Low-emissivity glazing
The present invention relates to a glazing coated with an assembly of thin layers using vacuum deposition, said glazing having reflective properties for infrared radiation, while retaining a high transmission in the visible range, and retaining its properties when subjected to a thermal treatment such as bending/toughening. The glazing comprises one or more silver-based layers and dielectric layers, of which at least one underlying dielectric layer in relation to at least one silver-based layer is a titanium oxide- or oxynitride-based layer such as TiMOx or TiMOxNy, in which M is a metal or a plurality of metals or silicon, wherein these metals or silicon are contained in sufficient atomic proportions to prevent a significant transformation of the crystallographic structure of the previously deposited titanium oxide-based layer under the action of the thermal treatment.
1. A glazing unit comprising an assembly of thin layers obtained by a vacuum deposition technique, said assembly of thin layers comprising:
a substrate;
a first silver-based layer;
a titanium oxide- or oxynitride-based dielectric layer of TiMO x or TiMO x N y underlying the first silver-based layer where M is selected from one or more of the group consisting of Zr, Nb, Hf, Ta, Nd, V, Ce, W, Mo, La, and Y,
wherein an atomic proportion of M in association with the titanium in the titanium oxide- or oxynitride-based layer, M/Ti, is not less than 0.1, and
wherein the assembly of thin layers does not comprise any layers of TiO x between the substrate and the first silver layer.
2. The glazing unit according to claim 1 , wherein the titanium oxide- or oxynitride-based layer is a titanium oxynitride-based layer and nitrogen is not higher than 30% of a N 2 /O 2 ratio in the titanium oxynitride-based layer.
3. The glazing unit according to claim 1 , wherein the titanium oxide- or oxynitride-based layer has a thickness of not less than 8 nm.
4. The glazing unit according to claim 1 , wherein the titanium oxide- or oxynitride-based layer has a refractive index higher than 2.2.
5. The glazing unit according to claim 1 , wherein a zinc oxide-based layer with a thickness at most equal to 10 nm is located below the first silver-based layer and in contact therewith.
6. The glazing unit according to claim 5 , wherein the zinc oxide-based layer is a layer selected from the group consisting of ZnO, ZnAlO z , ZnSnO z and ZnMgO z , in which the atomic proportion of Al/Zn, Sn/Zn or Mg/Zn is not higher than 0.15.
7. The glazing unit according to claim 1 , wherein the first silver-based layer is covered by at least one TiO w , titanium-based barrier layer with w≦2, or an NiCrO v layer or both.
8. The glazing unit according to claim 7 , wherein each of the TiO w and NiCrO v layers individually has a thickness of not more than 6 nm, and if both the TiO w layer and the NiCrO v layer are present they have a combined thickness of not more than 10 nm.
9. The glazing unit according to claim 1 , wherein the assembly of thin layers has a single silver-based layer in a quantity in the range of between 80 and 160 mg/m 2 .
10. The glazing unit according to claim 9 , wherein after a thermal treatment at a temperature higher than 650° C. and for a period of at least 3 minutes, the quality of the silver-based layer or layers is such that
Q×∈< 5.0
wherein Q is expressed in mg/m 2 and ∈ is the normal emissivity.
11. The glazing unit according to claim 1 , comprising a layer assembly:
glass/TiMO x or TiMO x Ny/ZnO or ZnAlO z or ZnSnO z or ZnMgO z /Ag/barrier/dielectric II.
12. The glazing unit according to claim 11 additionally comprising one or more dielectric layers located between the glass and the TiMO x or TiMO x N y layer and/or above this layer below the ZnO or ZnAlO z or ZnSnO z or ZnMgO z layer.
13. The glazing unit according to claim 12 , comprising one of the following structures:
(1) glass/dielectric/TiMO x or TiMO x N y /ZnO or ZnAlO z or ZnSnO z or ZnMgO z /Ag/barrier/dielectric II,
(2) glass/TiMO x or TiMO x N y /dielectric/ZnO or ZnAlO z or ZnSnO z or ZnMgO z /Ag/barrier/dielectric II, and
(3) glass/dielectric/TiMO x or TiMO x N y /dielectric/ZnO or ZnAlO z or ZnSnO z or ZnMgO z /Ag/barrier/dielectric II,
wherein the dielectric layers for the structure (3) are identical or different.
14. The glazing unit according to claim 13 , wherein the dielectric layers comprise at least one zinc and tin mixed oxide-based layer with atomic proportion of Zn/Sn in the range of between 30 and 70%.
15. The glazing unit according to claim 14 , wherein in addition to the TiMO x or TiMO x N y layer one or more additional dielectric layers (dielectric III) are located above and/or below this TiMO x or TiMO x N y layer.
16. The glazing unit according to claim 1 , comprising at least two silver-based layers, each of these layers having at least one underlying assembly of layers of
TiMO x or TiMO x N y /ZnO, ZnAlO z , ZnSnO z , or ZnMgO z .
17. The glazing according to claim 1 , wherein the assembly of thin layers has a reflective property for infrared radiation and a high transmission in the visible range.
18. The glazing according to claim 1 , wherein properties of the assembly of thin layers are not substantially changed when the glazing unit is subjected to a thermal treatment.
19. The glazing according to claim 1 , wherein the metal or metals are in sufficient atomic proportions to prevent a significant transformation of a crystallographic structure of the previously deposited titanium oxide-based layer under a thermal treatment.
20. The glazing according to claim 1 , wherein the assembly of thin layers has been heated to a temperature of 600° C. or more.
21. The glazing according to claim 1 , wherein the atomic proportion of M in association with the titanium in the titanium oxide- or oxynitride-based layer, M/Ti, is not less than 0.15, and wherein if the titanium oxide- or oxynitride-based layer is a titanium oxynitride-based layer nitrogen is not higher than 25% of the N 2 /O 2 ratio in the titanium oxynitride-based layer.
22. The glazing according to claim 1 , wherein the atomic proportion of M in association with the titanium in the titanium oxide- or oxynitride-based layer, M/Ti, is not less than 0.2, and wherein if the titanium oxide- or oxynitride-based layer is a titanium oxynitride-based layer nitrogen is not higher than 20% of the N 2 /O 2 ratio in the titanium oxynitride-based layer.
23. The glazing according to claim 1 , wherein M is selected from one or more of the group consisting of Zr, Nb, and Hf.
24. The glazing according to claim 1 , wherein the first silver layer is a closest silver layer to the substrate.
25. A glazing unit having an assembly of thin layers comprising:
glass/TiMO x or TiMO x Ny/ZnO or ZnAlO or ZnSnO z or ZnMgO z /Ag/barrier/dielectric II,
wherein the TiMO x or TiMO x N y is a dielectric layer where M is selected from one or more of the group consisting of Zr, Nb, Hf, Ta, Nd, V, Ce, W, Mo, La, Y, Al, and silicon,
wherein an atomic proportion of M in association with the titanium in the titanium oxide- or oxynitride-based layer, M/Ti, is not less than 0.1,
wherein the assembly of thin layers does not comprise any layers of TiO x between the substrate and the first silver layer, and
wherein the ZnO or ZnAlO z or ZnSnO z or ZnMgO z layer is in direct contact with the Ag layer and the Ag layer is a closest Ag layer to the glass.
26. The glazing unit according to claim 25 further comprising one or more dielectric layers located between the glass and the TiMO x or TiMO x N y layer and/or above this layer and below the ZnO or ZnAlO z or ZnSnO z or ZnMgO z layer.
27. The glazing unit according to claim 26 , comprising one of the following structures:
(1) glass/dielectric/TiMO x or TiMO x N y /ZnO or ZnAlO z or ZnSnO z or ZnMgO z /Ag/barrier/dielectric II,
(2) glass/TiMO x or TiMO x N y /dielectric/ZnO or ZnAlO z or ZnSnO z or ZnMgO z /Ag/barrier/dielectric II, and
(3) glass/dielectric/TiMO x or TiMO x N y /dielectric/ZnO or ZnAlO z or ZnSnO z or ZnMgO z /Ag/barrier/dielectric II,
wherein the dielectric layers for the structure (3) are identical or different.
28. The glazing unit according to claim 27 , wherein the dielectric or dielectric II layer comprises at least one zinc and tin mixed oxide-based layer with an atomic proportion of Zn/Sn in the range of between 30 and 70%.
29. The glazing unit according to claim 25 , wherein after a thermal treatment at a temperature higher than 650° C. and for a period of at least 3 minutes, the quality of the Ag layer or layers is such that
Q×∈< 5.0
wherein Q is expressed in mg/m 2 and ∈ is the normal emissivity.
30. The glazing unit according to claim 25 , wherein titanium oxide- or oxynitride-based layer is a titanium oxynitride-based layer and nitrogen is not higher than 30% in the N 2 /O 2 ratio in the titanium oxynitride-based layer.
31. The glazing according to claim 25 , wherein the metal or metals or silicon are in sufficient atomic proportions to prevent a significant transformation of a crystallographic structure of the previously deposited titanium oxide-based layer under a thermal treatment.
32. The glazing according to claim 25 , wherein M is selected from one or more of the group consisting of Zr, Nb, and Ta.
33. The glazing unit according to claim 25 , wherein the titanium oxide- or oxynitride-based layer has a thickness of not less than 8 nm.
34. A glazing unit comprising an assembly of thin layers obtained by a vacuum deposition technique, said assembly of thin layers comprising:
a substrate;
a first silver-based layer;
a titanium oxide- or oxynitride-based dielectric layer of TiMO x or TiMO x N y underlying the first silver-based layer where M is selected from one or more of the group consisting of Zr, Nb, Hf, Ta, Nd, V, Ce, W, Mo, La, Y, Al, and silicon,
wherein an atomic proportion of M in association with the titanium in the titanium oxide- or oxynitride-based layer, M/Ti, is not less than 0.1, and
wherein the assembly of thin layers does not comprise any layers of TiO x between the substrate and the first silver layer, and
wherein the titanium oxide- or oxynitride-based layer has a thickness of not less than 8 nm.
35. The glazing according to claim 34 , wherein M is selected from one or more of the group consisting of Zr, Nb, and Ta.