巴西专利BR112019018184B1 ARTICLE COATED WITH LOW EMISIVITY COATING WITH DOPED SILVER PROTECTIVE LAYER TO PROTECT SILVER-BASED

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专利摘要:
a coated article includes a low emissivity (low e) coating supported by a glass substrate. the low e coating includes at least one silver (ag) based infrared (ir) reflective layer provided adjacent and contacting at least one metallic or substantially metallic doped silver protective layer to improve the chemical durability characteristics of the low coating e. the silver-based reflective layer and the adjacent protective doped silver layer are part of a low emissivity (low e) coating and can be sandwiched between at least transparent dielectric layers. a barrier layer including ni and/or cr can be provided over and directly in contact with the protective doped silver layer in order to further improve the durability of the low e coating.
公开号:BR112019018184B1
申请号:R112019018184-9
申请日:2018-02-28
公开日:2021-06-22
发明作者:Yiwei Lu；Brent Boyce；Guowen Ding；Scott Jewhurst；Cesar Clavero；Daniel Schweigert；Guizhen Zhang；Daniel Lee
申请人:Guardian Glass, LLC；
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专利说明:

[0001] This application relates, in certain exemplary embodiments, to a coated article that includes at least one silver (Ag) based infrared (IR) reflective layer(s) which is situated adjacent to and at contact with at least one protective layer of metallic or substantially metallic doped silver (eg, from AgZn) to improve the thermal stability and/or chemical durability characteristics of the low E coating. the adjacent doped silver protective layer is part of a low emissivity (low E) coating, and can be sandwiched between at least transparent dielectric layers. A barrier layer including Ni and/or Cr can be provided over and directly in contact with the protective doped silver layer to further improve the durability of the Low E coating and reduce the likelihood of delamination occurring under chemical exposure. This Low E coating can be used in applications such as monolithic windows, insulating glass (IG) window units and the like. BACKGROUND AND SUMMARY OF EXEMPLIFYING MODALITIES OF THE INVENTION
[0002] Coated articles are known in the art for use in window applications such as insulating glass (VI) window units, vehicle windows, monolithic windows, and/or the like. In certain exemplary cases, coated article designers seek a combination of high visible transmission, substantially neutral color, low emissivity (or emittance), low sheet strength (Rs), low U values, in the context of IG window units and/or low specific resistivity. The characteristics of high visible transmission and substantially neutral color can allow coated articles to be used in applications where these characteristics are desired, such as in architectural or vehicle window applications, while the characteristics of low emissivity (low E), low resistance of sheet, and low specific resistivity allow such coated articles to block significant amounts of IR radiation to reduce, for example, unwanted heating of the interior of vehicles and buildings.
[0003] Low E coatings with at least one silver-based IR reflective layer are known in the art. For example, see US Patent Nos. 5,344,718, 6,576,349, 8,945,714, 9,371,684, 9,028,956, 9,556,070, 8,945,714 and 9,028,983, all of which are incorporated herein. reference title. Low E coatings on glass are widely used in commercial and residential buildings to save energy. Dual Ag Low E coating is a dominant Low E product due to its excellent low emissivity properties and excellent solar heat gain control.
[0004] However, conventional low E coatings with silver IR reflective layer(s) have problems associated with chemical durability and/or environmental durability, which limit their applications. One reason is that silver IR reflective layers are not very stable, especially for double silver type Low E coatings. When Ag degrades or is damaged, the optical, electrical and thermal (emissivity) properties of silver degrade. For example, a low-E solar control coating with a stack of glass/Si3N4/NiCr/Ag/NiCr/Si3N4 provides efficient solar control, but cannot reasonably withstand chemical environments such as acidic environmental conditions. HCl. While there are some durable Low E coatings on the market, their performance is especially poor compared to light gain to solar gain ratio (GLS) values of about 1.0 or less. The higher the GLS value, the more energy will be saved, so high GLS values are desirable. GLS is calculated as Tvis/SHGC, where SHGC is according to NRFC 2001.
[0005] Exemplary embodiments of this invention solve these problems by providing a low E coating that has enhanced silver durability (e.g., chemical durability) while maintaining high GLS values. Embodiments of this invention relate to an article coated with a low E coating including at least one silver (Ag) based infrared (IR) reflective layer(s) which is situated adjacent to, and in contact with at least one protective layer of metallic or substantially metallic doped silver (eg, from AgZn) to improve chemical durability. The silver-based IR reflective layer and adjacent doped silver protective layer are part of a low emissivity (low E) coating, and can be sandwiched between at least transparent dielectric layers. Surprisingly and unexpectedly, it was found that providing the silver-based IR reflective layer directly under and in contact with a doped silver layer provides better thermal stability, corrosion resistance and chemical durability of the layer(s)( s) silver-based IR reflector(s) and the low E coating as a whole, maintaining good optical and emissivity properties such as, when desired, high GLS values of at least 1.10 (most preferably steel minus 1.20, more preferably at least 1.30, and most preferably at least 1.60). A barrier layer including Ni and/or Cr can be provided over and directly in contact with the protective doped silver layer to further improve the durability of the Low E coating.
[0006] In an exemplary embodiment of the present invention, a coated article is provided that includes a coating supported by a glassy substrate, the coating comprising: a first dielectric layer on the glass substrate; a metallic or substantially metallic infrared (IR) reflecting layer comprising silver on the vitreous substrate, situated on at least the first dielectric layer; a protective layer comprising silver doped on the vitreous substrate situated on and directly in contact with the IR reflective layer comprising silver; a second dielectric layer on the vitreous substrate situated over at least the first dielectric layer, with the IR-reflective layer comprising silver, and the protective layer comprising doped silver; and the metal content of the protective layer comprising doped silver comprises from 80 to 99.5% of Ag and from 0.5 to 20% of dopant, in atomic %, where the dopant is one or more of: Zn, Cu , Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu and combinations thereof; and wherein the coating has a sheet resistance (Rs) of at most 11 ohms/square and a normal emissivity (En) of at most 0.2.
[0007] In certain exemplary embodiments of the present invention, a coated article is provided that includes a coating supported by a vitreous substrate, the coating comprising: a first dielectric layer on the vitreous substrate; a metallic or substantially metallic infrared (IR) reflecting layer comprising silver on the vitreous substrate, situated on at least the first dielectric layer; a protective layer comprising copper doped on the vitreous substrate situated on and directly in contact with the IR reflective layer comprising silver; a second dielectric layer on the vitreous substrate situated over at least the first dielectric layer, with the IR-reflective layer comprising silver, and the protective layer comprising doped copper; the metal content of the protective layer comprising doped copper comprises 80 to 99.5% Cu and 0.5 to 20% dopant, in atomic %, where the dopant is one or more of: Zn, Ag , Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu and combinations thereof; and wherein the coating has a sheet resistance (Rs) of at most 11 ohms/square and a normal emissivity (En) of at most 0.2.
[0008] In certain exemplary embodiments of the present invention, a method of manufacturing a coated article is provided that includes a coating supported by a vitreous substrate, the method comprising: depositing by ion bombardment a first dielectric layer on the vitreous substrate; ion bombardment deposition of a metallic or substantially metallic infrared (IR) reflecting layer comprising silver on the vitreous substrate, situated on at least the first dielectric layer; ion bombardment deposition of a metallic or substantially metallic protective layer comprising silver doped in the glassy substrate over and directly in contact with the IR reflective layer comprising silver, the metal content of the protective layer comprising doped silver, as deposited, it comprises from 80 to 99.5% of Ag and from 0.5 to 20% of dopant, in atomic %, where the dopant is one or more of: Zn, Cu, Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu and combinations thereof; and after deposition by ion bombardment of the metallic or substantially metallic protective layer comprising doped silver, depositing, by ion bombardment, a second dielectric layer on the vitreous substrate located over at least the first dielectric layer and the IR-reflective layer that comprises silver, and the coating having a foil resistance (Rs) of at most 11 ohms/square and a normal emissivity (En) of at most 0.2. BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Figure 1 is a cross-sectional view of a coated article, according to an exemplary embodiment of the present invention.
[0010] Figure 2 is a cross-sectional view of a coated article, according to another exemplary embodiment of the present invention. DETAILED DESCRIPTION OF EXEMPLARY MODALITIES OF THE INVENTION
[0011] Reference will now be made to the drawings, in which similar reference numerals indicate similar parts throughout the several views.
[0012] Certain embodiments of this invention pertain to a coated article that includes a vitreous substrate 1 that supports a low E 30, 40 coating. The low E 30, 40 coating is designed to exhibit enhanced silver durability (for example, chemical durability), maintaining high GLS values. Embodiments of this invention relate to an article coated with a low E coating including at least one silver (Ag) based infrared (IR) reflective layer(s) which is situated adjacent to, and in contact with at least one metallic or substantially metallic doped silver protective layer 10 (e.g., from or including AgZn, AgCu, AgNi, AgW, AgSn, AgSi, AgSiAl, AgZnAl, AgZnSi, AgZnSiCu and/or alloys thereof) to improve chemical durability. The IR reflective layers that include silver 9, 9' are preferably of different material than the doped silver protective layer 10 in the exemplary embodiments of this invention, with the IR reflective layer 9, 9' preferably being silver, which is not doped with any other metal or is only slightly doped as deposited due to possible interference between the ion bombardment chamber(s), and the protective layer being silver, which as deposited, is intentionally doped with another metal(s) as explained in the present invention. In addition, the doped silver protective layer 10 is preferably substantially thinner than the adjacent silver-based IR reflective layer 9, 9' in certain exemplary embodiments of this invention, as this allows visible transmission to be increased. . In certain exemplary embodiments, the doped silver protective layer 10 is at least 40 angstroms (A) thinner (more preferably, at least 50 Â thinner, more preferably at least 75 Â thinner, and with the maximum preferably at least 100 Â thinner) than the adjacent silver-based IR reflective layer 9, 9'. The silver based IR reflective layer 9, 9’ and the adjacent doped silver protective layer 10 are part of a low emissivity (low E) coating 30, 40, and can be sandwiched between at least transparent dielectric layers. Surprisingly and unexpectedly it has been found that providing the silver based IR reflective layer 9, 9' directly under and in contact with a doped silver layer 10 provides better thermal stability, corrosion resistance and chemical durability of the IR reflective layer(s) based on silver 9 and low E coating 30, 40 as a whole, maintaining good optical and emissivity properties as, when desired, high GLS values of at least 1.10 (more preferably at least 1.20, more preferably at least 1.30, and most preferably at least 1.60). It is noted that GLS values can be measured monolithically. A barrier layer 11, 26 including Ni and/or Cr can be provided over and directly in contact with the doped silver protective layer 10 to further improve the durability of the low E coating. Such coated articles can be used in applications such as in monolithic windows, insulating glass (IG) window units and the like. The articles of the present invention may optionally be coated with heat treated (e.g., thermally tempered).
[0013] Figure 1 is a cross-sectional view of a coated article, according to an exemplary embodiment of the present invention. The coated article includes the vitreous substrate 1 (e.g., a clear, green, bronze, or bluish green glass substrate of about 1.0 to 10.0 mm thick, more preferably from about 1.0 mm to 6.0 mm thick) and a multi-layer Low E coating (or layer system) 30 provided over substrate 1 directly or indirectly. As shown in Figure 1, the low E coating 30 is of or includes a transparent dielectric layer 2 of or including silicon nitride (eg Si3N4, or some other suitable stoichiometry), transparent dielectric layer including zinc oxide 7 (by example, ZnOx, where "x" can be about 1; or ZnAlOx, metallic or substantially metallic IR (infrared) reflective layer 9 of or including silver, metallic or substantially metallic doped silver protective layer 10 disposed directly over and in contact with the silver IR reflective layer 9, barrier layer 11 of or including an oxide and/or nitride of Ni and/or Cr (eg NiCrOx) and an outer coating of or including transparent dielectric layer including oxide of tin 13 and transparent dielectric layer including silicon nitride 15. Layers including silicon nitride 2 and/or 15 may additionally include Al, oxygen or the like, and tin oxide layer 13 may , similarly, additionally include other materials such as nitrogen, zinc or the like. Other layers and/or materials may also be provided in the coating, in certain exemplary embodiments of the present invention, and it is also possible that certain layers may be removed or split, in certain exemplary instances. For example, a zirconium oxide outer coating layer (not shown) may be disposed over layer 15 in certain exemplary embodiments of this invention. In addition, one or more of the layers discussed above may be doped with other materials, in certain exemplary embodiments of the present invention.
[0014] Figure 2 is a cross-sectional view of a coated article, according to another exemplary embodiment of the present invention. Unlike Figure 1, the low E 40 coating of Figure 2 contains two spaced apart silver-based IR reflective layers 9 and 9', which IR reflective layers 9 and 9' in Figure 2 are spaced apart by layers 23 -25. In both the Figure 1 and Figure 2 embodiments, the low-E coating includes at least one silver-based IR reflective layer disposed adjacent to, under and in contact with a metallic or substantially metallic doped silver protective layer 10 in order to improve the chemical durability of the low-E coating. In the low-E coating 40 of Figure 2, the doped silver protective layer 10 is disposed over and in contact with the upper silver layer 9', but there is no such protective silver layer Doped silver over and in contact with the lower silver layer 9. In alternatives to Figure 2, of the double silver modality, the respective doped silver protective layers 10 can be arranged over and in contact with both the silver IR reflective layer top 9' as with the bottom 9 silver IR reflective layer.
[0015] The low E 40 coating illustrated in Figure 2 is supported by the vitreous substrate 1 (for example, transparent glass, green, bronze, or blue-green substrate of about 1.0 to 10.0 mm thick, with more preferably, from about 1.0 mm to 6.0 mm in thickness), and includes the transparent dielectric layer of or including zinc stannate 22, the transparent dielectric particle layer of or including zinc oxide or zinc stannate 7, IR reflective layer based on metallic or substantially metallic lower silver 9, the barrier layer 23 over and directly in contact with the lower IR reflective layer, where the barrier layer 23 may be of or include NiCr, NiCrNx, NiCrMo, NiCrMoOx, NiCrMoNx, NiTiNbOx, nickel oxide (Ni), chromium/chromium oxide (Cr), TiOx or a nickel alloy oxide such as chromium-nickel oxide (NiCrOx) or other suitable material, transparent dielectric layer of or including zinc stannate 24, dielectric particle layer transparent of or including zinc oxide or zinc stannate 25, upper silver metallic or substantially metallic IR reflective layer 9', metallic or substantially metallic doped silver protective layer 10, disposed directly over and in contact with the reflective layer of IV to the metallic or substantially metallic 9' upper silver base, the barrier layer 26 over and directly in contact with the doped silver protective layer 10, where the barrier layer 26 may be of or include NiCr, NiCrNx, NiCrMo, NiCrMoOx, NiCrMoNx, NiTiNbOx, nickel oxide (Ni), chromium/chromium oxide (Cr), TiOx, or a nickel alloy oxide such as chromium-nickel oxide (NiCrOx), or other suitable material, a dielectric layer transparent 27 of or including zinc stannate, zinc oxide, tin oxide or the like, a transparent dielectric layer 28 of or including zinc oxide, tin oxide or other suitable material, and the transparent dielectric layer 15 of or including silicon nitride, silicon oxynitride and/or other suitable material. The silicon nitride inclusive layer 15 may additionally include Al, oxygen or the like. Other layers and/or materials may also be provided in the coating, in certain exemplary embodiments of the present invention, and it is also possible that certain layers may be removed or split, in certain exemplary instances. For example, a zirconium oxide outer coating layer (not shown) may be disposed over layer 15 in certain exemplary embodiments of this invention. In addition, one or more of the layers discussed above may be omitted from coating 40 or doped with other materials, in certain exemplary embodiments of the present invention.
[0016] Conventional silver-based low-E coatings have problems relating to chemical durability, as explained above, as in HCl and CASS solvents. Corrosion mechanisms include galvanic corrosion and oxidation competition. Bimetallic corrosion occurs when two metals, with different potentials, are in electrical contact while in an electrically conductive corrosive liquid. The effect of the two metals together increases the anode corrosion rate and reduces or even suppresses cathode corrosion. In this way, anode materials will corrode much faster, and cathode corrosion is suppressed. In the exemplary embodiments of this invention, the silver IR reflective layer 9, 9' is in the cathode position such that the silver cathode 9, 9' is protected by the sacrificial anode material of the protective layer 10. Doped silver 10 is provided as the direct neighbor of silver 9, 9' to the protective layer of silver 9, 9' from chemical corrosion, in low E stacks in accordance with exemplary embodiments of this invention. As explained above, in the embodiments of this invention of Figures 1 and 2, the relatively thin metallic or substantially metallic doped silver protective layer 10 may be of or include AgZn, AgCu, AgNi, AgW, AgSn, AgSi, AgSiAl, AgZnAl, AgZnSi, AgZnSiCu, and/or combinations thereof.
[0017] It should be noted that "substantially" metallic means metallic with an oxygen content of at most 10%, and more preferably, with an oxygen content of at most 5%, in atomic %. Substantially metallic layers 9, 9' and 10 may contain from 0 to 10% oxygen and/or nitrogen, and more preferably, from 0 to 5% oxygen and/or nitrogen (% atomic), and most preferably, from 0 to 2% oxygen and/or nitrogen, in the exemplary embodiments of this invention.
[0018] The Ag dopant content of the protective layer 10 in Figures 1 and 2 is preferably kept low, and the thickness of the protective layer 10 is preferably thin relative to the adjacent silver IR reflective layer 9, 9', in order to reduce the absorption of light by the protective layer 10 so that the visible transmission of the coated article can be kept high, if desired. In certain exemplary embodiments of this invention, the metal content of the protective layer 10 in Figures 1 and 2, and other embodiments, is preferably from 80 to 99.5% Ag, more preferably from 90 to 99% Ag, and most preferably from 95 to 99% Ag; and preferably from 0.5 to 20% dopant, more preferably from 1 to 10% dopant, and most preferably from 1 to 5% dopant, wherein the dopant is any one of Zn, Cu , Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu, or combinations thereof. Thus, in certain exemplary embodiments of this invention, the metal content of the protective layer 10 in Figures 1 and 2, and other embodiments, is preferably from 80 to 99.5% Ag, more preferably from 90 to 99% Ag, and most preferably from 95 to 99% Ag; and preferably from 0.5 to 20% Zn, more preferably from 1 to 10% Zn and most preferably from 1 to 5% Zn. In certain exemplary embodiments of this invention, the metal content of the protective layer 10 in Figures 1 and 2, and other embodiments, is preferably from 80 to 99.5% Ag, more preferably from 90 to 99% Ag, and most preferably from 95 to 99% Ag; and preferably from 0.5 to 20% Cu, more preferably from 1 to 10% Cu and most preferably from 1 to 5% Cu. In certain exemplary embodiments of this invention, the metal content of the protective layer 10 in Figures 1 and 2, and other embodiments, is preferably from 80 to 99.5% Ag, more preferably from 90 to 99% Ag, and most preferably from 95 to 99% Ag; and preferably from 0.5 to 20% Ni, more preferably from 1 to 10% Ni and most preferably from 1 to 5% Ni. In certain exemplary embodiments of this invention, the metal content of the protective layer 10 in Figures 1 and 2, and other embodiments, is preferably from 80 to 99.5% Ag, more preferably from 90 to 99% Ag, and most preferably from 95 to 99% Ag; and preferably from 0.5 to 20% W, more preferably from 1 to 10% W, and most preferably from 1 to 5% W. In certain exemplary embodiments of this invention, the metal content of the protective layer 10 in Figures 1 and 2, and other embodiments, is preferably from 80 to 99.5% Ag, more preferably from 90 to 99% Ag, and most preferably from 95 to 99% Ag; and preferably from 0.5 to 20% Sn, more preferably from 1 to 10% Sn and most preferably from 1 to 5% Sn. In certain exemplary embodiments of this invention, the metal content of the protective layer 10 in Figures 1 and 2, and other embodiments, is preferably from 80 to 99.5% Ag, more preferably from 90 to 99% Ag, and most preferably from 95 to 99% Ag; and preferably from 0.5 to 20% Si, more preferably from 1 to 10% Si and most preferably from 1 to 5% Si. The protective layer(s) ) 10, as deposited as through ion bombardment deposition, are preferably metallic or substantially metallic, with a maximum oxygen content of 10%, and more preferably, a maximum oxygen content of 5%, in atomic %. If an oxide layer such as NiCrOx 11 (or layer 26) is deposited by ion bombardment onto layer 10, then it is possible for layer 10 to be oxidized to some degree during the deposition of layer 11 thereon. However, if layer 11 (or layer 26) is not an oxide layer, and instead it is a nitride layer, then its deposition should not cause any significant oxidation of layer 10.
[0019] In cases of monolithic articles, the coated article only includes one substrate as a vitreous substrate 1 (see Figures 1 and 2). However, the monolithic coated articles of the present invention can be used in devices such as IV window units, for example, that include multiple vitreous substrates. Exemplary IV window units are illustrated and described, for example, in US Patent Nos. 5,770,321, 5,800,933, 6,524,714, 6,541,084 and US 2003/0150711, the disclosures of which are incorporated herein by reference. in the present invention. An example of an IV window unit may include, for example, the coated vitreous substrate 1 shown in Figures 1 and 2, coupled to another vitreous substrate via spacer(s), sealant(s) or the like, with a gap being defined between them. This gap between substrates in the VI unit modalities can, in certain cases, be filled with a gas such as argon (Ar). An exemplary IV unit may comprise a pair of separate substantially transparent glassy substrates, each about 3 to 4 mm thick, one of which is coated with a coating here, in certain example cases, where the gap between the substrates may be from about 5 to 30 mm, more preferably from about 10 to 20 mm, and most preferably from about 12 to 16 mm. In certain example cases, the coating can be placed on the side of the inner or outer glassy substrate 1 facing the gap.
[0020] A transparent dielectric layer that includes silicon nitride 2 is arranged for anti-reflective purposes, and it has been found that it makes it possible to reduce color changes. Silicon nitride layer 2 can be of or include Si3N4. Alternatively, silicon nitride layer 2 can be of the Si-rich type (not fully stoichiometric). In addition, one or both of silicon nitride layers 2 and/or 15 may additionally include a dopant, such as aluminum or stainless steel, and/or small amounts of oxygen. These layers can be deposited by ion bombardment, in certain exemplary modalities, or by any other suitable technique. It is possible that other materials such as titanium oxide, zinc stannate or tin oxide can be used for dielectric layer(s) 2 and/or 15.
[0021] The transparent dielectric particle layer 7 is of or includes zinc oxide (eg ZnO) in the embodiments of Figure 1 and Figure 2. The zinc oxide layer(s) 7 may contain other materials , as well as Al (eg to form ZnAlOx) in certain exemplary modalities. For example, in certain exemplary embodiments of the present invention, zinc oxide layer 7 may be doped with from about 1 to 10% Al (or B), more preferably from about 1 to 5% Al ( or B), and more preferably, from about 2 to 4% Al (or B). The use of zinc oxide 7 under the silver in layer 9 allows to achieve excellent silver quality. In certain exemplary embodiments (for example, to be discussed below), the layer that includes zinc oxide 7 can be formed by ion bombardment of a ZnO ceramic or metal or ZnO ceramic rotating magnetron ion bombardment target. It has been found that the use of the ceramic target in certain exemplary modalities (eg ZnO, which may or may not be doped with Al, F or the like) allows a high quality of silver to be achieved, thus resulting in a lower emissivity coating. Although the Zn:0 ratio in the ceramic target is stoichiometric, in certain exemplary embodiments, at least one ceramic target is substoichiometric comprising ZnOx (e.g., where 0.25 < x < 0.99, more preferably 0.50 < x < 0.97, and even more preferably, 0.70 < x < 0.96) can be used instead in the ion bombardment deposition of a layer that includes zinc oxide 7, which may be substoichiometric, in certain cases. It is possible that other materials such as zinc stannate, NiCr, NiCrNx, NiCrMoNx or ZnOx could be used for layer 7 in alternative embodiments of the present invention.
[0022] Still referring to Figures 1 and 2, the transparent infrared (IR) reflecting layers 9 and 9' are preferably conductive and metallic or substantially metallic, and preferably, they comprise or consist essentially of silver (Ag). The IR 9 and 9' reflective layers are not doped with other metal(s) in the preferred embodiments of this invention. The IR 9 and 9’ reflective layers help to allow the coating to have low E and/or good solar control characteristics such as low emittance, low sheet strength, and so on. In certain exemplary embodiments, the silver IR (Ag) reflective layers 9 and 9' are located over layers of particles including dielectric and transparent zinc oxide 7, 25, and one or both of the layer(s) 9 , 9' are located under and directly in contact with a 10-doped silver proactive layer.
[0023] Still referring to Figures 1 and 2, the barrier layers 11 and 26 may be of or include an oxide of Ni and/or Cr, or may be metallic and of or include Ni and/or Cr, and may be , for example, of nitride. In certain exemplary embodiments, barrier layers 11 and/or 26 may be, individually, or include, NiCr, NiCrNx, NiCrMo, NiCrMoOx, NiCrMoNx, NiTiNbOx, nickel oxide (Ni), chromium/chromium oxide (Cr), TiOx or a nickel alloy oxide such as chromium nickel oxide (NiCrOx) or other suitable material. Layers 11 and 26 can contain from about 0 to 20% nitrogen, and more preferably, from about 1 to 10% nitrogen, in certain exemplary embodiments of this invention. Layers 11 and 26 may or may not show gradual oxidation in the different embodiments of the present invention. Gradual oxidation means that the degree of oxidation in the layer changes through the thickness of the layer so that, for example, a barrier layer may have different degrees so that it is less oxidized at the contact interface with the immediately adjacent layer. than on a portion of the additional contact layer or further away from the doped silver protective layer 10. It is surprisingly observed that the presence of the barrier layers 11 and 26 over and directly in contact with the silver protective layer Doped 10 improves the chemical durability of the Low E coating by reducing the likelihood of delamination upon exposure to chemicals.
[0024] An exemplary outer coating, such as that shown in Figure 1, may be of or include transparent dielectric layers 13 and/or 15, in certain exemplary embodiments. Dielectric layer 13 can be of or include a metal oxide, such as tin oxide in certain exemplary embodiments of this invention. The metal oxide inclusive layer 13, such as tin oxide or zinc stannate, is used for anti-reflective purposes, and also improves the emissivity of the coated article and the stability and efficiency of the manufacturing process. The tin oxide inclusive layer 13 may be doped with other materials such as nitrogen and/or zinc in certain exemplary embodiments of this invention. The tin oxide-based layer 13 provides good durability and improves light transmission. Dielectric layer 15 can be of or include silicon nitride (eg, Si3N4 or other suitable stoichiometry) or any other material suitable in certain exemplary embodiments of this invention, such as silicon oxynitride. Silicon nitride layer 15 may additionally include another material such as aluminum as a dopant or small amounts of oxygen in certain exemplary embodiments of this invention. Optionally, other layers, such as a zirconium oxide outer coating, can be disposed above layer 15 in the outer coating in certain examples. Layer 15 is provided for durability purposes, and to protect the underlying layers. In certain exemplary embodiments, silicon nitride-based layer 15 can have a refractive index (n) of from about 1.9 to 2.2, and more preferably from about 1.95 to 2.05. In certain exemplary embodiments, Zr can be disposed in the silicon nitride of layer 15 (of layer 2 or layer 5). Thus, one or more of layers 2 and/or 15 may be or include SiZrNx and/or zirconium oxide, in certain exemplary embodiments of this invention.
[0025] Another layer (or layers) below or above the illustrated coating can also be provided. Thus, although the layer system or coating is "on" or "supported by" substrate 1 (directly or indirectly), another layer (or layers) can be provided between them. Thus, for example, the coating of Figure 1 can be considered "on" or "supported by" substrate 1, even if one or more other layers are disposed between layer 3 and substrate 1. In addition, certain layers of The illustrated coating may be removed in certain embodiments, while others may be added between the various layers, or the various layers may be split by another layer (or layers) added between the split sections in other embodiments of this invention without departing from the general spirit of certain embodiments of this invention.
[0026] Although various thicknesses may be used in different embodiments of the present invention, exemplifying thicknesses and materials for the respective layers on the vitreous substrate 1 in the embodiment of Figure 1 are as follows: from the vitreous substrate outward (e.g. , the Al content in the zinc oxide layer and the silicon nitride layers can be from about 1 to 10%, more preferably from about 1 to 3% in certain exemplary cases). Note that in Tables 1 and 2, barrier layers 11, 23, and 26 can be of or include any of the suitable materials discussed above, such as NiCr, NiCrNx, NiCrMo, NiCrMoOx, NiCrMoNx, NiTiNbOx, nickel oxide (Ni) , chromium/chromium oxide (Cr), TiOx or a chromium alloy oxide such as nickel-chromium oxide (NiCrOx). And in Tables 1 and 2, the protective silver doped layer 10 can be of or include AgZn, AgCu, AgNi, AgW, AgSn, AgSi, AgSiAl, AgZnAl, AgZnSi, AgZnSiCu and/or combinations thereof

[0027] Although various thicknesses can be used in different embodiments of the present invention, thicknesses and exemplifying materials for the respective layers on the vitreous substrate 1 in the embodiment of Figure 2 are as follows: from the vitreous substrate outward (e.g. , the Al content in the zinc oxide layer and the silicon nitride layers may be from about 1 to 10%, more preferably from about 1 to 3% in certain exemplary cases):

[0028] It has been found, surprisingly and unexpectedly, that providing the silver-based 9, 9' IR reflective layer directly under and in contact with a doped silver layer 10 provides better corrosion resistance, thermal stability and chemical durability of the silver-based IR reflective layer(s), 9, 9' and the low E 30, 40 coating as a whole, maintaining good optical and emissivity properties as, when desired, high GLS values. The Ag dopant content of the protective layer 10 is preferably kept low, and the thickness of the doped silver protective layer 10 is preferably substantially thinner relative to the adjacent silver IR reflective layer 9, 9', in order to reduce the absorption of light by the protective layer 10, so that the visible transmission of the coated article can be kept high, if desired. In the embodiments of Figures 1 and 2, for example, the doped silver protective layer 10 is preferably substantially thinner than the adjacent silver-based IR reflective layer 9, 9' in certain exemplary embodiments of this invention, because this allows visible transmission to be increased. In certain exemplary embodiments, the doped silver protective layer 10 is at least 40 angstroms (A) thinner (more preferably, at least 50 A thinner, more preferably, at least 75 thinner, and with the maximum preferably, at least 100 A thinner) than the adjacent silver-based IR reflective layer 9, 9'.
[0029] It has also surprisingly been found that the presence of barrier layers 11 and 26 over the doped silver protective layer 10 is particularly important for durability. The presence of barrier layers 11 and 26, in combination with the doped silver protective layer 10 over a silver based IR reflective layer 9, 9’ unexpectedly improved the chemical durability of the low E coating in a surprising way. When barrier layers 11, 26 were not present, delamination could take place by chemical test.
[0030] In certain exemplary embodiments of this invention, the coated articles in the present invention (for example, see Figures 1 and 2) may have the low E (low emissivity), solar and/or optical characteristics shown in Table 3, when measured monolithically, before and/or after any optional heat treatment such as thermal quenching.

[0031] Although the combination of IR reflective layer 9 (or 9') and silver doped protective layer 10 is used in the low E coatings of Figures 1 and 2, in certain exemplary embodiments of this invention discussed herein, it is possible to use the combination of the IR reflective layer 9 (or 9') and the doped silver protective layer 10 described herein in other low E coatings. For example and without limitation, the IR reflective layer(s) silver-based in low E coatings in any of US Patent Nos. 5,344,718, 6,576,349, 8,945,714, 9,371,684, 9,028,956, 9,556,070, 8,945,714 and/or 9,028 .983 (which are all incorporated herein by reference) may be replaced with the combination of the IR reflective layer 9 and the silver doped protective layer 10 discussed in the present invention, in the exemplary embodiments of this invention. In other words, for example, the silver-based IR reflective layer(s) in any of US Patent Nos. 5,344,718, 6,576,349, 8,945,714, 9,371,684 , 9,028,956, 9,556,070, 8,945,714 and/or 9,028,983, may be replaced by an IR reflective layer based on silver 9 and protective layer of doped silver 10, as is discussed in the present invention.
[0032] In alternative embodiments of the present invention, the protective layer 10, in any embodiment described herein, may be Cu-based rather than Ag-based. In other words, the metallic or substantially metallic protective layer 10 may be doped with Cu. Thus, in certain exemplary embodiments of this invention, the metal content of the protective layer 10 in Figures 1 and 2, and other embodiments, may be from 80 to 99.5% Cu, more preferably from 90 to 99% Cu. Cu, and most preferably from 95 to 99% Cu; and preferably from 0.5 to 20% dopant, more preferably from 1 to 10% dopant, and most preferably from 1 to 5% dopant, wherein the dopant is any one of Zn, Ag , Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiAg, or combinations thereof.
[0033] Example 1, as shown in Figure 2, according to an exemplary embodiment of the present invention, and Comparative Example (EC), were made and tested. Each of Example 1 and EC had the same Low E 40 coating, except that a protective layer of AgZn 10 (97% Ag and 3% Zn) was present in Example 1, but not present. in the Comparative Example (EC). Layer thicknesses for EC and Example 1 are as follows, with thicknesses expressed in nm.

[0034] The optical and thermal data for Example 1 and EC are as set out below, after the same heat treatment (HT) at at least 600 degrees C for at least eight minutes. Note that in the graph below, "normal emissivity" represents normal emissivity/emittance (En).

[0035] After HT, notable differences were observed between Example 1 and EC. In particular, the EC coating had at least five (5) times more defects in it after HT compared to the Example 1 coating. 9' silver IV surprisingly improved the thermal stability of the coating.
[0036] In addition, the same corrosion test was then carried out in Example 1 and Comparative Example (EC), in order to test their respective corrosion and durability characteristics. The test was a test that lasted two days, under conditions of high humidity (85%) and high temperature (85 degrees C). The differences between Example 1 and EC, after this test, were marked and surprising. After the HHHT test, the EC had many more defects, and worse, than Example 1. It could be seen through the microscope that Example 1 was much more durable in the HHHT test than EC was. Thus, it was also shown that the addition of the 10' doped silver protective layer over the 9' silver IR reflective layer surprisingly improved the durability of the coating.
[0037] In an exemplary embodiment of the present invention, a coated article is provided that includes a coating supported by a glassy substrate, the coating comprising: a first dielectric layer on the glass substrate; a metallic or substantially metallic infrared (IR) reflecting layer comprising silver on the vitreous substrate, situated on at least the first dielectric layer; a protective layer comprising silver doped on the vitreous substrate situated on and directly in contact with the IR reflective layer comprising silver; a second dielectric layer on the vitreous substrate situated over at least the first dielectric layer, with the IR-reflective layer comprising silver, and the protective layer comprising doped silver; and the metal content of the protective layer comprising doped silver comprises from 80 to 99.5% of Ag and from 0.5 to 20% of dopant, in atomic %, where the dopant is one or more of: Zn, Cu , Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu and combinations thereof; and wherein the coating has a sheet resistance (Rs) of at most 11 ohms/square and a normal emissivity (En) of at most 0.2.
[0038] In the coated article of the immediately preceding paragraph, the metal content of the protective layer comprising doped silver may comprise from 90 to 99% of Ag and from 1 to 10% of dopant, in atomic %, where the dopant is one or more from: Zn, Cu, Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu and combinations thereof.
[0039] In the coated article according to any of the preceding paragraphs, the metal content of the protective layer comprising doped silver may comprise from 95 to 99% Ag and 1 to 5% dopant, in atomic %, where the dopant is one or more of: Zn, Cu, Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu and combinations thereof.
[0040] In the coated article according to any of the three preceding paragraphs, the IR reflective layer may consist, or consist essentially, of silver.
[0041] In the coated article according to any of the four preceding paragraphs, the IR reflective layer may be metallic.
[0042] In the coated article according to any of the five preceding paragraphs, the protective layer comprising doped silver may be metallic or substantially metallic.
[0043] In the coated article according to any one of the six preceding paragraphs, the coated article may have a visible transmission of at least 40%, more preferably at least 50%, and more preferably at least 70%.
[0044] In the coated article according to any of the seven preceding paragraphs, the coated article may have a light gain to solar gain ratio (GLS) of at least 1.10, more preferably of at least 1.30 , and more preferably, at least 1.60.
[0045] In the coated article according to any one of the eight preceding paragraphs, the dopant may comprise Zn, and the metal content of the protective layer comprising doped silver may comprise from 90 to 99% Ag and from 1 to 10% Zn, in atomic %; more preferably, from 95 to 99% Ag and 1 to 5% Zn, in atomic %.
[0046] In the coated article according to any of the nine preceding paragraphs, the dopant may comprise Cu, and the metal content of the protective layer comprising doped silver may comprise from 90 to 99% Ag and from 1 to 10% Cu, in atomic %; more preferably, from 95 to 99% Ag and 1 to 5% Cu, in atomic %.
[0047] In the coated article according to any of the ten preceding paragraphs, the dopant may comprise Ni, the metal content of the protective layer comprising doped silver may comprise from 90 to 99% of Ag and from 1 to 10% of Ni, in atomic %; more preferably, from 95 to 99% Ag and 1 to 5% Ni, in atomic %.
[0048] In the coated article according to any of the eleven preceding paragraphs, the dopant may comprise W, the metal content of the protective layer comprising doped silver may comprise 90 to 99% Ag and 1 to 10% of W, in atomic %; more preferably, from 95 to 99% Ag and 1 to 5% W, in atomic %.
[0049] In the coated article according to any of the twelve preceding paragraphs, the dopant may comprise Sn, the metal content of the protective layer comprising doped silver may comprise 90 to 99% Ag and 1 to 10% of Sn, in atomic %; more preferably, from 9599% Ag and from 1 to 5% Sn, in atomic %.
[0050] In the coated article according to any of the thirteen preceding paragraphs, the dopant may comprise Si, the metal content of the protective layer comprising doped silver may comprise from 90 to 99% Ag and from 1 to 10% of Si, in atomic %; more preferably, from 95 to 99% Ag and 1 to 5% Si, in atomic %.
[0051] In the coated article according to any of the fourteen preceding paragraphs, the dopant may comprise Zn and Cu, and the metal content of the protective layer comprising doped silver may comprise from 80 to 99% of Ag and from 0.5 to 10% each of Zn and Cu, in atomic %.
[0052] In the coated article according to any of the fifteen preceding paragraphs, the dopant may comprise Zn and Si, and the metal content of the protective layer comprising doped silver may comprise from 80 to 99% of Ag and from 0.5 to 10% each of Zn and Si, in atomic %.
[0053] In the coated article of any of the sixteen preceding paragraphs, the coated article may be thermally tempered.
[0054] In the coated article according to any one of the preceding seventeen paragraphs, the protective layer comprising doped silver may be at least 40 Â thinner than the IR reflective layer comprising silver, and more preferably, at least 75 Â thinner, and even more preferably, at least 100 Â thinner.
[0055] In the coated article according to any one of the preceding eighteen paragraphs, the protective layer comprising doped silver may be about 3 to 70 Â thick, and the IR reflective layer comprising silver may be about 40 to 170 Â thick.
[0056] In the coated article according to any one of the nineteen preceding paragraphs, the protective layer comprising doped silver may be about 5 to 25 Â thick, and the IR reflective layer comprising silver may be about 60 to 155 Â thick.
[0057] In the coated article according to any one of the twenty preceding paragraphs, the protective layer comprising doped silver may be from about 8 to 15 thick, and/or the IR reflective layer comprising silver may be about 80 to 145 Â thick.
[0058] In the coated article according to any one of the preceding paragraphs, the first dielectric layer may comprise silicon nitride.
[0059] In the coated article, according to any one of the twenty-two paragraphs above, the coating may have a sheet resistance (Rs) of a maximum of 9 ohms/square and a normal emissivity (En) of a maximum of 0.11 .
[0060] In the coated article according to any one of the twenty-three preceding paragraphs, the coating may additionally comprise another infrared (IR) reflecting layer comprising silver which is separate and does not come into contact with the protective layer comprising doped silver.
[0061] In the coated article according to any one of the twenty-four preceding paragraphs, the coating may further comprise a dielectric layer comprising zinc oxide situated under and directly in contact with the IR reflective layer comprising silver.
[0062] In the coated article according to any one of the twenty-five preceding paragraphs, the coating may further comprise a barrier layer comprising Ni and/or Cr situated on and directly in contact with the protective layer comprising doped silver. The barrier layer can comprise a Ni and/or Cr nitride.
[0063] Although the invention has been described in connection with what is currently considered the most practical and preferred embodiment, it should be understood that the invention should not be limited to the disclosed embodiment, but rather is intended to cover various modifications and equivalent provisions included in the spirit and scope of the appended claims.

权利要求:
Claims (32)
[0001]
1. Coated article, characterized in that it includes a coating (30) supported by a vitreous substrate (1), the coating comprising: a first dielectric layer (2) on the vitreous substrate; an infrared (IR) reflecting layer (9) metallic or substantially metallic comprising silver on the vitreous substrate, situated on at least the first dielectric layer (2); a protective layer (10) comprising silver doped on the vitreous substrate situated on and directly in contact with the IR reflective layer (9) comprising silver; a second dielectric layer (13;15) on the vitreous substrate situated on at least the first dielectric layer (2), with the IR-reflective layer (9) comprising silver and the protective layer (10) comprising doped silver; and the metal content of the protective layer (10) which comprises doped silver comprises from 80 to 99.5% of Ag and from 0.5 to 20% of dopant, in atomic %, where the dopant is one or more of: Zn, Cu, Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu and combinations thereof.
[0002]
2. Coated article according to claim 1, characterized in that the metal content of the protective layer (10) which comprises doped silver comprises from 90 to 99% of Ag and from 1 to 10% of dopant, in atomic % , where the dopant is one or more of: Zn, Cu, Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu and combinations thereof.
[0003]
3. Coated article according to claim 1, characterized in that the metal content of the protective layer (10) which comprises doped silver comprises from 95 to 99% of Ag and from 1 to 5% of dopant, in atomic % , where the dopant is one or more of: Zn, Cu, Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu and combinations thereof.
[0004]
4. Coated article according to claim 1, characterized in that the IR reflective layer (9) consists essentially of silver.
[0005]
5. Coated article, according to claim 1, characterized in that the IR reflective layer (9) is metallic.
[0006]
6. Coated article according to claim 1, characterized in that the protective layer (10) comprising doped silver is metallic or substantially metallic.
[0007]
7. Coated article according to claim 1, characterized in that the dopant comprises Zn, and the metal content of the protective layer (10) comprising doped silver comprises from 90 to 99% of Ag and from 1 to 10% Zn, in atomic %.
[0008]
8. Coated article according to claim 1, characterized in that the dopant comprises Zn, and the metal content of the protective layer (10) comprising doped silver comprises from 95 to 99% of Ag and from 1 to 5% Zn, in % atomic.
[0009]
9. Coated article according to claim 1, characterized in that the dopant comprises Cu, and the metal content of the protective layer (10) comprising doped silver comprises from 90 to 99% of Ag and from 1 to 10% Cu, in atomic %.
[0010]
10. Coated article according to claim 1, characterized in that the dopant comprises Cu, and the metal content of the protective layer (10) comprising doped silver comprises from 95 to 99% of Ag and from 1 to 5% Cu, in % atomic.
[0011]
11. Coated article according to claim 1, characterized in that the dopant comprises Ni, and the metal content of the protective layer (10) comprising doped silver comprises from 90 to 99% of Ag and from 1 to 10% Ni, in % atomic.
[0012]
12. Coated article according to claim 1, characterized in that the dopant comprises Ni, and the metal content of the protective layer (10) comprising doped silver comprises from 95 to 99% of Ag and from 1 to 5% Ni, in % atomic.
[0013]
13. Coated article according to claim 1, characterized in that the dopant comprises W, and the metal content of the protective layer (10) comprising doped silver comprises from 90 to 99% of Ag and from 1 to 10% W, in % atomic.
[0014]
14. Coated article according to claim 1, characterized in that the dopant comprises W, and the metal content of the protective layer (10) comprising doped silver comprises from 95 to 99% of Ag and from 1 to 5% W, in % atomic.
[0015]
15. Coated article according to claim 1, characterized in that the dopant comprises Sn, and the metal content of the protective layer (10) comprising doped silver comprises from 90 to 99% of Ag and from 1 to 10% Sn, in atomic %.
[0016]
16. Coated article according to claim 1, characterized in that the dopant comprises Sn, and the metal content of the protective layer (10) comprising doped silver comprises from 95 to 99% of Ag and from 1 to 5% of Sn, in % atomic.
[0017]
17. Coated article according to claim 1, characterized in that the dopant comprises Si, and the metal content of the protective layer (10) comprising doped silver comprises from 90 to 99% of Ag and from 1 to 10% Si, in atomic %.
[0018]
18. Coated article according to claim 1, characterized in that the dopant comprises Si, and the metal content of the protective layer (10) comprising doped silver comprises from 95 to 99% of Ag and from 1 to 5% Si, in % atomic.
[0019]
19. Coated article according to claim 1, characterized in that the dopant comprises Zn and Cu, and the metal content of the protective layer (10) which comprises doped silver comprises from 80 to 99% of Ag and 0.5 to 10% each of Zn and Cu, in atomic %.
[0020]
20. Coated article according to claim 1, characterized in that the dopant comprises Zn and Si, and the metal content of the protective layer (10) which comprises doped silver comprises from 80 to 99% of Ag and 0.5 to 10% each of Zn and Si, in atomic %.
[0021]
21. Coated article according to claim 1, characterized in that the protective layer (10) comprising doped silver is at least 40 Â° thinner than the IR reflective layer (9) comprising silver.
[0022]
22. Coated article according to claim 1, characterized in that the protective layer (10) comprising doped silver is at least 75 Â° thinner than the IR reflective layer (9) comprising silver.
[0023]
23. Coated article according to claim 1, characterized in that the protective layer (10) which comprises doped silver is at least 100 Âµm thinner than the IR reflective layer (9) which comprises silver.
[0024]
24. Coated article according to claim 1, characterized in that the protective layer (10) comprising doped silver is from 3 to 70 Â thick, and the IR reflective layer (9) comprising silver is 40 thick. to 170 Â thick.
[0025]
25. Coated article according to claim 1, characterized in that the protective layer (10) comprising doped silver is 5 to 25 Âµm thick, and the IR reflective layer (9) comprising silver is 60 to 155 Â thick.
[0026]
26. Coated article according to claim 1, characterized in that the protective layer (10) comprising doped silver is 8 to 15 Â thick, and the IR reflective layer (9) comprising silver is 80 to 145 Â thick.
[0027]
27. Coated article according to claim 1, characterized in that the first dielectric layer (2) comprises silicon nitride.
[0028]
28. Coated article according to claim 1, characterized in that the coating further comprises another infrared (IR) reflecting layer (9) comprising silver that is separate and does not come into contact with the protective layer (10) comprising doped silver.
[0029]
29. Coated article according to claim 1, characterized in that the coating further comprises a dielectric layer (7) comprising zinc oxide situated under and directly in contact with the IR reflective layer (9) comprising silver.
[0030]
30. Coated article according to claim 1, characterized in that the coating further comprises a barrier layer (11) comprising Ni and/or Cr situated on and directly in contact with the protective layer (10) comprising doped silver .
[0031]
31. Coated article according to claim 1, characterized in that the barrier layer (11) comprises a Ni and/or Cr nitride.
[0032]
32. A method for manufacturing a coated article as defined in claim 1 which includes a coating (30) supported by a vitreous substrate (1), the method characterized in that it comprises: ion bombardment deposition of a first dielectric layer ( 2) on the vitreous substrate; deposition by ion bombardment of an infrared (IR) reflecting layer (9) metallic or substantially metallic comprising silver on the vitreous substrate, situated on at least the first dielectric layer (2); ion bombardment deposition of a metallic or substantially metallic protective layer (10) comprising silver doped in the glassy substrate over and directly in contact with the IR reflective layer (9) comprising silver, the metal content of the protective layer (10 ) which comprises doped silver, as deposited, comprises from 80 to 99.5% of Ag and from 0.5 to 20% of dopant, in atomic %, where the dopant is one or more of: Zn, Cu, Ni, W , Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu and combinations thereof; and after deposition by ion bombardment of the metallic or substantially metallic protective layer (10) comprising doped silver, depositing by ion bombardment a second dielectric layer (13; 15) on the vitreous substrate located on at least the first dielectric layer ( 2) and the IR reflective layer (9) comprising silver, and the coating having a sheet resistance (Rs) of at most 11 ohms/square and a normal emissivity (En) of at most 0.2.

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RU2019130724A|2021-04-01|

US20190203340A1|2019-07-04|

RU2019130724A3|2021-04-01|

EP3589596A2|2020-01-08|

CN110573467A|2019-12-13|

WO2018160616A2|2018-09-07|

US10233531B2|2019-03-19|

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US10787385B2|2018-07-16|2020-09-29|Guardian Glass, LLC|Low-E matchable coated articles having absorber film and corresponding methods|

CN109628880B|2018-12-28|2021-02-26|厦门美澜光电科技有限公司|Anti-oxidation and anti-corrosion lens with patterns and preparation method thereof|

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US10696584B1|2019-11-26|2020-06-30|Guardian Europe S.A.R.L.|Coated article with low-E coating having protective contact layer including Ag, Ni, and Cr for protecting silver based IR reflecting layer, and method of making same|

法律状态:
2020-08-11| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

2020-12-29| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2021-06-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/02/2018, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

US15/446,026|US10233531B2|2017-03-01|2017-03-01|Coated article with low-E coating having protective doped silver layer for protecting silver based IR reflecting layer, and method of making same|

US15/446,026|2017-03-01|

PCT/US2018/020084|WO2018160616A2|2017-03-01|2018-02-28|Coated article with low-e coating having protective doped silver layer for protecting silver based ir reflecting layer, and method of making same|

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