Coated article with low-E coating having zinc stannate based layer between IR reflecting layers for reduced mottling and corresponding method
09789750 · 2017-10-17
Assignee
- Centre Luxembourgeois de Recherches pour la Verre et la Ceramique S.A. (C.R.V.C.) (Grand Duche de Luxembourg, LU)
- Guardian Glass, Llc (Auburn Hills, MI)
Inventors
- Jose Ferreira (Rumelange, LU)
- Pierrot Pallotta (Villerupt, FR)
- Richard Blacker (Farmington Hills, MI, US)
- Muhammad Imran (Brownstown, MI)
Cpc classification
C03B40/033
CHEMISTRY; METALLURGY
B32B17/10036
PERFORMING OPERATIONS; TRANSPORTING
Y10T428/24628
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B32B17/10174
PERFORMING OPERATIONS; TRANSPORTING
C03C17/3626
CHEMISTRY; METALLURGY
C03C17/3681
CHEMISTRY; METALLURGY
C03C17/3639
CHEMISTRY; METALLURGY
C03C17/3618
CHEMISTRY; METALLURGY
International classification
B60J1/00
PERFORMING OPERATIONS; TRANSPORTING
C03B40/033
CHEMISTRY; METALLURGY
Abstract
A coated article is provided which may be heat treated (e.g., thermally tempered) and/or heat bent in certain example instances. In certain example embodiments, a zinc stannate based layer is provided between a tin oxide based layer and a silicon nitride based layer, and this has been found to significantly reduce undesirable mottling damage upon heat treatment/bending. This results in significantly improved bendability of the coated article in applications such as vehicle windshields and the like.
Claims
1. A coated article including a glass substrate supporting a coating thereon, the coating comprising: a first dielectric layer supported by the glass substrate; a first infrared (IR) reflecting layer comprising silver supported by the glass substrate and located over at least the first dielectric layer; a contact layer located over and directly contacting the first IR reflecting layer; a first layer comprising tin oxide from 200-320 angstroms thick located over at least the first IR reflecting layer and the first dielectric layer; a first layer comprising zinc stannate from 200-320 angstroms thick located over and contacting the first layer comprising tin oxide; a layer comprising silicon nitride from 80-200 angstroms thick located over at least the first layer comprising zinc stannate; a layer comprising zinc oxide located over and directly contacting the layer comprising silicon nitride; a second IR reflecting layer comprising silver on the glass substrate located over the layer comprising silicon nitride and directly contacting the layer comprising zinc oxide; and wherein a combined total thickness of the first layer comprising tin oxide and the first layer comprising zinc stannate is from 460-600 angstroms, and wherein each of the first layer comprising tin oxide and the first layer comprising zinc stannate are each at least 50 angstroms thicker than the layer comprising silicon nitride.
2. The coated article of claim 1, further comprising another layer comprising zinc oxide located under and contacting the first IR reflecting layer, and wherein the another layer comprising zinc oxide is over and contacting the first dielectric layer.
3. The coated article of claim 1, further comprising an overcoat layer comprising zirconium oxide.
4. The coated article of claim 1, wherein the layer comprising silicon nitride directly contacts the layer comprising zinc stannate.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
DETAILED DESCRIPTION OF EXAMPLES OF THE INVENTION
(4) Coated articles herein may be used in applications such as bent vehicle windshields, other types of vehicle windows, and/or any other suitable application such as in an IG or monolithic window unit.
(5) Certain example embodiments of this invention relate to a low-E coating 30 used in connection with a vehicle windshield or the like. In certain example embodiments, the coated article may be heat treated (e.g., thermally tempered, heat bent and/or heat strengthened) in making a vehicle windshield or the like. In certain example embodiments of this invention, the low-E coating 30 includes a zinc stannate based layer 14 provided over a tin oxide based layer 13, in a central portion of the layer stack between first and second IR reflecting layers 9 and 19 (e.g., see
(6) The second conventional coating shown above in the background section has a typical layer stack containing a layer of tin oxide as the main center dielectric. This layer is often deposited from two tin cathodes during a sputter-deposition process. This tin oxide undergoes a crystallization during heat treatment (e.g., as in tempering or windshield bending), which is associated with a significant change in stress of this layer moving from a strong compressive stress as deposited to a lesser or even tensile stress after heat treatment (HT). This stress change can occur very rapidly at certain temperatures during the heating cycle. In contrast, it has been found that the zinc stannate (ZnSnO) based layer 14 in certain example embodiments of this invention, between layers comprising tin oxide 13 and silicon nitride 15, does not undergo the same crystallization change upon heating/bending, and remains substantially amorphous after heating during the HT. There may be, however, a change of stress in the zinc stannate based layer with the heating, that is less rapid than is realized with the tin oxide layer. This change in stress occurs at a higher temperature for the zinc stannate based layer 14, than for the tin oxide layer in the conventional coating. For example, this change in stress can happen at about 400 degrees C. for the zinc stannate based layer 14, compared to at about 360 degrees C. for the central tin oxide dielectric layer in the conventional coating. Based on experimental results, it has been found that use of (a) glass . . . Ag . . . SnO/ZnSnO/SiN . . . Ag . . . according to certain embodiments of this invention, instead of the conventional (b) glass . . . Ag . . . SnO/SiN . . . Ag . . . , reduces the undesirable mottling effect. Moreover, the order of the zinc stannate (ZnSnO) based layer 14 being over top of the tin oxide based layer 13 has been found to be particularly important as well in reducing mottling, because reversing the order of these two layers has no or negative impact and mottling is still realized. When bent to the same bend degrees, windshields as shown in
(7) In certain example embodiments of this invention, improved mechanical durability and/or reduced damage upon heat treatment can be realized when thermodynamically stable silver based layers 9, 19 are deposited, and the use of the layer comprising zinc stannate 14 between layers comprising tin oxide 13 and silicon nitride 15 is believed to aid in providing such silver based layers with stability during heat treatment and/or bending even though the zinc stannate need not be in direct contact with the silver in certain example embodiments of this invention. In other words, it has unexpectedly been found that by providing the layer comprising zinc stannate 14 between layers comprising tin oxide 13 and silicon nitride 15, significantly improved bendability can be achieved.
(8) In certain example embodiments of this invention, coated articles with such a layer stack can be heat bent to a centerline convex value “x” of at least about 24 mm (e.g., see
(9) These surprisingly results, which in certain example instances are associated with the use of the combination layer stack portion of glass . . . Ag . . . SnO/ZnSnO/SiN . . . Ag . . . , are highly advantageous, since reduction in mottling damage, bendability and/or improved scratch resistance are typically desired features in coated articles such as vehicle windows, IG window units, and/or the like. In certain example embodiments, the dielectric zinc stannate (e.g., ZnSnO or the like) based layer 14 may include more Zn than Sn by weight. For example, the zinc stannate based layer 14 may include about 52% Zn and about 48% Sn (in addition to the oxygen) in certain example embodiments of this invention. Thus, for example, the zinc stannate based layer may be sputter-deposited using a metal target comprising about 52% Zn and about 48% Sn in certain example embodiments of this invention. Optionally, the zinc stannate based layer 14 may be doped with other metals such as Al or the like.
(10) Optionally, the provision of an overcoat layer of or including zirconium oxide (not shown) or the like can reduce and/or eliminate such thermal stability problems. In particular, in certain example embodiments of this invention, the use of a zirconium oxide inclusive overcoat layer in combination with the glass . . . Ag . . . SnO/ZnSnO/SiN . . . Ag . . . can result in a coated article which does not suffer from significant thermal stability issues (e.g., the coated article can realize acceptable visible transmission, a* and/or b* values following heat treatment and bending).
(11) Example advantages associated with certain example embodiments of this invention include a coated article which is capable of include one or more of: (a) being bent to greater extents in applications such as vehicle windshields or the like, (b) being able to maintain acceptable optical characteristics when bent to such extents, (c) reduced mottling damage upon heat treatment and bending, (d) realizing improved or good thermal stability with regard to visible transmission, color, emissivity (or emittance), and/or sheet resistance (R.sub.s); (e) realizing improved mechanical durability. In certain example embodiments, one or more of these characteristics/advantages can be achieved.
(12) In certain example embodiments of this invention, the coating includes a double-silver stack, although this invention is not so limited in all instances (e.g., three silver based layers can be used in certain instances). For example, in certain example embodiments of this invention, heat treated and/or heat bent coated articles having multiple IR reflecting layers (e.g., two spaced apart silver based layers) are capable of realizing a sheet resistance (R.sub.s) of less than or equal to 3.0 (more preferably less than or equal to 2.5, even more preferably less than or equal to 2.1, and most preferably less than or equal to 2.0). In certain example embodiments, following heat treatment and as measured in monolithic and/or laminated form, coated articles herein are capable of realizing a visible transmission (Ill. C, 2 degree) of at least about 70%, more preferably of at least about 75%, and most preferably of at least about 76%.
(13) 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., for a sufficient period to allow tempering, bending, and/or heat strengthening. In certain instances, the HT may be for at least about 4 or 5 minutes or more.
(14) Bending may be performed in any suitable manner. For example, and without limitation, in forming a windshield including a pair of glass substrates, two flat glass substrates (at least one with a coating thereon) can be placed in a bending furnace (e.g., on a bending mold) in an overlapping manner by interposing an optional lubricating powder such as sodium hydrogen carbonate, cerite, magnesium oxide, silica, or the like between contacting surfaces of the two glass substrates. The glass substrates are then heated using infrared (IR) emitting heating elements to a processing temperature(s) near a softening point of the glass (e.g., from about 550 to 850 degrees C., more preferably from about 580 to 750 degrees C.) in order to soften the overlapping glass substrates. Upon softening, the glass substrates (including any solar control coating such as a low-E coating thereon) are bent by their deadweight (i.e., sagging) along a shaping surface of a bending mold (not shown) into the desired curved shape appropriate for the vehicle windshield being made. A press bending apparatus may optionally be used after the glass is sufficiently softened (e.g., press bending may be conducted as the final step before cooling the glass). After being heat bent in such a manner, the bent glass substrates (with solar control coating still on the bent substrate) are separated from one another and a polymer inclusive interlayer sheet (e.g., PVB) is interposed therebetween. The bent glass substrates are then laminated to one another via the polymer inclusive interlayer (e.g., PVB) in order to form the resulting vehicle windshield.
(15)
(16) In monolithic instances, the coated article includes only one glass substrate 1 as illustrated in
(17) Dielectric layers 3 and 15 may be of or include silicon nitride in certain embodiments of this invention. Silicon nitride layers 3 and 15 may, among other things, improve heat-treatability of the coated articles, e.g., such as thermal tempering or the like, and may or may not include some oxygen. The silicon nitride of layers 3 and/or 15 may be of the stoichiometric type (i.e., Si.sub.3N.sub.4), or alternatively of the Si-rich type in different embodiments of this invention. For example, Si-rich silicon nitride 3 (and/or 15) combined with zinc stannate 14 and/or tin oxide 13 under a silver based IR reflecting layer 19 may permit the silver to be deposited (e.g., via sputtering or the like) in a manner which causes its sheet resistance to be lessened compared to if certain other material(s) were under the silver. Moreover, the presence of free Si in a Si-rich silicon nitride inclusive layer 3 and/or 15 may allow certain atoms such as sodium (Na) which migrate outwardly from the glass 1 during heat treatment (HT) to be more efficiently stopped by the Si-rich silicon nitride inclusive layer before they can reach the silver and damage the same.
(18) In certain example embodiments, when Si-rich silicon nitride is used in layer 3 and/or 15, the Si-rich silicon nitride layer as deposited may be characterized by Si.sub.xN.sub.y layer(s), where x/y may be from 0.76 to 1.5, more preferably from 0.8 to 1.4, still more preferably from 0.85 to 1.2. Moreover, in certain example embodiments, before and/or after HT the Si-rich Si.sub.xN.sub.y layer(s) may have an index of refraction “n” of at least 2.05, more preferably of at least 2.07, and sometimes at least 2.10 (e.g., 632 nm) (note: stoichiometric Si.sub.3N.sub.4 which may also be used has an index “n” of 2.02-2.04). In certain example embodiments, it has surprisingly been found that improved thermal stability is especially realizable when the Si-rich Si.sub.xN.sub.y layer(s) as deposited has an index of refraction “n” of at least 2.10, more preferably of at least 2.20, and most preferably from 2.2 to 2.4. Also, the Si-rich Si.sub.xN.sub.y layer in certain example embodiments may have an extinction coefficient “k” of at least 0.001, more preferably of at least 0.003 (note: stoichiometric Si.sub.3N.sub.4 has an extinction coefficient “k” of effectively 0). Again, in certain example embodiments, it has surprisingly been found that improved thermal stability can be realized when “k” for the Si-rich Si.sub.xN.sub.y layer(s) is from 0.001 to 0.05 as deposited (550 nm). It is noted that n and k tend to drop due to heat treatment.
(19) Any and/or all of the silicon nitride layers discussed herein may be doped with other materials such as stainless steel or aluminum in certain example embodiments of this invention. For example, any and/or all silicon nitride layers discussed herein may optionally include from about 0-15% aluminum, more preferably from about 1 to 10% aluminum, in certain example embodiments of this invention. The silicon nitride may be deposited by sputtering a target of Si or SiAl in an atmosphere including at least nitrogen gas in certain embodiments of this invention.
(20) Infrared (IR) reflecting layers 9 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 9 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.
(21) The upper contact layers 11 and 21 may be of or include nickel (Ni) oxide, chromium/chrome (Cr) oxide, or a nickel alloy oxide such as nickel chrome oxide (NiCrO.sub.x), or other suitable material(s), in certain example embodiments of this invention. The use of, for example, NiCrO.sub.x in these layers (11 and/or 21) allows durability to be improved. The NiCrO.sub.x of layers 11 and/or 21 may be fully oxidized in certain embodiments of this invention (i.e., fully stoichiometric), or alternatively may only be partially oxidized (i.e., sub-oxide). In certain instances, the NiCrO.sub.x layers 11 and/or 21 may be at least about 50% oxidized. Contact layers 11 and/or 21 (e.g., of or including an oxide of Ni and/or Cr) may or may not be oxidation graded in different embodiments of this invention. Oxidation grading means that the degree of oxidation in the layer changes throughout the thickness of the layer. For example, a contact layer 11 and/or 21 may be graded so as to be less oxidized at the contact interface with the immediately adjacent IR reflecting layer than at a portion of the contact layer(s) further or more/most distant from the immediately adjacent IR reflecting layer. Descriptions of various types of oxidation graded contact layers are set forth in U.S. Pat. No. 6,576,349, the disclosure of which is hereby incorporated herein by reference. Contact layers 11 and/or 21 (e.g., of or including an oxide of Ni and/or Cr) may or may not be continuous in different embodiments of this invention across the entire underlying IR reflecting layer.
(22) Dielectric layer 13 may be of or include tin oxide in certain example embodiments of this invention. However, it may be doped with certain other materials in other example embodiments, such as with Al or Zn in certain example alternative embodiments.
(23) Lower contact layers 7 and/or 17 in certain embodiments of this invention are of or include zinc oxide (e.g., ZnO). The zinc oxide of layers 7 and/or 17 may contain other materials as well such as Al (e.g., to form ZnAlO.sub.x). For example, in certain example embodiments of this invention, one or more of zinc oxide layers 7, 17 may be doped with from about 1 to 10% Al, more preferably from about 1 to 5% Al, and most preferably about 1 to 4% Al.
(24) Zinc stannate based layer 14 is provided over and contacting layer 13 comprising tin oxide and under and possibly contacting layer 15 of or including silicon nitride, in a central portion of the layer stack between first and second IR reflecting layers 9 and 19. As mentioned above, it has surprisingly been found that this layer stack significantly reduces mottling problems upon heat treatment, thereby resulting in a more durable coated article and/or a windshield that can be bent to a greater degree without suffering fatal mottling damage. In other words, unexpectedly, it has been found that the use of such a zinc stannate based layer, between tin oxide and silicon nitride inclusive layers, results in significantly improved bendability of coated articles in applications such as vehicle windshields or the like. In certain alternative embodiments, it is possible to dope the zinc stannate based layer 14 and/or tin oxide based layer 13 with other materials such as Al, Zn, N, or the like.
(25) Dielectric layer 23 may be of or include tin oxide in certain example embodiments of this invention. However, layer 23 is optional and need not be provided in certain example embodiments of this invention. Dielectric layer 25 may be of or include silicon nitride (e.g., Si.sub.3N.sub.4) or any other suitable material in certain example embodiments of this invention. Optionally, other layers may be provided above layer 25. Layer 25 is provided for durability purposes, and to protect the underlying layers during heat treatment and/or environmental use. In certain example embodiments, layer 25 may have an index of refraction (n) of from about 1.9 to 2.2, more preferably from about 1.95 to 2.05. Optionally, the provision of an overcoat layer of or including zirconium oxide (not shown) can reduce and/or eliminate certain thermal stability issues.
(26) In certain example embodiments, it has been found that good optical properties are achieved when the total thickness of the combination of zinc stannate based layer 14 and tin oxide inclusive layer 13 is from about 430 to 650 Å, more preferably from about 460 to 600 Å, and most preferably from about 500 to 540 Å. In certain example embodiments, zinc stannate based layer 14 and tin oxide inclusive layer 13 have approximately the same thickness, and do not differ in thickness from each other by more than about 100 Å, more preferably by no more than about 60 or 30 Å. Each of layers 13 and 14 is thicker than silicon nitride based layer 15 in certain example embodiments of this invention, preferably by at least about 50 Å, more preferably by at least about 75 or 100 Å.
(27) Other layer(s) below or above the illustrated coating may also be provided. Thus, while the layer system or coating is “on” or “supported by” substrate 1 (directly or indirectly), other layer(s) may be provided therebetween. Thus, for example, the coating of
(28) 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
(29) TABLE-US-00002 Example Materials/Thicknesses; FIG. 3 Embodiment Preferred Layer Range ({acute over (Å)}) More Preferred (Å) Example (Å) Glass (1-10 mm thick) Si.sub.xN.sub.y (layer 3) 40-450 Å 70-300 Å 186 Å ZnAlO.sub.x (layer 7) 10-300 {acute over (Å)} 40-150 {acute over (Å)} 107 Å Ag (layer 9) 50-250 {acute over (Å)} 80-120 {acute over (Å)} 107 Å NiCrO.sub.x (layer 11) 10-100 {acute over (Å)} 12-40 {acute over (Å)} 30 Å SnO.sub.2 (layer 13) 100-500 Å 200-320 Å 260 Å ZnSnO (layer 14) 100-500 Å 200-320 Å 260 Å Si.sub.xN.sub.y (layer 15) 50-450 {acute over (Å)} 80-200 {acute over (Å)} 131 Å ZnAlO.sub.x (layer 17) 10-300 {acute over (Å)} 40-150 {acute over (Å)} 119 Å Ag (layer 19) 50-250 {acute over (Å)} 80-220 {acute over (Å)} 103 Å NiCrO.sub.x (layer 21) 10-100 {acute over (Å)} 20-45 {acute over (Å)} 33 Å SnO.sub.2 (layer 23) 0-750 Å 70-180 Å 120 Å Si.sub.3N.sub.4 (layer 25) 10-750 {acute over (Å)} 190-400 {acute over (Å)} 320 Å
(30) In certain example embodiments of this invention, coated articles herein may have the following optical and solar characteristics when measured monolithically (before any optional HT). The sheet resistances (R.sub.s) herein take into account all IR reflecting layers (e.g., silver layers 9, 19).
(31) TABLE-US-00003 Optical/Solar Characteristics (Monolithic; pre-HT) Characteristic General More Preferred Most Preferred R.sub.s (ohms/sq.): <=5.0 <=4.0 <=3.0 E.sub.n: <=0.07 <=0.04 <=0.03 T.sub.vis (Ill. C 2°): >=70% >=75% >=77%
(32) In certain example embodiments, coated articles herein may have the following characteristics, measured monolithically for example, after heat treatment (HT):
(33) TABLE-US-00004 Optical/Solar Characteristics (Monolithic; post-HT) Characteristic General More Preferred Most Preferred R.sub.s (ohms/sq.): <=3.0 <=2.5 <=2.1 (or <=2.0) E.sub.n: <=0.07 <=0.04 <=0.03 T.sub.vis (Ill. C 2°): >=75% >=78% >=80% Transmitted Haze: <=0.5 <=0.4 <=0.38
(34) Moreover, in certain example laminated embodiments of this invention, coated articles herein which have been heat treated to an extent sufficient for tempering (and optionally heat bent), and which have been laminated (via index oil and/or a polymer inclusive interlayer) to another glass substrate may have the following optical/solar characteristics.
(35) TABLE-US-00005 Example Optical Characteristics (Laminated: post-HT) Characteristic General More Preferred T.sub.vis (or TY)(Ill. C 2°): >=70% >=75% a*.sub.t (Ill. C 2°): −6 to +1.0 −5 to 0.0 b*.sub.t (Ill. C 2°): −2.0 to +8.0 0.0 to 6.0 L* (Ill. C 2°): 80-95 88-95 R.sub.fY (Ill. C, 2 deg.): 1 to 13% 1 to 12% a*.sub.f (Ill. C, 2°): −5.0 to +2.0 −4.0 to +0.5 b*.sub.f (Ill. C, 2°): −14.0 to +10.0 −10.0 to +3.5 L* (Ill. C 2°): 30-45 33-41 R.sub.gY (Ill. C, 2 deg.): 1 to 12% 1 to 10% a*.sub.g (Ill. C, 2°): −5.0 to +3.0 −2.5 to +2.5 b*.sub.g (Ill. C, 2°): −20.0 to +10.0 −15.0 to 0 L* (Ill. C 2°): 30-40 33-38 Haze(transmissive): <=0.6 <=0.5
(36) The following examples are provided for purposes of example only, and are not intended to be limiting unless specifically claimed.
EXAMPLES
(37) The following Example was made via sputtering on a clear glass substrate 1 so as to have approximately the layer stack set forth below. This example is according to an example embodiment of this invention as shown in
(38) TABLE-US-00006 Layer Example 1 Glass Substrate Si.sub.xN.sub.y 186 ZnAlO 107 Ag 107 NiCrO.sub.x 30 SnO.sub.2 260 ZnSnO 260 Si.sub.xN.sub.y 131 ZnO 119 Ag 103 NiCrO.sub.x 33 SnO.sub.2 120 Si.sub.3N.sub.4 320
(39) After being sputter deposited onto the glass substrates, the Example coated article was heat treated in a manner sufficient for tempering and bending, and had the optical characteristics set forth in the optical tables above. Moreover, heat bending of the coated article with the structure of this Example shown in
(40) While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.