Low-E matchable coated articles having absorber film and corresponding methods
10759693 ยท 2020-09-01
Assignee
Inventors
- Yongli Xu (Plymouth, MI, US)
- Brent Boyce (Novi, MI)
- Salah Boussaad (Auburn, MI, US)
- Philip J. Lingle (Temperance, MI)
- Jingyu Lao (Saline, MI, US)
- Richard VERNHES (Auburn Hills, MI, US)
Cpc classification
C03C17/3607
CHEMISTRY; METALLURGY
C03C17/3668
CHEMISTRY; METALLURGY
C03C17/3626
CHEMISTRY; METALLURGY
C03C17/3681
CHEMISTRY; METALLURGY
C03C17/3642
CHEMISTRY; METALLURGY
C03C17/3639
CHEMISTRY; METALLURGY
International classification
B32B15/04
PERFORMING OPERATIONS; TRANSPORTING
B32B17/06
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A low-E coating has good color stability (a low E* value) upon heat treatment (HT). Thermal stability may be improved by the provision of an as-deposited crystalline or substantially crystalline layer of or including zinc oxide, doped with at least one dopant (e.g., Sn), immediately under an infrared (IR) reflecting layer of or including silver; and/or by the provision of at least one dielectric layer of or including an oxide of zirconium. These have the effect of significantly improving the coating's thermal stability (i.e., lowering the E* value). An absorber film may be designed to adjust visible transmission and provide desirable coloration, while maintaining durability and/or thermal stability. The dielectric layer (e.g., of or including an oxide of Zr) may be sputter-deposited so as to have a monoclinic phase in order to improve thermal stability.
Claims
1. A coated article including a coating on a glass substrate, wherein the coating comprises: a first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %), provided on the glass substrate; a first infrared (IR) reflecting layer comprising silver located on the glass substrate and directly over and contacting the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn; wherein no silicon nitride based layer is located directly under and contacting the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn; at least one dielectric layer having monoclinic phase and comprising an oxide of zirconium; wherein the at least one dielectric layer having monoclinic phase and comprising the oxide of zirconium is located: (1) between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %), and/or (2) between at least the first IR reflecting layer comprising silver and a second IR reflecting layer comprising silver of the coating; an absorber film including a layer comprising silver, wherein a ratio of a physical thickness of the first IR reflecting layer comprising silver to a physical thickness of the layer comprising silver of the absorber film is at least 5:1, and wherein the layer comprising silver of the absorber film does not directly contact the first IR reflecting layer; and wherein the coated article is configured to have, measured monolithically, at least two of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 3.0 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
2. The coated article of claim 1, wherein the absorber film further comprises a layer comprising an oxide of Ni and/or Cr located over and directly contacting the layer comprising silver of the absorber film.
3. The coated article of claim 1, wherein the absorber film is located over the first IR reflecting layer, so that the first IR reflecting layer is located between at least the absorber film and the glass substrate.
4. The coated article of claim 1, wherein the ratio of the physical thickness of the first IR reflecting layer comprising silver to the physical thickness of the layer comprising silver of the absorber film is at least 8:1.
5. The coated article of claim 1, wherein the ratio of the physical thickness of the first IR reflecting layer comprising silver to the physical thickness of the layer comprising silver of the absorber film is at least 10:1.
6. The coated article of claim 1, wherein the ratio of the physical thickness of the first IR reflecting layer comprising silver to the physical thickness of the layer comprising silver of the absorber film is at least 15:1.
7. The coated article of claim 1, wherein the layer comprising silver of the absorber film is less than 60 thick.
8. The coated article of claim 1, wherein the layer comprising silver of the absorber film is less than 30 thick.
9. The coated article of claim 1, wherein the layer comprising silver of the absorber film is less than 15 thick.
10. The coated article of claim 1, wherein the coated article is configured to have, measured monolithically, all three of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 3.0 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
11. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase is located at least between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %).
12. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase is located at least between at least the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating.
13. The coated article of claim 1, wherein the first crystalline or substantially crystalline layer comprising zinc oxide is doped with from about 1-20% Sn (wt. %).
14. The coated article of claim 1, wherein the first crystalline or substantially crystalline layer comprising zinc oxide is doped with from about 5-15% Sn (wt. %).
15. The coated article of claim 1, wherein the first crystalline or substantially crystalline layer comprising zinc oxide doped with Sn is crystalline or substantially crystalline as sputter-deposited.
16. The coated article of claim 1, wherein the coated article is configured to have, measured monolithically, all of: (i) a transmissive E* value of no greater than 2.5 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 2.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.0 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
17. The coated article of claim 1, wherein the coated article is configured to have, measured monolithically, at least two of: (i) a transmissive E* value of no greater than 2.3 upon a reference heat treatment for 16 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 2.0 upon the reference heat treatment for 16 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.0 upon the reference heat treatment for 16 minutes at a temperature of about 650 degrees C.
18. The coated article of claim 1, wherein said coating has a sheet resistance (R.sub.s) of no greater than 10 ohms/square.
19. The coated article of claim 1, wherein said coated article, measured monolithically, has a visible transmission of at least 40%.
20. The coated article of claim 1, wherein the coating as deposited further comprises a first amorphous or substantially amorphous layer comprising zinc stannate located on the glass substrate over at least the first IR reflecting layer comprising silver.
21. The coated article of claim 20, wherein the first amorphous or substantially amorphous layer comprising zinc stannate has a metal content of from about 40-60% Zn and from about 40-60% Sn (wt. %).
22. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase may be configured to have a monoclinic peak thereof reduce upon said reference heat treatment.
23. The coated article of claim 1, wherein the coating further comprises: a second IR reflecting layer comprising silver located on the glass substrate over at least the first IR reflecting layer comprising silver, a second crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %), located under and directly contacting the second IR reflecting layer comprising silver; wherein no silicon nitride based layer is located between the glass substrate and the second IR reflecting layer comprising silver; and wherein the layer comprising silver of the absorber film does not directly contact any of the first and second IR reflecting layers.
24. The coated article of claim 1, wherein the coated article is not thermally tempered.
25. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase and comprising zirconium oxide is located both: (1) between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %), and (2) between at least the first IR reflecting layer comprising silver and the absorber film.
26. The coated article of claim 25, wherein the at least one dielectric layer comprising monoclinic phase comprises from 0-5% nitrogen (atomic %).
27. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase comprises ZrO.sub.2.
28. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase consists essentially of the oxide of zirconium.
29. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase is configured to realize a density change of at least 0.25 g/cm.sup.3 upon said reference heat treatment.
30. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase is configured to realize a density change of at least 0.30 g/cm.sup.3 upon said reference heat treatment.
31. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase is configured to realize a density change of at least 0.35 g/cm.sup.3 upon said reference heat treatment.
32. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase comprises an oxide of zirconium, and has a metal content of at least 80% Zr.
33. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase and comprising the oxide of zirconium has a thickness of from 40-170 A.
34. The coated article of claim 1, wherein the at least one dielectric layer comprising monoclinic phase and comprising the oxide of zirconium, further comprises Si.
35. The coated article of claim 1, wherein the coated article is configured to have, measured monolithically, at least two of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
36. The coated article of claim 1, wherein the coated article is configured to have, measured monolithically, all three of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
37. A coated article including a coating on a glass substrate, wherein the coating comprises: a layer comprising zinc oxide provided on the glass substrate; a first infrared (IR) reflecting layer comprising silver located on the glass substrate and directly over and contacting the layer comprising zinc oxide; wherein no silicon nitride based layer is located directly under and contacting the layer comprising zinc oxide; at least one dielectric layer comprising monoclinic phase and comprising an oxide of zirconium; wherein the at least one dielectric layer comprising monoclinic phase and comprising the oxide of zirconium is located: (1) between at least the glass substrate and the layer comprising zinc oxide, and/or (2) between at least the first IR reflecting layer comprising silver and a second IR reflecting layer comprising silver of the coating; and wherein the coated article is configured to have, measured monolithically, at least two of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 3.0 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
38. The coated article of claim 37, wherein the coated article is not thermally tempered.
39. The coated article of claim 37, wherein the at least one dielectric layer comprising monoclinic phase includes two layers comprising zirconium oxide, one of which is located (1) between at least the glass substrate and the layer comprising zinc oxide, and the other of which is located (2) between at least the first and second IR reflecting layers comprising silver.
40. The coated article of claim 37, wherein the at least one dielectric layer comprising monoclinic phase comprises from 0-5% nitrogen (atomic %).
41. The coated article of claim 37, wherein the at least one dielectric layer comprising monoclinic phase and comprising the oxide of zirconium, further includes Si.
42. The coated article of claim 37, wherein the at least one dielectric layer comprising monoclinic phase consists essentially of an oxide of zirconium.
43. The coated article of claim 37, wherein the at least one dielectric layer comprising monoclinic phase is configured to realize a density change of at least 0.25 g/cm.sup.3 upon said reference heat treatment, and wherein the at least one dielectric layer comprising monoclinic phase may be configured to have a monoclinic peak thereof reduce upon said reference heat treatment.
44. The coated article of claim 37, wherein the at least one dielectric layer comprising monoclinic phase is configured to realize a density change of at least 0.30 g/cm.sup.3 upon said reference heat treatment.
45. The coated article of claim 37, wherein the at least one dielectric layer comprising monoclinic phase is configured to realize a density change of at least 0.35 g/cm.sup.3 upon said reference heat treatment.
46. The coated article of claim 37, wherein the at least one dielectric layer comprising monoclinic phase has a metal content of at least 80% Zr.
47. The coated article of claim 37, wherein the at least one dielectric layer comprising monoclinic phase has a thickness of from 40-250 A.
48. The coated article of claim 37, wherein the at least one dielectric layer comprising monoclinic phase further comprises tetragonal phase.
49. The coated article of claim 37, wherein the coated article is configured to have, measured monolithically, at least two of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
50. The coated article of claim 37, wherein the coated article is configured to have, measured monolithically, all three of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
51. A coated article including a coating on a glass substrate, wherein the coating comprises: a layer comprising zinc oxide provided on the glass substrate; a first infrared (IR) reflecting layer comprising silver located on the glass substrate and directly over and contacting the layer comprising zinc oxide; wherein no silicon nitride based layer is located directly under and contacting the layer comprising zinc oxide; at least one dielectric layer comprising monoclinic phase and comprising metal oxide; wherein the at least one dielectric layer comprising monoclinic phase and comprising metal oxide is located: (1) between at least the glass substrate and the layer comprising zinc oxide, and/or (2) between at least the first IR reflecting layer comprising silver and a second IR reflecting layer comprising silver of the coating; and wherein the coated article is configured to have, measured monolithically, at least two of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 3.0 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
52. A method of making a coated article including a coating on a glass substrate, the method comprising: sputter-depositing a layer comprising zinc oxide on the glass substrate; sputter-depositing a first infrared (IR) reflecting layer comprising silver on the glass substrate over and contacting the layer comprising zinc oxide; sputter-depositing at least one dielectric layer comprising monoclinic phase on the glass substrate, wherein the dielectric layer comprising monoclinic phase comprises an oxide of zirconium; wherein the at least one dielectric layer comprising monoclinic phase and comprising the oxide of zirconium is located: (1) between at least the glass substrate and the layer comprising zinc oxide, and/or (2) between at least the first IR reflecting layer comprising silver and a second IR reflecting layer comprising silver of the coating; and wherein the coated article is configured to have, measured monolithically, at least two of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 3.0 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
53. The method of claim 52, wherein said sputter-depositing the at least one dielectric layer comprising monoclinic phase on the glass substrate uses an oxygen gas flow of at least 6 ml/kW.
54. The method of claim 52, wherein said sputter-depositing the at least one dielectric layer comprising monoclinic phase on the glass substrate uses an oxygen gas flow of at least 8 ml/kW.
55. The method of claim 52, wherein said at least one dielectric layer comprising monoclinic phase comprises ZrO.sub.2.
56. The method of claim 52, wherein the coated article is configured to have, measured monolithically, all three of: (i) a transmissive E value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
57. The method of claim 52, further comprising heat treating the coated article via said reference heat treatment so that the at least one dielectric layer comprising monoclinic phase realizes a density change of at least 0.25 g/cm.sup.3 upon said reference heat treatment.
58. The method of claim 52, wherein said sputter-depositing the at least one dielectric layer comprising monoclinic phase on the glass substrate uses a metal target.
59. The method of claim 58, wherein said sputter-depositing the at least one dielectric layer comprising monoclinic phase on the glass substrate uses an oxygen gas flow of at least 6 ml/kW.
60. The method of claim 52, wherein said sputter-depositing the at least one dielectric layer comprising monoclinic phase on the glass substrate uses a ceramic target.
61. The method of claim 52, wherein said at least one dielectric layer comprising monoclinic phase further comprises tetragonal phase.
62. The method of claim 52, wherein the at least one dielectric layer comprising monoclinic phase is configured to have a monoclinic peak thereof reduce upon said reference heat treatment.
Description
IN THE DRAWINGS
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DETAILED DESCRIPTION OF CERTAIN EXEMPLARY EMBODIMENTS OF THE INVENTION
(60) Referring now more particularly to the accompanying drawings in which like reference numerals indicate like parts/layers/materials throughout the several views.
(61) Certain embodiments of this invention provide a coating or layer system that may be used in coated articles that may be used monolithically for windows, in insulating glass (IG) window units (e.g., on surface #2 or surface #3 in IG window unit applications), laminated window units, vehicle windshields, and/or other vehicle or architectural or residential window applications. Certain embodiments of this invention provide a layer system that combines one or more of high visible transmission, good durability (mechanical and/or chemical) before and/or after HT, and good color stability upon heat treatment. It will be shown herein how certain layers stacks surprisingly enable this unique combination.
(62) With regard to color stability, certain embodiments of this invention have excellent color stability (i.e., a low value of E*; where is indicative of change in view of heat treatment) with heat treatment (e.g., thermal tempering or heat bending) monolithically and/or in the context of dual pane environments such as IG units or windshields. Such heat treatments (HTs) often necessitate heating the coated substrate to temperatures of at least about 1100 F. (593 C.) and up to 1450 F. (788 C.) [more preferably from about 1100 to 1200 degrees F., and most preferably from 1150-1200 degrees F.] for a sufficient period of time to insure the end result (e.g., tempering, bending, and/or heat strengthening). Certain embodiments of this invention combine one or more of (i) color stability with heat treatment, and (ii) the use of a silver inclusive layer for selective IR reflection.
(63) Example embodiments of this invention relate to low-E coated articles that have approximately the same color characteristics as viewed by the naked eye both before and after heat treatment (e.g., thermal tempering), and corresponding methods. Such articles may in certain example embodiments combine one or more of: (1) desirable visible transmission characteristics, (2) good durability before and/or after heat treatment, (3) a low E* value which is indicative of color stability upon heat treatment (HT), and/or (4) an absorber film designed to adjust visible transmission and provide desirable coloration for the coated article, while maintaining durability and/or thermal stability.
(64) In certain example embodiments, the absorber film may be a multi-layer absorber film including a first layer 57 of or including silver (Ag), and a second layer 59 of or including NiCr which may be partially or fully oxided (NiCrO.sub.x). See
(65) A single layer of NiCr (or other suitable material) may also be used as an absorber film in low-E coatings in certain example embodiments of this invention. For example, see absorber film 42 in
(66) Surprisingly, and unexpectedly, it has been found that the provision of an as-deposited crystalline or substantially crystalline layer 3, 3 (and/or 13) (e.g., at least 50% crystalline, more preferably at least 60% crystalline) of or including zinc oxide, doped with at least one dopant (e.g., Sn), immediately under and directly contacting an infrared (IR) reflecting layer of or including silver 7 (and/or 19) in a low-E coating 30 has the effect of significantly improving the coating's thermal stability (i.e., lowering the E* value). Substantially crystalline as used herein means at least 50% crystalline, more preferably at least 60% crystalline, and most preferably at least 70% crystalline. One or more such crystalline, or substantially crystalline, layers 3, 3 13 may be provided under one or more corresponding IR reflecting layers comprising silver 7, 19, in various example embodiments of this invention. Thus, the crystalline or substantially crystalline layer 3 (or 3) and/or 13 of or including zinc oxide, doped with at least one dopant (e.g., Sn), immediately under an infrared (IR) reflecting layer 7 and/or 19 of or including silver may be used in single silver low-E coatings, double-silver low-E coatings (e.g., such as shown in
(67) It has also been surprisingly and unexpectedly found that the provision of a dielectric layer(s) (e.g., 2 and/or 2) of or including silicon oxide, zirconium oxide, silicon zirconium oxide and/or silicon zirconium oxynitride (e.g., SiZrO.sub.x, ZrO.sub.2, SiO.sub.2, and/or SiZrO.sub.xN.sub.y) also provides for improved thermal stability of the coated article as shown for example in
(68) The dielectric layer(s) (e.g., 2 and/or 2) of or including silicon oxide (e.g., SiO.sub.2), zirconium oxide (e.g., ZrO.sub.2), silicon zirconium oxide and/or silicon zirconium oxynitride may or may not be provided in combination with an as-deposited crystalline or substantially crystalline (e.g., at least 50% crystalline, more preferably at least 60% crystalline) layer(s) (e.g., 3 and/or 13) of or including zinc oxide, doped with at least one dopant (e.g., Sn), immediately under an infrared (IR) reflecting layer, in various example embodiments of this invention. Both approaches, which may be used together, but need not be used together, improve thermal stability thereby lowering E* values. For example, in certain embodiments where the dielectric layer(s) (e.g., 2 and/or 2) of or including silicon oxide (e.g., SiO.sub.2), zirconium oxide (e.g., ZrO.sub.2), silicon zirconium oxide and/or silicon zirconium oxynitride is used, the contact/seed layer immediately under one or both silver(s) may be of or including zinc oxide doped with aluminum (instead of with Sn) and that contact/seed layer need not be crystalline (e.g., see
(69) In certain example embodiments, it has surprisingly and unexpectedly been found that initially sputter-depositing the dielectric layer(s) 2 and/or 2 of or including zirconium oxide, zirconium oxynitride, silicon zirconium oxide and/or silicon zirconium oxynitride (e.g., SiZrO.sub.x, ZrO.sub.2, SiO.sub.2, and/or SiZrO.sub.xN.sub.y) so as to comprise a monoclinic phase crystalline structure is advantageous in that it results in improved thermal stability (lower E* value) and/or reduced change in visible transmission (e.g., T.sub.vis or TY) of the coated article upon heat treatment (HT). For example, see
(70) It has also surprisingly been found that increased thicknesses for the dielectric layer(s) 2 and/or 2 of or including silicon oxide, zirconium oxide, zirconium oxynitride, silicon zirconium oxide and/or silicon zirconium oxynitride (e.g., SiZrO.sub.x, ZrO.sub.2, SiO.sub.2, and/or SiZrO.sub.xN.sub.y) tend to result in smaller changes in sheet resistance (R.sub.s) and visible transmission upon HT, and thus lower E* values of the coated article. In certain example embodiments, one or both of the dielectric layer(s) 2 and/or 2 of or including silicon oxide, zirconium oxide, zirconium oxynitride, silicon zirconium oxide and/or silicon zirconium oxynitride (e.g., SiZrO.sub.x, ZrO.sub.2, SiO.sub.2, and/or SiZrO.sub.xN.sub.y) may each have a physical thickness of from about 10-400 angstroms (), more preferably from about 40-170 , and most preferably from about 80-140 .
(71) It has also been surprisingly and unexpectedly found that the provision of no silicon nitride based layer (e.g., Si.sub.3N.sub.4, optionally doped with 1-10% Al or the like) directly under and contacting the lowermost doped zinc oxide based layer 3 between the glass substrate 1 and the lowermost silver based layer 7, in combination with the crystallized or substantially crystallized phase of the doped zinc oxide based layer 3 as deposited, allows for improved thermal stability upon heat treatment (lower E* values) to be realized. For example, see the coatings of
(72) In certain example embodiments, it has also been found that providing an absorber layer (e.g., NiCr, NiCrN.sub.x, NbZr, and/or NbZrN.sub.x) 42 between the glass substrate and the dielectric layer 2 of or including silicon oxide, zirconium oxide, silicon zirconium oxide and/or silicon zirconium oxynitride (e.g., SiZrO.sub.x, ZrO.sub.2, SiO.sub.2, and/or SiZrO.sub.xN.sub.y) may advantageously reduce glass side visible reflection (R.sub.gY) of the coated article in a desirable manner and allows the visible transmission to be tuned in a desirable manner. The absorber layer 42 may be provided between and contacting a pair of silicon nitride based layers 41 and 43 (e.g., of or including Si.sub.3N.sub.4, optionally doped with 1-10% Al or the like, and optionally including from 0-10% oxygen) in certain example embodiments, such as shown in
(73) In certain example embodiments, measured monolithically, in view of the above structure (e.g., see
(74) In certain example embodiments, measured monolithically, the coated article is configured to have a visible transmission (T.sub.vis or Y), before or after any optional HT, of at least about 30%, more preferably of at least about 35%, more preferably of at least about 40%, more preferably of at least about 50%. In certain example embodiments, the low-E coating has a sheet resistance (SR or R.sub.s) of no greater than 20 ohms/square, more preferably no greater than 10 ohms/square, and most preferably no greater than 2.5 or 2.2 ohms/square, before and/or after optional heat treatment. In certain example embodiments, the low-E coating has a hemispherical emissivity/emittance (E.sub.h) of no greater than 0.08, more preferably no greater than 0.05, and most preferably no greater than 0.04.
(75) The value E* is important in determining whether or not upon heat treatment (HT) there is matchability, or substantial matchability, in the context of this invention. Color herein is described by reference to the conventional a*, b* values, which in certain embodiments of this invention are both negative in order to provide color in the desired substantially neutral color range tending to the blue-green quadrant. For purposes of example, the term a* is simply indicative of how much color value a* changes due to heat treatment.
(76) The term E* (and E) is well understood in the art and is reported, along with various techniques for determining it, in ASTM 2244-93 as well as being reported in Hunter et. al., The Measurement of Appearance, 2.sup.nd Ed. Cptr. 9, page 162 et seq. [John Wiley & Sons, 1987]. As used in the art, E* (and E) is a way of adequately expressing the change (or lack thereof) in reflectance and/or transmittance (and thus color appearance, as well) in an article after or due to heat treatment. E may be calculated by the ab technique, or by the Hunter technique (designated by employing a subscript H). E corresponds to the Hunter Lab L, a, b scale (or L.sub.h, a.sub.h, b.sub.h). Similarly, E* corresponds to the CIE LAB Scale L*, a*, b*. Both are deemed useful, and equivalent for the purposes of this invention. For example, as reported in Hunter et. al. referenced above, the rectangular coordinate/scale technique (CIE LAB 1976) known as the L*, a*, b* scale may be used, wherein: L* is (CIE 1976) lightness units a* is (CIE 1976) red-green units b* is (CIE 1976) yellow-blue units
(77) and the distance E* between L*.sub.o a*.sub.o b*.sub.o and L*.sub.1 a*.sub.i b*.sub.i is:
E*=[(L*).sup.2+(.sub.a*).sup.2+(b*).sup.2].sup.1/2(1)
where:
L*=L*.sub.1L*.sub.o(2)
a*=a*.sub.1a*.sub.o(3)
b*=b*.sub.1b*.sub.o(4)
where the subscript o represents the coated article before heat treatment and the subscript 1 represents the coated article after heat treatment; and the numbers employed (e.g., a*, b*, L*) are those calculated by the aforesaid (CIE LAB 1976) L*, a*, b* coordinate technique. In a similar manner, E may be calculated using equation (1) by replacing a*, b*, L* with Hunter Lab values a.sub.h, b.sub.h, L.sub.h. Also within the scope of this invention and the quantification of E* are the equivalent numbers if converted to those calculated by any other technique employing the same concept of E* as defined above.
(78) In certain example embodiments of this invention, the low-E coating 30 includes two silver-based IR reflecting layers (e.g., see
(79) Because of materials stability, baking at high temperature (e.g., 580-650 degrees C.) causes change to chemical compositions, crystallinity and microstructures or even phases of dielectric layer materials. High temperature also causes interface diffusion or even reaction, as a consequence composition, roughness and index change at interface locations. As a result, optical properties such as index n/k and optical thickness change upon heat treatment. The IR materials, for example Ag, have undergone change too. Typically, Ag materials go through crystallization, grain growth or even orientation change upon heat treatment. These changes often cause conductivity and particularly index n/k changes which have big impact to the optical and thermal properties of a low-E coating. In addition, the dielectric and the change of dielectrics also has a significant impact on IR reflecting layers such as silver undergoing heat treatment. Moreover, silver may have more change in one layer stack than in others merely because of the materials and the layer stacks themselves. If the silver changes are beyond some limit, then it may not be acceptable aesthetically after heat treatment. We have found that to get thermal stability of a low-E coating, doped zinc oxide crystallized materials on glass either directly or indirectly with a thin modification layer(s) may be used under silver of an IR reflecting layer. Crystalline or substantially crystalline doped zinc oxide in these locations has been found to change less during heat treatment, and result in smaller silver changes with respect to properties such as indices (e.g., n and/or k) and thus less overall color change upon heat treatment.
(80)
(81) As explained herein, it has been found that the presence of as-deposited crystalline or substantially crystalline layer 3 and/or 13 of or including zinc oxide, doped with at least one dopant (e.g., Sn), immediately under and directly contacting an infrared (IR) reflecting layer of or including silver 7 and/or 19 in a low-E coating 30 has the effect of significantly improving the coating's thermal stability (i.e., lowering the E* value). In certain example embodiments, the crystalline or substantially crystalline layer 3 and/or 13 of or including zinc oxide is doped with from about 1-30% Sn, more preferably from about 1-20% Sn, more preferably from about 5-15% Sn, with an example being about 10% Sn (in terms of wt. %).
(82) In certain example embodiments, the dielectric zinc stannate (e.g., ZnSnO, Zn.sub.2SnO.sub.4, or the like) based layers 11 and 23 may be deposited in an amorphous or substantially amorphous state (it/they may become crystalline or substantially crystalline upon heat treatment). It has been found that having similar amounts of Zn and Sn in the layer, or more Sn than Zn in the layer, helps ensure that the layer is deposited in an amorphous or substantially amorphous state. For example, the metal content of amorphous zinc stannate based layers 11 and 23 may include from about 30-70% Zn and from about 30-70% Sn, more preferably from about 40-60% Zn and from about 40-60% Sn, with examples being about 52% Zn and about 48% Sn, or about 50% Zn and 50% Sn (weight %, in addition to the oxygen in the layer) in certain example embodiments of this invention. Thus, for example, the amorphous or substantially amorphous zinc stannate based layers 11 and/or 23 may be sputter-deposited using a metal target comprising about 52% Zn and about 48% Sn, or about 50% Zn and about 50% Sn, in certain example embodiments of this invention. Optionally, the zinc stannate based layers 11 and 23 may be doped with other metals such as Al or the like. Depositing layers 11 and 23 in an amorphous, or substantially amorphous, state, while depositing layers 3 and 13 in a crystalline, or substantially crystalline, state, has been found to advantageously allow for improved thermal stability to be realized in combination with good optical characteristics such as acceptable transmission, color, and reflection. It is noted that zinc stannate layers 11 and/or 23 may be replaced with respective layer(s) of other material(s) such as tin oxide, zinc oxide, zinc oxide doped with from 1-20% Sn (as discussed elsewhere herein regarding layers 11, 13), or the like.
(83) Dielectric layer 25, which may be an overcoat, may be of or include silicon nitride (e.g., Si.sub.3N.sub.4, or other suitable stoichiometry) in certain embodiments of this invention, in order to improve the heat treatability and/or durability of the coated article. The silicon nitride may optionally be doped with Al and/or O in certain example embodiments, and also may be replaced with other material such as silicon oxide or zirconium oxide in certain example embodiments.
(84) Infrared (IR) reflecting layers 7 and 19 are preferably substantially or entirely metallic and/or conductive, and may comprise or consist essentially of silver (Ag), gold, or any other suitable IR reflecting material. IR reflecting layers 7 and 19 help allow the coating to have low-E and/or good solar control characteristics. The IR reflecting layers may, however, be slightly oxidized in certain embodiments of this invention.
(85) Other layer(s) below or above the illustrated coating in
(86) While various thicknesses and materials may be used in layers in different embodiments of this invention, example thicknesses and materials for the respective layers on the glass substrate 1 in the
(87) TABLE-US-00001 TABLE 1 Example Materials/Thicknesses; FIG. 1(a) Embodiment Layer More Example Glass Preferred Range ({acute over ()}) Preferred ({acute over ()}) () Sn-doped ZnO 20-900 (or 100-900) {acute over ()} 350-550 {acute over ()} 470 (layer 3) Ag (layer 7) 60-260 {acute over ()} 100-170 {acute over ()} 151 NiCrO.sub.x (layer 9) 10-100 {acute over ()} 20-45 {acute over ()} 41 ZnSnO (layer 11) 200-1200 {acute over ()} 500-900 {acute over ()} 736 Sn-doped ZnO 60-900 {acute over ()} 120-400 {acute over ()} 177 (layer 13) Ag (layer 19) 80-280 {acute over ()} 140-250 {acute over ()} 232 NiCrO.sub.x (layer 21) 10-100 {acute over ()} 20-45 {acute over ()} 41 ZnSnO (layer 23) 10-750 {acute over ()} 70-200 {acute over ()} 108 Si.sub.3N.sub.4 (layer 25) 10-750 {acute over ()} 100-240 {acute over ()} 191
(88) The
(89) When layer 2 (or 2, or 2) is of or includes SiZrO.sub.x and/or SiZrO.sub.xN.sub.y, it has been found that providing more Si than Zr in that layer is advantageous from an optical point of view with a low refractive index (n) and improved antireflection and other optical characteristics. For example, in certain example embodiments, when layer 2 (or 2, or 2) is of or includes SiZrO.sub.x and/or SiZrO.sub.xN.sub.y, metal content of the layer may comprise from 51-99% Si, more preferably from 70-97% Si, and most preferably from 80-90% Si, and from 1-49% Zr, more preferably from 3-30% Zr, and most preferably from 10-20% Zr (atomic %). In example embodiments, transparent dielectric layer 2 of or including SiZrO.sub.x and/or SiZrO.sub.xN.sub.y may have a refractive index (n), measured at 550 nm, of from about 1.48 to 1.68, more preferably from about 1.50 to 1.65, and most preferably from about 1.50 to 1.62.
(90) The
(91) The
(92) Referring to
(93) As explained above and shown in the figures, the coated article may include a dielectric layer(s) 2, 2 (e.g., ZrO.sub.2 or SiZrO.sub.x) as shown in
(94) The
(95) In the
(96) The silver based layer 57 of the absorber film is preferably sufficiently thin so that its primary function is to absorb visible light and provide desirable coloration (as opposed to being much thicker and primarily function as an IR reflection layer). The NiCr or NiCrO.sub.x 59 is provided over and contacting the silver 57 of the absorber film in order to protect the silver, and also to contribute to absorption. In certain example embodiments, the silver based layer 57 of the absorber film may be no more than about 30 thick, more preferably no greater than about 20 thick, and most preferably no greater than about 15 thick, and possibly no greater than about 12 thick, in certain example embodiments of this invention. In certain example embodiments, the NiCr based layer 59 of the absorber film may be from about 5-200 thick, more preferably from about 10-110 thick, and most preferably from about 40-90 thick. In certain example embodiments, the ratio of Ag/NiCrO.sub.x in the absorber film may be 1:Z (where 0.1<Z<20, more preferably where 2<Z<15, and most preferably where 3<Z<12), with an example being about 1:5.
(97) With respect to the silver based layer 57 of the absorber film being sufficiently thin so that its primary function is to absorb visible light and provide desirable coloration (as opposed to being much thicker and primarily function as an IR reflection layer), the ratio of the physical thickness of the IR reflecting layer 7 (e.g., silver) to the physical thickness of the silver based layer 57 is preferably at least 5:1, more preferably at least about 8:1, even more preferably at least about 10:1, and even more preferably at least about 15:1. Likewise, the ratio of the physical thickness of the IR reflecting layer 19 (e.g., silver) to the physical thickness of the silver based layer 57 is preferably at least 5:1, more preferably at least about 8:1, even more preferably at least about 10:1, and even more preferably at least about 15:1.
(98) While a single layer of NiCr (or other suitable material) may also be used as an absorber film in low-E coatings in certain example embodiments of this invention (e.g., see absorber film 42 in
(99) While the absorber film 57, 59 in
(100)
(101) It is noted that zinc stannate layers 11 and/or 23 may be replaced with respective layer(s) of other material(s) such as tin oxide, zinc oxide, zinc oxide doped with from 1-20% Sn (as discussed elsewhere herein regarding layers 3, 3, 13), or the like, in any embodiment herein.
(102) While various thicknesses and materials may be used in layers in different embodiments of this invention, example thicknesses and materials for the respective layers on the glass substrate 1 in the
(103) TABLE-US-00002 TABLE 1 Example Materials/Thicknesses; FIG. 1(i) Embodiment Layer More Example Glass Preferred Range ({acute over ()}) Preferred ({acute over ()}) () ZrO.sub.x/SiZrO.sub.x (layer 2) 10-600 10-400 80-140 Sn-doped ZnO 20-900 (or 100-900) {acute over ()} 100-550 {acute over ()} 223 (layer 3) Ag (layer 7) 60-260 {acute over ()} 100-170 {acute over ()} 151 NiCrO.sub.x (layer 9) 10-100 {acute over ()} 20-45 {acute over ()} 41 ZnSnO (layer 11) 100-1200 {acute over ()} 150-500 {acute over ()} 280 ZrO.sub.x/SiZrO.sub.x (layer 2) 10-600 10-400 80-140 Sn-doped ZnO 20-900 {acute over ()} 50-150 {acute over ()} 100 (layer 3) Ag (layer 57) 3-30 {acute over ()} 4-20 {acute over ()} 5-15 NiCrO.sub.x (layer 59) 5-200 {acute over ()} 10-110 {acute over ()} 40-90 Sn-doped ZnO 60-900 {acute over ()} 120-400 {acute over ()} 331 (layer 13) Ag (layer 19) 80-280 {acute over ()} 120-250 {acute over ()} 156 NiCrO.sub.x (layer 21) 10-100 {acute over ()} 20-45 {acute over ()} 41 ZnSnO (layer 23) 10-750 {acute over ()} 70-200 {acute over ()} 103 Si.sub.3N.sub.4 (layer 25) 10-750 {acute over ()} 100-240 {acute over ()} 214
(104) In certain embodiments of this invention, layer systems herein (e.g., see
(105) TABLE-US-00003 TABLE 2 Reflection/Color (R.sub.G) Before and/or After Heat Treatment General Preferred R.sub.gY (%) 5-35%, or 5-20% 8-18% a.sub.g* 5.0 to +4.0 3.5 to +2.0 b.sub.g* 16.0 to 0.0 14.0 to 5.0
Comparative Examples 1 and 2
(106)
(107) A difference between the first Comparative Example coating (see
(108) A second Comparative Example (CE 2) is shown in
(109) It can be seen in
(110) Accordingly, Comparative Example 2 (CE 2) in
(111) Examples 11-14, 19-21, and 26-33 below also demonstrate that replacing the bottom silicon nitride based layer of CE 2 with a SiZrO.sub.x or ZrO.sub.2 layer 2 dramatically improves/lowers E* values in an unexpected manner.
Examples 1-48
(112) Surprisingly and unexpectedly, it was found that when the lowermost dielectric stack 5, 6 of the Comparative Example (CE) (made up mostly by the zinc stannate layer which is amorphous as deposited) in
(113) The Example coated articles (each annealed and heat treated), Examples 1-48, were made in accordance with certain example embodiments of this invention. Indicated example coatings 30 were sputter-deposited via the sputtering conditions (e.g., gas flows, voltage, and power), sputtering targets, and to the layer thicknesses (nm) shown in
(114) For examples having approximately 3 mm thick glass substrates, in
(115)
(116) As shown in
(117) The coated article of Example 1, which had a 6 mm thick glass substrate 1, was then heat treated. As shown in
(118) It will be appreciated that these E* values for Example 1 (and also those for Examples 2-48) are much improved (significantly lower) than those of the prior art discussed in the background and compared to the values over 4.0 for the Comparative Examples (CEs) discussed above. Thus, the data from the examples demonstrates, for example, that when the lowermost dielectric stacks of the Comparative Examples was replaced with at least a crystalline or substantially crystalline Sn-doped zinc oxide layer of similar thickness (the rest of the stack remained substantially the same), with no silicon nitride based layer directly under and contacting the crystalline or substantially crystalline Sn-doped zinc oxide layer 3, the result was a much more thermally stable product with significant lower E* values and a much smaller change in Ag (111) peak height due to heat treatment.
(119) Other examples show these same unexpected results, compared to the Comparative Example. In general, the Examples demonstrate that the crystalline or substantially crystalline Sn-doped zinc oxide layer, and/or the layer(s) 2, 2 of or including SiZrO.sub.x, ZrO.sub.x, SiO.sub.2, significantly improved E* values. For example, Examples 1-10 had layer stacks generally shown by
(120) The layer stacks of Examples 1-10 are generally illustrated by
(121) For instance, comparing Examples 23-24 (SiZrO.sub.x layer 2 added to the center dielectric portion of the coating as shown in
(122) Furthermore, comparing Example 28 (SiZrO.sub.x layer 2 added to the center dielectric portion of the coating as shown in
(123) Examples 30-48 are generally illustrated by
(124) Comparing Examples 34-42 and 48, to Comparative Examples (CEs) 43-47, it can be seen that it has surprisingly and unexpectedly been found that initially sputter-depositing the dielectric layer(s) 2 and/or 2 of or including silicon oxide, zirconium oxide, zirconium oxynitride, silicon zirconium oxide and/or silicon zirconium oxynitride (e.g., SiZrO.sub.x, ZrO.sub.2, SiO.sub.2, and/or SiZrO.sub.xN.sub.y) so as to comprise a monoclinic phase crystalline structure in Examples 34-42 and 48 is advantageous in that it results in improved thermal stability (lower E* value) and/or reduced change in visible transmission (e.g., T.sub.vis or TY) of the coated article upon heat treatment (HT). Generally speaking, CEs 43-47, which may still be according to certain example embodiments of this invention, had less preferred (higher) E* values due to nonmonoclinic ZrO.sub.2 layers 2, 2, compared to Examples 34-42 and 48 which had monoclinic ZrO.sub.2 layers 2, 2 and thus improved/lower E* values. In certain example embodiments, in connection with certain sputtering equipment, the monoclinic phase (e.g., see the m-ZrO.sub.2 peaks in the upper graph of
(125)
(126)
(127)
(128) Comparing Examples 34-42, 48 to Comparative Examples (CEs) 43-47, it can be seen that Examples 34-42, 48 with the monoclinic ZrO.sub.2 layers 2 and 2 as-deposited realized lower/better E* values, and thus improved thermal stability and color matching upon HT, than did Examples 43-47 which had nonmonoclinic phase ZrO.sub.2 layers 2 and 2.
(129) Certain terms are prevalently used in the glass coating art, particularly when defining the properties and solar management characteristics of coated glass. Such terms are used herein in accordance with their well known meaning. For example, as used herein:
(130) Intensity of reflected visible wavelength light, i.e. reflectance is defined by its percentage and is reported as R.sub.xY or R.sub.x (i.e. the Y value cited below in ASTM E-308-85), wherein X is either G for glass side or F for film side. Glass side (e.g. G or g) means, as viewed from the side of the glass substrate opposite that on which the coating resides, while film side (i.e. F or f) means, as viewed from the side of the glass substrate on which the coating resides.
(131) Color characteristics are measured and reported herein using the CIE LAB a*, b* coordinates and scale (i.e. the CIE a*b* diagram, Ill. CIE-C, 2 degree observer). Other similar coordinates may be equivalently used such as by the subscript h to signify the conventional use of the Hunter Lab Scale, or Ill. CIE-C, 10 observer, or the CIE LUV u*v* coordinates. These scales are defined herein according to ASTM D-2244-93 Standard Test Method for Calculation of Color Differences From Instrumentally Measured Color Coordinates 9/15/93 as augmented by ASTM E-308-85, Annual Book of ASTM Standards, Vol. 06.01 Standard Method for Computing the Colors of Objects by 10. Using the CIE System and/or as reported in IES LIGHTING HANDBOOK 1981 Reference Volume.
(132) Visible transmittance can be measured using known, conventional techniques. For example, by using a spectrophotometer, such as a Perkin Elmer Lambda 900 or Hitachi U4001, a spectral curve of transmission is obtained. Visible transmission is then calculated using the aforesaid ASTM 308/2244-93 methodology. A lesser number of wavelength points may be employed than prescribed, if desired. Another technique for measuring visible transmittance is to employ a spectrometer such as a commercially available Spectrogard spectrophotometer manufactured by Pacific Scientific Corporation. This device measures and reports visible transmittance directly. As reported and measured herein, visible transmittance (i.e. the Y value in the CIE tristimulus system, ASTM E-308-85), as well as the a*, b*, and L* values, and glass/film side reflectance values, herein use the Ill. C., 2 degree observer standard.
(133) Another term employed herein is sheet resistance. Sheet resistance (R.sub.s) is a well known term in the art and is used herein in accordance with its well known meaning. It is here reported in ohms per square units. Generally speaking, this term refers to the resistance in ohms for any square of a layer system on a glass substrate to an electric current passed through the layer system. Sheet resistance is an indication of how well the layer or layer system is reflecting infrared energy, and is thus often used along with emittance as a measure of this characteristic. Sheet resistance may for example be conveniently measured by using a 4-point probe ohmmeter, such as a dispensable 4-point resistivity probe with a Magnetron Instruments Corp. head, Model M-800 produced by Signatone Corp. of Santa Clara, Calif.
(134) The terms heat treatment and heat treating as used herein mean heating the article to a temperature sufficient to achieve thermal tempering, heat bending, and/or heat strengthening of the glass inclusive coated article. This definition includes, for example, heating a coated article in an oven or furnace at a temperature of least about 580 degrees C., more preferably at least about 600 degrees C., including 650 degrees C., for a sufficient period to allow tempering, bending, and/or heat strengthening. In certain instances, the heat treatment may be for at least about 8 minutes or more as discussed herein.
(135) In an example embodiment of this invention, there is provided a coated article including a coating on a glass substrate, wherein the coating comprises: a first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %), provided on the glass substrate; a first infrared (IR) reflecting layer comprising silver located on the glass substrate and directly over and contacting the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn; wherein no silicon nitride based layer is located directly under and contacting the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn; at least one dielectric layer having monoclinic phase and comprising an oxide of zirconium (e.g., ZrO.sub.2), and optionally further including other element(s) such as Si; wherein the at least one dielectric layer comprising the oxide of zirconium is located: (1) between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %), and/or (2) between at least the first IR reflecting layer comprising silver and a second IR reflecting layer comprising silver of the coating; optionally an absorber film including a layer comprising silver, wherein a ratio of a physical thickness of the first IR reflecting layer comprising silver to a physical thickness of the layer comprising silver of the absorber film is at least 5:1 (more preferably at least 8:1, even more preferably at least 10:1, and most preferably at least 15:1); and wherein the coated article is configured to have, measured monolithically, at least two of: (i) a transmissive E* value of no greater than 3.0 due to a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 3.0 due to the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.5 due to the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
(136) The coated article of the immediately preceding paragraph may be configured to have, measured monolithically, all three of: (i) a transmissive E* value of no greater than 3.0 due to a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 3.0 due to the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.5 due to the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
(137) In the coated article of any of the preceding two paragraphs, the least one dielectric layer comprising the oxide of zirconium may be located at least between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %).
(138) In the coated article of any of the preceding three paragraphs, the least one dielectric layer comprising the oxide of zirconium may be located at least between at least the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating.
(139) In the coated article of any of the preceding four paragraphs, the at least one dielectric layer comprising the oxide of zirconium may include both a first layer comprising an oxide of zirconium, and a second layer comprising an oxide of zirconium (each of which may further include additional element(s) such as Si); wherein the first layer may be located between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %); and wherein the second layer may be located between at least the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating.
(140) In the coated article of any of the preceding five paragraphs, the at least one dielectric layer may comprise or consist essentially of the oxide of zirconium and/or an oxide of silicon and zirconium (e.g., SiZrO.sub.x). For instance, the dielectric layer comprising the oxide of silicon and zirconium may have a metal content of from 51-99% Si and from 1-49% Zr, more preferably from 70-97% Si and from 3-30% Zr (atomic %).
(141) In the coated article of any of the preceding six paragraphs, the at least one dielectric layer may comprise ZrO.sub.2.
(142) In the coated article of any of the preceding seven paragraphs, the first crystalline or substantially crystalline layer comprising zinc oxide may be doped with from about 1-20% Sn, more preferably from about 5-15% Sn (wt. %).
(143) In the coated article of any of the preceding eight paragraphs, the first crystalline or substantially crystalline layer comprising zinc oxide doped with Sn may be crystalline or substantially crystalline as sputter-deposited.
(144) The coated article according to any of the preceding nine paragraphs may be configured to have, measured monolithically, all of: (i) a transmissive E* value of no greater than 2.5 due to a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 2.5 due to the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.0 due to the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
(145) The coated article according to any of the preceding ten paragraphs may be configured to have, measured monolithically, at least two of: (i) a transmissive E* value of no greater than 2.3 due to a reference heat treatment for 16 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 2.0 due to the reference heat treatment for 16 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.0 due to the reference heat treatment for 16 minutes at a temperature of about 650 degrees C.
(146) The coated article according to any of the preceding eleven paragraphs may be configured so that the coating may have a sheet resistance (R.sub.s) of no greater than 20 ohms/square, more preferably no greater than 10 ohms/square, and most preferably no greater than 2.5 ohms/square.
(147) The coated article according to any of the preceding twelve paragraphs may have, measured monolithically, a visible transmission of at least 35%, more preferably of at least 50%, and more preferably of at least 68%.
(148) In the coated article of any of the preceding thirteen paragraphs, the coating as deposited may further comprise a first amorphous or substantially amorphous layer comprising zinc stannate located on the glass substrate over at least the first IR reflecting layer comprising silver. The first amorphous or substantially amorphous layer comprising zinc stannate may have a metal content of from about 40-60% Zn and from about 40-60% Sn (wt. %).
(149) In the coated article of any of the preceding fourteen paragraphs, the coating may further comprise a contact layer located over and directly contacting the first IR reflecting layer comprising silver. The contact layer may comprise Ni and/or Cr, and may or may not be oxided and/or nitrided.
(150) In the coated article of any of the preceding fifteen paragraphs, the coating may further comprise: the second IR reflecting layer comprising silver located on the glass substrate over at least the first IR reflecting layer comprising silver, a second crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %), located under and directly contacting the second IR reflecting layer comprising silver; and wherein no silicon nitride based layer need be located between the glass substrate and the second IR reflecting layer comprising silver.
(151) In the coated article of any of the preceding sixteen paragraphs, the coating may further comprise an amorphous or substantially amorphous layer, as deposited, comprising zinc stannate located on the glass substrate over at least the second IR reflecting layer comprising silver. The amorphous or substantially amorphous layer comprising zinc stannate, which is amorphous or substantially amorphous as deposited, may have a metal content of from about 40-60% Zn and from about 40-60% Sn (wt. %). In certain example embodiments, the coating may further comprise a layer comprising silicon nitride located over at least the amorphous or substantially amorphous layer comprising zinc stannate.
(152) The coated article of any of the preceding seventeen paragraphs may be thermally tempered.
(153) The coated article of any of the preceding eighteen paragraphs may further comprise a metallic or substantially metallic absorber layer located between the glass substrate and the first IR reflecting layer. The absorber layer may be sandwiched between and contacting first and second layers comprising silicon nitride. The absorber layer may comprise Ni and Cr (e.g., NiCr, NiCrMo), or any other suitable material such as NbZr. The dielectric layer comprising at least one of (a), (b), and (c) may be located between at least the absorber layer and the first crystalline or substantially crystalline layer comprising zinc oxide.
(154) In the coated article of any of the preceding nineteen paragraphs, the at least one dielectric layer comprising the oxide of zirconium may comprise from 0-20% nitrogen, more preferably from 0-10% nitrogen, and most preferably from 0-5% nitrogen (atomic %).
(155) In the coated article of any of the preceding twenty paragraphs, the absorber film may further comprises a layer comprising an oxide of Ni and/or Cr located over and directly contacting the layer comprising silver of the absorber film. In the coated article of any of the preceding twenty-one paragraphs, the absorber film may be located over the first IR reflecting layer, so that the first IR reflecting layer is located between at least the absorber film and the glass substrate.
(156) In the coated article of any of the preceding twenty-two paragraphs, the ratio of the physical thickness of the first IR reflecting layer comprising silver to the physical thickness of the layer comprising silver of the absorber film may be at least 8:1, more preferably at least 10:1, and even more preferably at least 15:1.
(157) In the coated article of any of the preceding twenty-three paragraphs, the layer comprising silver of the absorber film may be less than 30 thick, more preferably less than 20 thick, and even more preferably less than 15 thick.
(158) In the coated article of any of the preceding twenty-four paragraphs, the coated article need not be thermally tempered.
(159) In the coated article of any of the preceding twenty-five paragraphs, the at least one dielectric layer having monoclinic phase and comprising the oxide of zirconium may include two such layers comprising zirconium oxide and may be located both: (1) between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with from about 1-30% Sn (wt. %), and (2) between at least the first IR reflecting layer comprising silver and the absorber film.
(160) In the coated article of any of the preceding twenty-six paragraphs, the at least one dielectric layer having monoclinic phase may comprise from 0-5% nitrogen (atomic %).
(161) In the coated article of any of the preceding twenty-seven paragraphs, the at least one dielectric layer having monoclinic phase may comprise an oxide of zirconium (e.g., ZrO.sub.2), and may optionally further include Si.
(162) In the coated article of any of the preceding twenty-seven paragraphs, the at least one dielectric layer having monoclinic phase may consist essentially of an oxide of zirconium.
(163) In the coated article of any of the preceding twenty-eight paragraphs, the at least one dielectric layer having monoclinic phase may be configured to realize a density change of at least 0.25 g/cm.sup.3 upon said reference heat treatment, more preferably to realize a density change of at least 0.30 g/cm.sup.3 upon said reference heat treatment, and most preferably to realize a density change of at least 0.35 g/cm.sup.3 upon said reference heat treatment.
(164) In the coated article of any of the preceding twenty-nine paragraphs, the at least one dielectric layer having monoclinic phase may comprise an oxide of zirconium, and may have a metal content of at least 80% Zr.
(165) In the coated article of any of the preceding thirty paragraphs, the at least one dielectric layer having monoclinic phase may comprise an oxide of zirconium and/or may have a thickness of from 40-250 , more preferably from 40-170 , and most preferably from 80-140 .
(166) In the coated article of any of the preceding thirty-one paragraphs, the coated article may be configured to have, measured monolithically, two or three of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
(167) The coated article of any of the preceding thirty-two paragraphs may be provided as a monolithic window, or in an IG window unit coupled to another glass substrate.
(168) In to coated article of any of the preceding thirty-three paragraphs, the at least one dielectric layer comprising monoclinic phase may further comprise tetragonal phase before and/or after a reference heat treatment.
(169) In an example embodiment, there is provided a method of making a coated article including a coating on a glass substrate, the method comprising: sputter-depositing a layer comprising zinc on the glass substrate; sputter-depositing a first infrared (IR) reflecting layer comprising silver on the glass substrate over and contacting the layer comprising zinc oxide; sputter-depositing at least one dielectric layer (e.g., oxide of zirconium, such as ZrO.sub.2) having monoclinic phase on the glass substrate, wherein the dielectric layer having monoclinic phase comprises an oxide of zirconium (and which may further include other element(s) such as Si); wherein the at least one dielectric layer having monoclinic phase and comprising the oxide of zirconium is located: (1) between at least the glass substrate and the layer comprising zinc oxide, and/or (2) between at least the first IR reflecting layer comprising silver and a second IR reflecting layer comprising silver of the coating; and wherein the coated article is configured to have, measured monolithically, at least two of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 3.0 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 3.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C. T
(170) In the method of the immediately preceding paragraph, said sputter-depositing at least one dielectric layer having monoclinic phase on the glass substrate may use an oxygen gas flow of at least 6 ml/kW, more preferably an oxygen gas flow of at least 8 or 10 ml/kW.
(171) In the method of any of the preceding two paragraphs, the at least one dielectric layer having monoclinic phase may comprise ZrO.sub.2, and may further include Si.
(172) In the method of any of the preceding three paragraphs, the coated article may be configured to have, measured monolithically, at least two or all three of: (i) a transmissive E* value of no greater than 3.0 upon a reference heat treatment for 12 minutes at a temperature of about 650 degrees C., (ii) a glass side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C., and (iii) a film side reflective E* value of no greater than 1.5 upon the reference heat treatment for 12 minutes at a temperature of about 650 degrees C.
(173) The method of any of the preceding four paragraphs may further comprise heat treating the coated article via said reference heat treatment so that the at least one dielectric layer having monoclinic phase realizes a density change of at least 0.25 g/cm.sup.3 upon said reference heat treatment, more preferably at least 0.30 g/cm.sup.3, and most preferably of at least 0.35 g/cm.sup.3.
(174) In the method of any of the preceding five paragraphs, said sputter-depositing of the at least one dielectric layer having monoclinic phase on the glass substrate may use a metal target, or a ceramic target.
(175) In the method of any of the preceding six paragraphs, said at least one dielectric layer comprising monoclinic phase may further comprise tetragonal phase before and/or after said reference heat treatment.
(176) In the method of any of the preceding seven paragraphs, the at least one dielectric layer comprising monoclinic phase may be configured to have a monoclinic peak thereof reduce upon said reference heat treatment.
(177) Once given the above disclosure many other features, modifications and improvements will become apparent to the skilled artisan. Such other features, modifications and improvements are therefore considered to be a part of this invention, the scope of which is to be determined by the following claims: