# US 9,434,640 B2 · Method of making heat treated coated article with carbon based coating and protective film > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,434,640 B2 - Document ID: US9434640B2 - Status: Granted - Kind: B2 - Application number: 13/693,411 - Filed: 2012-12-04 - Published: 2014-06-05 - Granted: 2016-09-06 - Earliest claimed: 2012-12-04 - Assignees: Guardian Industries Corp. - Applicants: Guardian Industries Corp. - Inventors: Jens-Peter Muller; Herbert Lage; Thorsten Frost; Vijayen S. Veerasamy - Web page: https://patentgrep.com/patent/US9434640B2 ## CPC - C03C 17/3441: {comprising carbon, a carbide or oxycarbide} - 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 17/22: with other inorganic material (C03C17/34, C03C17/44 take precedence) - C03C 17/3435: {comprising a nitride, oxynitride, boronitride or carbonitride} - C03C 2217/216: ZnO - C03C 2217/24: Doped oxides - C03C 2217/281: Nitrides - C03C 2217/78: Coatings specially designed to be durable, e.g. scratch-resistant - C03C 2218/154: by sputtering - C03C 2218/322: Oxidation - C03C 2218/328: Partly or completely removing a coating - C03C 2218/355: Temporary coating - Y10T 156/10: Methods of surface bonding and/or assembly therefor - Y10T 428/30: Self-sustaining carbon mass or layer with impregnant or other layer - 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 - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract A method of making a heat treated (HT) or heat treatable coated article. A method of making a coated article includes a step of heat treating a glass substrate coated with at least layer of or including carbon (e.g., diamond-like carbon (DLC)) and an overlying protective film thereon. In certain example embodiments, the protective film may be of or include both (a) an oxygen blocking or barrier layer, and (b) a release layer of or including zinc oxide. Treating the zinc oxide inclusive release layer with plasma including oxygen (e.g., via ion beam treatment) improves thermal stability and/or quality of the product. Following and/or during heat treatment (e.g., thermal tempering, or the like) the protective film may be entirely or partially removed. ## Claims ### Claim 1 A method of making a coated article, the method comprising: depositing a release layer comprising zinc oxide on a glass substrate, wherein at least a layer comprising carbon is located between the glass substrate and the release layer comprising zinc oxide; plasma treating the layer comprising zinc oxide including ZnO—Zn cermet with at least oxygen ions to provide an ion beam treated layer comprising zinc oxide and to transform at least part of the ZnO—Zn cermet to a more stable ZnOx; depositing an oxygen barrier layer on the glass substrate over the plasma treated layer comprising zinc oxide; and wherein a protective film comprising the plasma treated layer comprising zinc oxide and the oxygen barrier layer are for protecting the layer comprising carbon during subsequent heat treatment in order to prevent significant burnoff of the layer comprising carbon. ### Claim 2 (depends on 1) The method of claim 1, wherein said ion beam treating comprises directing an ion beam including oxygen ions toward the release layer, wherein the ion beam is substantially free of carbon ions. ### Claim 3 (depends on 1) The method of claim 1, wherein said ion beam treating comprises directing an ion beam consisting essentially of oxygen ions toward the release layer. ### Claim 4 (depends on 1) The method of claim 1, wherein the release layer consists essentially of zinc oxide, which may optionally be doped with aluminum and/or nitrogen. ### Claim 5 (depends on 1) The method of claim 1, wherein said ion beam treating of the release layer causes a concentration of OH-groups at an outer surface of the release layer to drop by at least 5%. ### Claim 6 (depends on 1) The method of claim 1, wherein said ion beam treating of the release layer causes a concentration of OH-groups at an outer surface of the release layer to drop by at least 10%. ### Claim 7 (depends on 1) The method of claim 1, wherein the oxygen barrier layer comprises aluminum nitride. ### Claim 8 (depends on 1) The method of claim 1, wherein the oxygen barrier layer consists essentially of aluminum nitride. ### Claim 9 (depends on 1) The method of claim 1, wherein the oxygen barrier layer directly contacts the release layer that has been ion beam treated. ### Claim 10 (depends on 1) The method of claim 1, wherein the layer comprising carbon comprises diamond-like carbon (DLC). ### Claim 11 (depends on 1) The method of claim 1, further comprising heat treating the glass substrate with at least following layers thereon: the layer comprising carbon, the ion beam treated release layer, and the oxygen barrier layer; and wherein said heat treating comprises heating the glass substrate to temperature(s) sufficient for thermal tempering, heat strengthening, and/or heat bending of the glass substrate. ### Claim 12 (depends on 11) The method of claim 11, wherein the heat treating comprises heating the glass substrate at temperature(s) of at least 550 degrees C. ### Claim 13 (depends on 11) The method of claim 11, further comprising exposing the protective film to a release liquid and removing at least part of the protective film during and/or after the heat treating. ### Claim 14 (depends on 1) The method of claim 1, further comprising adhering first and second overlapping polymer based layers to an upper surface of the oxygen barrier layer. ### Claim 15 (depends on 1) The method of claim 1, further comprising sputter-depositing a layer comprising silicon nitride on the glass substrate, wherein the layer comprising silicon nitride is located between the glass substrate and the layer comprising carbon. ### Claim 16 (depends on 1) The method of claim 1, wherein at least prior to heat treatment the release layer that has been ion beam treated is located between and directly contacting the layer comprising carbon and the oxygen barrier layer. ### Claim 17 (depends on 1) The method of claim 1, wherein the layer comprising carbon comprises amorphous DLC and has more spa carbon-carbon bonds than sp2 carbon-carbon bonds. ### Claim 18 (depends on 1) The method of claim 1, wherein the layer comprising carbon comprises hydrogenated DLC. ### Claim 19 (depends on 1) The method of claim 1, wherein the coated article is substantially transparent at least following heat treating and removal of the protective film. ### Claim 20 (depends on 1) The method of claim 1, wherein after removing the oxygen barrier layer and the release layer, the layer comprising carbon is exposed so as to be an outermost layer of the coated article. ### Claim 21 (depends on 1) The method of claim 1, wherein the oxygen barrier layer is an outermost layer of the coating after the coated article has been made and is exposed to ambient atmosphere.