# US 9,751,800 B2 · Heat treatable coated article with tungsten-doped zirconium based layer(s) in coating > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,751,800 B2 - Document ID: US9751800B2 - Status: Granted - Kind: B2 - Application number: 13/760,239 - Filed: 2013-02-06 - Published: 2014-08-07 - Granted: 2017-09-05 - Earliest claimed: 2013-02-06 - Assignees: Guardian Glass, LLC - Applicants: Guardian Industries Corp. - Inventors: Jiangping Wang; Jason Barber - Web page: https://patentgrep.com/patent/US9751800B2 ## CPC - C03C 17/245: by deposition from the vapour phase - C03B 27/012: by heat treatment, e.g. for crystallisation; Heat treatment of glass products before tempering by cooling (C03B27/008, C03B27/016 take precedence) - C03C 17/225: {Nitrides} - C03C 17/23: Oxides (C03C17/02 takes precedence) - C03C 17/3411: {with at least two coatings of inorganic materials (C03C17/36, C03C17/42 take precedence)} - C03C 2217/22: ZrO2 - C03C 2217/24: Doped oxides - C03C 2217/281: Nitrides - C03C 2217/78: Coatings specially designed to be durable, e.g. scratch-resistant - C03C 2218/156: by magnetron sputtering - C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS - C03B: MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES ## Abstract In certain example embodiments, a coated article includes a tungsten-doped zirconium based layer before heat treatment (HT). The coated article is heat treated sufficiently to cause the tungsten-doped zirconium oxide and/or nitride based layer to result in a tungsten-doped zirconium oxide based layer that is scratch resistant and/or chemically durable. The doping of the layer with tungsten has been found to improve scratch resistance. ## Claims ### Claim 1 A method of making a heat treated coated article, the method comprising: having a coated article including a coating supported by a glass substrate, the coating comprising a tungsten-doped layer comprising an oxide and/or nitride of zirconium; and thermally tempering the coated article, including the glass substrate and the tungsten-doped layer comprising an oxide and/or nitride of zirconium, so that after the tempering a layer comprising tungsten-doped zirconium oxide is provided on the glass substrate. ### Claim 2 (depends on 1) The method of claim 1, wherein there is more zirconium than tungsten in each of (i) the tungsten-doped layer comprising an oxide and/or nitride of zirconium, and (ii) the layer comprising tungsten-doped zirconium oxide. ### Claim 3 (depends on 1) The method of claim 1, wherein a metal content of the layer comprising tungsten-doped zirconium oxide is from about 2-40% tungsten. ### Claim 4 (depends on 1) The method of claim 1, wherein a metal content of the layer comprising tungsten-doped zirconium oxide is from about 5-30% tungsten. ### Claim 5 (depends on 1) The method of claim 1, wherein a metal content of the layer comprising tungsten-doped zirconium oxide is from about 51-99% zirconium. ### Claim 6 (depends on 1) The method of claim 1, wherein a metal content of the layer comprising tungsten-doped zirconium oxide is from about 70-95% zirconium. ### Claim 7 (depends on 1) The method of claim 1, wherein the layer comprising tungsten-doped zirconium oxide includes W-doped ZrxOy where y/x is from about 1.2 to 2.5. ### Claim 8 (depends on 7) The method of claim 7, wherein y/x is from about 1.4 to 2.1. ### Claim 9 (depends on 1) The method of claim 1, wherein the layer comprising tungsten-doped zirconium oxide further comprises fluorine and/or carbon. ### Claim 10 (depends on 1) The method of claim 1, wherein prior to said tempering the tungsten-doped layer comprising an oxide and/or nitride of zirconium comprises tungsten-doped zirconium oxide. ### Claim 11 (depends on 1) The method of claim 1, wherein prior to said tempering the tungsten-doped layer comprising an oxide and/or nitride of zirconium comprises tungsten-doped zirconium oxynitride. ### Claim 12 (depends on 1) The method of claim 1, wherein prior to said tempering the tungsten-doped layer comprising an oxide and/or nitride of zirconium comprises tungsten-doped zirconium nitride. ### Claim 13 (depends on 1) The method of claim 1, wherein prior to the tempering, the coating further comprises a layer comprising diamond-like carbon located on the glass substrate over at least the tungsten-doped layer comprising an oxide and/or nitride of zirconium. ### Claim 14 (depends on 1) The method of claim 1, wherein prior to and/or after the tempering, the coating further comprises a dielectric layer between the glass substrate and the tungsten-doped layer comprising an oxide and/or nitride of zirconium. ### Claim 15 (depends on 1) The method of claim 1, wherein the layer comprising tungsten-doped zirconium oxide comprises a nanocrystalline cubic lattice structure. ### Claim 16 (depends on 1) The method of claim 1, wherein the layer comprising tungsten-doped zirconium oxide is an outermost layer of the coating following tempering. ### Claim 17 (depends on 1) The method of claim 1, wherein the tempered coated article has a visible transmission of at least 50%. ### Claim 18 A method of making a heat treated coated article, the method comprising: having a coated article including a coating supported by a glass substrate, the coating comprising a tungsten-doped layer comprising an oxide and/or nitride of zirconium; and heat treating the coated article, including the glass substrate and the tungsten-doped layer comprising an oxide and/or nitride of zirconium, so that after the heat treating a layer comprising tungsten-doped zirconium oxide is provided on the glass substrate. ### Claim 19 (depends on 18) The method of claim 18, wherein there is less tungsten than zirconium in at least one of (i) the tungsten-doped layer comprising an oxide and/or nitride of zirconium, and (ii) the layer comprising tungsten-doped zirconium oxide. ### Claim 20 (depends on 18) The method of claim 18, wherein a metal content of the layer comprising tungsten-doped zirconium oxide is from about 5-30% tungsten. ### Claim 21 (depends on 18) The method of claim 18, wherein a metal content of the layer comprising tungsten-doped zirconium oxide is from about 70-95% zirconium. ### Claim 22 (depends on 18) The method of claim 18, wherein the tungsten-doped layer comprising an oxide and/or nitride of zirconium is sputter-deposited by sputtering both a target comprising Zr and a target comprising W. ### Claim 23 (depends on 18) The method of claim 18, wherein the tungsten-doped layer comprising an oxide and/or nitride of zirconium is sputter-deposited by sputtering both a target comprising Zr and a target comprising tungsten carbide. ### Claim 24 (depends on 18) The method of claim 18, wherein prior to said heat treating the tungsten-doped layer comprising an oxide and/or nitride of zirconium comprises tungsten-doped zirconium oxynitride. ### Claim 25 (depends on 18) The method of claim 18, wherein after the heat treating the coating further comprises a dielectric layer between the glass substrate and the tungsten-doped layer comprising zirconium oxide. ### Claim 26 (depends on 18) The method of claim 18, wherein the layer comprising tungsten-doped zirconium oxide is an outermost layer of the coating following the heat treating. ### Claim 27 (depends on 18) The method of claim 18, wherein the coated article after the heat treating has a visible transmission of at least 50%. ### Claim 28 A method of making a heat treated coated article, the method comprising: having a coated article including a coating supported by a glass substrate, the coating comprising a layer comprising tungsten and/or tungsten carbide that directly contacts a layer comprising an oxide and/or nitride of zirconium; and thermally tempering the coated article, including the glass substrate and the layer comprising tungsten and/or tungsten carbide and the layer comprising an oxide and/or nitride of zirconium, so that migration occurs between the layers during said tempering and after the tempering a layer comprising tungsten-doped zirconium oxide is provided on the glass substrate.