Heat treatable coated article with substoichiometric zirconium oxide based layer and corresponding method
A layer of or including substoichiometric zirconium oxide is sputter deposited on a glass substrate via a substoichiometric zirconium oxide inclusive ceramic sputtering target of or including ZrO x . The coated article, with the substoichiometric ZrO x inclusive layer on the glass substrate, is then heat treated (e.g., thermally tempered) in an atmosphere including oxygen, which causes the substoichiometric ZrO x inclusive layer to transform into a scratch resistant layer of or including stoichiometric or substantially stoichiometric zirconium oxide (e.g., ZrO 2 ), and causes the visible transmission of the coated article to significant increase.
1. A method of making a heat treated coated article, the method comprising:
having a coated article including a coating on a glass substrate, the coating comprising a layer comprising substoichiometric zirconium oxide ZrO x that directly contacts the glass substrate, where “x” is from 1.50 to 1.97; and
heat treating the coated article, including the glass substrate with the layer comprising substoichiometric zirconium oxide ZrO x thereon, so that the heat treating causes visible transmission (T vis ) of the coated article to increase by at least 4% and causes the layer comprising substoichiometric zirconium oxide ZrO x to transform into a layer comprising substantially stoichiometric ZrO x where “x” is from 1.98 to 2.05, and wherein the heat treated coated article comprising the glass substrate and the layer comprising substantially stoichiometric ZrO x has a haze value of no greater than 0.3%.
2. The method of claim 1 , wherein the heat treated coated article comprising the glass substrate and the layer comprising substantially stoichiometric ZrO x has a haze value of no greater than 0.1%.
3. The method of claim 1 , wherein the heat treated coated article comprising the glass substrate and the layer comprising substantially stoichiometric ZrO x has a haze value of no greater than 0.08%.
4. The method of claim 1 , wherein the heat treating causes visible transmission (T vis ) of the coated article to increase by at least 7%.
5. The method of claim 1 , wherein the heat treating causes the layer comprising substoichiometric zirconium oxide ZrO x to transform into a layer comprising substantially stoichiometric ZrO x where “x” is from 1.99 to 2.02.
6. The method of claim 1 , wherein the heat treating causes the layer comprising substoichiometric zirconium oxide ZrO x to transform into a layer comprising stoichiometric ZrO x where “x” is 2.
7. The method of claim 1 , wherein the layer comprising substoichiometric zirconium oxide ZrO x consists of, or consists essentially of, substoichiometric zirconium oxide ZrO x .
8. The method of claim 1 , wherein the layer comprising substantially stoichiometric zirconium oxide ZrO x consists of, or consists essentially of, substantially stoichiometric zirconium oxide ZrO x .
9. The method of claim 1 , wherein in the layer comprising substoichiometric zirconium oxide ZrO x , “x” is from 1.60 to 1.90.
10. The method of claim 1 , wherein in the layer comprising substoichiometric zirconium oxide ZrO x , “x” is from 1.70 to 1.87.
11. The method of claim 1 , wherein after the heat treating the coated article has a visible transmission of at least 75%.
12. The method of claim 1 , wherein after the heat treating the coated article has a visible transmission of at least 80%.
13. The method of claim 1 , wherein after the heat treating the layer comprising substantially stoichiometric zirconium oxide ZrO x has a refractive index (n) of at least 2.21.
14. The method of claim 1 , wherein after the heat treating the layer comprising substantially stoichiometric zirconium oxide ZrO x has a refractive index (n) of at least 2.22.
15. The method of claim 1 , wherein, before and/or after the heat treating, the coated article further includes a layer comprising silicon nitride between the glass substrate and the layer comprising ZrO x .
16. The method of claim 1 , wherein, before and/or after the heat treating, the coated article further includes a layer comprising silver sandwiched between at least first and second dielectric layers on the glass substrate located between the glass substrate and the layer comprising ZrO x .
17. The method of claim 1 , wherein after the heat treating the coated article has a glass side reflective a* color value from −4 to +4 and a glass side reflective b* color value from −12 to +10.
18. The method of claim 1 , wherein after the heat treating the coated article has a glass side reflective a* color value from −2 to +2 and a glass side reflective b* color value from −9 to +8.
19. The method of claim 1 , wherein after the heat treating the coated article has a film side reflective a* color value from −4 to +4 and a film side reflective b* color value from −12 to +10.
20. The method of claim 1 , wherein after the heat treating the coated article has a film side reflective a* color value from −2 to +2 and a film side reflective b* color value from −9 to +8.
21. The method of claim 1 , wherein the layer comprising ZrO x is an uppermost layer of the coating, configured to be exposed to ambient atmosphere, before and/or after the heat treating.
22. The method of claim 1 , further comprising sputter depositing the layer comprising substoichiometric zirconium oxide ZrO x on the glass substrate, directly or indirectly, using at least one ceramic sputtering target comprising ZrO x where in the target “x” is from 1.50 to 1.97.
23. The method of claim 1 , further comprising sputter depositing the layer comprising substoichiometric zirconium oxide ZrO x on the glass substrate, directly or indirectly, using at least one ceramic sputtering target comprising ZrO x where in the target “x” is from 1.60 to 1.90.
24. The method of claim 1 , wherein after the heat treating the layer comprising ZrO x has a physical thickness of from 5 to 50 nm.
25. The method of claim 1 , wherein the heat treating comprises thermal tempering.
26. The method of claim 1 , wherein the heat treating comprises heat treating at temperature(s) of at least 580 degrees C.
27. A method of making a heat treated coated article, the method comprising:
having a coated article including a coating on a glass substrate, the coating comprising a layer comprising substoichiometric zirconium oxide ZrO x that directly contacts the glass substrate, where “x” is from 1.50 to 1.97;
heat treating the coated article, including the glass substrate with the layer comprising substoichiometric zirconium oxide ZrO x thereon, at temperature(s) of at least 580 degrees C. so that the heat treating causes visible transmission (T vis ) of the coated article to increase by at least 4% and causes the layer comprising substoichiometric zirconium oxide ZrO x to transform into a layer comprising substantially stoichiometric ZrO x where “x” is from 1.98 to 2.05, wherein after the heat treating the layer comprising substantially stoichiometric zirconium oxide ZrO x has a refractive index (n) of at least 2.21 and the coated article has a visible transmission of at least 75%; and
wherein after the heat treating the layer comprising substantially stoichiometric zirconium oxide ZrO x is an uppermost layer of the coating and is exposed to ambient atmosphere.
28. The method of claim 27 , wherein after the heat treating the coated article has a glass side reflective a* color value from −4 to +4 and a glass side reflective b* color value from −12 to +10.
29. The method of claim 27 , wherein after the heat treating the coated article has a glass side reflective a* color value from −2 to +2 and a glass side reflective b* color value from −9 to +8.
30. The method of claim 27 , wherein after the heat treating the coated article has a film side reflective a* color value from −4 to +4 and a film side reflective b* color value from −12 to +10.
31. The method of claim 27 , wherein after the heat treating the coated article has a film side reflective a* color value from −2 to +2 and a film side reflective b* color value from −9 to +8.