subranges beginning with a minimum value of 1 or greater and ending with a maximum value of 10 or less, such as 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. "a" or "an" refers to one or more.

[0018] Additionally, as used herein, the terms "formed over," "deposited over," or "provided over" mean formed, deposited, or provided, but not necessarily in contact with, a surface. For example, a coating layer "formed over" 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. Additionally, all documents referred to herein, including but not limited to issued patents and patent applications, should be considered "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 term "asymmetrical reflectivity" means that the visible light reflectance of a coating from one side is different from the visible light reflectance of a coating from the opposite side. The term "critical thickness" refers to the thickness above which the coating material forms a continuous, uninterrupted layer and below which the coating material forms discontinuous areas or islands of coating material rather than a continuous layer. The term "subcritical thickness" refers to a thickness below the critical thickness such that the coating material forms separate, unconnected areas of coating material. The term "islanded" refers to the coating material is not a continuous layer, but rather forms isolated areas or islands where the material is deposited.

[0019] For purposes of the following discussion, the coated articles described herein may be discussed with respect to use with architectural transparencies, such as, but not limited to, insulated glass units (IGUs). As used herein, the term "architectural transparency" refers to any transparency placed in a building, such as, but not limited to, windows and skylights. However, it should be understood that the coated articles described herein are not limited to use with such architectural transparencies, but can be implemented with transparencies in any desired field, such as, but not limited to, laminated or non-laminated residential and / or commercial windows, insulated glass units, and / or transparencies for land, air, space, water and underwater vehicles. In one aspect or embodiment, the coated articles described herein are transparencies for use in vehicles, such as windows or sunroofs. Thus, it should be understood that the specifically disclosed exemplary aspects or embodiments are presented merely to illustrate the general concepts of the invention, and the invention is not limited to these specific exemplary embodiments. Furthermore, while a typical "transparency" can have sufficient visible light transmittance so that the material can be seen through the transparency, a "transparency" need not be transparent to visible light, but may be translucent or opaque, i.e., "transparent" means having a visible light transmittance of greater than 0% up to 100%.

[0020] A non-limiting transparency 10 incorporating features of the present invention is shown in Figure IA. The transparency 10 can have any desired visible, infrared, or ultraviolet transmission and / or reflection.

[0021] The exemplary transparency 10 of FIG. 1A is in the form of a conventional insulating glass unit and includes a first ply 12 having a first major surface 14 (first surface) and an opposing second major surface 16 (second surface). In the illustrated non-limiting embodiment, the first major surface 14 faces the exterior of the building, i.e., is the exterior major surface, and the second major surface 16 faces the interior of the building. The transparency 10 also includes a second ply 18 having an interior (first) major surface 20 (third surface) and an exterior (second) major surface 22 (fourth surface) and spaced apart from the first ply 12. This numbering of the ply surfaces is consistent with conventional practice in the fenestration art. The first and second plies 12, 18 can be connected in any suitable manner, such as by adhesive bonding to a conventional spacer frame 24. A gap or chamber 26 is formed between the two plies 12, 18. The chamber 26 can be filled with a selected atmosphere, such as air, or a non-reactive gas, such as argon or krypton gas. A solar control coating 30 (or any of the other coatings described below) is formed on at least a portion of one of the plies 12, 18, such as, but not limited to, at least a portion of the second surface 16 or at least a portion of the third surface 20. However, the coating can also be on the first surface or the fourth surface, if desired. Examples of insulating glass units can be found, for example, in U.S. Pat. Nos. 4,193,236, 4,464,874, 5,088,258, and 5,106,663.

[0022] The exemplary transparency in FIG. 1B is in the form of a conventional transparency 110 for a vehicle, such as a window or sunroof. For clarity, seals, connectors, and opening features are not shown, nor is a complete vehicle shown. The transparency includes a first ply 112 having a first major surface 114 (first surface) and an opposing second major surface 116 (second surface) attached to a body of a vehicle 118 (partially shown). In the illustrated non-limiting embodiment, the first major surface 114 faces the exterior of the vehicle, i.e., is the exterior major surface, and the second major surface 116 faces the interior of the vehicle. Non-limiting examples of a body include an automobile roof in the case of a sunroof, an automobile door or frame in the case of an automobile window, or an airplane fuselage. The transparency may be attached to a mechanism capable of opening and closing the transparency, such as a car window or sunroof, as is commonly known in the vehicle arts. The solar control coating 130, or any of the other coatings described herein, is shown formed on the first surface 114, but may also be formed on at least a portion of the second surface 116.

[0023] In the broad practice of the invention, the plies 12, 18, 112 of the transparency 10, 110 can be the same or different materials. The plies 12, 18, 112 can include any desired material having any desired properties. For example, one or more of the plies 12, 18, 112 can be transparent or translucent to visible light. "Transparent" means having a visible light transmittance of greater than 0% up to 100%. Alternatively, one or more of the plies 12, 18, 112 can be translucent. "Translucent" means allowing electromagnetic energy (e.g., visible light) to pass through but diffusing this energy to obscure the viewer from an object on the opposite side. Examples of suitable materials include, but are not limited to, plastic substrates (e.g., acrylic polymers, such as polyacrylates; polyalkyl methacrylates, such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, and the like; polyurethanes; polycarbonates; polyalkyl terephthalates, such as polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, and the like; 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, 18, 112 can include conventional soda-lime silicate glass, borosilicate glass, or lead glass. The glass can be clear glass. By "clear glass" is meant non-tinted or non-colored glass. Alternatively, the glass can be tinted or otherwise colored glass. The glass can be annealed glass 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 having any value of optical properties, such as visible transmittance, ultraviolet transmittance, infrared transmittance, and / or total solar energy transmittance."Float glass" means glass formed by a conventional float process in which molten glass is deposited onto a molten metal bath and controllably cooled to form a float glass ribbon. Examples of float glass processes are disclosed in U.S. Patent Nos. 4,466,562 and 4,671,155.

[0024] Each of the plies 12, 18, 112 can include, for example, clear float glass or can be tinted or colored glass, and one ply 12, 18 can be clear glass and the other ply 12, 18 can be colored glass. Without limitation, examples of glasses suitable for the first ply 12 and / or second ply 18 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 plies 12, 18, 112 can be of any desired dimensions, such as length, width, shape, or thickness. In one exemplary automotive transparency, the first and second plies may each be from 1 mm to 10 mm thick, such as from 1 mm to 8 mm thick, such as from 2 mm to 8 mm thick, such as from 3 mm to 7 mm, such as from 5 mm to 7 mm, such as 6 mm thick.

[0025] In a non-limiting embodiment of the coated article described herein, the solar control coating 30, 130 of the present invention is deposited on at least a portion of at least one major surface of one of the glass plies 12, 18, 112. In the example according to FIG. 1A, the coating 30 is formed on at least a portion of the inner surface 16 of the outer glass ply 12, 112, and it should be understood that in addition, or alternatively, in a non-limiting example consistent with the present disclosure, a coating may be formed on at least a portion of the inner surface 20 of the inner glass ply 18. As used herein, the term "solar control coating" refers to a coating comprised of one or more layers or films that affect the solar properties of the coated article, such as, but not limited to, the amount of solar radiation, e.g., visible, infrared, or ultraviolet, reflected from, absorbed by, or transmitted through the coated article, the shading factor, the emissivity, etc. The solar control coating 30 can block, absorb, or filter selected portions of the solar spectrum, such as, but not limited to, the IR, UV, and / or visible spectrum.

[0026] The coatings described herein, such as the solar control coatings 30, 130, can be deposited by any useful method, such as, but not limited to, conventional chemical vapor deposition (CVD) and / or physical vapor deposition (PVD) methods. Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam evaporation and vacuum sputtering (such as, for example, 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, the coatings 30, 130 are deposited by MSVD. Examples of MSVD coating devices and methods are well understood to those skilled in the art and are described, for example, in U.S. Pat. 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.

[0027] FIG. 2 illustrates a schematic of an example of a coated article 200 according to the present disclosure. The coated article includes a substrate 210. The substrate 210 may include any desired characteristics and may be of any desired thickness. The substrate 210 may include any suitable transparent material, such as, for example, but not limited to, the polymeric, glass, and / or ceramic substrates described above in the context of plies 12, 18, and 112. In a non-limiting example, the substrate 210 may include a glass substrate as described above with reference to plies 12, 18, 112, as shown in FIG. 1A or FIG. 1B. However, it should be understood that the present invention is equally applicable to other substrates, such as those used in solar cells.

[0028] The functional layer 220 is disposed on at least a portion of the substrate 210. As used in FIGS. 2-6, the functional layer 220, 320, 420, 520 can be any functional coating. For example, it can include one or more dielectric films and / or one or more metal films. Alternatively, the functional layer 220, 320, 420, 520 can include, but is not limited to, a transparent conductive oxide (TCO), for example, as disclosed in U.S. Patent Application No. 15 / 669,414. The functional layer 220, 320, 420, 520 can include a stack described in any of U.S. Patent Application Publication No. 2017 / 0341977, U.S. Patent Application Publication No. 2014 / 0272453, U.S. Patent Application Publication No. 2011 / 0236715, and / or U.S. Patent Application Publication No. 15 / 669,414, or any portion thereof. Except as specifically described below, these exemplary stacks of functional layers are represented generally by elements 330, 430, and 530 in Figures 3-6, and details of aspects of stacks 330 and 530 are shown in and described with reference to Figures 3-6, respectively.

[0029] The functional layer may include one or more metal layers. One or more metal films in the functional layer 220, 320, 420, 520 may be composed of silver, gold, palladium, copper, aluminum, and / or mixtures and / or alloys of any of the foregoing. Any metal layer in the functional layer 220, 320, 420, 520 may be continuous or discontinuous.

[0030] One or more of the metal layers can be a continuous layer. The continuous metal layer has a thickness in the range of 50 Å to 200 Å, preferably 55 Å to 150 Å, more preferably 55 Å to 100 Å, and most preferably 60 Å to 80 Å.

[0031] 3, 4A, and 4B show an example in which the top layer of the functional layer 320 includes a dielectric layer referred to as the top dielectric layer 322 as the top film of the functional layer 320. An example of the top dielectric layer 322 of the functional layer 320 can have a thickness in the range of 50 Å to 750 Å, preferably 250 Å to 600 Å, more preferably, for example, 300 Å to 550 Å, and most preferably, 330 Å to 500 Å.

[0032] 4B, the top dielectric layer 322 may include a first film 324 shown over an optional primer layer 328, and a second film 326 over the first film and in contact with a protective coating 350. The first film 324 and the second film 326 of the top dielectric layer 322 may be metal oxide, metal nitride or metal oxynitride films. The metals of the first film 324 and the second film 326 may be titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum, silicon and mixtures thereof.

[0033] In one non-limiting embodiment, the first film 324 of the top dielectric layer 322 can be a zinc / tin alloy oxide. By "zinc / tin alloy oxide" it is meant both true alloys and mixtures of oxides. Zinc oxide can be deposited from a zinc cathode that contains other materials to improve the sputtering properties of the cathode. Thus, zinc / tin alloy oxide can be obtained from magnetron sputtering vacuum deposition from zinc and tin cathodes. For example, the zinc cathode can contain small amounts of tin (e.g., up to 20% by weight, up to 15% by weight, up to 10% by weight, or up to 5% by weight) to improve sputtering. The resulting zinc oxide film then contains a small percentage of tin oxide, e.g., up to 10% by weight tin oxide, e.g., up to 5% by weight tin oxide. A coating layer deposited from a zinc cathode with up to 10% by weight tin (added to increase the conductivity of the cathode) is referred to herein as a "zinc oxide film" even though small amounts of tin may be present. One non-limiting cathode can include zinc and tin in ratios of 5% to 95% zinc and 95% to 5% tin by weight, such as 10% to 90% zinc and 90% to 10% tin by weight, although other ratios of zinc to tin can be used.

[0034] One suitable metal alloy oxide that may be present in the first film 324 or the second film 226 is zinc stannate. X Sn 1-X O 2-X (Formula 1) refers to a composition of matter having the formula: where "x" ranges from greater than 0 to less than 1. For example, "x" can be greater than 0 and can be any fraction or decimal greater than 0 to less than 1. For example, when x=2 / 3, Formula 1 is Zn 2 / 3 Sn 1 / 3 O 4 / 3 And more generally, "Zn 2 SnO 4 The zinc stannate-containing film has one or more forms of Formula 1 in a predominant amount in the layer.

[0035] FIG. 4A discloses an embodiment of a coated article, comprising a substrate 310, a functional layer 320 according to any aspect or embodiment described herein, a protective coating 350 comprising a metal nitride film 356 on the functional layer 320, and a second protective film 360 on the metal nitride film 356. The functional layer comprises a top dielectric layer, for example as shown in FIG. 3 and FIG. 4B. In a non-limiting embodiment, the top dielectric layer 322 may be comprised of a metal oxide such as zinc stannate. In further non-limiting embodiments, the top dielectric layer 322 may have a refractive index between 1.5 and 2.1. In further non-limiting embodiments, the top dielectric layer 322 may have a refractive index between 1.7 and 1.9, and even more preferably between 1.8 and 1.85.

[0036] 4B, in another non-limiting example including a substrate 310, a functional layer 320 including a top dielectric layer 322, an optional primer layer 328, and a stack 330, such as that described with reference to FIG. 3, the top dielectric layer 322 of the functional layer 320 may include a first film 324 composed of or consisting of a metal oxide, such as zinc oxide, deposited on at least a portion of the optional primer layer 328. A second film 326 of the top dielectric layer 322 of the functional layer 320, disposed on at least a portion of the first film 324, may include zinc stannate.

[0037] As shown in Figures 3-4B, the functional layer 320 may also include an optional primer layer 328 disposed under the dielectric layer 322. The optional primer layer 328 may be a single film or multiple film layers. The optional primer layer 328 may include an oxygen scavenging material that may be sacrificed during the deposition process to prevent degradation or oxidation of the metal layer 334 during the sputtering process or subsequent heating process. The optional primer layer 328 may also absorb at least a portion of the electromagnetic radiation, such as visible light, that passes through the coating 300. Examples of materials useful for the optional primer layer 328 include titanium, silicon, silicon dioxide, silicon nitride, silicon oxynitride, nickel chromium alloys (e.g., Inconel), zirconium, aluminum, alloys of silicon and aluminum, alloys including cobalt and chromium (e.g., Stellite®), and mixtures of any of the foregoing. In a non-limiting embodiment, the optional primer layer 328 may include titanium, or titanium and aluminum, deposited as a metal, with at least a portion of the titanium, or titanium and aluminum being subsequently oxidized. The optional primer layer 328 can have a thickness in the range of 5 Å to 50 Å, e.g., 10 Å to 35 Å, e.g., 15 Å to 35 Å, e.g., 10 Å to 20 Å, e.g., 10 Å to 30 Å, e.g., 20 Å to 30 Å, e.g., 30 Å to 40 Å. In another example, the optional primer layer 328 can have a thickness in the range of 5 Å to 50 Å, e.g., 10 Å to 25 Å, e.g., 15 Å to 25 Å, e.g., 15 Å to 22 Å, e.g., 25 Å to 36 Å. As shown, the optional primer layer 328, if present, is disposed under and in direct contact with the first film 324 of the dielectric layer 322. Although shown in the drawings, it should be understood that examples in accordance with the present invention do not necessarily include the optional primer layer 328.

[0038] Referring to FIG. 2A, a protective coating 250 is disposed on at least a portion of the functional layer 220 and is the top layer of the coated article. The protective coating 250 can help protect underlying coating layers, such as the functional layer 220 and any of its component films and layers, from mechanical and / or chemical attack. FIG. 2B shows a substrate 210 and a protective coating 250 similar in structure to the coated article shown in FIG. 2A, but including a first functional layer 220, which is the same as the functional layer 220 of FIG. 2A, and a second functional layer 220' disposed below the first functional layer 220 and above the substrate 210. The first functional layer 220 can be the same as or different from the second functional layer 220'. For example, but not limited to, the first functional layer 220 includes a dielectric layer, a metal layer on the dielectric layer, and optionally a primer layer on the metal layer, and the top dielectric layer includes a metal oxide film on the metal layer and on the primer layer if a primer layer is present. The second functional layer 220' includes a second dielectric layer over the substrate 210, a second metal layer over the second dielectric layer, and optionally a second primer layer over the second metal layer. In one example, one of the first and / or second metal layers is subcritical. In another example, neither is subcritical. In yet another example, the coated article includes a third functional layer (not shown) below the second functional layer 220' and above the substrate 210, which may or may not be the same as either the first or second functional layers 220, 220'. It is noted that multiple smaller functional layers may be stacked to produce a larger functional layer, which may or may not have properties inherent to any particular combination of smaller functional layers, such as having single silver, double silver, and triple silver coatings, optionally including one or more subcritical silver layers.

[0039] In one embodiment of the present invention, referring to FIG. 4A, the protective layer 350 may include silicon oxide, silicon oxynitride, silicon nitride, a mixture of any two or more of the foregoing, and / or an alloy of any of the foregoing, which may improve the durability of the functional layer 320. The protective layer 350 may include silicon oxide, silicon oxynitride, and / or silicon nitride deposited with other materials having good electrical conductivity to improve the sputtering of silicon. For example, during deposition, the silicon cathode may include a small amount (e.g., up to 20% by weight, up to 15% by weight, up to 10% by weight, or up to 5% by weight) of aluminum to improve sputtering. In that case, the resulting protective layer includes a similar percentage of aluminum, e.g., up to 15% by weight of aluminum, e.g., up to 10% by weight of aluminum, e.g., up to 5% by weight of aluminum. A coating layer deposited from a silicon cathode with up to 10% by weight of aluminum added to increase the conductivity of the cathode is referred to herein as a "silicon oxide", "silicon oxynitride", or "silicon nitride" layer or film, even though a small amount of aluminum may be present. It is believed that the small amount of aluminum in the cathode (e.g., 15% by weight or less, e.g., 10% by weight or less, e.g., 5% by weight or less) forms aluminum nitride in the primarily silicon nitride protective layer 350. In the case of a silicon nitride layer, the protective layer 350 may be formed in a nitrogen atmosphere, although it should be understood that other gases, such as oxygen, may be present in the atmosphere during deposition of the protective layer 350.

[0040] In another embodiment, referring to FIG. 4B, the protective coating 350 may be comprised of a metal nitride 356, e.g., a film of silicon nitride, disposed over and in contact with a metal oxynitride 354, e.g., a film of SiON, disposed over and in contact with the top dielectric layer 322 of the functional layer 320. Examples of metal oxynitride films 354 may also or alternatively include two or more metal nitrides and / or alloys of one or more metal nitrides. Examples of metal nitride films 356 may also or alternatively include mixtures of two or more metal oxynitrides and / or alloys of one or more metal oxynitrides. The protective coating 350 may improve the durability of the functional layer 320. The protective coating 350 may be deposited using other materials with good electrical conductivity to improve sputtering of the metal.

[0041] The protective coating 250, 350 has a total thickness (i.e., the sum of all thicknesses of layers or films within the protective coating (250, 350)) in the range of 320 Å to 800 Å, 420 Å to 800 Å, 400 Å to 700 Å, 500 Å to 800 Å, 600 Å to 700 Å, 580 Å to 630 Å, or 620 Å to 670 Å.

[0042] The atomic ratio of oxygen to nitrogen in the metal oxynitride can vary from 0% to 100% by weight, with weight % referring to the ratio of the mass of N or O to the total mass of N+O in the composition excluding the metal of the metal oxynitride. Thus, referring to FIG. 4B, the metal oxynitride film 354 includes 0% nitrogen by weight and 100% or less nitrogen by weight. The metal oxynitride film 354 includes greater than 0% oxygen by weight and 15% or less oxygen by weight, 10% or less oxygen, 5% or less oxygen by weight. Non-limiting examples of useful atomic ratios of oxygen to nitrogen in the metal oxynitride layer include, but are not limited to, for example, 99.9% to 0.1% N with 0.1% to 99.9% O, 99% to 1% N with 1% to 99% O, or 90% to 10% N with 10% to 90% O.

[0043] In one embodiment, the oxynitride is an oxynitride of the same metal as the metal nitride layer 356 in contact with the metal oxynitride layer 354. In another embodiment, the metal oxynitride layer 354 is a graded layer, where the portion of the oxynitride layer closest to the top dielectric layer 322 contains a greater amount of oxygen and the opposite portion of the metal oxynitride layer 354, e.g., the portion closest to the metal nitride layer 356, contains a greater amount of nitrogen, e.g., in the atomic ratios described above. In one embodiment, the metal oxynitride layer 354 and the metal nitride layer 356 form a continuous single graded layer. In another embodiment, the metal oxynitride layer 354 is applied over the metal oxide layer and / or between the metal oxide layer and the metal nitride layer. In another embodiment, the metal nitride layer 356 is not present and the metal oxynitride film 354 is a graded layer, where the amount of oxygen in the metal oxynitride film decreases with increasing distance from the top dielectric layer. For example, the portion of the oxynitride layer closest to the top dielectric layer 322 may contain a greater amount of oxygen, and the opposite portion of the oxynitride layer 354 may contain a greater amount of nitrogen, for example, in the atomic ratios described above, such as, but not limited to, 0.1%-99.9% O with 99.9%-0.1% N, 1%-99% O with 99%-1% N, or 10%-90% O with 90%-10% N.

[0044] In a protective coating 350 according to the present disclosure, the metal oxynitride film 354, such as a film composed of silicon oxynitride, may have a refractive index of at least 1.4 and no more than 2.3. In one embodiment, the metal oxynitride film 354 has a refractive index of at least 1.45 and no more than 2.2. In another embodiment, the metal oxynitride film 354 has a refractive index of at least 1.75 and no more than 2.1. In yet another embodiment, the metal oxynitride film 354 has a refractive index of at least 1.8 and no more than 2.1. It should be understood that the refractive index of the metal oxynitride film 354 depends, at least in part, on the weight percentage of nitrogen present in the metal oxynitride film 354. The protective coating 350 may be a top layer of a coated article.

[0045] The metal oxynitride film 354 can have a thickness in the range of >0 Å (greater than 0 Å) to 400 Å, such as 70 Å to 400 Å, 100 Å to 400 Å, 280 Å to 330 Å, or 110 Å to 130 Å. In embodiments where the metal oxynitride film 354 is a graded layer, the only film in the protective coating, or there is no metal nitride film in the protective coating, it can have a thickness of 200 Å to 400 Å, preferably 225 Å to 375 Å, more preferably 250 Å to 350 Å, and most preferably 280 Å to 330 Å.

[0046] The metal nitride film 356 can have a thickness in the range of >0 Å (greater than 0 Å) to 400 Å, such as 70 Å to 400 Å, 100 Å to 400 Å, 250 Å to 400 Å, 280 Å to 330 Å, 200 Å to 250 Å, 200 Å to 400 Å, or 100 Å to 150 Å. In embodiments without a metal oxynitride layer and / or without a second protective film, the metal nitride film 356 can have a thickness in the range of 100 Å to 400 Å, preferably 250 Å to 400 Å, and most preferably 280 Å to 330 Å. In embodiments where the protective coating includes the metal oxynitride film 354 and a second protective layer, the metal nitride film 356 can have a thickness in the range of 100 Å to 400 Å, preferably 150 Å to 330 Å, more preferably 175 Å to 300 Å, and most preferably 200 Å to 250 Å. In embodiments where the protective coating includes both a metal nitride 356 film and a second protective film 360, the metal oxynitride film can have a thickness of 50 Å to 200 Å, preferably 75 Å to 175 Å, more preferably 100 Å to 150 Å, and most preferably 110 Å to 130 Å.

[0047] In certain embodiments, the invention has a total thickness of metal oxynitride film 354 (if present) and / or metal nitride film 356 (if present) that can be from 200 Å to 800 Å, e.g., from 320 Å to 800 Å, from 320 Å to 370 Å, or from 280 Å to 330 Å.

[0048] The combined layer of metal nitride, metal oxynitride, metal nitride, and / or second protective film, such as TiAlO, can have a thickness in the range of >0 Å (greater than 0 Å) to 1000 Å, e.g., 170 Å to 800 Å, 320 Å to 370 Å, 280 Å to 330 Å, 320 Å to 800 Å, 310 Å to 360 Å, 130 Å to 430 Å, 320 Å to 800 Å, or 350 Å to 400 Å.

[0049] 3 and 4B, the metal oxynitride film 354 of the protective coating 350 creates a strong bond between the metal nitride film 356 and the metal oxide of the second film 326 of the top dielectric layer 322 of the functional layer 320. An example consistent with this disclosure includes a silicon nitride film 356 disposed in contact with at least a portion of the silicon oxynitride film 354, which is disposed in contact with at least a portion of the zinc stannate top dielectric layer 322.

[0050] In examples consistent with this disclosure, it should be understood that the silicon in the metal nitride film 356 and / or the metal oxynitride film 354 may be at least partially replaced with oxides, oxynitrides, and nitrides, respectively, of other metals. These other metals may be the same or different between the films 354, 356. The metals may be titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum, silicon, and mixtures thereof.

[0051] 4A and 4B, a coated article according to any aspect or embodiment of the coated article described herein may include a second protective film 360. The second protective film 360 is shown disposed on the metal nitride film 356 and may include, for example, a metal oxide or metal nitride layer. The second protective film 360 may be titania, alumina, silica, zirconia, tin oxide, mixtures thereof, or alloys thereof. For example, the second protective film 360 may include a mixture of silica and alumina, a mixture of titania and alumina, or zirconia. An example of the second film 360 may include TiAlO. Non-limiting examples of the second protective film 360 may have a thickness in the range of 10 Å to 80 Å, such as 25 Å to 75 Å, such as 35 Å to 55 Å. It should be understood that the second protective film 360 may be applied, for example as a top layer, to any other configuration of top dielectric layers, metal nitride, and metal oxynitride films consistent with the present disclosure. Alternatively, additional functional or protective layers may be applied over the second protective film 360. Likewise, it should be understood that the coated article need not include the second protective film 360.

[0052] In a non-limiting example, the coated article may include an additional protective layer (not shown) disposed over the second protective film 360. This additional protective layer can be any material used to form the protective coating 350, or the second protective film 360, or any material that can be used as a topcoat.

[0053] A primer, such as optional primer 328 described above, may be disposed on and / or in direct contact with any of the metal layers of functional layer 320 or any metal layer that is a continuous layer. In one non-limiting embodiment, the primer is not in direct contact with the discontinuous (subcritical) metal layers. In this embodiment, the primer is not applied directly on or in direct contact with the discontinuous layers. However, a primer layer may be disposed on and in direct contact with each of the continuous metal layers. Additionally, the primer may be titanium or a mixture or alloy of titanium and aluminum, such as, but not limited to, titanium aluminide.

[0054] With reference to Figure 5, a transparent article 400 may include a substrate 410, a functional layer 420, and a protective coating 450. Although not shown, some examples may also include a second protective film 360 (Figure 4B) according to the present disclosure, although it should be understood that the second protective film 360 may also not be included. In the example shown in Figure 5, the protective coating 450 may include a second protective film consistent with the second protective film 360 disclosed above, or any other composition or topcoat known in the art consistent with this disclosure. The functional layer 420 may include a stack of metal layers, dielectric layers, and primer layers consistent with the present disclosure.

[0055] With further reference to FIG. 5, the functional layer 420 includes a top dielectric layer 422. The top dielectric layer 422 may be disposed at least partially on the primer layer 428 in accordance with the present disclosure. In a non-limiting example, the top dielectric layer 422 may consist of a single layer and have a refractive index of at least 1.5 and no more than 2.1, more preferably at least 1.9 and no more than 1.9, and even more preferably at least 1.8 and no more than 1.85. In an example according to the present disclosure, the top dielectric layer 422 may consist of zinc stannate. The characteristics of the top dielectric layer 422 may match those of the top dielectric layer 322. In another example, the top dielectric layer 322, 422 does not include zinc 90 (containing 90% zinc oxide, 10% tin oxide).

[0056] Careful testing has shown that a top dielectric layer 322 containing zinc stannate improves the durability of the stack under such conditions and reduces corrosion / glare defects. Furthermore, the use of a top dielectric layer 322 made of zinc stannate disposed on the top primer layer 328 of the functional layer 320 does not affect color control. Alternatively, zinc oxide or zinc 90 may be used in the top dielectric layer. Alternatively, the top dielectric layer can have two films, the bottom film being a zinc oxide film and the top film being a zinc stannate film.

[0057] Referring to Figure 6, coated article 500 includes a substrate 510, a functional layer 520 on substrate 510, and a protective coating 550 on functional layer 520 according to any embodiment or aspect described herein. Functional layer 520 includes a functional stack 530 including a metal oxide layer 531 according to any embodiment or aspect described herein, and a metal layer 534 on metal oxide layer 531 according to any embodiment or aspect described herein. An optional primer layer 528 according to any embodiment or aspect described herein is deposited on metal layer 534. Functional layer 520 also includes a top dielectric layer 522 according to any aspect or embodiment described herein. Protective coat 550 is a protective coating according to any aspect or embodiment described herein. In one embodiment, the substrate 510 is glass, the metal oxide layer 531 comprises a dielectric layer, such as a layer 532 of zinc oxide with a second layer 533 of zinc stannate on the zinc oxide layer, the metal layer 534 comprises or consists of Ag, the primer layer 528 comprises or consists of Ti or TiAl, the dielectric layer 522 comprises or consists of zinc oxide and / or zinc stannate, and the protective coating 550 comprises SiON or Si 3 N 4 and a second protective film 560 over the metal nitride layer 552. In one embodiment, for example, with reference to Figure 6, the metal nitride layer 552 of the protective coating 550 includes a silicon oxynitride layer 554 over and in contact with the metal oxide layer 522, and a silicon nitride layer 556 over and in contact with the silicon oxynitride layer 554.

[0058] Tables 1-6 provide examples of useful coated articles according to the present disclosure, including thicknesses and preferred thicknesses of the various layers.

[0059] [Table 1]

[0060] [Table 2]

[0061] [Table 3]

[0062] [Table 4]

[0063] Table 5 - SiON on dielectric film with TiAlO protective layer

[0064] [Table 5]

[0065] [Table 6]

[0066] The following provide examples of coated articles according to the present disclosure, however, it should be understood that the invention is not limited to these specific embodiments.

[0067] example Examples 1-6 are examples of coated articles according to the present invention. The examples show embodiments in which the functional layer includes two dielectric layers and one metal layer, however, additional dielectric and / or metal layers may be present according to the present invention. Additionally, while the examples show embodiments in which the top layer is either a metal oxynitride film, a metal nitride film, or a second protective film, it is understood that additional functional coatings and / or additional protective layers may be applied over the top layer shown in the examples. Additionally, while the examples show coatings on a piece of glass, it is understood that the coatings may be applied to laminated glass, automotive glass, insulated glass units, and the like.

[0068] Example 1 A substrate is coated with a functional layer. The substrate was glass. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer disposed on the substrate. The first dielectric layer includes a zinc stannate film and a zinc oxide film. The metal layer is disposed on the zinc oxide film of the first dielectric layer. The metal layer is a continuous silver layer. A primer layer is disposed on the metal layer and a second dielectric layer is disposed on the primer layer. The second dielectric layer includes zinc stannate. A protective layer is disposed on the second dielectric layer of the functional layer and includes SiN and a second protective layer disposed on the SiN layer and includes TiAlO. All thicknesses are approximate. [Table 7]

[0069] Example 2 A glass substrate is coated with a functional layer. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer. The first dielectric layer is disposed on the substrate and includes a zinc stannate film and a zinc oxide film disposed on the zinc stannate film. The metal layer is disposed on the first dielectric layer. The metal layer is a continuous silver layer. The primer layer is disposed on the metal layer. The second dielectric layer is disposed on the primer layer. The second dielectric layer of this exemplary coated article includes a first zinc oxide film and a second zinc stannate film disposed on the first layer. A protective coating is disposed on the functional layer and in contact with the zinc stannate film of the second dielectric layer. The first protective layer includes SiN. The second protective layer is disposed on the first protective layer and includes TiAlO. All thicknesses are approximate. [Table 8]

[0070] Example 3 The substrate is coated with a functional layer. The substrate may be any suitable material, such as glass. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer disposed on the substrate. The first dielectric layer includes a zinc stannate film and a zinc oxide film. The metal layer is disposed on the zinc oxide film of the first dielectric layer. The metal layer is a continuous silver layer. A primer layer is disposed on the metal layer and a second dielectric layer is disposed on the primer layer. The second dielectric layer is comprised of zinc stannate. A protective coating is disposed on the second dielectric layer of the functional layer and includes a SiN layer and a SiON layer disposed between the SiN layer and the dielectric layer. All thicknesses are approximate. [Table 9]

[0071] Example 4 A glass substrate is coated with a functional layer. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer that is a top layer of the functional layer. The first dielectric layer is disposed on the substrate and includes a zinc stannate film and a zinc oxide film disposed on the zinc stannate film. The metal layer is disposed on the first dielectric layer. The metal layer is a continuous silver layer. The primer layer is disposed on the metal layer. A second dielectric layer is disposed on the primer layer. The second dielectric layer of this exemplary coated article is comprised of a zinc stannate film. A protective coating is disposed on the functional layer and is in contact with the zinc stannate second dielectric layer. The protective coating is disposed on the second dielectric layer of the functional layer and includes a SiN layer and a SiON layer disposed between the SiN layer and the dielectric layer. All thicknesses are approximate. The second protective layer is disposed on the SiN layer and includes TiAlO. All thicknesses are approximate. [Table 10]

[0072] Example 5 A glass substrate is coated with a functional layer. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer. The first dielectric layer is disposed on the substrate and includes a zinc stannate film and a zinc oxide film disposed on the zinc stannate film. The metal layer is disposed on the first dielectric layer. The metal layer is a continuous silver layer. The primer layer is disposed on the metal layer. The second dielectric layer is disposed on the primer layer. The second dielectric layer of this exemplary coated article includes a zinc stannate film. A protective coating is disposed on the functional layer and in contact with the zinc stannate film of the second dielectric layer. The first protective layer includes SiON. The second protective layer is disposed on the first protective layer and includes TiAlO. All thicknesses are approximate. [Table 11]

[0073] Example 6 The glass substrate is coated with a functional layer. The functional layer includes a first dielectric layer, a metal layer, a primer layer, and a second dielectric layer. The first dielectric layer is disposed on the substrate and includes a zinc stannate film and a zinc oxide film disposed on the zinc stannate film. The metal layer is disposed on the first dielectric layer. The metal layer is a continuous silver layer. The primer layer is disposed on the metal layer. The second dielectric layer is disposed on the primer layer. The second dielectric layer of this exemplary coated article includes a zinc stannate film. A protective coating is disposed on the functional layer and is in contact with the zinc stannate film of the second dielectric layer. The first protective layer includes a gradient film of SiON, with the N content increasing and the O content decreasing in the direction from the zinc stannate film to the second protective layer including TiAlO disposed on the first protective layer. All thicknesses are approximate. [Table 12]

[0074] The following numbered paragraphs illustrate various aspects of the present invention.

[0075] Clause 1. A coated article comprising a substrate, a first functional layer on at least a portion of the substrate, and a protective coating on at least a portion of the functional layer, wherein a top layer of the functional layer is a metal oxide film, and the protective coating comprises one or more layers of a metal nitride, a metal oxynitride, or a combination thereof.

[0076] Clause 2. The coated article of clause 1, wherein the metal nitride, metal oxynitride, or combination thereof is at least one of silicon nitride, silicon oxynitride, or combination thereof.

[0077] Clause 3. The coated article of clause 1, wherein the protective coating includes a metal oxynitride film in contact with at least a portion of the uppermost metal oxide film of the first functional layer, and a metal nitride film in contact with at least a portion of the metal oxynitride film.

[0078] Clause 4. The coated article of any one of clauses 1 to 3, wherein the protective coating comprises a silicon nitride film.

[0079] Clause 5. The coated article of any one of clauses 1 to 3, wherein the protective coating comprises a silicon oxynitride film.

[0080] Clause 6. The coated article of clause 3, wherein the metal oxynitride film is a gradient layer, where a portion of the metal oxynitride film closest to a top layer of the first functional layer contains a greater amount of oxygen than a portion of the metal oxynitride film closest to the metal nitride film.

[0081] Clause 7. The coated article of clause 1, wherein the protective coating includes a metal oxynitride film over and in contact with at least a portion of the metal oxide film of a top layer of the first functional layer, and the metal oxynitride film is a gradient layer, wherein the amount of oxygen in the metal oxynitride film decreases with increasing distance from the top layer of the first functional layer, or wherein the portion of the metal oxynitride film closest to the top layer of the first functional layer contains a greater amount of oxygen than the portion of the metal oxynitride film furthest from the top layer of the first functional layer.

[0082] Clause 8. The coated article of clause 7, wherein the metal oxynitride of the gradient layer is silicon oxynitride.

[0083] Clause 9. The coated article of any one of clauses 1 to 8, wherein the metal oxide film of the top dielectric layer of the first functional layer comprises zinc stannate or zinc oxide, the metal oxide film immediately underlying and in contact with the protective coating.

[0084] Clause 10. The coated article of any one of clauses 1 to 9, wherein the first functional layer comprises a dielectric layer over at least a portion of the substrate, a metal layer over at least a portion of the dielectric layer, and a top layer over at least a portion of the metal layer.

[0085] Clause 11. The coated article of clause 10, wherein the first functional layer further comprises a primer layer over the metal layer and under at least a portion of the top layer.

[0086] Clause 12. The coated article of clause 10 or 11, wherein the dielectric layer comprises one or more layers comprising zinc oxide and / or zinc stannate, the metal layer comprises Ag, Cu, Au and / or Pd, and / or the top layer comprises zinc oxide and / or zinc stannate.

[0087] Clause 13. A coated article according to clause 12, wherein the topmost layer of the functional layer does not contain zinc oxide.

[0088] Clause 14. The coated article of any one of clauses 1 to 13, further comprising a second functional layer under at least a portion of the first functional layer and over at least a portion of the substrate.

[0089] Clause 15. The coated article of clause 14, wherein the second functional layer comprises a second dielectric layer, a second metal layer on the second dielectric layer, and optionally a second primer layer on the metal layer.

[0090] Clause 16. The coated article of any one of clauses 1 to 15, further comprising a second protective coating disposed at least partially on the one or more layers of metal nitride, metal oxynitride, or combinations thereof, the second protective coating comprising at least one of titania, alumina, silica, zirconia, a mixture of any two or more of the foregoing, or an alloy of any one or more of the foregoing.

[0091] Clause 17. The second protective film is TiO 2 and / or TiAlO.

[0092] Clause 18. The coated article of any one of clauses 1 to 17, wherein the functional layer comprises a metal layer and a primer layer over at least a portion of the metal layer.

[0093] Clause 19. The coated article of clause 18, wherein the primer layer comprises titanium or titanium and aluminum, and at least a portion of the titanium or titanium and aluminum is optionally oxidized after the titanium or titanium and aluminum is deposited on the metal layer.

[0094] Clause 20. The coated article of clause 18, wherein the metal layer comprises silver, gold, palladium, copper, or a mixture of any of the foregoing.

[0095] Clause 21. The coated article of any one of clauses 18 to 20, wherein the metal layer is a continuous metal film.

[0096] Clause 22. A coated article according to any one of clauses 18 to 21, wherein the metal layer comprises silver, copper or a mixture thereof.

[0097] Clause 23. The coated article of clause 1, comprising a glass substrate, a first layer of zinc stannate on at least a portion of the glass substrate, a layer of zinc oxide on at least a portion of the layer of zinc stannate, a layer of silver on at least a portion of the layer of zinc oxide, a primer layer comprising Ti, TiAl and / or an oxide thereof on at least a portion of the layer of silver, a second layer of zinc stannate or zinc oxide on at least a portion of the primer layer, a metal oxynitride layer comprising silicon oxynitride directly on at least a portion of the second layer of zinc stannate, a metal nitride layer comprising silicon directly on at least a portion of the metal oxynitride layer, and a second protective layer comprising Ti, TiAl and / or an oxide of any of the foregoing on at least a portion of the metal nitride layer.

[0098] Clause 24. The coated article of clause 1, comprising a glass substrate, a first layer of zinc stannate over at least a portion of the glass substrate, a layer of zinc oxide over at least a portion of the layer of zinc stannate, a layer of silver over at least a portion of the layer of zinc oxide, a primer layer comprising Ti, TiAl and / or an oxide of any of the foregoing over at least a portion of the layer of silver, a second layer of zinc stannate over at least a portion of the primer layer, a metal oxynitride layer comprising silicon over at least a portion of the second layer of zinc stannate, a metal nitride layer comprising silicon over at least a portion of the metal oxynitride layer, and a second protective layer comprising TiAlO over at least a portion of the metal nitride layer.

[0099] Clause 25. The coated article of clause 1, comprising: a glass substrate; a first layer of zinc stannate having a thickness in the range of 250 Å to 400 Å on at least a portion of the glass substrate; a layer of zinc oxide having a thickness in the range of 70 Å to 90 Å on at least a portion of the layer of zinc stannate; a layer of silver having a thickness in the range of 70 Å to 90 Å on at least a portion of the layer of zinc oxide; a primer layer comprising Ti having a thickness in the range of 10 Å to 30 Å on at least a portion of the layer of silver; a second layer of zinc stannate having a thickness in the range of 30 Å to 100 Å on at least a portion of the primer layer; a metal oxynitride layer comprising SiON directly on at least a portion of the second layer of zinc stannate and having a thickness in the range of 70 Å to 400 Å; a metal nitride layer comprising SiN directly on at least a portion of the metal oxynitride layer and having a thickness in the range of 100 Å to 400 Å; and a second protective layer comprising TiAlO on the metal nitride layer and having a thickness in the range of 100 Å to 400 Å.

[0100] Clause 26. Coated articles according to any one of clauses 1 to 25 attached to the bodywork of a vehicle.

[0101] Clause 27. A coated article according to clause 26 fitted to a motor vehicle as a sunroof.

[0102] Clause 28. A coated article of any one of clauses 1 to 25 attached to an insulating glass unit.

[0103] Clause 29. A coated article comprising a substrate, a functional layer having a top layer on at least a portion of the substrate, and a protective coating on at least a portion of the functional layer, wherein the top layer of the functional layer is a dielectric layer having a refractive index of at least 1.5 and no greater than 2.1.

[0104] Clause 30. A coated article according to clause 29, wherein the top layer of the functional layer comprises zinc stannate.

[0105] Clause 31. A coated article according to clause 29, in which the topmost layer of the functional layer does not contain zinc oxide.

[0106] Clause 32. A coated article comprising a substrate, a functional layer on at least a portion of the substrate, and a protective coating on at least a portion of the functional layer, wherein the functional layer comprises at least one metal layer and a primer layer disposed at least partially on and in contact with at least a portion of the at least one metal layer, and a top layer of the functional layer is disposed on and in contact with at least a portion of the primer layer, and the top layer of the functional layer does not comprise zinc oxide.

[0107] Clause 33. An insulating glass unit comprising a first ply having a first surface and a second surface, a second ply having a third surface and a fourth surface, and a coating comprising a functional layer and a protective coating as described in any of clauses 1 to 31, wherein the coating is disposed over at least a portion of the second surface or the third surface.

[0108] Clause 34. An insulating glass unit as in clause 33, wherein a coating is disposed on the second surface.

[0109] Clause 35. The insulating glass unit of clause 33 or 34, further comprising a space between the second surface of the first ply and the third surface of the second ply, the space being filled with a gas.

[0110] Clause 36. An insulating glass unit as claimed in clause 35, wherein the gas is argon.

[0111] Clause 37. An automotive glazing article comprising a first ply having a first surface and a second surface, and a coating comprising a functional layer and a protective coating as described in any of clauses 1 to 31, wherein the coating is disposed on at least a portion of the first surface or the second surface.

[0112] Clause 38. The automotive glass article of clause 34, wherein a coating is disposed on the second surface.

[0113] It will be readily appreciated by those skilled in the art that modifications may be made to the present invention without departing from the concepts disclosed in the foregoing description. Accordingly, the specific embodiments detailed herein are illustrative only and are not intended to limit the scope of the present invention, which is to be accorded the full scope of the appended claims and any and all equivalents thereof.

Claims

1. A substrate; a first functional layer on at least a portion of the substrate, the first functional layer comprising a layer of silver on at least a portion of the substrate; a layer of a metal oxynitride including silicon directly over at least a portion of the first functional layer; On at least a portion of the metal oxynitride layer, Ti, TiAl, silicon oxide, silicon oxynitride, TiO ２ , TiAlO, or a combination thereof; and Including, the metal oxynitride layer comprising silicon is a gradient layer, wherein a portion of the metal oxynitride layer closest to the first functional layer comprises a greater amount of oxygen than a portion of the metal oxynitride layer closest to the protective layer. Coated articles.

2. The coated article of claim 1, wherein the first functional layer comprises zinc stannate in direct contact with the substrate.

3. The coated article of claim 1, wherein the first functional layer comprises a dielectric layer on at least a portion of the substrate and a layer of silver on at least a portion of the dielectric layer.

4. The coated article of claim 3, further comprising a primer layer over at least a portion of the silver layer and under at least a portion of the protective layer.

5. The coated article of claim 4, wherein the primer layer comprises titanium, silicon, silicon dioxide, silicon nitride, silicon oxynitride, nickel-chromium alloy, zirconium, aluminum, an alloy containing cobalt and chromium, titanium and aluminum, or a combination thereof.

6. A method for producing the coated article of claim 5 by oxidizing at least a portion of the primer layer after the primer layer is disposed on the silver layer.

7. The coated article of claim 4, wherein the dielectric layer comprises one or more layers comprising zinc oxide or zinc stannate.

8. The article described in claim 1, further comprising a second functional layer beneath at least a portion of the first functional layer and over at least a portion of the substrate.

9. The article of claim 1 , wherein the protective layer is directly overlying the layer of metal oxynitride.

10. A glass substrate; a first layer of zinc stannate over at least a portion of the glass substrate; a layer of zinc oxide over at least a portion of the first layer of zinc stannate; a layer of silver over at least a portion of said layer of zinc oxide; a layer of a metal oxynitride comprising silicon on at least a portion of the layer of silver; a protective layer over at least a portion of the layer of metal oxynitride; Including, the metal oxynitride layer comprising silicon is a gradient layer, the portion of the metal oxynitride layer closest to the silver layer containing a greater amount of oxygen than the portion of the metal nitride layer closest to the protective layer. Goods.

11. The article of claim 10, further comprising a primer layer over at least a portion of the silver layer.

12. The article of claim 11, further comprising a second layer of zinc oxide or zinc stannate directly over at least a portion of the primer layer.

13. The article of claim 10, wherein the protective layer comprises silicon nitride, titanium oxide, titanium aluminum oxide, silicon oxide, silicon oxynitride, or a combination thereof.

14. A glass substrate; a first layer of zinc stannate on at least a portion of the glass substrate, the first layer having a thickness in the range of 250 Å to 400 Å; a layer of zinc oxide on at least a portion of the first layer of zinc stannate, the layer of zinc oxide having a thickness in the range of 70 Å to 90 Å; a layer of silver on at least a portion of the layer of zinc oxide, the layer of silver having a thickness in the range of 70 Å to 90 Å; a layer of a metal oxynitride comprising silicon on at least a portion of the layer of silver, the metal oxynitride layer having a thickness in the range of 70 Å to 400 Å; a protective layer having a thickness in the range of 100 Å to 400 Å; Including, the metal oxynitride layer comprising silicon is a gradient layer, the portion of the metal oxynitride layer closest to the silver layer containing a greater amount of oxygen than the portion of the metal nitride layer closest to the protective layer. Goods.

15. The article of claim 14, further comprising a primer layer on at least a portion of the silver layer, the primer layer having a thickness in the range of 10 Å to 30 Å.

16. The article of claim 15, wherein the primer layer comprises Ti, TiAl, an oxide or suboxide of Ti, or an oxide or suboxide of TiAl.

17. The article of claim 14, further comprising a second layer of zinc stannate on at least a portion of the silver layer, the second layer of zinc stannate having a thickness in the range of 30 Å to 100 Å.

18. The article of claim 14, wherein the protective layer comprises silicon nitride, titanium oxide, titanium aluminum oxide, silicon oxide, silicon oxynitride, or a combination thereof.

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