This application relates in certain example embodiments to a coated article including at least one silver (Ag) based infrared (IR) reflecting layer(s) that is provided adjacent to and contacting at least one protective metallic or substantially metallic doped silver layer (e.g., AgZn) in order to improve thermal stability and/or chemical durability characteristics of the low-E coating. The silver based IR reflecting layer and adjacent protective doped silver layer are part of a low emissivity (low-E) coating, and may be sandwiched between at least transparent dielectric layers. A barrier layer including Ni and/or Cr may be provided over and directly contacting the protective doped silver layer in order to further improve durability of the low-E coating and reduce the likelihood of delamination upon chemical exposure. Such low-E coating may be used in applications such as monolithic windows, insulated glass (IG) window units, and the like.
Coated articles are known in the art for use in window applications such as insulating glass (IG) window units, vehicle windows, monolithic windows, and/or the like. In certain example instances, designers of coated articles often strive for a combination of high visible transmission, substantially neutral color, low emissivity (or emittance), low sheet resistance (Rs), low U-values in the context of IG window units, and/or low specific resistivity. High visible transmission and substantially neutral color may permit coated articles to be used in applications where these characteristics are desired such as in architectural or vehicle window applications, whereas low-emissivity (low-E), low sheet resistance, and low specific resistivity characteristics permit such coated articles to block significant amounts of IR radiation so as to reduce for example undesirable heating of vehicle or building interiors.
Low-E coatings having at least one silver based IR reflecting layer are known in the art. For example, see U.S. Pat. Nos. 5,344,718, 6,576,349, 8,945,714, 9,371,684, 9,028,956, 9,556,070, 8,945,714, 9,028,983, which are all hereby incorporated herein by reference. Low-E coatings on glass are widely used in commercial and residential buildings to save energy. The double Ag low-E coating is a dominant low-E product due to its excellent low emissivity properties and excellent control of solar heat gain.
However, conventional low-E coatings with silver IR reflecting layer(s) have problems associated with chemical durability and/or environmental durability which limit their applications. A reason is that the silver IR reflecting layers are not very stable, especially for double silver type low-E coatings. Once the Ag is decayed or damaged, the silver's optical, electrical, and thermal (emissivity) properties are degraded. For example, a solar control low-E coating with stack of glass/Si3N4/NiCr/Ag/NiCr/Si3N4 provides efficient solar control, but cannot reasonably survive chemical environments such as HCl acid environmental conditions. While there are some durable low-E coatings in the market, their performances are poor especially with respect to undesirably low light-to-solar gain ratio (LSG) values of around 1.0 or less. The higher the LSG value, the more energy saved, so that high LSG values are desirable. LSG is calculated as Tvis/SHGC, where SHGC is according to NRFC 2001.
Example embodiments of this invention solve these problems by providing a low-E coating that has improved silver durability (e.g., chemical durability), while maintaining high LSG values. Example embodiments of this invention relate to a coated article with a low-E coating including at least one silver (Ag) based infrared (IR) reflecting layer(s) that is provided adjacent to and contacting at least one protective metallic or substantially metallic doped silver layer (e.g., AgZn) in order to improve chemical durability. The silver based IR reflecting layer and adjacent protective doped silver layer are part of a low emissivity (low-E) coating, and may be sandwiched between at least transparent dielectric layers. It has surprisingly and unexpectedly been found that providing the silver based IR reflecting layer directly under and contacting a doped silver layer provides for improved thermal stability, corrosion resistance and chemical durability of the silver based IR reflecting layer(s) and the overall low-E coating, while maintaining good optical and emissivity properties such as, when desired, high LSG 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). A barrier layer including Ni and/or Cr may be provided over and directly contacting the protective doped silver layer in order to further improve durability of the low-E coating.
In an example embodiment of this invention, there is provided a coated article including a coating supported by a glass substrate, the coating comprising: a first dielectric layer on the glass substrate; an metallic or substantially metallic infrared (IR) reflecting layer comprising silver on the glass substrate located over at least the first dielectric layer; a protective layer comprising doped silver on the glass substrate located over and directly contacting the IR reflecting layer comprising silver; a second dielectric layer on the glass substrate located over at least the first dielectric layer, the IR reflecting layer comprising silver, and the protective layer comprising doped silver; wherein metal content of the protective layer comprising doped silver comprises from 80-99.5% Ag and from 0.5 to 20% dopant, 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 no greater than 11 ohms/square and a normal emissivity (En) of no greater than 0.2.
In certain example embodiments of this invention, there is provided a coated article including a coating supported by a glass substrate, the coating comprising: a first dielectric layer on the glass substrate; an metallic or substantially metallic infrared (IR) reflecting layer comprising silver on the glass substrate located over at least the first dielectric layer; a protective layer comprising doped copper on the glass substrate located over and directly contacting the IR reflecting layer comprising silver; a second dielectric layer on the glass substrate located over at least the first dielectric layer, the IR reflecting layer comprising silver, and the protective layer comprising doped copper; wherein metal content of the protective layer comprising doped copper comprises from 80-99.5% Cu and from 0.5 to 20% dopant, 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 no greater than 11 ohms/square and a normal emissivity (En) of no greater than 0.2.
In certain example embodiments of this invention, there is provided a method of making a coated article including a coating supported by a glass substrate, the method comprising: sputter depositing a first dielectric layer on the glass substrate; sputter depositing a metallic or substantially metallic infrared (IR) reflecting layer comprising silver on the glass substrate located over at least the first dielectric layer; sputter depositing a metallic or substantially metallic protective layer comprising doped silver on the glass substrate over and directly contacting the IR reflecting layer comprising silver, wherein metal content of the protective layer comprising doped silver as deposited comprises from 80-99.5% Ag and from 0.5 to 20% dopant, atomic %, where the dopant is one or more of: Zn, Cu, Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu, and combinations thereof; and after sputter depositing the metallic or substantially metallic protective layer comprising doped silver, sputter depositing a second dielectric layer on the glass substrate located over at least the first dielectric layer and the IR reflecting layer comprising silver, and wherein the coating has a sheet resistance (Rs) of no greater than 11 ohms/square and a normal emissivity (En) of no greater than 0.2.
Referring now to the drawings in which like reference numerals indicate like parts throughout the several views.
Example embodiments of this invention relate to a coated article including a glass substrate 1 that supports a low-E coating 30, 40. The low-E coating 30, 40 is designed to have improved silver durability (e.g., chemical durability), while maintaining high LSG values. Example embodiments of this invention relate to a coated article with a low-E coating including at least one silver (Ag) based infrared (IR) reflecting layer(s) 9, 9′ that is provided adjacent to and contacting at least one protective metallic or substantially metallic doped silver layer 10 (e.g., of or including AgZn, AgCu, AgNi, AgW, AgSn, AgSi, AgSiAl, AgZnAl, AgZnSi, AgZnSiCu, and/or their alloys) in order to improve chemical durability. Silver inclusive IR reflecting layers 9, 9′ are preferably of different material than doped silver protective layer 10 in example embodiments of this invention, with IR reflecting layer 9, 9′ preferably being of silver that is either not doped with any other metal, or only slightly doped as deposited due to possible crosstalk between sputtering chamber(s), and protective layer 10 being of silver that as deposited is intentionally doped with another metal(s) as explained herein. Moreover, protective doped silver layer 10 is preferably substantially thinner than the adjacent silver based IR reflecting layer 9, 9′ in certain example embodiments of this invention, because this allows visible transmission to be increased. In certain example embodiments, protective doped silver layer 10 is at least 40 angstroms (Å) thinner (more preferably at least 50 Å thinner, even more preferably at least 75 Å thinner, and most preferably at least 100 Å thinner) than the adjacent silver based IR reflecting layer 9, 9′. The silver based IR reflecting layer 9, 9′ and adjacent protective doped silver layer 10 are part of a low emissivity (low-E) coating 30, 40, and may be sandwiched between at least transparent dielectric layers. It has surprisingly and unexpectedly been found that providing the silver based IR reflecting layer 9, 9′ directly under and contacting a doped silver layer 10 provides for improved thermal stability, corrosion resistance and chemical durability of the silver based IR reflecting layer(s) 9 and the overall low-E coating 30, 40, while maintaining good optical and emissivity properties such as, when desired, high LSG 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). Note that LSG values may be measured monolithically. A barrier layer 11, 26 including Ni and/or Cr may be provided over and directly contacting the protective doped silver layer 10 in order to further improve durability of the low-E coating. Such coated articles may be used in applications such as monolithic windows, insulated glass (IG) window units, and the like. Coated articles herein may optionally be heat treated (e.g., thermally tempered).
The low-E coating 40 illustrated in
Conventional silver based low-E coatings have chemical durability issues as explained above, such as in the HCl and CASS solvents. Mechanisms for corrosion include galvanic corrosion and oxidation competition. Bimetallic corrosion occurs when two metals, with different potentials, are in electrical contact while in an electrically conducting corrosive liquid. The effect of two metals together increases the corrosion rate of the anode and reduces or even suppresses corrosion of the cathode. Thus the anode materials will be corroded much faster, and corrosion of the cathode is suppressed. In example embodiments of this invention, silver IR reflecting layer 9, 9′ is at the cathode position, so that the cathode silver 9, 9′ will be protected by the sacrificial anode material of protective layer 10. Doped silver layer 10 is provided as the direct neighbor of silver 9, 9′ to protect silver of layer 9, 9′ from chemical corrosion in low-E stacks according to example embodiments of this invention. As explained above, in the
Note that “substantially” metallic means metallic with no more than 10% oxygen content, more preferably no more than 5% oxygen content, atomic %. Substantially metallic layers 9, 9′ and 10 may contain from 0-10% oxygen and/or nitrogen, more preferably from 0-5% oxygen and/or nitrogen (atomic %), most preferably from 0-2% oxygen and/or nitrogen, in example embodiments of this invention.
The dopant content in the Ag of protective layer 10 in
In monolithic instances, the coated article includes only one substrate such as glass substrate 1 (see
Silicon nitride inclusive transparent dielectric layer 2 is provided for antireflection purposes, and have been found to allow color shifts to be reduced. Silicon nitride layer 2 may be of or include Si3N4. Alternatively, the silicon nitride layer 2 may be of the Si-rich type (not fully stoichiometric). Moreover, one or both of the silicon nitride layers 2 and/or 15 may further include a dopant such as aluminum or stainless steel, and/or small amounts of oxygen. These layers may be deposited via sputtering in certain example embodiments, or via any other suitable technique. It is possible that other materials such as titanium oxide, zinc stannate, or tin oxide may be used for transparent dielectric layer(s) 2 and/or 15.
Transparent dielectric seed layer 7 is of or includes zinc oxide (e.g., ZnO) in the
Still referring to
Still referring to
An example overcoat, such as shown in
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
While various thicknesses may be used in different embodiments of this invention, example thicknesses and materials for the respective layers on the glass substrate 1 in the
While various thicknesses may be used in different embodiments of this invention, example thicknesses and materials for the respective layers on the glass substrate 1 in the
It has surprisingly and unexpectedly been found that providing the silver based IR reflecting layer 9, 9′ directly under and contacting a doped silver layer 10 provides for improved corrosion resistance, thermal stability, and chemical durability of the silver based IR reflecting layer(s) 9, 9′ and the overall low-E coating 30, 40, while maintaining good optical and emissivity properties such as, when desired, high LSG values. The dopant content in the Ag of protective layer 10 is preferably kept low, and the thickness of doped silver protective layer 10 is preferably substantially thinner than the adjacent silver IR reflecting layer 9, 9′, in order to reduce light absorption by protective layer 10 so that visible transmission of the coated article can be kept high if desired. In the
It has also been surprisingly found that the presence of barrier layers 11 and 26 over the protective doped silver layer 10 are particularly important to durability. The presence of barrier layers 11 and 26, in combination with the protective doped silver layer 10 over a silver based IR reflecting layer 9, 9′, unexpectedly improved chemical durability of the low-E coating in a surprising manner. When the barrier layers 11, 26 were not present, delamination can occur upon chemical testing.
In certain example embodiments of this invention, coated articles herein (e.g., see
While the combination of IR reflecting layer 9 (or 9′) and silver doped protective layer 10 is used in the low-E coatings of
In alternative embodiments of this invention, protective layer 10 in any embodiment described herein may be based on Cu instead of Ag. In other words, metallic or substantially metallic protective layer 10 may be doped Cu. Thus, in certain example embodiments of this invention, metal content of protective layer 10 in
Example 1 as shown in
Optical and thermal data for Example 1 and the CE are as follows, after the same heat treatment (HT) at at least 600 degrees C. for at least eight minutes. Note that in the chart below “normal emissivity” stands for normal emmisivity/emittance (En).
After the HT, there were noticeable differences between Example 1 and the CE. In particular, the coating of the CE had at least five (5) times as many defects in it after the HT compared to the coating of Example 1. Thus, it has been demonstrated that the addition of the doped silver protective layer 10 over silver IR reflecting layer 9′ surprisingly improves thermal stability of the coating.
Additionally, the same corrosion test was then performed on Example 1 and the Comparative Example (CE), in order to test their respective corrosion/durability characteristics. The testing was a high humidity (85%) and high temperature (85 degrees C.) (HHHT) two day test. The differences between Example 1 and the CE following this testing were pronounced and surprising. After the HHHT test, the CE had many more, and much worse, defects than Example 1. It could be seen via the microscope that Example 1 was much more durable in the HHHT test than was the CE. Thus, it has also been demonstrated that the addition of the doped silver protective layer 10 over silver IR reflecting layer 9′ surprisingly improves durability of the coating.
In an example embodiment of this invention, there is provided a coated article including a coating supported by a glass substrate, the coating comprising: a first dielectric layer on the glass substrate; an metallic or substantially metallic infrared (IR) reflecting layer comprising silver on the glass substrate located over at least the first dielectric layer; a protective layer comprising doped silver on the glass substrate located over and directly contacting the IR reflecting layer comprising silver; a second dielectric layer on the glass substrate located over at least the first dielectric layer, the IR reflecting layer comprising silver, and the protective layer comprising doped silver; wherein metal content of the protective layer comprising doped silver comprises from 80-99.5% Ag and from 0.5 to 20% dopant, 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 no greater than 11 ohms/square and a normal emissivity (En) of no greater than 0.2.
In the coated article of the immediately preceding paragraph, metal content of the protective layer comprising doped silver may comprise from 90-99% Ag and from 1 to 10% dopant, atomic %, where the dopant is one or more of: Zn, Cu, Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu, and combinations thereof
In the coated article of any of the preceding two paragraphs, metal content of the protective layer comprising doped silver may comprise from 95-99% Ag and from 1 to 5% dopant, atomic %, where the dopant is one or more of: Zn, Cu, Ni, W, Sn, Si, SiAl, ZnAl, ZnSi, ZnSiCu, and combinations thereof
In the coated article of any of the preceding three paragraphs, the IR reflecting layer may consist or consist essentially of silver.
In the coated article of any of the preceding four paragraphs, the IR reflecting layer may be metallic.
In the coated article of any of the preceding five paragraphs, the protective layer comprising doped silver may be metallic or substantially metallic.
In the coated article of any of the preceding six paragraphs, the coated article may have a visible transmission of at least 40%, more preferably of at least 50%, and most preferably of at least 70%.
In the coated article of any of the preceding seven paragraphs, the coated article may have a light-to-solar gain ratio (LSG) of at least 1.10, more preferably of at least 1.30, and even more preferably of at least 1.60.
In the coated article of any of the preceding eight paragraphs, the dopant may comprise Zn, and metal content of the protective layer comprising doped silver may comprise from 90-99% Ag and from 1 to 10% Zn, atomic %; more preferably from 95-99% Ag and from 1 to 5% Zn, atomic %.
In the coated article of any of the preceding nine paragraphs, the dopant may comprise Cu, and metal content of the protective layer comprising doped silver may comprise from 90-99% Ag and from 1 to 10% Cu, atomic %; more preferably from 95-99% Ag and from 1 to 5% Cu, atomic %.
In the coated article of any of the preceding ten paragraphs, the dopant may comprise Ni, and wherein metal content of the protective layer comprising doped silver may comprise from 90-99% Ag and from 1 to 10% Ni, atomic %; more preferably from 95-99% Ag and from 1 to 5% Ni, atomic %.
In the coated article of any of the preceding eleven paragraphs, the dopant may comprise W, and wherein metal content of the protective layer comprising doped silver may comprise from 90-99% Ag and from 1 to 10% W, atomic %; more preferably from 95-99% Ag and from 1 to 5% W, atomic %.
In the coated article of any of the preceding twelve paragraphs, the dopant may comprise Sn, and wherein metal content of the protective layer comprising doped silver may comprise from 90-99% Ag and from 1 to 10% Sn, atomic %; more preferably from 95-99% Ag and from 1 to 5% Sn, atomic %.
In the coated article of any of the preceding thirteen paragraphs, the dopant may comprise Si, and wherein metal content of the protective layer comprising doped silver may comprise from 90-99% Ag and from 1 to 10% Si, atomic %; more preferably from 95-99% Ag and from 1 to 5% Si, atomic %.
In the coated article of any of the preceding fourteen paragraphs, the dopant may comprise Zn and Cu, and metal content of the protective layer comprising doped silver may comprise from 80-99% Ag and from 0.5 to 10% of each of Zn and Cu, atomic %.
In the coated article of any of the preceding fifteen paragraphs, the dopant may comprise Zn and Si, and metal content of the protective layer comprising doped silver may comprise from 80-99% Ag and from 0.5 to 10% of each of Zn and Si, atomic %.
In the coated article of any of the preceding sixteen paragraphs, the coated article may be thermally tempered.
In the coated article of any of the preceding seventeen paragraphs, the protective layer comprising doped silver may be at least 40 Å thinner than is the IR reflecting layer comprising silver, more preferably at least 75 Å thinner, and even more preferably at least 100 Å thinner.
In the coated article of any of the preceding eighteen paragraphs, the protective layer comprising doped silver may be from about 3-70 Å thick, and/or the IR reflecting layer comprising silver may be from about 40-170 Å thick.
In the coated article of any of the preceding nineteen paragraphs, the protective layer comprising doped silver may be from about 5-25 Å thick, and/or the IR reflecting layer comprising silver may be from about 60-155 Å thick.
In the coated article of any of the preceding twenty paragraphs, the protective layer comprising doped silver may be from about 8-15 Å thick, and/or the IR reflecting layer comprising silver may be from about 80-145 Å thick.
In the coated article of any of the preceding twenty one paragraphs, the first dielectric layer may comprise silicon nitride.
In the coated article of any of the preceding twenty two paragraphs, the coating may have a sheet resistance (Rs) of no greater than 9 ohms/square and a normal emissivity (En) of no greater than 0.11.
In the coated article of any of the preceding twenty three paragraphs, the coating may further comprise another infrared (IR) reflecting layer comprising silver that is spaced apart from and does not contact the protective layer comprising doped silver.
In the coated article of any of the preceding twenty four paragraphs, the coating may further comprise a dielectric layer comprising zinc oxide located under and directly contacting the IR reflecting layer comprising silver.
In the coated article of any of the preceding twenty five paragraphs, the coating may further comprise a barrier layer comprising Ni and/or Cr located over and directly contacting the protective layer comprising doped silver. The barrier layer may comprise a nitride of Ni and/or Cr.
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.
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