# US 9,038,419 B2 · Method of making heat treated coated article using 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 9,038,419 B2 - Document ID: US9038419B2 - Status: Granted - Kind: B2 - Application number: 13/491,743 - Filed: 2012-06-08 - Published: 2013-12-12 - Granted: 2015-05-26 - Earliest claimed: 2012-06-08 - Assignees: Centre Luxembourgeois de Recherches pour le Verre et la Ceramique S.A. (C.R.V.C.); Guardian Industries Corp. - Applicants: Jens-Peter Müller; Vijayen S. Veerasamy - Inventors: Jens-Peter Müller; Vijayen S. Veerasamy - Web page: https://patentgrep.com/patent/US9038419B2 ## CPC - C03C 17/22: with other inorganic material (C03C17/34, C03C17/44 take precedence) - C03B 25/02: in a discontinuous way - C03B 27/00: Tempering {or quenching} glass products - C03C 17/3435: {comprising a nitride, oxynitride, boronitride or carbonitride} - C03C 17/3441: {comprising carbon, a carbide or oxycarbide} - C03C 2217/78: Coatings specially designed to be durable, e.g. scratch-resistant - C03C 2218/328: Partly or completely removing a coating - 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) substantially transparent coated article to be used in shower door applications, window applications, tabletop applications, or any other suitable applications. Certain embodiments relate to a method of making a coated article including 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. 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 oxynitride (e.g., ZnOxNz). 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 heat treated coated article, the method comprising: heat treating a coated glass substrate, the coated glass substrate comprising, prior to the heat treating, a glass substrate, a layer comprising diamond-like carbon (DLC) on the glass substrate, and a protective film on the glass substrate over at least the layer comprising DLC, wherein the protective film includes a release layer and an oxygen barrier layer, the release layer and the oxygen barrier layer being of different material, and wherein the release layer comprises zinc oxynitride ZnOxNz where a nitrogen to oxygen ratio z/x in the release layer is from 0.55 to 0.77: during said heat treating of the coated glass substrate with the layer comprising DLC and the protective film thereon, the protective film prevents significant burnoff of the layer comprising DLC, and wherein the heat treating comprises heating the glass substrate to temperature(s) sufficient for thermal tempering, heat strengthening, and/or heat bending; and exposing the protective film to a release liquid and removing at least part of the protective film during and/or after said heat treating. ### Claim 2 (depends on 1) The method of claim 1, wherein the release layer consists essentially of zinc oxynitride, optionally doped with aluminum. ### Claim 3 (depends on 1) The method of claim 1, wherein the nitrogen to oxygen ratio z/x in the release layer is from 0.60 to 0.77. ### Claim 4 (depends on 1) The method of claim 1, wherein the nitrogen to oxygen ratio z/x in the release layer is from 0.63 to 0.77. ### Claim 5 (depends on 1) The method of claim 1, wherein the protective film further comprises a layer comprising silicon nitride located over at least the oxygen barrier layer. ### Claim 6 (depends on 1) The method of claim 1, wherein the coated glass substrate further comprises a layer comprising silicon nitride located between the glass substrate and the layer comprising DLC. ### Claim 7 (depends on 1) The method of claim 1, wherein the heat treating comprises heating the glass substrate with the layer comprising DLC and the protective film thereon using at least temperature(s) of at least 550 degrees C. ### Claim 8 (depends on 1) The method of claim 1, wherein the oxygen barrier layer comprises aluminum nitride. ### Claim 9 (depends on 1) The method of claim 1, wherein the oxygen barrier layer consists essentially of aluminum nitride. ### Claim 10 (depends on 1) The method of claim 1, wherein the release layer is located between at least the glass substrate and the oxygen barrier layer. ### Claim 11 (depends on 1) The method of claim 1, wherein the release layer and the oxygen barrier layer directly contact each other. ### Claim 12 (depends on 1) The method of claim 1, wherein the layer comprising DLC comprises amorphous DLC and has more sp3 carbon-carbon bonds than sp2 carbon-carbon bonds. ### Claim 13 (depends on 1) The method of claim 1, wherein the layer comprising DLC has an average hardness of at least 20 GPa. ### Claim 14 (depends on 1) The method of claim 1, wherein the layer comprising DLC is hydrogenated. ### Claim 15 (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 16 (depends on 1) The method of claim 1, wherein after said removing step at least part of the layer comprising DLC is exposed so as to be an outermost layer of the coated article. ### Claim 17 A method of making a heat treated coated article, the method comprising: heat treating a coated glass substrate, the coated glass substrate comprising, prior to the heat treating, a glass substrate, a layer comprising carbon on the glass substrate, and a protective film on the glass substrate over at least the layer comprising carbon, wherein the protective film includes a release layer and an oxygen barrier layer, wherein the release layer comprises zinc oxynitride ZnOxNz and where at least one of: (i) a nitrogen to oxygen ratio z/x in the release layer is at least 0.40, and/or (ii) a ratio of nitrogen gas to oxygen gas during sputtering in an atmosphere in which the release layer is sputter-deposited is from 0.55 to 0.77: during said heat treating of the coated glass substrate with the layer comprising carbon and the protective film thereon, the protective film prevents significant burnoff of the layer comprising carbon, and wherein the heat treating comprises heating the glass substrate to temperature(s) sufficient for thermal tempering, heat strengthening, and/or heat bending; and removing at least part of the protective film during and/or after said heat treating. ### Claim 18 (depends on 17) The method of claim 17, wherein the release layer consists essentially of zinc oxynitride, optionally doped with aluminum. ### Claim 19 (depends on 17) The method of claim 17, wherein the heat treating comprises heating the glass substrate with the layer comprising carbon and the protective film thereon using at least temperature(s) of at least 550 degrees C. ### Claim 20 (depends on 17) The method of claim 17, wherein the oxygen barrier layer comprises aluminum nitride.