Magnetron sputtering vapor deposition coating composition comprising light absorbing material

Abstract

A coated article includes a substrate and a metallic functional layer over at least a portion of the substrate. The metal functional layer contains a metal alloy, a metal oxide, a metal nitride, a metal nitrogen oxide, or molybdenum. Another coated article includes a glass substrate and a coating over at least a portion of the substrate. The coating comprises a dielectric layer, a metal functional layer and a protective layer. An insulating glass unit and a method of making a coated article are also provided.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 406,291 filed on September 14, 2022 and U.S. Patent Application No. 18 / 244,988 filed on September 12, 2023, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present invention generally relates to coated articles 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 methods of making the coated articles thereof. Background Art

[0004] Solar control coatings are known in the art of architectural and vehicle transparencies. These solar control coatings block or filter a selected range of electromagnetic radiation, such as in the solar infrared or solar ultraviolet radiation range, to reduce the amount of solar energy entering the vehicle or building. This reduction in solar energy transmission helps reduce the load on the cooling unit of the vehicle or building.

[0005] High temperature manufacturing process such as pyrolysis spraying process can allow sunlight control coating to be mechanically and chemically durable, so that coating can be used on the first surface of building glass window. However, coating may be rough, have poor film quality, and material quality and thickness can not be accurately controlled by this spraying technology. As an alternative, magnetron sputtering vapor deposition (MSVD) is an advanced technology with respect to material quality and thickness and composition uniformity. Typical MSVD coating is soft due to low temperature process, and does not have good durability. Therefore, it is desirable to provide a coating that can be deposited by MSVD, which has enhanced chemical and mechanical durability. Summary of the invention

[0006] The coated article of the present invention comprises a substrate and a metal functional layer on at least a portion of the substrate. The metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide and iron aluminum cobalt oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride and iron aluminum cobalt nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt oxynitride, chromium aluminum cobalt oxy ...oxynitride, or molybdenum.

[0007] Another coated article of the present invention comprises a glass substrate and a coating over at least a portion of the substrate. The coating comprises a dielectric layer over the substrate, a metal functional layer, and a protective layer over the metal functional layer. The metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy, and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide, and iron aluminum cobalt oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride, and iron aluminum cobalt nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt oxynitride, chromium aluminum cobalt oxy ...oxynitride, or molybdenum.

[0008] The present invention also relates to a method for preparing a coated article. The method includes providing a substrate and forming a metal functional layer over at least a portion of the substrate. The metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide and iron aluminum cobalt oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride and iron aluminum cobalt nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt nitride, chromium aluminum cobalt nitride and iron aluminum cobalt nitride, or molybdenum. The metal functional layer is formed by a process comprising depositing a metal alloy, a metal oxide, a metal nitride, a metal oxynitride or molybdenum by magnetron sputtering vapor deposition.

[0009] The present invention also relates to another method for making a coated article. The method includes providing a substrate and forming a coating over at least a portion of the substrate. The coating comprises a dielectric layer over the substrate, a metal functional layer, and a protective layer over the metal functional layer. The metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide and iron aluminum cobalt oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride and iron aluminum cobalt nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt nitride, chromium aluminum cobalt oxynitride and iron aluminum cobalt nitride, or molybdenum. The metal functional layer is formed by a process comprising depositing a metal alloy, a metal oxide, a metal nitride, a metal oxynitride or molybdenum by magnetron sputtering vapor deposition.

[0010] The present invention also relates to an insulating glass unit, comprising a first ply and a second ply, wherein the first ply comprises a surface No. 1 and a surface No. 2 opposite to the surface No. 1, and the second ply comprises a surface No. 3 and a surface No. 4 opposite to the surface No. 3. The second ply is separated from the first ply, and the first ply and the second ply are connected together. A coating is applied over at least a portion of surface No. 2 or surface No. 3, wherein the coating comprises: a dielectric layer over the substrate; a metal functional layer; and a protective layer over the metal functional layer; wherein the metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide, iron aluminum cobalt oxide and chromium iron zinc oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride, iron aluminum cobalt nitride and chromium iron zinc nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt oxynitride, chromium aluminum cobalt oxynitride, iron aluminum cobalt oxy ... molybdenum. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The present invention will be described with reference to the following drawings, wherein like reference numerals identify like parts throughout.

[0012] Figure 1A is a side view (not to scale) of an insulating glass unit (IGU) having a coating of the present invention.

[0013] Figure 1B is a cross-sectional view (not to scale) of an exemplary transparent member having a coating of the present invention.

[0014] Figure 2 is a side view (not to scale) of a coating incorporating features of the present invention.

[0015] Figure 3 is a side view (not to scale) of another coating incorporating features of the present invention.

[0016] Figure 4 is a side view (not to scale) of another coating incorporating features of the present invention.

[0017] Figure 5 is a side view (not to scale) of another coating incorporating features of the present invention.

[0018] Figure 6 is a side view (not to scale) of another coating incorporating features of the present invention.

[0019] Figure 7 is a side view (not to scale) of another coating incorporating features of the present invention.

[0020] Figure 8 is a side view (not to scale) of another coating incorporating features of the present invention.

[0021] Figures 9A-9D The results of the Cleveland condensation test are shown for coated articles of the present invention.

[0022] Fig. 10A and 10B The Cleveland Coagulation Test results for coated articles of the present invention are shown.

[0023] Figures 11A-11D The Cleveland Coagulation Test results for coated articles of the present invention are shown. DETAILED DESCRIPTION

[0024] As used herein, spatial or directional terms, such as "left", "right", "inside", "outside", "above", "below", etc., refer to the present invention as shown in the accompanying drawings. However, it should be understood that the present invention can take various alternative orientations, and therefore, these terms should not be considered restrictive. In addition, as used herein, all numbers used in the specification and claims to represent dimensions, physical properties, processing parameters, amounts of ingredients, reaction conditions, etc. should be understood to be modified by the term "about" in all cases. Therefore, the numerical values ​​set forth in the following specification and claims can vary according to the desired properties sought to be obtained by the present invention, unless otherwise indicated. At least, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be interpreted in accordance with the numerical value of the reported significant figures and by applying ordinary rounding techniques. In addition, all ranges disclosed herein should be understood to include starting and ending range values ​​and any and all sub-ranges contained therein. For example, a reference to a range of "1 to 10" should be considered to include any and all subranges between (and including) a minimum of 1 and a maximum of 10; that is, all subranges starting with a minimum of 1 or greater and ending with a maximum of 10 or less, such as 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. In addition, as used herein, the term "formed above," "deposited above," or "provided above" means formed on, deposited on, or provided on a surface but not necessarily in contact with the surface. For example, a coating "formed above" a substrate does not exclude the presence of one or more other coatings or films of the same or different composition between the formed coating and the substrate. As used herein, the term "polymer" or "polymerized" includes oligomers, homopolymers, copolymers, and terpolymers, such as polymers formed from two or more types of monomers or polymers. The term "visible region" or "visible light" refers to electromagnetic radiation with a wavelength in the range of 380 nm to 800 nm. The term "infrared region" or "infrared radiation" refers to electromagnetic radiation having a wavelength in the range of greater than 800 nm to 100,000 nm. The term "ultraviolet region" or "ultraviolet radiation" refers to electromagnetic energy with a wavelength in the range of 300 nm to less than 380 nm. In addition, all documents cited herein, such as but not limited to granted patents and patent applications, should be considered to be "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" may include one or more "films", and a "coating" or "coating stack" may include one or more "layers". The terms "metal" and "metal oxide" include silicon and silicon dioxide, respectively, as well as traditionally recognized metals and metal oxides, even though silicon may not be conventionally considered a metal. Unless otherwise indicated, thickness values ​​are geometric thickness values.

[0025] The discussion of the present invention may describe certain features as being "particularly" or "preferably" within certain limitations (e.g., "preferably", "more preferably" or "most preferably" within certain limitations). It should be understood that the present invention is not limited to these specific or preferred limitations, but encompasses the entire scope of the disclosure.

[0026] As used herein, the 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 does not include the weight of any oxide, nitride, or oxynitride component. One of ordinary skill in the art will readily appreciate that, as used herein, the weight percent of a metal functional layer refers to the weight percent of a metal target used to deposit the metal functional layer.

[0027] 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, such as, but not limited to, the amount of solar radiation, such as visible light, infrared light, or ultraviolet radiation, reflected from, absorbed by, or transmitted through the coated article; shading factor; emissivity, etc. Solar control coatings may block, absorb, or filter selected portions of the solar spectrum, such as, but not limited to, the IR, UV, and / or visible spectrum.

[0028] The present invention relates to a coated article. The coated article comprises a substrate. The substrate comprises a metal functional layer over at least a portion of the substrate. The metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide and iron aluminum cobalt oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride and iron aluminum cobalt nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt nitride, chromium aluminum cobalt nitride and iron aluminum cobalt nitride, or molybdenum. Optionally, the coated article may also have a protective layer, a base layer or a dielectric layer. For example, the coated article comprises a substrate coated with a coating, wherein the coating comprises a dielectric layer, a metal functional layer, a protective layer and an optional second dielectric layer and / or a base layer.

[0029] The coated article 10 includes a substrate 12. The substrate 12 can be any desired material having any desired properties, such as being transparent, opaque, or translucent to visible light. For example, the substrate 12 can be transparent or translucent to visible light. "Transparent" means having a visible light transmittance of greater than 0% to 100%. Alternatively, the substrate 12 can be translucent. "Translucent" means allowing electromagnetic energy (e.g., visible light) to pass through but diffusing the energy so that objects on the side opposite to the observer are not clearly visible. Examples of suitable materials include, but are not limited to, plastic substrates (e.g., acrylic polymers, such as polyacrylates; polyalkyl methacrylates, such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, etc.; polyurethanes; polycarbonates; polyalkyl terephthalates, such as polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, etc.; polymers containing polysiloxanes; or copolymers of any monomers used to prepare these, or any mixtures thereof); ceramic substrates; glass substrates; or mixtures or combinations of any of the above. For example, substrate 12 can be conventional soda-lime silicate glass, borosilicate glass, or leaded glass. The glass can be clear glass. "Clear glass" refers to non-tinted or non-colored glass. Alternatively, the glass can be tinted or other colored glass. The glass can be annealed or heat-treated glass. As used herein, the term "heat-treated" refers to tempered or at least partially tempered. The glass may be of any type, such as conventional float glass, and may be of any composition having any optical properties, such as any values ​​of visible light transmittance, ultraviolet transmittance, infrared transmittance, and / or total solar energy transmittance. "Float glass" refers to glass formed by a conventional float process in which molten glass is deposited onto a molten metal bath and controllably cooled to form a float glass ribbon. Examples of float glass processes are disclosed in U.S. Patents 4,466,562 and 4,671,155.

[0030] The substrate 12 can be, for example, a transparent float glass, or can be a tinted or colored glass. The substrate 12 can have any desired size, such as length, width, shape or thickness. In an exemplary automotive transparent part, the substrate 12 can be 1 mm to 10 mm thick, such as 1 mm to 8 mm thick, such as 2 mm to 8 mm, such as 3 mm to 7 mm, such as 5 mm to 7 mm, such as 4 mm to 6 mm thick. In a non-limiting embodiment in which the substrate 12 is an architectural transparent part, the substrate 12 can be 1 mm to 30 mm thick, such as 2.5 mm to 25 mm thick, such as 2.5 mm to 10 mm thick.

[0031] Non-limiting examples of glass 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®, all of which are commercially available from PPG Industries of Pittsburgh, Pennsylvania.

[0032] In some embodiments, substrate 12 can be a monolithic glazing. "Monolithic" means having a single structural support or structural member, such as having a single substrate.

[0033] The coated article 10 has a metallic functional layer 60 deposited over at least a portion of a major surface of a substrate 12. The metallic functional layer 60 provides (a) reflection of electromagnetic radiation in at least a portion of the infrared radiation region of the electromagnetic spectrum, such as in the solar infrared radiation region and / or the thermal infrared radiation region of the electromagnetic spectrum, and / or (b) absorption of electromagnetic radiation in at least a portion of one or more regions of the electromagnetic spectrum, such as in the visible radiation region and / or the infrared radiation region and / or the ultraviolet radiation region of the electromagnetic spectrum.

[0034] The metal functional layer 60 may include a metal alloy, such as but not limited to a metal alloy including silicon and / or cobalt, or a metal alloy including 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 may include a metal oxide or a metal suboxide, such as but not limited to a metal oxide including cobalt. Non-limiting examples of suitable metal oxides for the metal functional layer 60 include iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide, and iron aluminum cobalt oxide.

[0035] Alternatively, the metal functional layer 60 may include a metal nitride or a metal sub-nitride, such as, but not limited to, a metal nitride including cobalt. Non-limiting examples of suitable metal nitrides for the metal functional layer 60 include iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride, and iron aluminum cobalt nitride.

[0036] Alternatively, the metal functional layer 60 may include a metal oxynitride, such as, but not limited to, a metal oxynitride including cobalt. Non-limiting examples of suitable metal oxynitrides for the metal functional layer 60 include iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt oxynitride, chromium aluminum cobalt oxynitride, and iron aluminum cobalt oxynitride.

[0037] Alternatively, the metallic functional layer 60 may include a metal, such as molybdenum.

[0038] The metal functional layer 60 may include a material having non-magnetic properties. For example, the metal alloy or metal oxide used for the metal functional layer 60 may include less than 90% by weight of magnetic material, such as less than 87% by weight of magnetic material, based on the total weight of the metal component. As used herein, the term "magnetic material" refers to a material that generates a magnetic field, and includes metals such as iron, cobalt and nickel, as well as rare earth metals. The metal alloy, metal oxide, metal nitride, metal oxynitride or molybdenum used for the metal functional layer 60 may include less than 90% by weight of magnetic metal, such as less than 87% by weight of magnetic metal, based on the total weight of the metal component.

[0039] In an exemplary embodiment, the metallic functional layer 60 includes cobalt. For example, the metallic functional layer 60 may include a metal alloy, a metal oxide, a metal nitride, or a metal oxynitride including cobalt in a range of 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 %, based on the total weight of the metal component. In one non-limiting embodiment, the metallic functional layer 60 comprises chromium cobalt oxide comprising 60 wt % to 100 wt % cobalt and / or 0 wt % to 40 wt % chromium, 60 wt % to 90 wt % cobalt and 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.

[0040] In some embodiments, the metallic functional layer 60 may be substantially free of iron, may be substantially free of iron, or may be completely free of iron. As used herein, the term "substantially free" means that the metallic functional layer contains less than 1 wt % iron, "substantially free" means that the metallic functional layer contains less than 0.1 wt % iron, and "completely free" means less than 0.01 wt % iron.

[0041] In another exemplary embodiment, the metal functional layer 60 comprises silicon. For example, the metal functional layer 60 may comprise a metal alloy, a metal oxide, a metal nitride, or a metal oxynitride, which comprises silicon in the range of 50% to 99% by weight, 60% to 99% by weight, 75% to 99% by weight, 80% to 99% by weight, 85% to 99% by weight, or 90% to 99% by weight. In a non-limiting embodiment, the metal functional layer 60 comprises a silicon aluminum alloy, which comprises 70% to 100% by weight of silicon and 0% to 30% by weight of aluminum, such as 80% to 95% by weight of silicon and 5% to 20% by weight of aluminum; such as 85% to 99% by weight of silicon and 1% to 15% by weight of aluminum, such as 85% to 95% by weight of silicon and 5% to 15% by weight of aluminum, or 90% to 95% by weight of silicon and 5% to 10% by weight of aluminum.

[0042] In another exemplary embodiment, the metallic functional layer comprises silicon and cobalt. For example, the metallic functional layer 60 may comprise a metal alloy, a metal oxide, a metal nitride, or a metal oxynitride comprising silicon in a range of 30 wt % to 85 wt % and cobalt in a range of 15 wt % to 70 wt %, such as from 50 wt % to 90 wt % silicon and from 10 wt % to 50 wt % cobalt, such as from 50 wt % to 70 wt % silicon and from 30 wt % to 50 wt % cobalt, such as from 65 wt % to 75 wt % silicon and from 25 wt % to 35 wt % cobalt.

[0043] The metallic functional layer 60 may have any desired thickness, for example 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.

[0044] The coated article 10 may include a protective layer 80, for example Figure 2In the non-limiting embodiment shown, it is deposited over the metallic functional layer 60 to help protect underlying layers, such as the metallic 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 to prevent or reduce the ingress of ambient oxygen into the 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 an exemplary embodiment, the protective layer 80 can include a layer having one or more metal oxide materials, such as, but not limited to, oxides of aluminum, silicon, or mixtures thereof. For example, the protective coating 80 can be a single coating that includes 0 wt% to 100 wt% aluminum oxide and / or 100 wt% to 0 % silica, for example 5 wt % to 95 (e.g. 45) 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 and 50 wt % to 30 wt % silica, for example 35 wt % to 100 wt % Aluminum oxide and 65 wt % to 0 wt % silicon dioxide, such as 70 wt % to 90 wt % aluminum oxide and 30 wt % to 10 wt % silicon dioxide, such as 75 wt % to 85 wt % aluminum oxide and 25 wt % to 15 wt % silicon dioxide, such as 88 wt % aluminum oxide and 12 wt % silicon dioxide, such as 65 wt % to 75 wt % aluminum oxide and 35 wt % to 25 wt % silicon dioxide, such as 70 wt % aluminum oxide and 30 wt % silicon dioxide, such as 60 wt % to less than 75 wt % aluminum oxide and greater than 25 wt % to 40 wt % silicon dioxide. Other materials may also be present, such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium and / or oxides thereof, in order to adjust the refractive index of the protective layer 80, 92. In a non-limiting embodiment, the refractive index of the protective layer 80, 92 may be in the range of 1 to 3, such as 1 to 2, such as 1.4 to 2, such as 1.4 to 1.8.

[0045] In one non-limiting embodiment, the protective layer 80 is a combined coating of silicon dioxide and aluminum oxide. The protective coating 80 can be sputtered from two cathodes (e.g., one silicon and one aluminum) or from a single cathode containing both silicon and aluminum. The silicon / aluminum oxide protective layer 80 can be written as Si x Al 1-x O (1.5+x) / 2 , where x can vary from greater than 0 to less than 1.

[0046] In another non-limiting embodiment, protective layer 80 comprises a combination of titanium dioxide and aluminum oxide.

[0047] In one non-limiting embodiment, the protective layer 80 may include silicon oxide (SiO x ), silicon nitride (Si 3 N 4 or SiN x ), silicon oxynitride (SiO x N y ), silicon alumina (SiAlO x ), Silicon Aluminum Nitride (SiAlN x ), silicon aluminum oxynitride (SiAlO x N y ), mixtures thereof and / or alloys thereof, and which can provide increased durability for the metal functional layer 60. The protective layer 80 can be formed of silicon nitride deposited with other materials having superior electrical conductivity to improve the sputtering of silicon. For example, during deposition, the silicon cathode may include a small amount (e.g., up to 20 weight %, up to 15 weight %, up to 10 weight % or up to 5 weight %) of aluminum to improve sputtering. In this case, the resulting silicon nitride protective layer will include a small percentage of aluminum, such as up to 15 weight % aluminum, such as up to 10 weight % aluminum, such as up to 5 weight % aluminum. The coating deposited from a silicon cathode having up to 10 weight % aluminum (added to enhance the conductivity of the cathode) is referred to herein as a "silicon nitride" layer, even though a small amount of aluminum may be present. A small amount of aluminum in the cathode (e.g., less than or equal to 15 weight %, such as less than or equal to 10 weight %, such as less than or equal to 5 weight %) is believed to form aluminum nitride in the protective layer 80 that is primarily silicon nitride. The protective layer 80 may be formed in a nitrogen atmosphere; however, it should be understood that other gases, such as oxygen, may be present in the atmosphere during deposition of the protective layer 80 .

[0048] The protective layer 80 may have any desired thickness. The protective layer 80 may 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, 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. In addition, the protective layer 80 may have a non-uniform thickness. "Non-uniform thickness" means that the thickness of the protective layer 80 may vary on a given unit area, for example, the protective layer 80 may have high points or areas and low points or areas.

[0049] In another non-limiting embodiment, the protective layer 80 can be a multilayer coating, which includes a first film and a second film formed above the first film. The first film can include aluminum oxide, silicon dioxide, titanium dioxide, zirconium oxide, tin oxide or a mixture thereof. In a specific non-limiting embodiment, the first film can include aluminum oxide or a mixture or alloy containing aluminum oxide and silicon dioxide. For example, the first film can include a silicon dioxide / aluminum oxide mixture, the mixture has more than 5% by weight of aluminum oxide, such as more than 10% by weight of aluminum oxide, such as more than 15% by weight of aluminum oxide, such as more than 30% by weight of aluminum oxide, such as more than 40% by weight of aluminum oxide, such as 50% to 70% by weight of aluminum oxide, such as 60% to 100% by weight of aluminum oxide and 0% to 40% by weight of silicon dioxide, such as 60% by weight of aluminum oxide and 40% by weight of silicon dioxide. In another example, the first layer can include zinc stannate. In another example, the first film can include zirconium oxide. In a non-limiting embodiment, the first film can have a thickness in a range from greater than 0 nm to 1000 nm, such as 10 nm to 25 nm, such as 10.1 nm to 25 nm, such as 15 nm to 20 nm, such as 16 nm.

[0050] The second film of the protective layer 80 may include, for example, a metal oxide or a metal nitride. The second film may be titanium dioxide, aluminum oxide, silicon dioxide, zirconium oxide, tin oxide, a mixture thereof, or an alloy thereof. For example, the second film may include a mixture of titanium dioxide and aluminum oxide; a mixture of titanium dioxide and silicon dioxide; or zirconium oxide. An example of the second film may include a titanium dioxide / aluminum oxide mixture having 40 wt % to 60 wt % aluminum oxide and 40 wt % to 60 wt % titanium dioxide; 45 wt % to 55 wt % aluminum oxide and 45 wt % to 55 wt % titanium dioxide; 48 wt % to 52 wt % aluminum oxide and 48 wt % to 52 wt % titanium dioxide; 49 wt % to 51 wt % aluminum oxide and 49 wt % to 51 wt % titanium dioxide; or 50 wt % aluminum oxide and 50 wt % titanium dioxide. An example of the second film may include titanium alumina (TiAlO). Another example of the second film is a silica / alumina mixture having greater than 40 wt% silica, such as greater than 50 wt% silica, such as greater than 60 wt% silica, such as greater than 70 wt% silica, such as greater than 80 wt% silica, such as 80 wt% to 90 wt% (such as 45%) silica and 10 wt% to 20 wt% alumina, such as 85 wt% silica and 15 wt% alumina. In a non-limiting embodiment, the thickness of the second film may be 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, such as 22 nm. Non-limiting examples of suitable protective layers are described in, for example, U.S. Patent Application Publications 2004 / 0106017A1; 2002 / 0172775A1; 2003 / 0228484A1; 2004 / 0023080A1; 2004 / 0023038A1; and 2003 / 0228476A1.

[0051] In a non-limiting example, the protective layer 80 may include an additional third film formed above the second film. The third film may be a film of any material used to form the first film or the second film. The third film may, for example, contain aluminum oxide, silicon dioxide, titanium dioxide, zirconium oxide, tin oxide, or a mixture thereof. For example, the third film may contain a mixture of silicon dioxide and aluminum oxide. In another example, the third film contains zirconium oxide.

[0052] In one non-limiting embodiment, the coated article 10 may optionally include a base layer 50, such as Figure 3As shown, it is deposited above the substrate 12 and below the metal functional layer 60. The base layer 50 can provide various performance advantages to the coating 30, such as acting as a sodium ion barrier between the substrate 12 and the overlying coating. 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 include tin oxide (SnO x ), silicon oxide (SiO x ), silicon nitride (Si 3 N 4 or SiN x ), silicon oxynitride (SiO x N x ), silicon alumina (SiAlO x ), Silicon Aluminum Nitride (SiAlN x ), silicon aluminum oxynitride (SiAlO x N x ), mixtures thereof and / or alloys thereof. The base layer 50 may be a multilayer coating comprising a first film and a second film formed on the first film. In a non-limiting embodiment, the base layer optionally comprises one or more films, each of which comprises SnO x 、SiO x 、Si 3 N 4 、SiO x N x 、SiAlO x 、SiAlN x or SiAlO x N x For example, the base layer may optionally include two films, each of which includes SiAlO x or SiAlN x .

[0053] In a non-limiting embodiment, the base layer 50 may optionally include a metal nitride such as Si 3 N 4 and / or a film of SiAlN disposed above and in contact with a metal oxynitride film such as SiAlON. Additionally or alternatively, examples of metal oxynitride films may also include alloys and / or mixtures of metal nitrides.

[0054] The optional base layer 50 can have any desired thickness. The base layer 50 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.

[0055] In one non-limiting embodiment, the coated article 10 may include at least one dielectric layer. Figure 4 , 5 As shown in FIG. 6 , a dielectric layer 40 is deposited above the substrate 12 and below the metal functional layer 60. Figure 4 and 5 As shown, dielectric layer 40 is deposited over substrate 12 and below metal functional layer 60. In another embodiment, coated article 10 may include dielectric layer 40 ( Figure 6 ).

[0056] Alternatively, the coated article 10 may include a dielectric layer 70 deposited above the metallic functional layer 60 and below the protective layer 80 ( Figure 7 In another non-limiting embodiment, the dielectric layer 70 is above the protective layer 80 and is the outermost layer ( Figure 8 ).

[0057] The dielectric layer(s) 40, 70 may be a single layer, or may include more than one film of anti-reflective material and / or dielectric material, such as, but not limited to, metal oxides, oxides of metal alloys, metal nitrides, metal oxynitrides, or mixtures thereof. The dielectric layer(s) 40, 70 may be transparent to visible light. Examples of suitable metal oxides for the dielectric layer(s) 40, 70 include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, and mixtures thereof. These metal oxides may have small amounts of other materials, such as manganese in bismuth oxide, tin in indium oxide, and the like. 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. In addition, doped metal oxides may be used, such as antimony or indium doped tin oxides or nickel or boron doped silicon oxides. The dielectric layer(s) 40, 70 may be a substantially single phase film, such as a metal oxide film, such as zinc stannate, or may be a mixture of phases consisting of zinc and tin oxides, or may consist of a plurality of films. For example, the dielectric layer(s) may comprise one or more films selected from zinc tin oxide, zinc oxide, silicon dioxide, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0058] The dielectric layer(s) 40, 70 (whether single or multi-layer) may 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.

[0059] The coated article 10 may include more than one dielectric layer. Each dielectric layer may include the same or different material as the other dielectric layers in the coated article and have the same or different thickness as the other dielectric layers in the coated article. For example, the coated article 10 may include at least two dielectric layers. In one non-limiting embodiment, the coated article may have a first dielectric layer 40 above the substrate 12 and below the metallic functional layer 60, and a second dielectric layer 70 above the metallic functional layer 60 and below the protective layer 80, such as Figure 5 shown.

[0060] In a non-limiting embodiment, the coated article 10 may optionally include a primer layer above the metal functional layer 60. The primer layer may be a monofilm or a multifilm layer. The primer layer may include an oxygen capture material, which may be sacrificial during deposition to prevent degradation or oxidation of the metal functional layer 60 during sputtering or subsequent heating. The primer layer may also absorb at least a portion of the electromagnetic radiation, such as visible light, that passes through the coating 30. Examples of materials that may be used for the primer layer include titanium, silicon, silicon dioxide, silicon nitride, silicon oxynitride, nickel, zirconium, aluminum, cobalt, chromium, titanium, aluminum, its alloy or its mixture. In a 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 titanium, or titanium and aluminum, or zinc and aluminum are 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®.

[0061] The thickness of the primer layer may be 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.

[0062] The present invention also relates to a coated article comprising a glass substrate and a coating over at least a portion of the substrate. The coating comprises a dielectric layer over the substrate, a metal functional layer, and a protective layer over the metal functional layer. The metal functional layer comprises a metal alloy selected from a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, or a titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide, iron aluminum cobalt oxide, and chromium iron zinc oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride, iron aluminum cobalt nitride, and chromium iron zinc nitride, or a metal nitride selected from cobalt oxide nitride, iron cobalt oxide nitride, chromium cobalt oxide nitride, chromium iron cobalt oxide nitride, copper cobalt oxide nitride, chromium aluminum cobalt oxide nitride, iron aluminum cobalt oxide nitride, and chromium iron zinc nitride, or a metal nitride selected from cobalt oxide nitride, iron cobalt oxide nitride, chromium cobalt oxide nitride, chromium iron cobalt oxide nitride, copper cobalt oxide nitride, chromium aluminum cobalt oxide nitride, iron aluminum cobalt oxide nitride, and chromium iron zinc oxide nitride, or molybdenum. The dielectric layer, the metal functional layer, and the protective layer of the coating can be any layer previously described herein. Optionally, the coating further comprises a second dielectric layer, a primer layer and / or a base layer. The optional second dielectric layer, the optional primer layer and the optional base layer of the coating are any layers previously described herein.

[0063] Figure 2 An exemplary non-limiting coated article 10 of the present invention is shown. The coated article 10 includes a metallic functional layer 60 deposited over and optionally in direct contact with a substrate 12. The coated article 10 also includes a protective layer 80 deposited over and optionally in direct contact with the metallic functional layer 60. The metallic functional layer 60 and the protective layer 80 constitute a coating 30 over and optionally in direct contact with at least a portion of the substrate 12. The substrate 12 can be glass.

[0064] Figure 3 Another exemplary non-limiting coated article 10 of the present invention is shown. The coated article 10 includes a base layer 50 deposited over and optionally in direct contact with a substrate 12. The coated article 10 also includes a metallic functional layer 60 deposited over and optionally in direct contact with the base layer 50. The coated article 10 also includes an outermost protective layer 80 deposited over and optionally in direct contact with the metallic functional layer 60. The base layer 50, the metallic functional layer 60, and the protective layer 80 constitute a coating 30 over and optionally in direct contact with at least a portion of the substrate 12. The substrate 12 can be glass.

[0065] Figure 4Another exemplary non-limiting coated article 10 of the present invention is shown. The coated article 10 includes a dielectric layer 40 deposited over and optionally in direct contact with at least a portion of a substrate 12. The coated article 10 also includes a metallic functional layer 60 deposited over and optionally in direct contact with the dielectric layer 40. The coated article 10 also includes a protective layer 80 deposited over and optionally in direct contact with the metallic functional layer 60. The dielectric layer 40, the metallic functional layer 60, and the protective layer 80 constitute a coating 30 over and optionally in direct contact with at least a portion of the substrate 12. The substrate 12 can be glass.

[0066] Figure 5 Another exemplary non-limiting coated article 10 of the present invention is shown. The coated article 10 includes a first dielectric layer 40 deposited over and optionally in direct contact with at least a portion of a substrate 12. The coated article 10 also includes a metallic functional layer 60 deposited over and optionally in direct contact with the dielectric layer 40. The coated article 10 also includes a second dielectric layer 70 deposited over and optionally in direct contact with the metallic functional layer 60. The coated article 10 also includes a protective layer 80 deposited over and optionally in direct contact with the second dielectric layer 70. The first dielectric layer 40, the metallic functional layer 60, the second dielectric layer 70, and the protective layer 80 constitute a coating 30 located over and optionally in direct contact with at least a portion of the substrate 12. The substrate 12 can be glass.

[0067] Figure 6 Another exemplary non-limiting coated article 10 of the present invention is shown. The coated article 10 includes a first dielectric layer 40 deposited over and optionally in direct contact with at least a portion of a substrate 12. The coated article 10 also includes a base layer 50 deposited over and optionally in direct contact with the dielectric layer 40. The coated article 10 also includes a metallic functional layer 60 deposited over and optionally in direct contact with the base layer 50. The coated article 10 also includes a protective layer 80 deposited over and optionally in direct contact with the metallic functional layer 60. The dielectric layer 40, the base layer 50, the metallic functional layer 60, and the protective layer 80 constitute a coating 30 deposited over and optionally in direct contact with at least a portion of the substrate 12. The substrate 12 can be glass.

[0068] Figure 7 Another exemplary non-limiting coated article 10 of the present invention is shown. The coated article 10 includes a metallic functional layer 60 deposited over and optionally in direct contact with a substrate 12. The coated article 10 also includes a dielectric layer 70 deposited over and optionally in direct contact with the metallic functional layer 60. The coated article 10 also includes a protective layer 80 deposited over and optionally in direct contact with the dielectric layer 70. The metallic functional layer, the dielectric layer, and the protective layer constitute a coating 30 deposited over and optionally in direct contact with at least a portion of the substrate 12. The substrate 12 can be glass.

[0069] Figure 8 Another exemplary non-limiting coated article 10 of the present invention is shown. The coated article 10 includes a metallic functional layer 60 deposited over and optionally in direct contact with a substrate 12. The coated article 10 also includes a protective layer 80 deposited over and optionally in direct contact with the metallic functional layer 60. The coated article 10 also includes a dielectric layer 70 deposited over and optionally in direct contact with the protective layer 80. The metallic functional layer 60, the protective layer 80, and the dielectric layer 70 constitute a coating 30 deposited over and optionally in direct contact with at least a portion of the substrate 12. The substrate 12 can be glass.

[0070] (One or more) dielectric layer 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) method. The example of CVD method includes spray pyrolysis. The example of PVD method includes electron beam evaporation and vacuum sputtering (such as magnetron sputtering vapor deposition (MSVD)). Other coating methods can also be used, such as but not limited to sol-gel deposition. In a non-limiting embodiment, the layer of coating 30 can be deposited by MSVD. Examples of MSVD coating apparatus and methods are well understood by those of ordinary skill in the art and are described, for example, in U.S. Patents 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 a magnetron sputtering target to deposit the metallic functional layer 60.

[0071] The coating 30 of the present invention can provide desired physical properties, including but not limited to durability, such as moisture resistance and chemical resistance, to the coated article 10. In some non-limiting embodiments, it is found that the presence of (one or more) dielectric layers 40, 70 and / or protective layer 80 enhances the durability of the coating.

[0072] In one non-limiting implementation of the present invention, the coated article 10 passes a conventional Cleveland condensation test (CCC test), as measured in a Cleveland condensation chamber (QCT condensation tester, commercially available from Q-Panel, Inc., Cleveland, Ohio) with a deionized (DI) water chamber at about 60 degrees Celsius (° C.). In some embodiments, the coated article 10 with the dielectric layer(s) 40, 70 passes the CCC test, as compared to the coated article without the dielectric layer(s) 40, 70. In one non-limiting embodiment, the coated article 10 has a transmission chromatic aberration (DECMC, T) of less than 10, such as less than 7, less than 5, less than 1, or less than 0.5 after 50 days. In one non-limiting embodiment, the coated article 10 has a film-side reflection chromatic aberration (DECMC, Rf) of less than 20, such as less than 15, or less than 10, less than 5, less than 1, or less than 0.5 after 50 days. In one non-limiting embodiment, the coated article 10 has a glass side reflection ellipsometric difference (DECMC, Rg) of less than 18, such as less than 15, or less than 13 after 50 days.

[0073] In one non-limiting implementation of the present invention, the film loss of the coated article 10 after immersion in 10N (27.5%) sulfuric acid at 52° C. for 30 minutes can be less than 12%, such as less than 10% (standard chemical durability test). In some embodiments, the coated article 10 including the dielectric layer(s) 40, 70 passes the standard chemical durability test compared to the coated article without the dielectric layer(s) 40, 70.

[0074] The materials used for the coating (e.g., the metallic functional layer 60) can be selected to obtain the desired color characteristics of the coated article 10. The coating 30 can be substantially composed of the materials described herein to obtain the desired color characteristics of the coating. For example, the coating 30 substantially composed of the materials described herein may include additional materials, provided that the color characteristics of the coating are not affected. The color coordinates a*, b*, and L* are color coordinates of the traditional CIE (1931) and CIELAB systems understood by those of ordinary skill in the art.

[0075] In one non-limiting implementation of the present invention, the coated article 10 has a transmittance L* in the range of 55 to 75. For example, in the range of 60 to 75, 59 to 70, 67 to 73, or 70 to 75.

[0076] In one non-limiting implementation of the present invention, the coated article 10 has a transmittance (T) a* in the range of 0.0 to 3.5, such as in the range of 0.0 to 3.0, 0.5 to 3.0, or 0.8 to 3.0.

[0077] In one non-limiting implementation of the present invention, the coated article 10 has a transmittance (T) b* in the range of 6.5 to 11.5, such as in the range of 6.5 to 11.0, 7.0 to 11.0, or 7.5 to 11.0.

[0078] In one non-limiting implementation of the present invention, the coated article 10 has a visible light transmittance (LTA) in the range of 20 to 50. For example, in the range of 25 to 50, 30 to 40, 38 to 48, or 42 to 47.

[0079] In one non-limiting implementation of the present invention, the coated article 10 has a film side reflectance (Rf) L* in the range of 35 to 70. For example, in the range of 35 to 65, 40 to 65, 40 to 55, or 60 to 65.

[0080] In one non-limiting implementation of the present invention, the coated article 10 has an Rf a* in the range of -5.0 to -1.0, such as in the range of -5.0 to -2.0 or -5.0 to -3.0.

[0081] In one non-limiting implementation of the present invention, the coated article 10 has an Rf b* in the range of -3.5 to 7.5, such as in the range of -3.0 to 7.5, -3.0 to 5.0, 0.0 to 7.5, or 1.0 to 7.0.

[0082] In one non-limiting implementation of the invention, the coated article 10 has a glass side reflection (Rg) L* in the range of 40 to 65. For example, in the range of 40 to 60, 45 to 60, 50 to 65, 50 to 60, 55 to 65, or 55 to 60.

[0083] In one non-limiting implementation of the invention, the coated article 10 has an Rg a* in the range of -7.5 to -4.0, such as -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.

[0084] In one non-limiting implementation of the invention, the coated article 10 has an Rg b* in the range of -11.0 to 4.0, such as -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.

[0085] Certain embodiments of the present invention are particularly useful in solar control coatings for architectural and automotive transparencies.

[0086] The present invention also relates to a method for preparing a coated article. A substrate is provided. A metal functional layer is formed over at least a portion of the substrate, wherein the metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide and iron aluminum cobalt oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride and iron aluminum cobalt nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt nitride, chromium aluminum cobalt nitride and iron aluminum cobalt nitride, or molybdenum. The metal functional layer is formed by a process comprising depositing a metal alloy, a metal oxide, a metal nitride, a metal nitride or molybdenum by magnetron sputtering vapor deposition. The method may also optionally further include forming a protective layer. The protective layer may be any protective layer described herein. The method may also optionally further include forming at least one dielectric layer. The at least one dielectric layer can be any of the dielectric layers described herein. The method can also optionally further include forming a base layer. The optional base layer can be any optional base layer described herein. The method can also optionally further include forming a primer layer. The optional primer layer can be any primer layer described herein.

[0087] The present invention also relates to a method for preparing a coated article, wherein a substrate is provided and a coating is formed over at least a portion of the substrate. The coating comprises a dielectric layer over the substrate, a metal functional layer, and a protective layer over the metal functional layer. The metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide, iron aluminum cobalt oxide and chromium iron zinc oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride, iron aluminum cobalt nitride and chromium iron zinc nitride, or a metal nitride selected from cobalt oxide nitride, iron cobalt oxide nitride, chromium cobalt oxide nitride, chromium iron cobalt oxide nitride, copper cobalt oxide nitride, chromium aluminum cobalt oxide nitride, iron aluminum cobalt oxide and chromium iron zinc oxide, or a metal nitride selected from cobalt oxide nitride, iron cobalt oxide nitride, chromium cobalt oxide nitride, chromium iron cobalt oxide nitride, copper cobalt oxide nitride, chromium aluminum cobalt oxide nitride, iron aluminum cobalt oxide nitride and chromium iron zinc oxide, or molybdenum. The metal functional layer is formed by a process comprising depositing a metal alloy, a metal oxide, a metal nitride, a metal oxynitride or molybdenum by a magnetron sputtering vapor deposition method. The metal functional layer can be any metal functional layer described herein. The dielectric layer and the protective layer can be any dielectric layer and protective layer described herein. The coating can optionally further include a second dielectric layer. The second dielectric layer can be any dielectric layer described herein. The coating can optionally further include a base layer. The optional base layer can be any base layer described herein. The coating can optionally further include a primer layer. The optional primer layer can be any primer layer described herein.

[0088] The coated articles described herein can be used for architectural transparent parts, such as but not limited to insulating glass units. As used herein, the term "architectural transparent parts" refers to any transparent parts located on a building, such as but not limited to windows and skylights. However, it should be understood that the present invention is not limited to the use of such architectural transparent parts, but can be implemented using transparent parts in any desired field, such as but not limited to laminated or non-laminated residential and / or commercial windows, insulating glass units and / or transparent parts for land, air, space, water and underwater vehicles. Therefore, it should be understood that the specifically disclosed exemplary embodiments are only used to explain the general concept of the present invention, and the present invention is not limited to these specific exemplary embodiments. In addition, although a typical "transparent part" may have sufficient visible light transmittance so that the material can be observed through the transparent part, in the practice of the present invention, the "transparent part" does not need to be transparent to visible light, but can be translucent or opaque.

[0089] Figure 1A A non-limiting insulating glass unit 110 incorporating features of the present invention is provided. The insulating glass unit 110 includes a first ply 112 having a first major surface 114 (surface No. 1) and an opposing second major surface 116 (surface No. 2). In the non-limiting embodiment shown, the first major surface 114 faces the exterior of the building, i.e., is an 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 having an exterior (first) major surface 120 (surface No. 3) and an interior (second) major surface 122 (surface No. 4) and is spaced apart from the first ply 112. In some embodiments, the insulating glass unit 110 includes a third ply having a surface No. 5 and an opposing surface No. 6. This numbering of the ply surfaces is consistent with conventional practice in the fenestration art.

[0090] The plies 112, 118 may have any desired transmittance and / or reflectance for visible light, infrared radiation, or ultraviolet radiation. For example, the plies 112, 118 may have any desired amount of visible light transmittance, such as greater than 0% up to 100%. The plies 112, 118 may each be, for example, clear float glass, or may be tinted or colored glass, or one ply 112, 118 may be clear glass while the other ply 112, 118 is colored glass. Although not limiting the present invention, examples of glass suitable for the first ply 112 and / or the second ply 118 are described in U.S. Patents 4,746,347; 4,792,536; 5,030,593; 5,030,594; 5,240,886; 5,385,872; and 5,393,593.

[0091] The first and second plies 112, 118 can be connected together in any suitable manner, such as by 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. A coating 130 is formed over at least a portion of one of the plies 112, 118, such as but not limited to at least a portion of the No. 2 surface 116 or at least a portion of the No. 3 surface 120. However, if desired, the coating 130 can also be on the No. 1 surface 114 or the No. 4 surface 122. The coating 130 can include, be substantially composed of, or be composed of any coating described herein. Examples of insulating glass units can be found in, for example, U.S. Patents 4,193,236; 4,464,874; 5,088,258; and 5,106,663.

[0092] The coated articles described herein may be used in vehicle transparencies, such as windows or glazing. Figure 1B In the non-limiting vehicle transparent part 210 in combination with the features of the present invention is provided. For the sake of clarity, seals, connectors and opening mechanisms are not shown, nor is the entire vehicle shown. The transparent part comprises a first ply 212 installed in the main body (partially shown) of a vehicle 218, which has a first major surface 214 (surface No. 1) and a second major surface 216 (surface No. 2) relative. In the non-limiting embodiment shown, the first major surface 214 faces the outside of the vehicle, and is therefore an external major surface, and the second major surface 216 faces the inside of the vehicle. The non-limiting example of the vehicle body includes: in the case of a daylighting window, it is a car roof, in the case of a car window, it is a car door or frame, or is the fuselage of an aircraft. As widely known in the field of vehicles, the transparent part can be fixed to the mechanism, and thus the transparent part (such as a car window or a daylighting window) can be opened and closed. It is shown that the coating 230 is formed above the surface No. 1 214, but it can be formed above at least a portion of the surface No. 2 216. Coating 230 may comprise, consist essentially of, or consist of any coating described herein.

[0093] The invention is further described in the following numbered clauses:

[0094] Item 1. A coated article comprising: a substrate; and a metal functional layer over at least a portion of the substrate; wherein the metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide and iron aluminum cobalt oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride and iron aluminum cobalt nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt oxynitride, chromium aluminum cobalt oxynitride and iron aluminum cobalt nitride, or molybdenum.

[0095] Item 2. The coated article of Item 1, wherein the metallic functional layer comprises less than 90 wt % magnetic metal.

[0096] Item 3. The coated article of Item 1 or 2, wherein the metallic 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.

[0097] Item 4. The coated article of any one of Items 1 to 3, wherein the metallic functional layer comprises 60 wt % to 100 wt % cobalt, 60 wt % to 90 wt % cobalt, or 58 wt % to 70 wt % cobalt.

[0098] Item 5. The coated article of any one of Items 1 to 4, wherein the metallic functional layer comprises chromium cobalt oxide.

[0099] Clause 6. The coated article of any of Clauses 1 to 5, wherein the metallic 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.

[0100] Item 7. The coated article of any one of Items 1 to 3, wherein the metallic functional layer comprises 60 wt % to 99 wt % silicon.

[0101] Item 8. The coated article of any one of Items 1 to 3 or 7, wherein the metallic functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

[0102] Item 9. The coated article of any of Items 1 to 3, 7 or 8, wherein the metallic 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.

[0103] Item 10. The coated article of any one of Items 1 to 3, 7 or 8, wherein the metallic 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.

[0104] Item 11. The coated article of any one of Items 1 to 10, wherein the metallic functional layer is substantially free of iron, essentially free of iron, or completely free of iron.

[0105] Item 12. The coated article of any one of Items 1 to 11, further comprising a protective layer over the metallic functional layer.

[0106] Item 13. The coated article of Item 12, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or a mixture thereof.

[0107] Item 14. The coated article of Item 12 or 13, wherein the protective layer comprises titanium dioxide, silicon dioxide, aluminum oxide, silicon oxide, silicon aluminum oxide, silicon nitride, silicon aluminum nitride, aluminum silicon oxynitride, zirconium oxide, or mixtures thereof.

[0108] Clause 15. The coated article of any of Clauses 12 to 14, wherein the protective layer has a thickness of 5 nm to 70 nm, 5 nm to 30 nm, 30 nm to 70 nm, or 10 nm to 30 nm.

[0109] Item 16. The coated article of any one of Items 1 to 15, further comprising a base layer above the glass substrate and below the metallic functional layer.

[0110] Item 17. The coated article of Item 16, wherein the metallic functional layer comprises silicon.

[0111] Item 18. The coated article of Item 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.

[0112] Item 19. The coated article of any one of Items 1 to 18, further comprising at least one dielectric layer.

[0113] Item 20. The coated article of Item 19, wherein the dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silicon dioxide, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0114] Item 21. The coated article of Item 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.

[0115] Clause 22. The coated article of any one of Clauses 1 to 21, wherein the substrate is a glass substrate.

[0116] Item 23. A coated article comprising: a glass substrate; and a coating over at least a portion of the substrate, the coating comprising: a dielectric layer over the substrate; a metal functional layer; and a protective layer over the metal functional layer; wherein the metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide, iron aluminum cobalt oxide and chromium iron zinc oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride, iron aluminum cobalt nitride and chromium iron zinc nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt oxynitride, chromium aluminum cobalt oxynitride, iron aluminum cobalt oxynitride and chromium iron zinc nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt oxynitride, chromium aluminum cobalt oxynitride, iron aluminum cobalt oxynitride and chromium iron zinc nitride, or molybdenum.

[0117] Item 24. The coated article of Item 23, wherein the metallic functional layer is located over the dielectric layer; and wherein the metallic functional layer comprises silicon.

[0118] Item 25. The coated article of Item 23 or 24, further comprising a second dielectric layer over the metallic functional layer; wherein the protective layer is located over the second dielectric layer.

[0119] Item 26. The coated article of any one of Items 23 to 25, further comprising a base layer over the dielectric layer; wherein the metallic functional layer is located over the base layer.

[0120] Item 27. The coated article of Item 23, wherein the dielectric layer is located over the metallic functional layer; the protective layer is located over the dielectric layer; and the metallic functional layer comprises cobalt.

[0121] Item 28. The coated article of Item 23 or 25, wherein the dielectric layer is located over the protective layer; and the metallic functional layer comprises silicon.

[0122] Item 29. The coated article of any one of Items 23 to 28, wherein the metallic functional layer comprises less than 90% by weight of magnetic metal.

[0123] Clause 30. The coated article of any of Clauses 23 to 29, wherein the metallic functional layer has a thickness in a range of 20 nm to 40 nm, 20 nm to 60 nm, 30 nm to 45 nm, or 20 nm to 30 nm.

[0124] Item 31. The coated article of any one of Items 23, 25 to 27, 29 or 30, wherein the metallic functional layer comprises 60 wt % to 100 wt % cobalt, 60 wt % to 90 wt % cobalt, or 58 wt % to 70 wt % cobalt.

[0125] Item 32. The coated article of any one of Items 23, 25 to 27, or 29 to 31, wherein the metallic functional layer comprises chromium cobalt oxide.

[0126] Clause 33. The coated article of any of clauses 23, 25 to 27, or 29 to 32, wherein the metallic 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.

[0127] Item 34. The coated article of any one of Items 23 to 26 or 28 to 30, wherein the metallic functional layer comprises 60 wt % to 99 wt % silicon.

[0128] Item 35. The coated article of any one of Items 23 to 30 or 34, wherein the metallic functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

[0129] Clause 36. The coated article of any of clauses 23 to 26, 28 to 30, 34 or 35, wherein the metallic 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.

[0130] Item 37. The coated article of any one of Items 23 to 30, 34 or 35, wherein the metallic 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.

[0131] Item 38. The coated article of any one of Items 23 to 37, wherein the metallic functional layer is substantially free of iron, essentially free of iron, or completely free of iron.

[0132] Item 39. The coated article of any one of Items 23 to 38, wherein the dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silicon dioxide, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0133] Item 40. The coated article of any one of Items 23 to 39, wherein the dielectric layer comprises silicon nitride or aluminum silicon nitride.

[0134] Item 41. The coated article of any of Items 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.

[0135] Item 42. The coated article of any one of Items 23 to 41, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or a mixture thereof.

[0136] Item 43. The coated article of any one of Items 23 to 42, wherein the protective layer comprises at least one of titanium dioxide, silicon dioxide, aluminum oxide, silicon oxide, aluminum silicon oxide, silicon nitride, aluminum silicon nitride, aluminum silicon oxynitride, zirconium oxide, or mixtures thereof.

[0137] Clause 44. The coated article of any of Clauses 23 to 43, wherein the protective layer has a thickness of 5 nm to 70 nm, 5 nm to 30 nm, 30 nm to 70 nm, or 10 nm to 30 nm.

[0138] Item 45. The coated article of any one of Items 26 or 29 to 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.

[0139] Item 46. A method for preparing a coated article, comprising: providing a substrate; and forming a metal functional layer over at least a portion of the substrate; wherein the metal functional layer comprises a metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide, iron aluminum cobalt oxide and chromium iron zinc oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride, iron aluminum cobalt nitride and chromium iron zinc nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt nitride, chromium aluminum cobalt oxynitride, iron aluminum cobalt oxynitride and chromium iron zinc nitride, or a metal nitride selected from cobalt oxynitride, iron cobalt oxynitride, chromium cobalt oxynitride, chromium iron cobalt oxynitride, copper cobalt oxynitride, chromium aluminum cobalt oxynitride, iron aluminum cobalt oxynitride and chromium iron zinc nitride, or molybdenum; and wherein 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 vapor deposition.

[0140] Item 47. The method of Item 46, wherein the metallic functional layer comprises less than 90 wt % magnetic metal.

[0141] Item 48. The method of Item 46 or 47, wherein the metallic 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.

[0142] Item 49. The method of any of Items 46 to 48, wherein the metallic functional layer comprises 60 wt % to 100 wt % cobalt, 60 wt % to 90 wt % cobalt, or 58 wt % to 70 wt % cobalt.

[0143] Item 50. The method of any one of Items 46 to 49, wherein the metallic functional layer comprises chromium cobalt oxide.

[0144] Item 51. The method according to any one of Items 46 to 50, wherein the metallic 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.

[0145] Item 52. The method of any one of Items 46 to 48, wherein the metallic functional layer comprises 60 wt % to 99 wt % silicon.

[0146] Item 53. The method of any one of Items 46 to 48 or 51, wherein the metallic functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

[0147] Item 54. The method of any one of items 46 to 48, 51 or 52, wherein the metallic 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.

[0148] Item 55. The method of any one of Items 46 to 48, 51 or 52, wherein the metallic 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.

[0149] Item 56. The method of any one of Items 46 to 55, wherein the metallic functional layer is substantially free of iron, essentially free of iron, or completely free of iron.

[0150] Clause 57. The method of any of Clauses 46 to 56, further comprising a protective layer over the metallic functional layer.

[0151] Item 58. The method of Item 57, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or a mixture thereof.

[0152] Item 59. The method of Item 57 or 58, wherein the protective layer comprises titanium dioxide, silicon dioxide, aluminum oxide, silicon oxide, aluminum silicon oxide, silicon nitride, aluminum silicon nitride, aluminum silicon oxynitride, zirconium oxide, or a mixture thereof.

[0153] Clause 60. The method of any of Clauses 57 to 59, wherein the protective layer has a thickness of 5 nm to 70 nm, 5 nm to 30 nm, 30 nm to 70 nm, or 10 nm to 30 nm.

[0154] Item 61. The method of any one of Items 46 to 60, further comprising a base layer above the glass substrate and below the metal functional layer.

[0155] Item 62. The method of Item 61, wherein the metallic functional layer comprises silicon.

[0156] Item 63. The method of Item 61 or 62, wherein the base layer has a thickness of from 30 nm to 110 nm, from 30 nm to 80 nm, or from 70 nm to 110 nm.

[0157] Item 64. The coated article of any one of Items 46 to 63, further comprising at least one dielectric layer.

[0158] Item 65. The method of Item 64, wherein the dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silicon dioxide, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0159] Clause 66. The method of clause 64 or 65, wherein each dielectric layer has a thickness of from 5 nm to 140 nm, from 80 nm to 120 nm, from 100 nm to 140 nm, or from 1 nm to 10 nm.

[0160] Clause 67. The method of any one of Clauses 46 to 66, wherein the substrate is a glass substrate.

[0161] Clause 68. A method of preparing a coated article, comprising: providing a substrate; and forming a coating over at least a portion of the substrate; wherein the coating comprises a dielectric layer over the substrate; a metal functional layer; and a protective layer over the metal functional layer; wherein 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, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide, iron aluminum cobalt oxide, and chromium iron zinc oxide. The metal functional layer is formed by a process comprising depositing a metal alloy, a metal oxide, a metal nitride, a metal nitride or a molybdenum by a magnetron sputtering vapor deposition method.

[0162] Item 69. The method of Item 68, wherein the metallic functional layer is located over the dielectric layer; and wherein the metallic functional layer comprises silicon.

[0163] Clause 70. The method of Clause 68 or 69, further comprising a second dielectric layer over the metal functional layer; wherein the protective layer is over the second dielectric layer.

[0164] Clause 71. The method of any one of Clauses 68 to 70, further comprising a base layer over the dielectric layer; wherein the metal functional layer is located over the base layer.

[0165] Clause 72. The method of Clause 68, wherein the dielectric layer is located above the metallic functional layer; the protective layer is located above the dielectric layer; and the metallic functional layer comprises cobalt.

[0166] Item 73. The method of Item 68 or 70, wherein the dielectric layer is located over the protective layer; and the metallic functional layer comprises silicon.

[0167] Item 74. The method of any one of Items 68 to 73, wherein the metallic functional layer comprises less than 90 wt % magnetic metal.

[0168] Clause 75. The method of any of Clauses 68 to 74, wherein the metallic functional layer has a thickness in a range of 20 nm to 40 nm, 20 nm to 60 nm, 30 nm to 45 nm, or 20 nm to 30 nm.

[0169] Item 76. The method of any one of Items 68, 70 to 72, 74 or 75, wherein the metallic functional layer comprises 60 wt % to 100 wt % cobalt, 60 wt % to 90 wt % cobalt, or 58 wt % to 70 wt % cobalt.

[0170] Clause 77. The method of any one of clauses 68, 70 to 72, or 74 to 76, wherein the metallic functional layer comprises chromium cobalt oxide.

[0171] Clause 78. A method according to any one of clauses 68, 70 to 72 or 74 to 77, wherein the metallic 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.

[0172] Item 79. The method of any one of Items 68 to 71 or 73 to 75, wherein the metallic functional layer comprises 60 wt % to 99 wt % silicon.

[0173] Clause 80. The method of any one of Clauses 68 to 75 or 79, wherein the metallic functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

[0174] Item 81. The method of any one of items 68 to 71, 73 to 75, 79 or 80, wherein the metallic 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.

[0175] Clause 82. The method of any of clauses 68 to 75, 79 or 80, wherein the metallic 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.

[0176] Clause 83. The method of any one of Clauses 68 to 82, wherein the metallic functional layer is substantially free of iron, essentially free of iron, or completely free of iron.

[0177] Item 84. The method of any one of Items 68 to 83, wherein the dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silicon dioxide, silicon aluminum oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide, and titanium nitride.

[0178] Clause 85. The method of any one of Clauses 68 to 84, wherein the dielectric layer comprises silicon nitride or aluminum silicon nitride.

[0179] Clause 86. The method of any 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.

[0180] 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.

[0181] Clause 88. The method of any of Clauses 68 to 87, wherein the protective layer comprises at least one of titanium dioxide, silicon dioxide, aluminum oxide, silicon oxide, aluminum silicon oxide, silicon nitride, aluminum silicon nitride, aluminum silicon oxynitride, zirconium oxide, or mixtures thereof.

[0182] Clause 89. The method of any of Clauses 68 to 88, wherein the protective layer has a thickness of 5 nm to 70 nm, 5 nm to 30 nm, 30 nm to 70 nm, or 10 nm to 30 nm.

[0183] Clause 90. The method of any one of clauses 71 or 74 to 89, wherein the base layer has a thickness of from 30 nm to 110 nm, from 30 nm to 80 nm, or from 70 nm to 110 nm.

[0184] Clause 91: An insulating glass unit comprising: a first ply including a surface No. 1 and a surface No. 2 opposite to the surface No. 1; a second ply including a surface No. 3 and a surface No. 4 opposite to the surface No. 3, wherein the second ply is separated from the first ply and wherein the first ply and the second ply are connected together; and a coating over at least a portion of the surface No. 2 or the surface No. 3, wherein the coating comprises: a dielectric layer over the substrate; a metal functional layer; and a protective layer over the metal functional layer; wherein the metal functional layer comprises a selected A metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide, iron aluminum cobalt oxide and chromium iron zinc oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride, iron aluminum cobalt nitride and chromium iron zinc nitride, or a metal nitride selected from cobalt oxide nitrogen, iron cobalt oxide nitrogen, chromium cobalt oxide nitrogen, chromium iron cobalt oxide nitrogen, copper cobalt oxide nitrogen, chromium aluminum cobalt oxide nitrogen, iron aluminum cobalt oxide nitrogen, and chromium iron zinc oxide nitrogen, or molybdenum.

[0185] Clause 92. The insulating glass unit of Clause 91, wherein the metallic functional layer is located above the dielectric layer; and wherein the metallic functional layer comprises silicon.

[0186] Clause 93. The insulating glass unit of Clause 91 or 92, further comprising a second dielectric layer over the metal functional layer; wherein the protective layer is located over the second dielectric layer.

[0187] Clause 94. The insulating glass unit of any one of Clauses 91 to 93, further comprising a base layer overlying the dielectric layer; wherein the metal functional layer is located overlying the base layer.

[0188] Clause 95. The insulating glass unit of Clause 91, wherein the dielectric layer is located above the metallic functional layer; the protective layer is located above the dielectric layer; and the metallic functional layer comprises cobalt.

[0189] Item 96. The insulating glass unit of Item 91 or 93, wherein the dielectric layer is located above the protective layer; and the metallic functional layer comprises silicon.

[0190] Clause 97. The insulating glass unit of any one of Clauses 91 to 96, wherein the metallic functional layer comprises less than 90% by weight of magnetic metal.

[0191] Clause 98. The insulating glass unit of any of Clauses 91 to 97, wherein the metallic 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.

[0192] Clause 99. The insulating glass unit of any of Clauses 91, 93 to 95, 97 or 98, wherein the metallic functional layer comprises 60 wt % to 100 wt % cobalt, 60 wt % to 90 wt % cobalt, or 58 wt % to 70 wt % cobalt.

[0193] Clause 100. The insulating glass unit of any one of Clauses 91, 93 to 95, or 97 to 99, wherein the metallic functional layer comprises chromium cobalt oxide.

[0194] Clause 101. An insulating glass unit according to any of clauses 91, 93 to 95, or 97 to 100, wherein the metallic functional layer comprises 60% to 100% by weight cobalt and 0% to 40% by weight chromium, 60% to 90% by weight cobalt and 10% to 40% by weight chromium, or 70% to 88% by weight cobalt and 12% to 30% by weight chromium.

[0195] Clause 102. The insulating glass unit of any of Clauses 91 to 94 or 96 to 98, wherein the metallic functional layer comprises 60 wt % to 99 wt % silicon.

[0196] Clause 103. The insulating glass unit of any one of Clauses 91 to 98 or 102, wherein the metallic functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.

[0197] Clause 104. The insulating glass unit of any of clauses 91 to 94, 96 to 98, 102 or 103, wherein the metallic 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.

[0198] Clause 105. The insulating glass unit of any of Clauses 91 to 98, 111 or 112, wherein the metallic 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.

[0199] Clause 106. The insulating glass unit of any one of Clauses 91 to 105, wherein the metallic functional layer is substantially free of iron, essentially free of iron, or completely free of iron.

[0200] Clause 107. The insulating glass unit of any of Clauses 91 to 106, wherein the dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silicon dioxide, silicon aluminum oxide, silicon nitride, aluminum nitride, aluminum silicon nitride, titanium oxide, and titanium nitride.

[0201] Clause 108. The insulating glass unit of any one of Clauses 91 to 107, wherein the dielectric layer comprises silicon nitride or aluminum silicon nitride.

[0202] Clause 109. The method of any 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.

[0203] Clause 110. The insulating glass unit of any one of Clauses 91 to 109, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or a mixture thereof.

[0204] Clause 111. The insulating glass unit of any of Clauses 91 to 110, wherein the protective layer comprises at least one of titanium dioxide, silicon dioxide, aluminum oxide, silicon oxide, aluminum silicon oxide, silicon nitride, aluminum silicon nitride, aluminum silicon oxynitride, zirconium oxide, or mixtures thereof.

[0205] Clause 112. The insulating glass unit of any of Clauses 91 to 111, wherein the protective layer has a thickness of 5 nm to 70 nm, 5 nm to 30 nm, 30 nm to 70 nm, or 10 nm to 30 nm.

[0206] Clause 113. The insulating glass unit of any of Clauses 94 or 97 to 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.

[0207] The following examples illustrate various embodiments of the present invention. However, it should be understood that the present invention is not limited to these specific embodiments.

[0208] Example

[0209] Table 1 shows exemplary coated articles 1-4 of the present invention. The thickness reported is the physical thickness in nanometers (nm). The substrate is 6 mm clear glass. Co 80 Cr 20 (80 wt% cobalt and 20 wt% chromium) or Co 80 Cr 15 Cobalt chromium oxide (CoCrO) was deposited on a glass substrate by MSVD using a target (85 wt% cobalt and 15 wt% chromium). x ) layer. Silicon nitride (SiN x ) layer. Deposition of silicon aluminum oxide (SiAlO x )'s outer protective layer.

[0210] Table 1

[0211] Table 2 shows exemplary coated articles 5-7 of the present invention. The thickness reported is the physical thickness in nm. The substrate is 6 mm clear glass. Si 95 Al 5 A silicon aluminum alloy (SiAl) layer was deposited on a glass substrate using a target made of an alloy (95 wt% silicon and 5 wt% aluminum) by MSVD. Silicon aluminum oxide (SiAlO) was deposited on top of the SiAl layer. x )'s outer protective layer.

[0212] Table 2

[0213] Table 3 shows exemplary coated articles 8-13 of the present invention. The thickness reported is the physical thickness in nm. The substrate is 6 mm clear glass. Si 70 Co 30 A silicon-cobalt metal alloy (SiCo) layer was deposited on a glass substrate by MSVD using a target made of an alloy (70 wt.% silicon and 30 wt.% cobalt) and a silicon-cobalt metal alloy (SiAlO) layer was deposited on top of the SiCo layer. x )'s outer protective layer.

[0214] Table 3

[0215] Table 4 shows exemplary coated articles 14-16 of the present invention. The reported thickness is the physical thickness in nm. The substrate is 6 mm clear glass. Silicon aluminum nitride (SiAlN x ) layer (Sample 14). 70 Co 30 alloy (70 wt% silicon and 30 wt% cobalt) targets, deposited by MSVD on glass substrates (Samples 15 and 16) or on optional SiAlN x A silicon cobalt metal alloy (SiCo) layer is deposited on the SiCo layer (Sample 14). A silicon aluminum oxide (SiAlO x ) layer (Samples 14 and 15). Optionally, in the optional SiAlO x SiAlN is deposited on the SiCo layer (sample 15) or SiCo layer (sample 16). x In the optional SiAlN x Another SiAlO layer is optionally deposited x layer (Sample 16).

[0216] Table 4

[0217] Table 5 shows exemplary coated articles 17-24 of the present invention. The thickness reported is the physical thickness in nm. The substrate is 6 mm clear glass. A first aluminum silicon nitride (SiAlN x ) layer. Using Si 70 Co 30 alloy (70 wt% silicon and 30 wt% cobalt) target, by MSVD on SiAlN x A silicon-cobalt metal alloy (SiCo) layer is deposited on the SiCo layer. A second SiAlN x In the second SiAlN x Optional silicon aluminum oxide (SiAlO x ) protective layer.

[0218] Table 5

[0219] Spectral properties

[0220] Table 6 shows the spectral properties of samples 1-4 of Table 1. "T" indicates transmittance, "Rf" indicates reflectance on the film or coating side, and "Rg" indicates reflectance on the glass side.

[0221] Table 6

[0222] Table 7 shows the spectral properties of samples 8-13 of Table 3.

[0223] Table 7

[0224] Table 8 shows the spectral properties of samples 14-16 of Table 4.

[0225] Table 8

[0226] Table 9 shows the spectral properties of samples 21-24 of Table 5.

[0227] Table 9

[0228] Durability

[0229] After heating (60°C DI water chamber), the CCC test results of samples 1 to 4 are shown in Figures 9A-9D For silicon aluminum nitride (SiAlN x ) layer (samples 1 and 2), the color change (DECMC T, Rf) after 20 days was greater than 2. However, in the case of CoCrO x There is a thin SiN layer between the protective layerx The coatings of the layers (Samples 3 and 4) showed a color change (DECMC T, Rf) of less than 1 after 50 days and passed the CCC test.

[0230] Samples 1-4 passed the standard chemical durability test. Samples 1-4 showed less than 12% film loss after immersion in 10N (27.5%) sulfuric acid at 52°C for 30 minutes.

[0231] The results of sample 7 (after heating, 60°C DI water chamber) passing the CCC test are shown in Fig. 10A and 10B After 50 days, the film side reflection color change (DECMC of Rf, Fig. 10A ) and transmittance color change (DECMC of T, Fig. 10B ) is less than 0.5. Sample 7 passed the standard chemical durability test.

[0232] Table 10 shows the CCC test results for Samples 8-13 (after heating, 60°C DI water chamber). The abbreviation "nd" means "not determined".

[0233] Table 10

[0234] Table 11 shows the CCC test results for Samples 14 to 16.

[0235] Table 11

[0236] CCC test results for samples 17-24 (after heating, 60°C DI water chamber) are shown in Figures 11A-11D . Coatings without protective layer (samples 17-20, Fig. 11C and 11D ) did not pass the CCC test. However, the coatings with protective layers (samples 21-24, Fig.11A and 11B ) showed a film side reflection color change of less than 1 after 50 days (DECMC of Rf, Fig.11A ) and a transmittance color change of less than 0.5 (DECMC of T, Fig. 11B ).

[0237] Those skilled in the art will readily appreciate that the present invention may be modified without departing from the concepts disclosed in the foregoing description. Therefore, the specific embodiments described in detail herein are merely illustrative and do not limit the scope of the present invention, which is given by the full breadth of the appended claims and any and all equivalents thereof.

Claims

1. A coated product comprising: Base material; as well as a metallic functional layer over at least a portion of the substrate; The metal functional layer comprises: A metal alloy selected from silicon aluminum alloy, silicon cobalt alloy, niobium tungsten alloy and titanium tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium iron cobalt oxide, copper cobalt oxide, chromium aluminum cobalt oxide, and iron aluminum cobalt oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium iron cobalt nitride, copper cobalt nitride, chromium aluminum cobalt nitride, and iron aluminum cobalt nitride, or a cobalt oxide nitrogen, iron cobalt oxide nitrogen, chromium cobalt oxide nitrogen, chromium iron cobalt oxide nitrogen, copper cobalt oxide nitrogen, chromium aluminum cobalt oxide nitrogen, and iron aluminum cobalt oxide nitrogen, or molybdenum.

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

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

4. The coated article according to claim 1, wherein the metallic functional layer comprises 60% to 100% by weight of cobalt, The metallic functional layer contains chromium cobalt oxide.

5. The coated article according to claim 1, wherein the metallic functional layer comprises 60% to 99% by weight of silicon, The metal functional layer comprises a silicon-aluminum alloy or a silicon-cobalt alloy.

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

7. The coated article according to claim 6, further comprising a base layer above the substrate and below the metallic functional layer; The metallic functional layer contains silicon.

8. The coated article according to claim 1, further comprising at least one dielectric layer, The dielectric layer comprises one or more films selected from zinc tin oxide, zinc oxide, silicon dioxide, aluminum silicon oxide, silicon nitride, aluminum nitride, silicon aluminum nitride, titanium oxide and titanium nitride.

9. A coated product comprising: Glass substrate; as well as A coating over at least a portion of the substrate, the coating comprising: a dielectric layer over the substrate; Metal functional layer; as well as a protective layer over the metallic functional layer; The metal functional layer comprises a metal alloy selected from silicon-aluminum alloy, silicon-cobalt alloy, niobium-tungsten alloy and titanium-tungsten alloy, or a metal oxide selected from cobalt oxide, iron cobalt oxide, chromium cobalt oxide, chromium-iron cobalt oxide, copper cobalt oxide, chromium-aluminum cobalt oxide, iron-aluminum cobalt oxide and chromium-iron-zinc oxide, or a metal nitride selected from cobalt nitride, iron cobalt nitride, chromium cobalt nitride, chromium-iron cobalt nitride, copper cobalt nitride, chromium-aluminum cobalt nitride, iron-aluminum cobalt nitride and chromium-iron-zinc nitride, or a metal nitride selected from cobalt oxide nitrogen, iron cobalt oxide nitrogen, chromium cobalt oxide nitrogen, chromium-iron cobalt oxide nitrogen, copper cobalt oxide nitrogen, chromium-aluminum cobalt oxide nitrogen, iron-aluminum cobalt oxide and chromium-iron-zinc nitride, or a metal nitride selected from cobalt oxide nitrogen, iron cobalt oxide nitrogen, chromium cobalt oxide nitrogen, chromium-iron cobalt oxide nitrogen, and chromium-iron-zinc oxide nitrogen, or molybdenum.

10. The coated article according to claim 9, wherein the metallic functional layer is located above the dielectric layer; and The metallic functional layer contains silicon.

11. The coated article according to claim 10, further comprising a second dielectric layer over the metallic functional layer; The protection layer is located above the second dielectric layer.

12. The coated article according to claim 10, further comprising a base layer over the dielectric layer; The metal functional layer is located above the base layer.

13. The coated article according to claim 9, wherein the dielectric layer is located above the metallic functional layer; The protective layer is located above the dielectric layer; and The metallic functional layer contains cobalt.

14. The coated article of claim 9, wherein the dielectric layer is located over the protective layer; and The metallic functional layer contains silicon.

15. A method for preparing a coated article, comprising: Providing a substrate; as well as forming a metallic functional layer over at least a portion of the substrate; wherein the metal functional layer comprises a metal alloy selected from silicon-aluminum alloy, silicon-cobalt alloy, niobium-tungsten alloy and titanium-tungsten alloy, or a metal oxide selected from cobalt oxide, iron-cobalt oxide, chromium-cobalt oxide, chromium-iron-cobalt oxide, copper-cobalt oxide, chromium-aluminum-cobalt oxide, iron-aluminum-cobalt oxide and chromium-iron-zinc oxide, or a metal nitride selected from cobalt nitride, iron-cobalt nitride, chromium-cobalt nitride, chromium-iron-cobalt nitride, copper-cobalt nitride, chromium-aluminum-cobalt nitride, iron-aluminum-cobalt nitride and chromium-iron-zinc nitride, or a metal nitride selected from cobalt oxidenitride, iron-cobalt oxidenitride, chromium-cobalt oxidenitride, chromium-iron-cobalt oxidenitride, copper-cobalt oxidenitride, chromium-aluminum-cobalt oxidenitride, iron-aluminum-cobalt oxide ... oxide, or a metal nitride selected from molybdenum; and 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 a magnetron sputtering vapor deposition method.

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