Magnetron sputtering deposited coating compositions containing light absorbing materials

Abstract

The coated article includes a substrate and a metal functional layer on at least a portion of the substrate. The metal functional layer includes a metal alloy, a metal oxide, a metal nitride, a metal oxynitride, or molybdenum. Another coated article includes a glass substrate and a coating on at least a portion of the substrate. The coating includes a dielectric layer, a metal functional layer, and a protective layer. The present invention also provides methods for making the coated article and an insulating glass unit.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Application No. 63 / 406,291, filed September 14, 2022, and U.S. Patent Application No. 18 / 244,988, filed September 12, 2023, the disclosures of which are incorporated by reference in their entireties.

[0002] (Technical field) The present invention generally relates to a coated article comprising a substrate and a metallic functional layer comprising a metal alloy, a metal oxide, a metal nitride, a metal oxynitride, and / or molybdenum, and a method for making the coated article. [Background technology]

[0003] (Technical Considerations) Solar control coatings are known in the field of architectural and vehicular transparencies. These solar control coatings block or filter selected ranges of electromagnetic radiation, such as the solar infrared or solar ultraviolet radiation ranges, to reduce the amount of solar energy that enters a vehicle or building. This reduction in solar energy transmittance helps reduce the load on the vehicle's or building's cooling units.

[0004] High-temperature fabrication processes, such as pyrolytic spray processes, can make solar control coatings mechanically and chemically durable, allowing them to be used on the first surface of architectural glass windows. However, these coatings can be rough and have poor film quality, and this spray technique does not allow for precise control of material quality and thickness. As an alternative, magnetron sputtering deposition (MSVD) is an advanced technique that achieves both material quality and uniformity in thickness and composition. Typical MSVD coatings are soft due to the low-temperature process, and therefore have poor durability. Therefore, it is desirable to provide a coating that can be deposited by MSVD that has enhanced chemical and mechanical durability. Summary of the Invention

[0005] The coated article of the present invention includes a substrate and a metallic functional layer on at least a portion of the substrate, the metallic functional layer comprising a metal alloy selected from the group consisting of silicon-aluminum alloys, silicon-cobalt alloys, niobium-tungsten alloys, and titanium-tungsten alloys, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride, or molybdenum.

[0006] Another coated article of the invention includes a glass substrate and a metal functional layer over at least a portion of the substrate, the coating including a dielectric layer over the substrate, the metal functional layer, and a protective layer over the metal functional layer. The metal functional layer comprises a metal alloy selected from the group consisting of silicon-aluminum alloy, silicon-cobalt alloy, niobium-tungsten alloy, and titanium-tungsten alloy; a metal oxide selected from the group consisting of cobalt oxide, cobalt-iron oxide, cobalt-chromium oxide, cobalt-iron-chromium oxide, cobalt-copper oxide, cobalt-aluminum-chromium oxide, and cobalt-aluminum-iron oxide; a metal nitride selected from the group consisting of cobalt nitride, cobalt-iron nitride, cobalt-chromium nitride, cobalt-iron-chromium nitride, cobalt-copper nitride, cobalt-aluminum-chromium nitride, and cobalt-aluminum-iron nitride; a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt-iron oxynitride, cobalt-chromium oxynitride, cobalt-iron-chromium oxynitride, cobalt-copper oxynitride, cobalt-aluminum-chromium oxynitride, and cobalt-aluminum-iron oxynitride; or molybdenum.

[0007] The present invention also relates to a method for producing a coated article, the method comprising providing a substrate and forming a metallic functional layer on at least a portion of the substrate. The metal functional layer comprises a metal alloy selected from the group consisting of silicon-aluminum alloy, silicon-cobalt alloy, niobium-tungsten alloy, and titanium-tungsten alloy; a metal oxide selected from the group consisting of cobalt oxide, cobalt-iron oxide, cobalt-chromium oxide, cobalt-iron-chromium oxide, cobalt-copper oxide, cobalt-aluminum-chromium oxide, and cobalt-aluminum-iron oxide; a metal nitride selected from the group consisting of cobalt nitride, cobalt-iron nitride, cobalt-chromium nitride, cobalt-iron-chromium nitride, cobalt-copper nitride, cobalt-aluminum-chromium nitride, and cobalt-aluminum-iron nitride; a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt-iron oxynitride, cobalt-chromium oxynitride, cobalt-iron-chromium oxynitride, cobalt-copper oxynitride, cobalt-aluminum-chromium oxynitride, and cobalt-aluminum-iron oxynitride; or molybdenum. The metallic functional layer is formed by a process that includes depositing a metal alloy, a metal oxide, a metal nitride, a metal oxynitride, or molybdenum by magnetron sputtering deposition.

[0008] The present invention also relates to another method for making a coated article, which method includes providing a substrate and forming a coating on at least a portion of the substrate. The metal functional layer comprises a metal alloy selected from the group consisting of silicon-aluminum alloy, silicon-cobalt alloy, niobium-tungsten alloy, and titanium-tungsten alloy; a metal oxide selected from the group consisting of cobalt oxide, cobalt-iron oxide, cobalt-chromium oxide, cobalt-iron-chromium oxide, cobalt-copper oxide, cobalt-aluminum-chromium oxide, and cobalt-aluminum-iron oxide; a metal nitride selected from the group consisting of cobalt nitride, cobalt-iron nitride, cobalt-chromium nitride, cobalt-iron-chromium nitride, cobalt-copper nitride, cobalt-aluminum-chromium nitride, and cobalt-aluminum-iron nitride; a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt-iron oxynitride, cobalt-chromium oxynitride, cobalt-iron-chromium oxynitride, cobalt-copper oxynitride, cobalt-aluminum-chromium oxynitride, and cobalt-aluminum-iron oxynitride; or molybdenum. The metallic functional layer is formed by a process that includes depositing a metal alloy, a metal oxide, a metal nitride, a metal oxynitride, or molybdenum by magnetron sputtering deposition.

[0009] The present invention also relates to an insulated glass unit including a first ply having a No. 1 surface and a No. 2 surface opposite the No. 1 surface, and a second ply having a No. 3 surface and a No. 4 surface opposite the No. 3 surface, the second ply being spaced apart from the first ply and the first and second plies being connected to each other. A coating is applied over at least a portion of the No. 2 or No. 3 surface, the coating including a dielectric layer over the substrate; a metal functional layer; and a protective layer over the metal functional layer, the metal functional layer being selected from the group consisting of silicon aluminum alloys, silicon cobalt alloys, niobium tungsten alloys, and titanium tungsten alloys, or a metal alloy selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide. The metal oxide may comprise a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum.

[0010] The present invention will be described with reference to the following drawings, in which like reference numerals identify like parts throughout. [Brief explanation of the drawings]

[0011] [Figure 1A] FIG. 1A is a side view (not to scale) of an insulated glass unit (IGU) having a coating of the present invention.

[0012] [Figure 1B] FIG. 1B is a cross-sectional view (not to scale) of an exemplary transparency having a coating of the present invention.

[0013] [Figure 2] FIG. 2 is a side view (not to scale) of a coating incorporating features of the present invention.

[0014] [Figure 3] FIG. 3 is a side view (not to scale) of another coating incorporating features of the present invention.

[0015] [Figure 4] FIG. 4 is a side view (not to scale) of another coating incorporating features of the present invention.

[0016] [Figure 5] FIG. 5 is a side view (not to scale) of another coating incorporating features of the present invention.

[0017] [Figure 6] FIG. 6 is a side view (not to scale) of another coating incorporating features of the present invention.

[0018] [Figure 7] FIG. 7 is a side view (not to scale) of another coating incorporating features of the present invention.

[0019] [Figure 8] FIG. 8 is a side view (not to scale) of another coating incorporating features of the present invention.

[0020] [Figure 9] 9A, 9B, 9C, and 9D show the results of the Cleveland Condensation Test for coated articles of the present invention.

[0021] [Figure 10] 10A and 10B show the results of the Cleveland Condensation Test for coated articles of the present invention.

[0022] [Figure 11] 11A, 11B, 11C, and 11D show the results of the Cleveland Condensation Test for coated articles of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0023] As used herein, spatial or directional terms such as "left," "right," "inside," "outside," "top," and "bottom" refer 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, quantities of ingredients, reaction conditions, and the like, used in the specification and claims, should be understood to be modified in each instance by the term "about." Accordingly, 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 stated 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, e.g., 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. Furthermore, as used herein, the terms "formed over," "deposited over," or "provided over" mean formed, deposited, or provided on a surface, but not necessarily in contact with the 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. 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. Furthermore, all documents referenced herein, including but not limited to issued patents and patent applications, are 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, respectively, as well as conventionally recognized metals and metal oxides, although silicon may not traditionally be considered a metal. Thickness values ​​are geometric thickness values ​​unless indicated to the contrary.

[0024] In describing the present invention, certain features may be described as "particularly" or "preferably" within certain limitations (e.g., "preferably," "more preferably," or "most preferably," within certain limitations). It is to be understood that the present invention is not limited to these particular or preferred limitations, but rather encompasses the full scope of the disclosure.

[0025] As used herein, weight percent (wt%) of a metal oxide, metal alloy, metal nitride, or metal oxynitride is based on the total weight of the metal component and excludes the weight of the oxide, nitride, or oxynitride component. Those skilled in the art will readily appreciate that weight percent of a metal functional layer as used herein refers to the weight percent of the metal target used to deposit the metal functional layer.

[0026] The coating of the present invention may be a solar control coating. As used herein, the term "solar control coating" refers to a coating composed of one or more layers or films that affect the solar properties of the coated article (e.g., but not limited to, the amount of solar radiation (e.g., visible, infrared, or ultraviolet radiation) reflected from, absorbed by, or transmitted through the coated article; shading coefficient; emissivity, etc.). Solar control coatings can block, absorb, or filter selected portions of the solar spectrum (e.g., but not limited to, the IR spectrum, UV spectrum, and / or visible spectrum).

[0027] The present invention relates to a coated article, the coated article comprising a substrate, the substrate comprising a metallic functional layer on at least a portion of the substrate. The metal functional layer comprises a metal alloy (selected from the group consisting of silicon-aluminum alloy, silicon-cobalt alloy, niobium-tungsten alloy, and titanium-tungsten alloy), or a metal oxide (selected from the group consisting of cobalt oxide, cobalt-iron oxide, cobalt-chromium oxide, cobalt-iron-chromium oxide, cobalt-copper oxide, cobalt-aluminum-chromium oxide, and cobalt-aluminum-iron oxide), or a metal nitride (selected from the group consisting of cobalt nitride, cobalt-iron nitride, cobalt-chromium nitride, cobalt-iron-chromium nitride, cobalt-copper nitride, cobalt-aluminum-chromium nitride, and cobalt-aluminum-iron nitride), or a metal oxynitride (selected from the group consisting of cobalt oxynitride, cobalt-iron oxynitride, cobalt-chromium oxynitride, cobalt-iron-chromium oxynitride, cobalt-copper oxynitride, cobalt-aluminum-chromium oxynitride, and cobalt-aluminum-iron oxynitride), or molybdenum. Optionally, the coated article may also have a protective layer, a base layer, or a dielectric layer. For example, the coated article includes a substrate coated with a coating, where the coating includes a dielectric layer, a metal functional layer, a protective layer, and optionally a second dielectric layer and / or a base layer.

[0028] The coated article 10 includes a substrate 12. The substrate 12 can be composed of any desired material having any desired properties, such as opaque, translucent, or transparent to visible light. For example, the substrate 12 can be transparent or translucent to visible light. "Transparent" means that the visible light transmittance is greater than 0% and up to 100%. Alternatively, the substrate 12 can be translucent. "Translucent" means that electromagnetic energy (e.g., visible light) passes through but diffuses this energy so that objects on the opposite side of the viewer are not clearly visible. Examples of suitable materials include, but are not limited to, plastic substrates (e.g., acrylic polymers such as polyacrylate; polyalkyl methacrylates such as polymethyl methacrylate, polyethyl methacrylate, and polypropyl methacrylate; polyurethanes, polycarbonates, polyalkyl terephthalates such as polyethylene terephthalate (PET), polypropylene terephthalate, and polybutylene terephthalate; polysiloxane-containing polymers; or copolymers of any monomers for preparing these, or any mixtures thereof); ceramic substrates; glass substrates; or mixtures or combinations of any of the above. For example, the substrate 12 can include conventional soda-lime silicate glass, borosilicate glass, or leaded glass. The glass can be clear glass. "Clear glass" means non-tinted or uncolored glass. Alternatively, the glass can be tinted or otherwise colored 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 of any composition having any optical properties, such as visible light transmittance, ultraviolet light transmittance, infrared light 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 US Pat. Nos. 4,466,562 and 4,671,155.

[0029] Substrate 12 can be, for example, clear float glass, or can be tinted or colored glass. Substrate 12 can have any desired dimensions, such as length, width, shape, or thickness. In one exemplary automotive transparency, the thickness of substrate 12 can 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, such as from 3 mm to 7 mm, such as from 5 mm to 7 mm, or such as from 6 mm thick. In one non-limiting embodiment in which substrate 12 is an architectural transparency, the thickness of substrate 12 can be from 1 mm to 30 mm thick, such as from 2.5 mm to 25 mm thick, such as from 2.5 mm to 10 mm thick.

[0030] Non-limiting examples of glasses that can be used in the practice of the present invention include clear glass, Starphire®, Solargreen®, Solextra®, GL-20®, GL-35™, Solarbronze®, Solargray® glass, Pacifica® glass, SolarBlue® glass, and Optiblue® glass, which are commercially available from PPG Industries Inc. of Pittsburgh, Pennsylvania.

[0031] In some embodiments, substrate 12 can be monolithic glass. "Monolithic" means having a single structural support or member, for example, having a single substrate.

[0032] Coated article 10 has a metallic functional layer 60 deposited on at least a portion of a major surface of substrate 12. The metallic functional layer provides (a) reflection of electromagnetic radiation in the infrared radiation region of the electromagnetic spectrum, e.g., at least a portion of the solar infrared radiation region and / or the thermal infrared radiation region of the electromagnetic spectrum, and / or (b) absorption of electromagnetic radiation in one or more regions of the electromagnetic spectrum, e.g., at least a portion of the visible radiation region and / or the infrared radiation region and / or the ultraviolet radiation region of the electromagnetic spectrum.

[0033] The metal functional layer 60 can include a metal alloy, such as, but not limited to, a metal alloy containing silicon and / or cobalt, or a metal alloy containing tungsten. Non-limiting examples of suitable metal alloys include silicon-aluminum alloys, silicon-cobalt alloys, niobium-tungsten alloys, and titanium-tungsten alloys. Alternatively, the metal functional layer 60 can include a metal oxide or metal suboxide, such as, but not limited to, a cobalt-containing metal oxide. Non-limiting examples of metal oxides suitable for the metal functional layer 60 include cobalt-iron oxide, cobalt-chromium oxide, cobalt-iron-chromium oxide, cobalt-copper oxide, cobalt-aluminum-chromium oxide, and cobalt-aluminum-iron oxide.

[0034] Alternatively, the metal functional layer 60 can comprise a metal nitride or metal subnitride, such as, but not limited to, a metal nitride comprising cobalt. Non-limiting examples of metal nitrides suitable for the metal functional layer 60 include cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and the like.

[0035] Alternatively, the metal functional layer 60 can comprise a metal oxynitride, such as, but not limited to, a metal oxynitride comprising cobalt. Non-limiting examples of metal oxynitrides suitable for the metal functional layer 60 include cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride.

[0036] Alternatively, the metal functional layer 60 can include a metal such as molybdenum.

[0037] The metal functional layer 60 may include a material with non-magnetic properties. For example, the metal alloy or metal oxide used in the metal functional layer 60 may include less than 90 wt% magnetic material, for example, less than 87 wt% magnetic material, based on the total weight of the metal components. As used herein, the term "magnetic material" refers to a material that generates a magnetic field and includes iron, cobalt, nickel, and rare earth metals. The metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum used in the metal functional layer 60 may include less than 90 wt% magnetic metal, for example, less than 87 wt% magnetic metal, based on the total weight of the metal components.

[0038] In an exemplary embodiment, the metal functional layer 60 includes cobalt. For example, the metal functional layer 60 may include a metal alloy, metal oxide, metal nitride, or metal oxynitride that includes 50 wt% to 100 wt%, 60 wt% to 100 wt%, 60 wt% to 90 wt%, 58 wt% to 70 wt%, 70 wt% to 89 wt%, 75 wt% to 89 wt%, or 80 wt% to 85 wt% of cobalt, based on the total weight of the metal components. In one non-limiting embodiment, the metal functional layer 60 comprises a cobalt chromium oxide containing 60 wt% to 100 wt% cobalt and / or 0 wt% to 40 wt% chromium, 60 wt% to 90 wt% cobalt and / or 10 wt% to 40 wt% chromium, 58 wt% to 70 wt% cobalt and 30 wt% to 42 wt% chromium, 70 wt% to 99 wt% cobalt and 1 wt% to 30 wt% chromium, 70 wt% to 88 wt% cobalt and 12 wt% to 30 wt% chromium, or 80 wt% to 85 wt% cobalt and 15 wt% to 20 wt% chromium.

[0039] In some embodiments, the metal functional layer 60 may be substantially free, essentially free, or completely free of iron. As used in this context, the term "substantially free" means that the metal functional layer contains less than 1 wt% iron, the term "essentially free" means that the metal functional layer contains less than 0.1 wt% iron, and "completely free" means that the metal functional layer contains less than 0.01 wt% iron.

[0040] In another exemplary embodiment, the metal functional layer 60 includes silicon. For example, the metal functional layer 60 may include a metal alloy, metal oxide, metal nitride, or metal oxynitride containing silicon in the range of 50 wt% to 99 wt%, 60 wt% to 99 wt%, 75 wt% to 99 wt%, 80 wt% to 99 wt%, 85 wt% to 99 wt%, or 90 wt% to 99 wt%. In one non-limiting embodiment, the metal functional layer 60 comprises a silicon-aluminum alloy comprising 70 wt% to 100 wt% silicon and 0 wt% to 30 wt% aluminum, such as 80 wt% to 95 wt% silicon and 5 wt% to 20 wt% aluminum, such as 85 wt% to 99 wt% silicon and 1 wt% to 15 wt% aluminum, such as 85 wt% to 95 wt% silicon and 5 wt% to 15 wt% aluminum, or 90 wt% to 95 wt% silicon and 5 wt% to 10 wt% aluminum.

[0041] In another exemplary embodiment, the metal functional layer 60 includes silicon and cobalt. For example, the metal functional layer 60 may include a metal alloy, metal oxide, metal nitride, or metal oxynitride including 30 wt% to 85 wt% silicon and 15 wt% to 70 wt% cobalt, e.g., 50 wt% to 90 wt% silicon and 10 wt% to 50 wt% cobalt, e.g., 50 wt% to 70 wt% silicon and 30 wt% to 50 wt% cobalt, e.g., 65 wt% to 75 wt% silicon and 25 wt% to 35 wt% cobalt.

[0042] The metal functional layer 60 can have any desired thickness, such as in the range of 1 nm to 100 nm, 5 nm to 50 nm, 10 nm to 50 nm, 10 nm to 45 nm, 20 nm to 40 nm, 20 nm to 50 nm, 20 nm to 60 nm, 30 nm to 45 nm, 10 nm to 35 nm, or 20 nm to 30 nm.

[0043] The coated article 10 can include a protective layer 80, which, for example, in the non-limiting embodiment shown in FIG. 2 , is deposited on the metal functional layer 60 and serves to protect underlying layers, such as the metal functional layer, from mechanical and chemical attack during processing. The protective layer 80 can be the outermost layer of the coating 30. The protective layer 80 can be an oxygen barrier coating layer, which can prevent or reduce the ingress of ambient oxygen into underlying layers of the coating 30, such as during heating or bending. The protective layer 80 can be any desired material or mixture of materials. For example, the protective layer can include a metal oxide layer, a metal nitride layer, or a mixture thereof. In one exemplary embodiment, the protective layer 80 can include a layer having one or more metal oxide materials, such as, but not limited to, aluminum oxide, silicon oxide, or a mixture thereof. For example, the protective coating 80 can be a single coating layer containing alumina in the range of 0 wt% to 100 wt% and / or silica in the range of 100 wt% to 0 wt%, where the alumina and / or silica ranges can be, for example, 5 wt% to 95 wt% alumina and 95 wt% to 5 wt% silica, for example, 10 wt% to 90 wt% alumina and 90 wt% to 10 wt% silica, for example, 15 wt% to 90 wt% alumina and 85 wt% to 10 wt% silica, for example, 50 wt% to 75 wt% alumina and 50 wt% to 25 wt% silica, for example, 50 wt% to 70 wt% alumina. alumina and 50 wt% to 30 wt% silica, for example, 35 wt% to 100 wt% alumina and 65 wt% to 0 wt% silica, for example, 70 wt% to 90 wt% alumina and 30 wt% to 10 wt% silica, for example, 75 wt% to 85 wt% alumina and 25 wt% to 15 wt% silica, for example, 88 wt% alumina and 12 wt% silica, for example, 65 wt% to 75 wt% alumina and 35 wt% to 25 wt% silica, for example, 70 wt% alumina and 30 wt% silica, for example, 60 wt% to less than 75 wt% alumina and more than 25 wt% to 40 wt% silica.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 layers 80, 92. In one non-limiting embodiment, the refractive index of the protective layers 80, 92 may 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.

[0044] In one non-limiting embodiment, the protective layer 80 is a combination coating of silica and alumina. The protective layer 80 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 / aluminum oxide protective layer 80 can be Si x Al 1-x O (1.5+x) / 2 where x varies from greater than 0 to less than 1.

[0045] In another non-limiting embodiment, protective layer 80 comprises a combination of titania and alumina.

[0046] In one non-limiting embodiment, the protective layer 80 is silicon oxide (SiO x ), silicon nitride (Si3N4 or SiN x ), silicon oxynitride (SiO x N y ), silicon aluminum oxide (SiAlO x ), silicon aluminum nitride (SiAlN x ), silicon aluminum oxynitride (SiAlO x N y), mixtures thereof, and / or alloys thereof, which can improve the durability of the metal functional layer 60. The protective layer 80 may be formed of silicon nitride deposited with other materials having good electrical conductivity to improve the sputtering of silicon. For example, during deposition, the silicon cathode may contain 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 this case, the resulting silicon nitride protective layer will contain 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. A coating layer deposited from a silicon cathode containing up to 10 wt% aluminum (added to increase the cathode's conductivity) is referred to herein as a "silicon nitride" layer, even if a small amount of aluminum is present. It is believed that small amounts of aluminum in the cathode (e.g., 15 wt % or less, e.g., 10 wt % or less, e.g., 5 wt % or less) form aluminum nitride in a primarily silicon nitride protective layer 80. While protective layer 80 may be formed in a nitrogen atmosphere, it should be understood that other gases, such as oxygen, may be present in the atmosphere during deposition of protective layer 80.

[0047] The protective layer 80 can be any desired thickness. The protective layer 80 can have a thickness ranging from 1 nm to 250 nm, 1 nm to 150 nm, 5 nm to 150 nm, 10 nm to 120 nm, 100 nm to 140 nm, 5 nm to 70 nm, 30 nm to 70 nm, 5 nm to 30 nm, or 10 nm to 30 nm. The protective layer 80 is the outermost layer of the coated article. Furthermore, the protective layer 80 can have a non-uniform thickness. By "non-uniform thickness," we mean that the thickness of the protective layer 80 can vary over a given unit area; for example, the protective layer 80 can have high or low portions or regions of high or low pressure.

[0048] In another non-limiting embodiment, the protective coating 80 can be a multilayer 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 one 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 greater than 5 wt% alumina, e.g., greater than 10 wt% alumina, e.g., greater than 15 wt% alumina, e.g., greater than 30 wt% alumina, e.g., greater than 40 wt% alumina, e.g., 50 wt% to 70 wt% alumina, e.g., a silica / alumina mixture including 60 wt% to 100 wt% alumina and 0 wt% to 40 wt% silica (e.g., 60 wt% alumina and 40 wt% silica). In another example, the first layer can include zinc stannate. In another example, the first film can include zirconia. In one non-limiting embodiment, the first film can have a thickness in the range of greater than 0 nm to 1,000 nm, such as 10 nm to 25 nm, such as 10.1 nm to 25 nm, such as 15 nm to 20 nm, or such as 16 nm.

[0049] The second film of the protective layer 80 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 titania / alumina mixtures including 40 wt%-60 wt% alumina and 40 wt%-60 wt% titania, 45 wt%-55 wt% alumina and 45 wt%-55 wt% titania, 48 wt%-52 wt% alumina and 48 wt%-52 wt% titania, 49 wt%-51 wt% alumina and 49 wt%-51 wt% titania, or 50 wt% alumina and 50 wt% titania. An example of the second film is titanium aluminum oxide (TiAlO). Another example of the second film is a silica / alumina mixture having more than 40 wt% silica, such as more than 50 wt% silica, such as more than 60 wt% silica, such as more than 70 wt% silica, or more than 80 wt% silica, for example, a silica / alumina mixture having 80 wt% to 90 wt% silica and 10 wt% to 20 wt% alumina (e.g., 85 wt% silica and 15 wt% alumina). In a non-limiting embodiment, the second film can have a thickness in the range of greater than 0 nm to 2,000 nm, such as 5 nm to 500 nm, such as 5 nm to 200 nm, such as 10 nm to 100 nm, such as 20 nm to 50 nm, such as 22 nm to 35 nm, or 22 nm. Non-limiting examples of suitable protective layers are described, for example, in U.S. Patent Application Publication Nos. 2004 / 0106017A1, 2002 / 0172775A1, 2003 / 0228484A1, 2004 / 0023080A1, 2004 / 0023038A1, and 2003 / 0228476A1.

[0050] In a non-limiting example, the protective layer 80 may 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.

[0051] In one non-limiting embodiment, the coated article 10 can optionally include a base layer 50, which may be deposited over the substrate 12 and below the metallic functional layer 60, for example, as shown in FIG. 3. The base layer 50 can provide various performance benefits to the coating 30, such as acting as a sodium ion barrier between the substrate 12 and the overlying coating layer. The base layer 50 can include any of the materials described above with respect to the outermost protective layer 80. For example, the base layer can be made of tin oxide (SnO x ), silicon oxide (SiO x ), silicon nitride (Si3N4 or SiN x ), silicon oxynitride (SiO x N x ), aluminum silicon oxide (SiAlO x ), silicon aluminum nitride (SiAlN x ), silicon aluminum oxynitride (SiAlO x N x ), mixtures thereof, and / or alloys thereof. Base layer 50 can be a multi-layer coating including a first film and a second film formed on the first film. In one non-limiting embodiment, the base layer optionally includes one or more films, each of which may be SnO x , SiO x , Si3N4, SiO x N x , SiAlO x , SiAlN x , or SiAlO x N xFor example, the base layer optionally includes two films, each of which is made of SiAlO x or SiAlN x Includes:

[0052] In one non-limiting embodiment, the base layer 50 may optionally be composed of a film of a metal nitride, such as Si3N4 and / or SiAlN, disposed on and in contact with a film of a metal oxynitride, such as SiAlON. Examples of metal oxynitride films may also or alternatively include alloys and / or mixtures of metal nitrides.

[0053] The optional base layer 50 can be of any desired thickness, and can have a thickness in the range of 1 nm to 250 nm, 1 nm to 150 nm, 5 nm to 150 nm, 10 nm to 120 nm, 15 nm to 100 nm, 30 nm to 110 nm, 100 nm to 140 nm, 70 nm to 110 nm, or 30 nm to 80 nm.

[0054] In one non-limiting embodiment, the coated article 10 can include at least one dielectric layer, such as dielectric layer 40, deposited over the substrate 12 and below the metal functional layer 60, for example, as shown in Figures 4, 5, and 6. As shown in Figures 4 and 5, the dielectric layer 40 is deposited over the substrate 12 and below the metal functional layer 60. In another embodiment, the coated article 10 can include a dielectric layer 40 deposited over the substrate 12 and below the base layer 50 (Figure 6).

[0055] Alternatively, the coated article 10 can include a dielectric layer 70 that is deposited over the metal functional layer 60 and below the protective layer 80 (FIG. 7). In another non-limiting embodiment, the dielectric layer 70 is above the protective layer 80 and is the outermost layer (FIG. 8).

[0056] The dielectric layer 40, 70 may be a single layer or may include two or more films of antireflective and / or dielectric materials, such as, but not limited to, metal oxides, oxides of metal alloys, metal nitrides, metal oxynitrides, or mixtures thereof. The dielectric layer 40, 70 may be transparent to visible light. Examples of metal oxides suitable for the dielectric layer 40, 70 include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, and tin, and mixtures thereof. These metal oxides may contain small amounts of other materials, such as manganese in bismuth oxide or tin in indium oxide. In addition, oxides of metal alloys or metal mixtures may be used, such as oxides containing zinc and tin (e.g., zinc stannate, as defined below), oxides of indium-tin alloys, silicon nitride, silicon aluminum nitride, or aluminum nitride. Furthermore, doped metal oxides may be used, such as tin oxide doped with antimony or indium, or silicon oxide doped with nickel or boron. The dielectric layer 40, 70 can be a substantially single phase film, such as a metal oxide film such as zinc stannate, or can be a mixture of phases composed of zinc and tin oxides, or can be composed of multiple films. For example, the dielectric layer can include one or more films selected from zinc tin oxide, zinc oxide, silica, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0057] The dielectric layers 40, 70 (single film or multilayer film) can have any thickness, for example, in the range of 1 nm to 200 nm, 1 nm to 150 nm, 1 nm to 100 nm, 5 nm to 140 nm, 5 nm to 100 nm, 10 nm to 50 nm, 30 nm to 70 nm, 80 nm to 120 nm, 100 nm to 140 nm, or 1 nm to 10 nm.

[0058] The coated article 10 may include multiple dielectric layers. Each dielectric layer may be composed of the same or different material as the other dielectric layers in the coated article and may have the same or different thicknesses. For example, the coated article 10 may include at least two dielectric layers. In one non-limiting embodiment, the coated article may include a first dielectric layer 40 directly above the substrate 12 and below the metal functional layer 60, and a second dielectric layer 70 directly above the metal functional layer 60 and below the protective layer 80, as shown in FIG. 5.

[0059] In one non-limiting embodiment, the coated article 10 can optionally include a primer layer over the metal functional layer 60. The primer layer can be a single film or multiple film layers. The primer layer can include an oxygen-scavenging material that can be sacrificed during the deposition process to prevent degradation or oxidation of the metal functional layer 60 during the sputtering process or subsequent heating process. The primer layer can also absorb at least a portion of the electromagnetic radiation, such as visible light, that passes through the coating 30. Examples of materials useful for the primer layer include titanium, silicon, silicon dioxide, silicon nitride, silicon oxynitride, nickel, zirconium, aluminum, cobalt, chromium, titanium, aluminum, alloys thereof, or mixtures thereof. In one non-limiting embodiment, the primer layer includes titanium, titanium and aluminum, or zinc and aluminum, which are deposited as metals, and at least a portion of the titanium, titanium and aluminum, or zinc and aluminum is subsequently oxidized. In another embodiment, the primer layer includes a nickel-chromium alloy, such as Inconel. In another embodiment, the primer layer includes a cobalt-chromium alloy, such as Stellite®.

[0060] The primer layer may have a thickness in the range of 0.5 nm to 5 nm, such as 1 nm to 4 nm, for example 1 nm to 2.5 nm.

[0061] The present invention also relates to a coated article comprising a glass substrate and a coating on at least a portion of the substrate, the coating comprising a dielectric layer on the substrate, a metal functional layer, and a protective layer on the metal functional layer. The metal functional layer comprises a metal alloy selected from the group consisting of silicon-aluminum alloy, silicon-cobalt alloy, niobium-tungsten alloy, and titanium-tungsten alloy; a metal oxide selected from the group consisting of cobalt oxide, cobalt-iron oxide, cobalt-chromium oxide, cobalt-iron-chromium oxide, cobalt-copper oxide, cobalt-aluminum-chromium oxide, cobalt-aluminum-iron oxide, and zinc-iron-chromium oxide; a metal nitride selected from the group consisting of cobalt nitride, cobalt-iron nitride, cobalt-chromium nitride, cobalt-iron-chromium nitride, cobalt-copper nitride, cobalt-aluminum-chromium nitride, cobalt-aluminum-iron nitride, and zinc-iron-chromium nitride; a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt-iron oxynitride, cobalt-chromium oxynitride, cobalt-iron-chromium oxynitride, cobalt-copper oxynitride, cobalt-aluminum-chromium oxynitride, cobalt-aluminum-iron oxynitride, and zinc-iron-chromium oxynitride; or molybdenum. The dielectric layer, metal functional layer, and protective layer of the coating can be any of the layers described herein above. Optionally, the coating further comprises a second dielectric layer, a primer layer, and / or a base layer. Any second dielectric layer, any primer layer, and any base layer of the coating can be any of the layers described herein above.

[0062] A non-limiting example of a coated article 10 of the present invention is shown in Figure 2. The coated article 10 includes a metal functional layer 60, which is deposited on, and optionally in direct contact with, a substrate 12. The coated article 10 further includes a protective layer 80, which is deposited on, and optionally in direct contact with, the metal functional layer 60. The metal functional layer 60 and the protective layer 80 form a coating 30, which is on, and optionally in direct contact with, at least a portion of the substrate 12. The substrate 12 may be glass.

[0063] Another example of a non-limiting coated article 10 of the present invention is shown in Figure 3. The coated article 10 includes a base layer 50, which is deposited on, and optionally in direct contact with, a substrate 12. The coated article 10 further includes a metal functional layer 60, which is deposited on, and optionally in direct contact with, the base layer 50. The coated article 10 further includes an outermost protective layer 80, which is deposited on, and optionally in direct contact with, the metal functional layer 60. The base layer 50, the metal functional layer 60, and the protective layer 80 form a coating 30, which is over, and optionally in direct contact with, at least a portion of the substrate 12. The substrate 12 may be glass.

[0064] Another example of a non-limiting coated article 10 of the present invention is shown in Figure 4. The coated article 10 includes a dielectric layer 40, which is deposited on, and optionally in direct contact with, at least a portion of a substrate 12. The coated article further includes a metal functional layer 60, which is deposited on, and optionally in direct contact with, the dielectric layer 40. The coated article 10 further includes a protective layer 80, which is deposited on, and optionally in direct contact with, the metal functional layer 60. The dielectric layer 40, the metal functional layer 60, and the protective layer 80 form a coating 30, which is deposited on, and optionally in direct contact with, at least a portion of the substrate 12. The substrate 12 may be glass.

[0065] Another example of a non-limiting coated article 10 of the present invention is shown in Figure 5. The coated article 10 includes a first dielectric layer 40, which is deposited on, and optionally in direct contact with, at least a portion of the substrate 12. The coated article 10 further includes a metal functional layer 60, which is deposited on, and optionally in direct contact with, the dielectric layer 40. The coated article 10 further includes a second dielectric layer 70, which is deposited on, and optionally in direct contact with, the metal functional layer 60. The coated article 10 further includes a protective layer 80, which is deposited on, and optionally in direct contact with, the second dielectric layer 70. First dielectric layer 40, metal functional layer 60, second dielectric layer 70, and protective layer 80 form coating 30, which overlies, and optionally is in direct contact with, at least a portion of substrate 12. Substrate 12 may be glass.

[0066] Another example of a non-limiting coated article 10 of the present invention is shown in Figure 6. The coated article 10 comprises a first dielectric layer 40, which is deposited on, and optionally in direct contact with, at least a portion of the substrate 12. The coated article 10 further comprises a base layer 50, which is deposited on, and optionally in direct contact with, the dielectric layer 40. The coated article 10 further comprises a metal functional layer 60, which is deposited on, and optionally in direct contact with, the base layer 50. The coated article 10 further comprises a protective layer 80, which is deposited on, and optionally in direct contact with, the metal functional layer 60. The dielectric layer 40, the base layer 50, the metal functional layer 60, and the protective layer 80 form a coating 30, which is deposited on at least a portion of the substrate 12 and optionally in direct contact with at least a portion of the substrate 12. The substrate 12 may be glass.

[0067] Another example of a non-limiting coated article 10 of the present invention is shown in Figure 7. The coated article 10 includes a metal functional layer 60, which is deposited on, and optionally in direct contact with, a substrate 12. The coated article 10 further includes a dielectric layer 70, which is deposited on, and optionally in direct contact with, the metal functional layer 60. The coated article 10 further includes a protective layer 80, which is deposited on, and optionally in direct contact with, the dielectric layer 70. The metal functional layer, the dielectric layer, and the protective layer form a coating 30, which is deposited on, and optionally in direct contact with, at least a portion of the substrate 12. The substrate 12 may be glass.

[0068] Another example of a non-limiting coated article 10 of the present invention is shown in Figure 8. The coated article 10 includes a metal functional layer 60, which is deposited on, and optionally in direct contact with, a substrate 12. The coated article 10 further includes a protective layer 80, which is deposited on, and optionally in direct contact with, the metal functional layer 60. The coated article 10 further includes a dielectric layer 70, which is deposited on, and optionally in direct contact with, the protective layer 80. The metal functional layer 60, the protective layer 80, and the dielectric layer 70 form a coating 30, which is deposited on, and optionally in direct contact with, at least a portion of the substrate 12. The substrate 12 may be glass.

[0069] The dielectric layers 40, 70, optional base layer 50, metal functional layer 60, protective layer 80, and optional primer layer 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 (such as magnetron sputter deposition (MSVD)). Other coating methods can also be used, such as, but not limited to, sol-gel deposition. In one non-limiting embodiment, the layers of coating 30 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. In one non-limiting embodiment, a cobalt chromium alloy is used as the magnetron sputtering target to deposit the metallic functional layer 60.

[0070] The coating 30 of the present invention can impart desirable physical properties, including, but not limited to, durability properties such as moisture resistance and chemical resistance, to the coated article 10. In some non-limiting embodiments, the presence of the dielectric layer 40, 70 and / or protective layer 80 has been found to improve the durability of the coating.

[0071] In one non-limiting embodiment of the present invention, the coated article 10 passes the conventional Cleveland Condensation Test (CCC Test) when measured at about 60°C using a Cleveland Condensation Chamber (QCT Condensation Tester commercially available from Q-Panel Company, Cleveland, Ohio) equipped with a deionized (DI) water chamber. In some embodiments, the coated article 10 having the dielectric layer 40, 70 passes the CCC Test, as compared to a coated article without the dielectric layer 40, 70. In one non-limiting embodiment, the coated article 10 has a transmission elliptical color difference (DECMC, T) of less than 10 after 50 days, e.g., less than 7, less than 5, less than 1, or less than 0.5. In one non-limiting embodiment, the coated article 10 has a film-side reflection elliptical color difference (DECMC, Rf) of less than 20 after 50 days, e.g., less than 15, or less than 10, less than 5, less than 1, or less than 0.5. In one non-limiting embodiment, the coated article 10 has a glass-side reflective elliptical color difference (DECMC, Rg) of less than 18, such as less than 15, or less than 13 after 50 days.

[0072] In one non-limiting embodiment of the present invention, the coated article 10 may experience less than 12%, for example less than 10%, film loss after 30 minutes of immersion in 10 N (27.5%) sulfuric acid at 52° C. (standard chemical durability test). In some embodiments, the coated article 10 including the dielectric layer 40, 70 passes the standard chemical durability test, as compared to a coated article without the dielectric layer 40, 70.

[0073] Materials used in coating layers, such as metal functional layer 60, can be selected to achieve desired color characteristics of the coated article 10. Coating 30 may consist essentially of the materials described herein so that the desired color characteristics of the coating are achieved. For example, a coating 30 consisting essentially of the materials described herein may include additional materials as long as the color characteristics of the coating are not affected. Color Coordinates a * , b * , and L *are color coordinates in the conventional CIE (1931) and CIELAB systems, as will be understood by those skilled in the art.

[0074] In one non-limiting embodiment of the present invention, the coated article 10 has a transmission L * For example, the range is 60 to 75, 59 to 70, 67 to 73, or 70 to 75.

[0075] In one non-limiting embodiment of the present invention, the coated article 10 has a transmission (T)a in the range of 0.0 to 3.5. * For example, it is in the range of 0.0 to 3.0, 0.5 to 3.0, or 0.8 to 3.0.

[0076] In one non-limiting embodiment of the present invention, the coated article 10 has a Transmission (T)b in the range of 6.5 to 11.5. * For example, it is in the range of 6.5 to 11.0, 7.0 to 11.0, or 7.5 to 11.0.

[0077] In one non-limiting embodiment of the present invention, the coated article 10 has a visible light transmission (LTA) in the range of 20-50, such as 25-50, 30-40, 38-48, or 42-47.

[0078] In one non-limiting embodiment of the present invention, the coated article 10 has a film side reflectance (Rf) L in the range of 35-70. * For example, it is in the range of 35 to 65, 40 to 65, 40 to 55, or 60 to 65.

[0079] In one non-limiting embodiment of the present invention, the coated article 10 has an Rf a in the range of -5.0 to -1.0. * For example, the range is from −5.0 to 2.0, or from −5.0 to 3.0.

[0080] In one non-limiting embodiment of the present invention, the coated article 10 has an Rf b in the range of -3.5 to 7.5. *For example, the range is −3.0 to 7.5, −3.0 to 5.0, 0.0 to 7.5, or 1.0 to 7.0.

[0081] In one non-limiting embodiment of the present invention, the coated article 10 has a glass side reflectance (Rg) L in the range of 40-65. * For example, the range is 40 to 60, 45 to 60, 50 to 65, 50 to 60, 55 to 65, or 55 to 60.

[0082] In one non-limiting embodiment of the present invention, the coated article 10 has an Rg a range of -7.5 to -4.0. * For example, the range is -7.0 to -4.0, -6.0 to -4.0, -7.5 to -5.0, -7.0 to -5.0, -7.5 to -6.0, or -7.0 to -6.0.

[0083] In one non-limiting embodiment of the present invention, the coated article 10 has an Rg b range of -11.0 to 4.0. * For example, the range is −11.0 to 3.5, 1.0 to 4.0, 1.0 to 3.5, −11.0 to −7.0, −9.5 to −7.5, or −6.5 to −5.0.

[0084] Certain embodiments of the present invention are particularly useful for solar control coatings for architectural and automotive transparencies.

[0085] The present invention also relates to a method for making a coated article.A substrate is provided. A metal functional layer is formed on at least a portion of the substrate, the metal functional layer comprising a metal alloy selected from the group consisting of silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy, and titanium tungsten alloy; a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide; a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride; a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride; or molybdenum. The metal functional layer is formed by a process including depositing a metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum by magnetron sputtering deposition. The method may also optionally further include forming a protective layer. The protective layer may be any of the protective layers described herein. The method may also optionally further include forming at least one dielectric layer. The at least one dielectric layer may be any of the dielectric layers described herein. The method may also optionally further include forming a base layer. The optional base layer may be any of the base layers described herein. The method may also optionally further include forming a primer layer. The optional primer layer may be any of the primer layers described herein.

[0086] The present invention also relates to a method for producing a coated article, in which a substrate is provided and a coating is formed on at least a portion of the substrate, the coating including a dielectric layer on the substrate, a metal functional layer, and a protective layer on the metal functional layer. The metal functional layer comprises a metal alloy selected from the group consisting of silicon-aluminum alloy, silicon-cobalt alloy, niobium-tungsten alloy, and titanium-tungsten alloy; a metal oxide selected from the group consisting of cobalt oxide, cobalt-iron oxide, cobalt-chromium oxide, cobalt-iron-chromium oxide, cobalt-copper oxide, cobalt-aluminum-chromium oxide, cobalt-aluminum-iron oxide, and zinc-iron-chromium oxide; a metal nitride selected from the group consisting of cobalt nitride, cobalt-iron nitride, cobalt-chromium nitride, cobalt-iron-chromium nitride, cobalt-copper nitride, cobalt-aluminum-chromium nitride, cobalt-aluminum-iron nitride, and zinc-iron-chromium nitride; a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt-iron oxynitride, cobalt-chromium oxynitride, cobalt-iron-chromium oxynitride, cobalt-copper oxynitride, cobalt-aluminum-chromium oxynitride, cobalt-aluminum-iron oxynitride, and zinc-iron-chromium oxynitride; or molybdenum. The metallic functional layer is formed by a process including depositing a metal alloy, a metal oxide, a metal nitride, a metal oxynitride, or molybdenum by magnetron sputtering deposition. The metallic functional layer can be any of the metallic functional layers described herein. The dielectric layer and the protective layer can be any of the dielectric layers and protective layers described herein. The coating may further include an optional second dielectric layer. The second dielectric layer may be any of the dielectric layers described herein. The coating may further include an optional base layer. The optional base layer may be any of the base layers described herein. The coating may further include an optional primer layer. The optional primer layer may be any of the primer layers described herein.

[0087] The coated articles described herein can be used in architectural transparencies, such as, but not limited to, insulated glass units. 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 present invention is not limited to use with such architectural transparencies and can be implemented with transparencies in any desired field, such as laminated or non-laminated residential and / or commercial windows, insulated glass units, and / or transparencies for land, air, space, water, and underwater vehicles. Accordingly, it should be understood that the specifically disclosed exemplary embodiments are presented merely to illustrate the general concepts of the present invention, and that the present invention is not limited to these particular exemplary embodiments. Furthermore, while a typical "transparency" can have sufficient visible light transmittance to allow materials to be seen through the transparency, in the practice of the present invention, a "transparency" need not be transparent to visible light; it may be translucent or opaque.

[0088] 1A illustrates a non-limiting insulating glass unit 110 incorporating features of the present invention. The insulating glass unit 110 includes a first ply 112 having a first major surface 114 (No. 1 surface) and an opposing second major surface 116 (No. 2 surface). In the illustrated non-limiting embodiment, the first major surface 114 faces the exterior of the building, i.e., is the exterior major surface, and the second major surface 116 faces the interior of the building. The insulating glass unit 110 also includes a second ply 118 spaced apart from the first ply 112, having an exterior (first) major surface 120 (No. 3 surface) and an interior (second) major surface 122 (No. 4 surface). In some embodiments, the insulating glass unit 110 includes a third ply having an opposite No. 6 surface from a No. 5 surface. This numbering of the ply surfaces is consistent with conventional practice in the fenestration art.

[0089] The plies 112, 118 can have any desired transmittance and / or reflectance of visible light, infrared radiation, or ultraviolet radiation. For example, the plies 112, 118 can have any desired amount of visible light transmittance, such as greater than 0% to 100%. Each of the plies 112, 118 can be, for example, clear float glass, or tinted or colored glass, or one ply 112, 118 can be clear glass and the other ply 112, 118 can be colored glass. Although not limiting to the present invention, examples of suitable glasses for the first ply 112 and / or the second ply 118 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.

[0090] The first ply 112 and the second ply 118 can be connected to each other in any suitable manner, such as adhesively bonding to a conventional spacer frame 124. A gap or chamber 126 is formed between the two plies 112, 118. The chamber 126 can be filled with a selected atmosphere, such as air, or a non-reactive gas, such as argon or krypton gas. A coating 130 is formed on at least a portion of the plies 112, 118, such as, but not limited to, on at least a portion of the No. 2 surface 116 or on at least a portion of the No. 3 surface 120. However, the coating 130 can also be formed on the No. 1 surface 114 or the No. 4 surface 122, if desired. The coating 130 can comprise, consist essentially of, or consist of any of the coatings described herein. Examples of insulating glass units are described, for example, in U.S. Patent Nos. 4,193,236, 4,464,874, 5,088,258, and 5,106,663.

[0091] The coated articles described herein can be used in vehicle transparencies, such as windows and sunroofs. FIG. 1B illustrates a non-limiting vehicle transparency 210 incorporating features of the present invention. For clarity, seals, connectors, and opening / closing mechanisms are not shown, nor is the entire vehicle. The transparency includes a first ply 212 having a first major surface 214 (No. 1 surface) attached to the body of a vehicle 218 (partially shown) and an opposing second major surface 216 (No. 2 surface). In the illustrated non-limiting embodiment, the first major surface 214 faces the exterior of the vehicle and is therefore the exterior major surface, while the second major surface 216 faces the interior of the vehicle. Non-limiting examples of vehicle bodies include the roof of an automobile for a sunroof, the door or frame of an automobile for an automobile window, or the fuselage of an airplane. As is well known in the vehicle arts, the transparency may be attached to a mechanism that allows the automobile window or sunroof to be opened or closed. Coating 230 is shown as being formed on No. 1 surface 214, but may also be formed on at least a portion of No. 2 surface 216. Coating 230 may include, consist essentially of, or consist of any of the coatings described herein.

[0092] The invention is further described in the following numbered clauses:

[0093] Clause 1: A coated article comprising a substrate and a metallic functional layer on at least a portion of the substrate, wherein the metallic functional layer is a metal alloy selected from the group consisting of silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy, and titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide, or cobalt nitride. the coated article comprising a metal nitride selected from the group consisting of cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride, or molybdenum.

[0094] Clause 2: The coated article of clause 1, wherein the metal functional layer comprises less than 90 wt% of a magnetic metal.

[0095] Clause 3: The coated article of clause 1 or 2, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm, 20 nm to 60 nm, 30 nm to 45 nm, or 20 nm to 30 nm.

[0096] Clause 4: The coated article of any one of clauses 1-3, wherein the metal functional layer comprises 60 wt% to 100 wt% cobalt, 60 wt% to 90 wt% cobalt, or 58 wt% to 70 wt% cobalt.

[0097] Clause 5: The coated article of any one of clauses 1-4, wherein the metal functional layer comprises cobalt chromium oxide.

[0098] Clause 6: The coated article of any one of clauses 1 to 5, wherein the metal functional layer comprises 60 wt% to 100 wt% cobalt and 0 wt% to 40 wt% chromium, 60 wt% to 90 wt% cobalt and 10 wt% to 40 wt% chromium, or 70 wt% to 88 wt% cobalt and 12 wt% to 30 wt% chromium.

[0099] Clause 7: The coated article of any one of clauses 1 to 3, wherein the metal functional layer comprises 60 wt% to 99 wt% silicon.

[0100] Clause 8: The coated article of any one of clauses 1-3 or 7, wherein the metallic functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

[0101] Clause 9: The coated article of any one of clauses 1 to 3, 7, or 8, wherein the metal functional layer comprises 70 wt% to 100 wt% silicon and 0 wt% to 30 wt% aluminum, 80 wt% to 95 wt% silicon and 5 wt% to 20 wt% aluminum, or 85 wt% to 95 wt% silicon and 5 wt% to 15 wt% aluminum.

[0102] Clause 10: The coated article of any one of clauses 1-3, 7, or 8, wherein the metal functional layer comprises 30 wt% to 85 wt% silicon and 15 wt% to 70 wt% cobalt, or 50 wt% to 70 wt% silicon and 30 wt% to 50 wt% cobalt.

[0103] Clause 11: The coated article of any one of clauses 1 to 10, wherein the metal functional layer is essentially free, substantially free, or completely free of iron.

[0104] Clause 12: The coated article of any one of clauses 1 to 11, further comprising a protective layer over the metal functional layer.

[0105] Clause 13: The coated article of clause 12, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or a mixture thereof.

[0106] Clause 14: The coated article of clause 12 or 13, wherein the protective layer comprises titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or a mixture thereof.

[0107] Clause 15: The coated article of any one of clauses 12 to 14, wherein the protective layer has a thickness of 5 nm to 70 nm, 5 nm to 30 nm, 30 to 70 nm, or 10 nm to 30 nm.

[0108] Clause 16: The coated article of any one of clauses 1 to 15, further comprising a base layer over the glass substrate and below the metal functional layer.

[0109] Clause 17: The coated article of clause 16, wherein the metal functional layer comprises silicon.

[0110] Clause 18: The coated article of clause 16 or 17, wherein the base layer has a thickness of 30 nm to 110 nm, 30 nm to 80 nm, or 70 nm to 110 nm.

[0111] Clause 19: The coated article of any one of clauses 1 to 18, further comprising at least one dielectric layer.

[0112] Clause 20: The coated article of clause 19, wherein the dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silica, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0113] Clause 21: The coated article of clause 19 or 20, wherein each dielectric layer has a thickness of 5 nm to 140 nm, 80 nm to 120 nm, 100 nm to 140 nm, or 1 nm to 10 nm.

[0114] Clause 22: The coated article of any one of clauses 1 to 21, wherein the substrate is a glass substrate.

[0115] Clause 23: A coated article comprising a glass substrate and a coating on at least a portion of the substrate, the coating comprising: a dielectric layer on the substrate; a metal functional layer; and a protective layer on the metal functional layer; the metal functional layer being a metal alloy selected from the group consisting of silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy, and titanium tungsten alloy, or a metal alloy selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide. or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum.

[0116] Clause 24: The coated article of clause 23, wherein a metal functional layer is present on the dielectric layer, and the metal functional layer comprises silicon.

[0117] Clause 25: The coated article of clause 23 or 24, further comprising a second dielectric layer over the metal functional layer, the protective layer being over the second dielectric layer.

[0118] Clause 26: The coated article of any one of clauses 23-25, further comprising a base layer over the dielectric layer, the metal functional layer being on the base layer.

[0119] Clause 27: The coated article of clause 23, wherein a dielectric layer is present on the metal functional layer, and a protective layer is present on the dielectric layer, and the metal functional layer comprises cobalt.

[0120] Clause 28: The coated article of clause 23 or 25, wherein a dielectric layer is present on the protective layer and the metal functional layer comprises silicon.

[0121] Clause 29: The coated article of any one of clauses 23 to 28, wherein the metal functional layer comprises less than 90 wt% of magnetic metal.

[0122] Clause 30: The coated article of any one of clauses 23 to 29, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm, 20 nm to 60 nm, 30 nm to 45 nm, or 20 nm to 30 nm.

[0123] Clause 31: The coated article of any one of clauses 23, 25-27, 29, or 30, wherein the metal functional layer comprises 60 wt% to 100 wt% cobalt, 60 wt% to 90 wt% cobalt, or 58 wt% to 70 wt% cobalt.

[0124] Clause 32: The coated article of any one of clauses 23, 25-27, or 29-31, wherein the metal functional layer comprises cobalt chromium oxide.

[0125] Clause 33: The coated article of any one of clauses 23, 25-27, or 29-32, wherein the metal functional layer comprises 60 wt% to 100 wt% cobalt and 0 wt% to 40 wt% chromium, 60 wt% to 90 wt% cobalt and 10 wt% to 40 wt% chromium, or 70 wt% to 88 wt% cobalt and 12 wt% to 30 wt% chromium.

[0126] Clause 34: The coated article of any one of clauses 23-26 or 28-30, wherein the metal functional layer comprises 60 wt% to 99 wt% silicon.

[0127] Clause 35: The coated article of any one of clauses 23-30, or 34, wherein the metallic functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

[0128] Clause 36: The coated article of any one of clauses 23-26, 28-30, 34, or 35, wherein the metal functional layer comprises 70 wt% to 100 wt% silicon and 0 wt% to 30 wt% aluminum, 80 wt% to 95 wt% silicon and 5 wt% to 20 wt% aluminum, or 85 wt% to 95 wt% silicon and 5 wt% to 15 wt% aluminum.

[0129] Clause 37: The coated article of any one of clauses 23-30, 34, or 35, wherein the metal functional layer comprises 30 wt% to 85 wt% silicon and 15 wt% to 70 wt% cobalt, or 50 wt% to 70 wt% silicon and 30 wt% to 50 wt% cobalt.

[0130] Clause 38: The coated article of any one of clauses 23 to 37, wherein the metal functional layer is essentially free, substantially free, or completely free of iron.

[0131] Clause 39: The coated article of any one of clauses 23 to 38, wherein the dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silica, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0132] Clause 40: The coated article of any one of clauses 23-39, wherein the dielectric layer comprises silicon nitride or silicon aluminum nitride.

[0133] Clause 41: The coated article of any one of clauses 23 to 40, wherein the dielectric layer has a thickness of 5 nm to 140 nm, 80 nm to 120 nm, 100 nm to 140 nm, or 1 nm to 10 nm.

[0134] Clause 42: The coated article of any one of clauses 23 to 41, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or a mixture thereof.

[0135] Clause 43: The coated article of any one of clauses 23-42, wherein the protective layer comprises at least one of titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or a mixture thereof.

[0136] Clause 44: The coated article of any one of Clauses 23 to 43, wherein the protective layer has a thickness of 5 nm to 70 nm, 5 nm to 30 nm, 30 to 70 nm, or 10 nm to 30 nm.

[0137] Clause 45: The coated article of any one of clauses 26 or 29-44, wherein the base layer has a thickness of 30 nm to 110 nm, 30 nm to 80 nm, or 70 nm to 110 nm.

[0138] Clause 46: A method for producing a coated article, the method comprising the steps of providing a substrate and forming a metallic functional layer on at least a portion of the substrate, wherein the metallic functional layer is a metal alloy selected from the group consisting of silicon aluminum alloys, silicon cobalt alloys, niobium tungsten alloys, and titanium tungsten alloys, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal oxide selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium oxide, the metal functional layer comprises a metal nitride selected from the group consisting of cobalt nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum; and the metal functional layer is formed by a process comprising depositing the metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum by magnetron sputtering deposition.

[0139] Clause 47: The method of clause 46, wherein the metal functional layer comprises less than 90 wt% of a magnetic metal.

[0140] Clause 48: The method of clause 46 or 47, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm, 20 nm to 60 nm, 30 nm to 45 nm, or 20 nm to 30 nm.

[0141] Clause 49: The method of any one of Clauses 46 to 48, wherein the metal functional layer comprises 60 wt% to 100 wt% cobalt, 60 wt% to 90 wt% cobalt, or 58 wt% to 70 wt% cobalt.

[0142] Clause 50: The method of any one of clauses 46 to 49, wherein the metal functional layer comprises cobalt chromium oxide.

[0143] Clause 51: The method of any one of clauses 46 to 50, wherein the metal functional layer comprises 60 wt% to 100 wt% cobalt and 0 wt% to 40 wt% chromium, 60 wt% to 90 wt% cobalt and 10 wt% to 40 wt% chromium, or 70 wt% to 88 wt% cobalt and 12 wt% to 30 wt% chromium.

[0144] Clause 52: The method of any one of clauses 46 to 48, wherein the metal functional layer comprises 60 wt% to 99 wt% silicon.

[0145] Clause 53: The method of any one of clauses 46-48 or 51, wherein the metal functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

[0146] Clause 54: The method of any one of clauses 46 to 48, 51, or 52, wherein the metal functional layer comprises 70 wt% to 100 wt% silicon and 0 wt% to 30 wt% aluminum, 80 wt% to 95 wt% silicon and 5 wt% to 20 wt% aluminum, or 85 wt% to 95 wt% silicon and 5 wt% to 15 wt% aluminum.

[0147] Clause 55: The method of any one of clauses 46-48, 51, or 52, wherein the metal functional layer comprises 30 wt% to 85 wt% silicon and 15 wt% to 70 wt% cobalt, or 50 wt% to 70 wt% silicon and 30 wt% to 50 wt% cobalt.

[0148] Clause 56: The method of any one of clauses 46 to 55, wherein the metal functional layer is essentially free, substantially free, or completely free of iron.

[0149] Clause 57: The method of any one of clauses 46 to 56, further comprising a protective layer over the metal functional layer.

[0150] Clause 58: The method of clause 57, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or a mixture thereof.

[0151] Clause 59: The method of clause 57 or 58, wherein the protective layer comprises titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or a mixture thereof.

[0152] Clause 60: The method of any one of Clauses 57 to 59, wherein the protective layer has a thickness of 5 nm to 70 nm, 5 nm to 30 nm, 30 to 70 nm, or 10 nm to 30 nm.

[0153] Clause 61: The coated article of any one of clauses 46 to 60, further comprising a base layer over the glass substrate and below the metal functional layer.

[0154] Clause 62: The method of clause 61, wherein the metal functional layer comprises silicon.

[0155] Clause 63: The method of clause 61 or 62, wherein the base layer has a thickness of 30 nm to 110 nm, 30 nm to 80 nm, or 70 nm to 110 nm.

[0156] Clause 64: The coated article of any one of clauses 46 to 63, further comprising at least one dielectric layer.

[0157] Clause 65: The method of clause 64, wherein the dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silica, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0158] Clause 66: The method of clause 64 or 65, wherein each dielectric layer has a thickness of 5 nm to 140 nm, 80 nm to 120 nm, 100 nm to 140 nm, or 1 nm to 10 nm.

[0159] Clause 67: The method of any one of Clauses 46 to 66, wherein the substrate is a glass substrate.

[0160] Clause 68: A method for producing a coated article, the method comprising the steps of providing a substrate and forming a coating on at least a portion of the substrate, the coating comprising: a dielectric layer on the substrate; a metal functional layer; and a protective layer on the metal functional layer; the metal functional layer being a metal alloy selected from the group consisting of silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy, and titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal oxide selected from the group consisting of cobalt nitride, cobalt the metal functional layer comprises a metal nitride selected from the group consisting of cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum; the metal functional layer is formed by a process comprising depositing the metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum by magnetron sputtering deposition; The above method.

[0161] Clause 69: The method of clause 68, wherein a metal functional layer is present on the dielectric layer, the metal functional layer comprising silicon.

[0162] Clause 70: The method of clause 68 or 69, further comprising a second dielectric layer over the metal functional layer, the protective layer being over the second dielectric layer.

[0163] Clause 71: The method of any one of clauses 68 to 70, further comprising a base layer on the dielectric layer, the metal functional layer being on the base layer.

[0164] Clause 72: The method of clause 68, wherein a dielectric layer is present on the metal functional layer, and a protective layer is present on the dielectric layer, and the metal functional layer comprises cobalt.

[0165] Clause 73: The method of clause 68 or 70, wherein a dielectric layer is present on the protective layer and the metal functional layer comprises silicon.

[0166] Clause 74: The method of any one of clauses 68 to 73, wherein the metal functional layer comprises less than 90 wt% of magnetic metal.

[0167] Clause 75: The method of any one of Clauses 68 to 74, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm, 20 nm to 60 nm, 30 nm to 45 nm, or 20 nm to 30 nm.

[0168] Clause 76: The method of any one of clauses 68, 70-72, 74, or 75, wherein the metal functional layer comprises 60 wt% to 100 wt% cobalt, 60 wt% to 90 wt% cobalt, or 58 wt% to 70 wt% cobalt.

[0169] Clause 77: The method of any one of clauses 68, 70-72, or 74-76, wherein the metal functional layer comprises cobalt chromium oxide.

[0170] Clause 78: The method of any one of clauses 68, 70-72, or 74-77, wherein the metal functional layer comprises 60 wt% to 100 wt% cobalt and 0 wt% to 40 wt% chromium, 60 wt% to 90 wt% cobalt and 10 wt% to 40 wt% chromium, or 70 wt% to 88 wt% cobalt and 12 wt% to 30 wt% chromium.

[0171] Clause 79: The method of any one of clauses 68 to 71 or 73 to 75, wherein the metal functional layer comprises 60 wt% to 99 wt% silicon.

[0172] Clause 80: The method of any one of clauses 68-75 or 79, wherein the metal functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

[0173] Clause 81: The method of any one of clauses 68-71, 73-75, 79, or 80, wherein the metal functional layer comprises 70 wt% to 100 wt% silicon and 0 wt% to 30 wt% aluminum, 80 wt% to 95 wt% silicon and 5 wt% to 20 wt% aluminum, or 85 wt% to 95 wt% silicon and 5 wt% to 15 wt% aluminum.

[0174] Clause 82: The method of any one of clauses 68-75, 79, or 80, wherein the metal functional layer comprises 30 wt% to 85 wt% silicon and 15 wt% to 70 wt% cobalt, or 50 wt% to 70 wt% silicon and 30 wt% to 50 wt% cobalt.

[0175] Clause 83: The method of any one of clauses 68 to 82, wherein the metal functional layer is essentially free, substantially free, or completely free of iron.

[0176] Clause 84: The method of any one of clauses 68 to 83, wherein the dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silica, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0177] Clause 85: The method of any one of clauses 68 to 84, wherein the dielectric layer comprises silicon nitride or silicon aluminum nitride.

[0178] Clause 86: The method of any one of Clauses 68 to 85, wherein the dielectric layer has a thickness of 5 nm to 140 nm, 80 nm to 120 nm, 100 nm to 140 nm, or 1 nm to 10 nm.

[0179] Clause 87: The method of any one of clauses 68 to 86, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or a mixture thereof.

[0180] Clause 88: The method of any one of clauses 68 to 87, wherein the protective layer comprises at least one of titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or a mixture thereof.

[0181] Clause 89: The method of any one of Clauses 68 to 88, wherein the protective layer has a thickness of 5 nm to 70 nm, 5 nm to 30 nm, 30 to 70 nm, or 10 nm to 30 nm.

[0182] Clause 90: The method of any one of clauses 71 or 74-89, wherein the base layer has a thickness of 30 nm to 110 nm, 30 nm to 80 nm, or 70 nm to 110 nm.

[0183] Clause 91: An insulating glass unit comprising: a first ply having a No. 1 surface and a No. 2 surface opposite the No. 1 surface; and a second ply having a No. 3 surface and a No. 4 surface opposite the No. 3 surface, the second ply being spaced apart from the first ply, the first ply and the second ply being connected to each other; a coating on at least a portion of the No. 2 surface or the No. 3 surface, the coating comprising: a dielectric layer on the substrate; a metal functional layer; and a protective layer on the metal functional layer; the metal functional layer being selected from the group consisting of a silicon-aluminum alloy, a silicon-cobalt alloy, a niobium-tungsten alloy, and a titanium-tungsten alloy, or a metal alloy selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, an oxide, a metal oxide selected from the group consisting of cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide; a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride; or a metal oxynitride selected from the group consisting of cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride; or molybdenum.

[0184] Clause 92: An insulating glass unit according to clause 91, wherein a metal functional layer is present on the dielectric layer, the metal functional layer comprising silicon.

[0185] Clause 93: The insulated glass unit of clause 91 or 92, further comprising a second dielectric layer over the metal functional layer, the protective layer being over the second dielectric layer.

[0186] Clause 94: The insulated glass unit of any one of clauses 91-93, further comprising a base layer over the dielectric layer, the metal functional layer being over the base layer.

[0187] Clause 95: An insulating glass unit according to clause 91, wherein a dielectric layer is present on the metal functional layer, a protective layer is present on the dielectric layer, and the metal functional layer comprises cobalt.

[0188] Clause 96: An insulating glass unit according to clause 91 or 93, wherein a dielectric layer is present on the protective layer and the metal functional layer comprises silicon.

[0189] Clause 97: The insulated glass unit of any one of clauses 91-96, wherein the metal functional layer comprises less than 90 wt% of a magnetic metal.

[0190] Clause 98: The insulating glass unit of any one of clauses 91 to 97, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm, 20 nm to 60 nm, 30 nm to 45 nm, or 20 nm to 30 nm.

[0191] Clause 99: The insulated glass unit of any one of clauses 91, 93-95, 97, or 98, wherein the metal functional layer comprises 60 wt% to 100 wt% cobalt, 60 wt% to 90 wt% cobalt, or 58 wt% to 70 wt% cobalt.

[0192] Clause 100: The insulated glass unit of any one of clauses 91, 93-95, or 97-99, wherein the metal functional layer comprises cobalt chromium oxide.

[0193] Clause 101: The insulated glass unit of any one of clauses 91, 93-95, or 97-100, wherein the metal functional layer comprises 60 wt% to 100 wt% cobalt and 0 wt% to 40 wt% chromium, 60 wt% to 90 wt% cobalt and 10 wt% to 40 wt% chromium, or 70 wt% to 88 wt% cobalt and 12 wt% to 30 wt% chromium.

[0194] Clause 102: The insulated glass unit of any one of clauses 91-94 or 96-98, wherein the metal functional layer comprises 60 wt% to 99 wt% silicon.

[0195] Clause 103: The insulated glass unit of any one of clauses 91-98 or 102, wherein the metal functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

[0196] Clause 104: The insulated glass unit of any one of clauses 91-94, 96-98, 102, or 103, wherein the metal functional layer comprises 70 wt% to 100 wt% silicon and 0 wt% to 30 wt% aluminum, 80 wt% to 95 wt% silicon and 5 wt% to 20 wt% aluminum, or 85 wt% to 95 wt% silicon and 5 wt% to 15 wt% aluminum.

[0197] Clause 105: The insulated glass unit of any one of clauses 91-98, 111, or 112, wherein the metal functional layer comprises 30 wt% to 85 wt% silicon and 15 wt% to 70 wt% cobalt, or 50 wt% to 70 wt% silicon and 30 wt% to 50 wt% cobalt.

[0198] Clause 106: The insulated glass unit of any one of clauses 91-105, wherein the metal functional layer is essentially free, substantially free, or completely free of iron.

[0199] Clause 107: An insulated glass unit according to any one of clauses 91 to 106, wherein the dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silica, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0200] Clause 108: The insulated glass unit of any one of clauses 91 to 107, wherein the dielectric layer comprises silicon nitride or silicon aluminum nitride.

[0201] Clause 109: The insulating glass unit of any one of clauses 91 to 108, wherein the dielectric layer has a thickness of 5 nm to 140 nm, 80 nm to 120 nm, 100 nm to 140 nm, or 1 nm to 10 nm.

[0202] Clause 110: The insulated glass unit of any one of clauses 91-109, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or a mixture thereof.

[0203] Clause 111: An insulated glass unit according to any one of clauses 91 to 110, wherein the protective layer comprises at least one of titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or a mixture thereof.

[0204] Clause 112: The insulating glass unit of any one of clauses 91 to 111, wherein the protective layer has a thickness of 5 nm to 70 nm, 5 nm to 30 nm, 30 to 70 nm, or 10 nm to 30 nm.

[0205] Clause 113: The insulating glass unit of any one of clauses 94 or 97-112, wherein the base layer has a thickness of 30 nm to 110 nm, 30 nm to 80 nm, or 70 nm to 110 nm.

[0206] The following examples illustrate various embodiments of the present invention, although it should be understood that the invention is not limited to these particular embodiments. [Example]

[0207] Table 1 shows exemplary coated articles 1-4 of the present invention. The reported thicknesses are physical thicknesses in nanometers (nm). The substrate was 6 mm clear glass. Co was coated on the glass substrate. 80 Cr 20 (80wt% cobalt and 20wt% chromium) or Co 80 Cr 15 Cobalt chromium oxide (CoCrO) was prepared by MSVD using a (85 wt% cobalt and 15 wt% chromium) target. x A silicon nitride (SiN) layer was deposited on the cobalt chromium oxide layer. x) layer was optionally deposited. x ) was deposited on the outer protective layer. [Table 1]

[0208] Table 2 shows exemplary coated articles 5 through 7 of the present invention. The reported thicknesses are physical thicknesses in nm. The substrate was 6 mm clear glass. Si was deposited on the glass substrate. 95 A silicon aluminum metal alloy (SiAl) layer was deposited by MSVD using an Al5 alloy (95 wt% silicon and 5 wt% aluminum) target. On top of the SiAl layer, silicon aluminum oxide (SiAlO x ) was deposited on the outer protective layer. [Table 2]

[0209] Table 3 shows exemplary coated articles 8 to 13 of the present invention. The reported thicknesses are physical thicknesses in nm. The substrate was 6 mm clear glass. Si was coated on the glass substrate. 70 Co 30 A silicon-cobalt metal alloy (SiCo) layer was deposited by MSVD using an alloy (70 wt% silicon and 30 wt% cobalt) target. On top of the SiCo layer, silicon aluminum oxide (SiAlO x ) was deposited on the outer protective layer. [Table 3]

[0210] Table 4 shows exemplary coated articles 14-16 of the present invention. The reported thickness is the physical thickness in nm. The substrate was 6 mm clear glass. Silicon aluminum nitride (SiAlN) was deposited on the glass substrate. x) layer was optionally deposited on a glass substrate (Sample 14). x On top of the layer (sample 14), Si 70 Co 30 A silicon-cobalt metal alloy (SiCo) layer was deposited by MSVD using an alloy (70 wt% silicon and 30 wt% cobalt) target. On top of the SiCo layer, silicon aluminum oxide (SiAlO x ) layer was optionally deposited (Samples 14 and 15). x layer (sample 15), or on a SiCo layer (sample 16), x An optional SiAlN layer was deposited. x On top of the layer, another SiAlO x A layer was optionally deposited (Sample 16). [Table 4]

[0211] Table 5 shows exemplary coated articles 17-24 of the present invention. The reported thicknesses are physical thicknesses in nm. The substrate was 6 mm clear glass. A first silicon aluminum nitride (SiAlN) was deposited on the glass surface. x ) layer was deposited. x On the layer, Si 70 Co 30 A silicon-cobalt metal alloy (SiCo) layer was deposited by MSVD using an alloy (70 wt% silicon and 30 wt% cobalt) target. A second SiAlN layer was deposited on top of the SiCo layer. x A second SiAlN layer was deposited. x On top of the layer, an optional silicon aluminum oxide (SiAlO x ) was deposited as a protective layer. [Table 5]

[0212] <Spectral characteristics> Table 6 shows the spectral characteristics of Samples 1 to 4 in Table 1. "T" indicates transmission, "Rf" indicates film side or coating side reflection, and "Rg" indicates glass side reflection. [Table 6]

[0213] Table 7 shows the spectral characteristics of Samples 8 to 13 in Table 3. [Table 7]

[0214] Table 8 shows the spectral characteristics of Samples 14 to 16 in Table 4. [Table 8]

[0215] Table 9 shows the spectral characteristics of Samples 21 to 24 in Table 5. [Table 9]

[0216] <Durability characteristics> The CCC test results (60°C DI water chamber) of Samples 1 to 4 after heating are shown in Figures 9A to 9D. x The coatings without the CoCrO layer (Sample 1 and Sample 2) showed a color change (DECMCT, Rf) of more than 2 after 20 days. x The coatings with a thin SiNx layer between the coating and the protective layer (Sample 3 and Sample 4) showed a color change (DECMCT, Rf) of less than 1 after 50 days and passed the CCC test.

[0217] Samples 1-4 passed standard chemical durability tests, exhibiting less than 12% film loss after 30 minutes of immersion in 10N (27.5%) sulfuric acid at 52°C.

[0218] Passing CCC test results (after heating, 60°C DI water chamber) for Sample 7 are shown in Figures 10A and 10B. The film-side reflected color change (DECMC of Rf, Figure 10A) and transmitted color change (DECMC of T, Figure 10B) were less than 0.5 after 50 days. Sample 7 passed the standard chemical durability test.

[0219] Table 10 shows the CCC test results for Samples 8 to 13 (after heating, 60°C DI water chamber). The abbreviation "nd" means "not determined." [Table 10]

[0220] Table 11 shows the CCC test results for Samples 14 to 16. [Table 11]

[0221] The CCC test results (after heating, 60°C DI water chamber) for Samples 17-24 are shown in Figures 11A-11D. The coatings without a protective layer (Samples 17-20, Figures 11C and 11D) did not pass the CCC test. However, the coatings with a protective layer (Samples 21-24, Figures 11A and 11B) showed a film-side reflected color change (DECMC of Rf, Figure 11A) of less than 1 and a transmitted color change (DECMC of T, Figure 11B) of less than 0.5 after 50 days.

[0222] Those skilled in the art will readily appreciate 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 do not limit the scope of the invention, which is intended to encompass the full scope of the appended claims and all equivalents thereof.

Claims

1. A substrate; a metal functional layer on at least a portion of the substrate; 1. A coated article comprising: the metal functional layer is a metal alloy selected from the group consisting of silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy, and titanium tungsten alloy; or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide; or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride; or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride; or molybdenum; The coated article.

2. The coated article of claim 1 , wherein the metallic functional layer comprises less than 90 wt % of the magnetic metal.

3. The coated article of claim 1, wherein the metallic functional layer has a thickness in the range of 20 nm to 40 nm.

4. The coated article of claim 1 , wherein the metallic functional layer comprises 60 wt % to 100 wt % cobalt, and the metallic functional layer comprises cobalt chromium oxide.

5. The coated article of claim 1 , wherein the metallic functional layer comprises 60 wt % to 99 wt % silicon, and the metallic functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

6. The coated article of claim 1 , further comprising a protective layer over the metal functional layer, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or a mixture thereof.

7. The coated article of claim 6 , further comprising a base layer over the substrate and under the metal functional layer, the metal functional layer comprising silicon.

8. 10. The coated article of claim 1, further comprising at least one dielectric layer, the dielectric layer comprising one or more films selected from zinc tin oxide, zinc oxide, silica, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

9. A glass substrate; a coating on at least a portion of the substrate; and 1. A coated article comprising: a dielectric layer over the substrate; a metal functional layer; A protective layer on top of the metal functional layer Including, the metal functional layer is a metal alloy selected from the group consisting of silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy, and titanium tungsten alloy; or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide; or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride; or a metal oxynitride selected from the group consisting of cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride; or molybdenum; The coated article.

10. The coated article of claim 9 , wherein a metallic functional layer is present on the dielectric layer, the metallic functional layer comprising silicon.

11. The coated article of claim 10 further comprising a second dielectric layer over the metal functional layer, the protective layer being over the second dielectric layer.

12. The coated article of claim 10 further comprising a base layer over the dielectric layer, the metal functional layer being over the base layer.

13. 10. The coated article of claim 9, wherein a dielectric layer is present on the metallic functional layer, a protective layer is present on the dielectric layer, and the metallic functional layer comprises cobalt.

14. The coated article of claim 9 , wherein the dielectric layer is present on the protective layer and the metallic functional layer comprises silicon.

15. 1. A method for producing a coated article, the method comprising: providing a substrate; forming a metal functional layer on at least a portion of the substrate; Including, the metal functional layer comprises a metal alloy selected from the group consisting of silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy, and titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum; The metal functional layer is formed by a process including depositing a metal alloy, a metal oxide, a metal nitride, a metal oxynitride, or molybdenum by magnetron sputtering deposition; The above method.

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