Coated article with low-e coating having multilayer overcoat and method of making same.

EMELIA HERNANDEZ PRIEGQ | 00001000000405397295 | Administration Service

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MX 2019 78931

ITEM COVERED WITH LOW-E COATING THAT HAS AN EXTERIOR COATING OF MULTIPLE LAYERS AND METHOD TO DO THE SAME

FIELD OF THE INVENTION

This invention relates to coated articles that include a low-E (low emissivity) coating and a multi-layer outer coating that includes at least one substantially metallic layer. In certain exemplary embodiments, the low-E coating may include at least one infrared (IR) reflective layer of a material such as silver and the substantially metallic layer of the outer coating may be of or may include niobium-zirconium (NbZr ) and / or zirconium (Zr). These coated articles can be used in the context of monolithic windows, insulated glass window units (IG), laminated windows and / or other suitable applications.

BACKGROUND AND SUMMARY OF THE INVENTION

Coated articles that have low-E coatings are known in the field. For example, see the following United States Patent Documents which describe low E coatings and all of which are incorporated herein by reference in their entirety: United States Patents Nos. 6,686,050, 6,749,941, 6,863,928, 7,166,359, 7,390,572, 7,462,398, 7,534,496, 7,597,962, 7,597,963, 7,655,313, 7,771,830, 7,858,191, 7,879,448, 7,897,260, 7,998,320 and 8,017,243. A bajaE coating is intended to provide efficient solar control in applications such as windows and includes at least one IR reflective layer sandwiched between two contact layers. The contact layers which sandwich an IR reflective layer between them are sometimes referred to as barrier layers. The contact layer directly below and that makes contact with an IR reflective layer is often made of a material such as ZnO, NiCr or NiCrO_x and the contact layer directly above and making contact with an IR reflective layer is often made of a material such as NiCr or NiCrO_x. The contact / barrier layer provided directly above and in contact with an IR reflective layer is to protect the IR reflective layer from aggressive environments during ionic spraying of overlying layers as well as during the life of the coating and to provide adhesion between the reflective IR layer and an overlying dielectric layer. However, in order to meet the desired optical and transmission requirements typically of low-E coatings, the contact layer provided on top of an IR reflective layer generally needs to be very thin. The thin upper contact / barrier layers can often provide sufficient durability when the coating is used inside an insulating glass window (IG) unit where the coating is not directly exposed to the environment. However, for monolithic applications where the coating is directly exposed to the environment (either directly exposed to the interior of a building or home or exposed directly to the outside atmosphere), sometimes a thin upper contact / barrier layer is not sufficient by itself to protect the IR reflective layer (for example, silver layer) against environmental attacks.

Thus, while conventional low-E coatings provide efficient solar control and are good overall coatings, they are sometimes deficient in terms of one or more of: (a) corrosion resistance to acid solutions and / or alkaline (for example, 80% HCI boiling test and / or 20% NaOH boiling test); (b) mechanical performance such as scratch resistance; and / or (c) durability. Accordingly, there is a need in the field of a coated article that includes a low-E coating and which has improved durability characteristics, but which still has the acceptable thermal performance capability (eg, blocking of a reasonable amount of IR radiation) and / or heat treatment (HT). One purpose of this invention is to satisfy at least one of the needs listed above and / or other needs which will become apparent to the skilled artisan once the following description is provided.

In certain exemplary embodiments of this invention, an improved outer coating is provided for a low-E coating for the purpose of improving its overall durability. In certain exemplary embodiments, the low-E coating may include at least one infrared (IR) reflective layer of a material such as silver and the outer coating to protect the low-E coating includes a substantially metallic layer. In certain exemplary embodiments, the substantially metallic layer of the outer coating may be of niobium-zirconium (NbZr) or zirconium (Zr). In certain exemplary embodiments, the substantially metallic layer (for example, NbZr or Zr) of the outer coating is sandwiched between respective underlying and overlying dielectric layers (eg, of or including silicon nitride). Thus, in certain exemplary embodiments the substantially metallic layer (for example, NbZr or Zr) of the outer coating is not in contact with any metallic IR reflective layer (for example, it is not in contact with any Ag or Au layer) . In certain exemplary embodiments, the outer coating may further include an overlying dielectric layer of or that includes zirconium oxide (eg, ZrO₂) which may be the layer in the highest position of the coating in relation to the underlying substrate holding the coating. It has surprisingly been discovered that this outer coating improves the durability of the coating in terms of protection of the IR reflective layer (s) of chemicals, scratches, scratch corrosion, fingerprint corrosion, environmental damage and mechanical damage These coated articles can be used in the context of monolithic windows, insulated glass window units (IG), laminated windows and / or other suitable applications.

The coated article can be heat treated or not (for example it can be thermally tempered) in different embodiments of this invention. The heat treatment (HT) can be for at least about 5 minutes at a temperature (s) of at least about 58 0 ° C, so that it is sufficient for thermal tempering or the like.

In certain exemplary embodiments of this invention, when the substantially metallic layer of the outer coating is or includes NbZr, the ratio of Zr / Nb (atomic%) in the NbZr based layer may be from about 0.001 to 1.0, more preferably from about 0.001 to 0.60, more preferably from about 0.004 to 0.50 and even more preferably from about 0.05 to 0.2, where an exemplary ratio of Zr / Nb is about 0.1. In certain exemplary embodiments, the NbZr based layer of the outer coating may include about 0.1 to 60% Zr, more preferably about 0.1 to 40% Zr, even more preferably 1 to 20% Zr, even more preferably of 2 to 15% Zr, more preferably about 5 to 15% Zr and much more preferably 8 to 12% Zr (atomic%). These Zr intervals have application in NbZr based layers both metallic and slightly oxidized and / or nitride.

In certain exemplary embodiments of this invention, a coated article is provided that includes a layer system supported by a glass substrate, the layer system comprises: a first dielectric layer on the glass substrate; an infrared radiation (IR) reflective layer comprising silver on the glass substrate above at least the first dielectric layer; a contact layer on the glass substrate on top of and making contact directly with the IR reflective layer; a second dielectric layer on the glass substrate above at least the contact layer; a layer comprising niobium-zirconium on the glass substrate above and making contact directly with the second dielectric layer; a third dielectric layer on the glass substrate above and making contact directly with the layer comprising niobium-zirconium; and a layer comprising zirconium oxide on the glass substrate above at least the third dielectric layer.

In certain exemplary embodiments of this invention, a coated article is provided that includes a layer system supported by a glass substrate, the layer system comprises: a first dielectric layer on the glass substrate; an IR reflective layer comprising silver on the glass substrate above at least the first dielectric layer; a contact layer on the glass substrate on top of and making contact directly with the IR reflective layer; a second dielectric layer on the glass substrate above at least the contact layer; a substantially metallic layer comprising zirconium on the glass substrate above and making contact directly with the second dielectric layer; and a third dielectric layer on the glass substrate above and making contact directly with the substantially metallic layer comprising zirconium.

In certain exemplary embodiments of this invention, a coated article is provided that includes a layer system supported by a substrate, the layer system comprises: a first dielectric layer on the substrate; an IR reflective layer comprising silver on the substrate above at least the first dielectric layer; a contact layer on the substrate above and making contact directly with the IR reflective layer; a second dielectric layer on the substrate above at least the contact layer; a substantially metallic layer comprising niobium-zirconium or NiCrMo on the substrate above and making contact directly with the second dielectric layer; and a third dielectric layer on the substrate above and making contact, directly with the substantially metallic layer.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a partial cross-sectional view of one embodiment of a monolithic coated article (heat treated or not heat treated) in accordance with an exemplary embodiment of this invention.

Figure 2 is a partial cross-sectional view of one embodiment of a monolithic coated article (heat treated or not heat treated) in accordance with an exemplary embodiment of this invention.

Figure 3 is a partial cross-sectional view of an IG window unit that includes the coating of Figure 1 and / or Figure 2 in accordance with an exemplary embodiment of this invention.

<td>DETAILED DESCRIPTION OF</td><td>CERTAIN</td><td colspan="2">EXAMPLE MODES</td><td>FROM</td>

<td>THE INVENTION</td><td></td><td></td><td></td><td></td>

<td>Now it's done</td><td colspan="2">reference more</td><td>particularly</td><td>to</td>

<td>the associated drawings</td><td>in the</td><td>which</td><td>the numbers</td><td>from</td>

Similar references indicate similar parts for all the various views.

Certain embodiments of this invention provide coated articles that can be used in windows such as monolithic windows (eg, vehicle, residential and / or architectural windows), IG window units, laminated windows, skylights, transparent freezer doors and / or other suitable applications.

A multi-layer outer coating is provided for a low-E coating in order to improve its overall durability. In certain exemplary embodiments, the low-E coating may include at least one infrared (IR) reflective layer 9 of a material such as silver and the outer coating to protect the reflective layer (s) of IR includes a substantially metallic layer 15. In certain exemplary embodiments, the substantially metallic layer 15 of the multilayer outer coating may be of niobium-zirconium (NbZr) or zirconium (Zr). In certain exemplary embodiments, the substantially metallic layer 15 of the outer coating is sandwiched between the respective underlying and overlying dielectric layers 13 and 17 respectively. Thus, in certain exemplary embodiments the substantially metallic layer 15 of the outer coating is not in contact with any metallic IR reflective layer (for example, it is not in contact with any Ag or Au layer). In certain exemplary embodiments, the outer coating may further include a dielectric layer superimposed on or that includes zirconium oxide (e.g., ZrO₂) 19 which may be the layer in the highest position of the coating 3 in relation to the underlying substrate 1 that supports the coating. It has surprisingly been discovered that this multi-layer outer coating improves the durability of the coating in terms of protection of the IR reflective layer (s) of chemicals, scratches, scratch corrosion, fingerprint corrosion, environmental damage and mechanical damage. These coated articles can be used in the context of monolithic windows, insulated glass (IG) window units, laminated windows and / or other suitable applications. The multi-layer outer coating, which includes the substantially metallic layer 15, is capable of providing improved durability for the coating while at the same time not significantly sacrificing desired optical characteristics. For example, together with the improved durability, the coated article is capable of achieving a desired visible transmission, desired optical characteristics such as color, good IR reflectance / blocking and good color stability in heat treatment (HT) in certain embodiments. copies of this invention.

Coated articles in accordance with the preferred embodiments of this invention have a visible transmission, before and / or after the optional HT, of at least about 3%, more preferably of at least about 40%, wherein the exemplary ranges Visible transmission are about 4060%, more preferably about 45-55%. Coated articles according to preferred embodiments of this invention have a sheet resistance (R_s), before and / or after the optional HT, less than about 30 ohms / square, more preferably less than about 20 ohms / square and much more preferably less than about 15 ohms / square. For example, coated articles according to certain exemplary embodiments of this invention may have a sheet strength of approximately 10-13 ohms / square when coated, which will drop to approximately 8-10 ohms / square if the coated article is thermally tempered. .

Figure 1 illustrates a coated article according to an exemplary embodiment of this invention. The coated article shown in Figure 1 includes glass substrate 1 (for example, a clear glass, green, bronze or blue-green color substrate of about 1.0 to 10.0 mm thick, more preferably about 1.0 mm to 6.0 mm thick) and a multi-layer coating 3 (or a layer system) provided on the substrate 1 either directly or indirectly. As shown in Figure 1, the coating 3 includes the dielectric layer 5, the lower contact layer 7 (for example, of or including Ni, Cr, NiCr and / or NiCrO_x), the IR reflecting layer 9 of or including silver, gold or the like, the upper contact / barrier layer 11 (for example, of or including Ni, Cr, NiCr and / or NiCrO_x), the dielectric layer 13 (for example, of or including silicon nitride), the substantially metallic barrier layer 15 (for example, of or including NbZr and / or Zr), the dielectric layer 17 (for example, of or which includes silicon nitride) and the upper dielectric layer 19 (for example, of or including zirconium oxide). It can be said that the outer coating is made up to layers 15, 17 and 19 or alternatively it can be said that it is made up to layers 13, 15, 17 and 19 in different exemplary cases. The silicon nitride layers raised herein (for example, see layers 5, 13, 17) can be impurified (for example, approximately 0.1 to 12%) with aluminum and / or oxygen in certain exemplary embodiments of this invention. and the zirconium oxide layers raised herein (for example, see layer 19) can also be impurified (for example, approximately 0.1 to 12%) with aluminum in certain exemplary embodiments of this invention. Layer 19 of or which includes a Zr oxide may also include at least one of Ti, Al and Mo in certain exemplary embodiments. Other layers and / or materials may also be provided in certain exemplary embodiments of this invention and it is also possible that certain layers may be removed or divided in certain exemplary cases.

Coating together 3 includes at least layers 5-19. It is noted that the terms oxide and nitride used herein include several stoichiometries. For example, the term silicon nitride includes Si₃N₄ stoichiometric, as well as non-stoichiometric silicon nitride such as Si-rich silicon nitride. Layers 5-19 can be deposited on the substrate 1 via the magnetron ion spray, any other type of ion spray or by any other suitable technique in different embodiments of this invention.

The infrared radiation (IR) reflective layer is preferably substantially or completely metallic and / or conductive and may comprise or consist essentially of silver (Ag), gold or any other suitable IR reflective material. The reflective layer of IR 9 helps to allow the coating to have low-E and / or good solar control characteristics such as low emittance, low sheet resistance and so on. However, the IR reflecting layer 9 can be oxidized slightly in certain embodiments of this invention. In the embodiment of Figure 1, the coating includes only one IR reflective layer 9 of or which includes Ag and / or Au, but in alternative embodiments multiple IR reflective layers 9 of that type can be provided as in other low coatings. -AND. In certain exemplary modalities, in the reflective layer (s) of IR 9 the Ag can be alloyed with Pd, Cu or both Pd and Cu, with approximately 0.5-2% (by weight or atomic%) of each of Pd and Cu. Other potential alloys for layer (s) 9 include Ag and one or more of Co, C, Mg, Ta, W, NiMg, PdGa, CoW, Si, Ge, Au, Pt, Ru, Sn, Al, Μη, V, In, Zn, Ir, Rh and / or Mo. In general, the concentrations of impurifiers (of materials other than Ag) may be in the range of 0.2-5% (by weight or atomic%), more preferably between 0.2-2.5%. Operation within these ranges can help silver maintain the desirable optical characteristics of the Ag 9-based layer that could otherwise be lost under the alloy, thereby helping to maintain the overall optical characteristics of the battery while also increasing chemical durability, against corrosion and / or mechanical. As with the other layers raised in this document, the silver-based IR reflective layer 9 can be deposited by ionic spraying on the substrate 1.

The upper and lower contact layers 7 and 11 may be of or may include Ni, Cr, NiCr and / or NiCrO_x in certain exemplary embodiments of this invention. In this way, the contact layers 7 and 11 can be metallic or substantially metallic in preferred embodiments and can be oxidized in certain cases. In certain exemplary embodiments, the upper and lower contact layers 7, 11 may be of or may include nickel (Ni), chromium / chromium (Cr), a nickel alloy such as nickel-chromium (NiCr), Haynes alloy, a Ni inclusive ternary alloy such as NiCrMo, an oxide of any of these or other suitable material (s). For example, one of those layers (for example, layer 7) may be of or may include zinc oxide instead of NiCr. For example, the use of NiCr in these layers is for durability in certain exemplary cases and the thicknesses provided allow low Δ * values ​​to be achieved with HT. The contact layers 7 and 11 (for example, of or including Ni and / or Cr) may be continuous or, not in different embodiments of this invention through the entire IR reflective layer.

In certain exemplary embodiments , one or both layers of NiCr 7, 11 include about 70-81% Ni, about 15-19% Cr, about 36% Al and possibly about 0-4% (or 1 -4%) of Fe and can be oxidized in certain exemplary cases so that the metallic portion of the layer is characterized by those percentages. An example is 76.5% Ni, 17% Cr, 4.3% Al and optionally approximately 2.2% Fe, for one or both layers 7, 11.

In certain exemplary embodiments, one or both of the contact layers 7, 11 are of or include a ternary alloy inclusive of Ni. In other exemplary embodiments, the inclusive ternary alloy of Ni may further include Ti, Cr, Nb, Zr, Mo, W, Co and / or combinations thereof. The inclusive Ni ternary alloy of layer 7 and / or 11 may be of or may include Ni_xCr_YMo_z, Neither_xYou_YCr_z, Neither_xYou_YNb_z, Neither_xNb_YZr_z, Neither_xCr_YZr_z, Neither_xYou_YMo_z, Neither_xZr_YMo_z, Neither_xNb_YMo_z, Neither_xCr_YMo_z, Neither_xW_YCr_z, Neither_xW_YMo_z, Neither_xW_YZr_z, Neither_xW_YNb_z, Neither_xW_YYou_z, Neither_xCO_YMo_zzNeither_xCo_YCr_z, Neither_xCo_YMo_z, Neither_xCo_YZr_z, Neither_xCo_YNb_z and / or Ni_xCo_YYou_z. In certain cases, the Ni 7 and / or 11 inclusive ternary alloy barrier layer (for example, comprising materials such as nickel, chromium and / or molybdenum, etc.) has (1) good adhesion to the IR reflective layer ; (2) good corrosion resistance to acid and / or alkaline solutions; (3) protection during optional oxidation at high temperatures; and (4) good chemical and / or mechanical durability as a whole. In certain exemplary embodiments, one or both of the contact layers 7, 11 comprise Cr and Mo and more particularly may be of or may include 54-58% by weight of Ni, 20-22.5% by weight of Cr and

12.5-14.5% by weight of Mo and can be oxidized in certain exemplary cases so that the metallic portion of the layer is characterized by those percentages. In certain exemplary embodiments, one or both of the contact layers 7, 11 are of or include an Ni alloy of NiCr, NiTi and / or NiCrMo and layers 7 and 11 may be of the same or different materials. In certain exemplary embodiments, one or both of the contact layers 7, 11 may be of or may include 60-65% by weight of Ni, 12-17% by weight of Cr and 20-25% by weight of Mo and be they can oxidize in certain exemplary cases so that the metallic portion of the layer is characterized by those percentages. In certain exemplary embodiments of this invention, one or both of the contact layers 7, 11 may be or may include 63-67% by weight of Ni, 1-2% by weight of Cr and 25-3 0% by weight of Mo and they can be oxidized in certain exemplary cases so that the metallic portion of the layer is characterized by those percentages.

It has been found advantageously that NiCrMo based alloys (for example Hallestoy C22, BC1 and / or B3), for use in the contact layer (s) 7 and / or 11, can protect a coating that includes At least one layer based on silver 9 is better than layers consisting essentially of NiCr in some cases. Additionally, NiCrMo-based alloys can protect the coated article from visible damage in certain cases. It is further believed that the NiCrMo of layer 11 can form an alloy with the overlying dielectric layer 13 in the coating, which can improve the performance of this layer against alkaline solutions and boiling water.

This may be particularly true in embodiments where the dielectric layer 13 is based on silicon.

Tables 1-3 below show the compositions of three exemplary modalities of NiCrMo-based alloys (for example, C22, BC1 and B3) for use in one or both contact layers 7, 11. Thus, one or both of the contact layers 7, 11 may be of or may include the following materials shown in Tables 1-3, may be metallic or substantially metallic and may oxidize in certain exemplary cases so that the metal portion of layer 7 and / or 11 is characterized by the percentages shown in Table 1, Table 2 or Table 3.

<td>Table 1:</td><td>Neither_xCryMo_z</td><td>(for example, in% in</td><td>C22) - Elementary composition weight</td>

<td>Element</td><td>Favorite</td><td>Most Preferred</td><td>Example</td>

<td>Neither</td><td> 40-70%</td><td> 50-60%</td><td>54-58% (for example, 56%)</td>

<td>Cr</td><td> 5-40%</td><td> 10-30%</td><td> 20-22.5%</td>

<td>Mo</td><td> 5-30%</td><td> 10-20%</td><td> 12.5-14.5%</td>

<td>Faith</td><td> 0-15%</td><td> 0-10%</td><td>1-5% (for example, 3%)</td>

<td>W</td><td> 0-15%</td><td> 0-10%</td><td>1-5% (for example, 3%)</td>

<td>Co</td><td> 0-15%</td><td> 0-10%</td><td>1-5% (for example, 3%)</td>

<td>Yes</td><td> 0-2%</td><td> 0-1%</td><td>= &lt;0.2% (for example, 0.08%)</td>

<td>Mn</td><td> 0-3%</td><td> 0-2%</td><td>= &lt;1% (for example 0.5%)</td>

<td>C</td><td> 0-1%</td><td> 0-0.5%</td><td>= &lt;0.1% (for example 0.01%)</td>

<td>V</td><td> 0-2%</td><td> 0-1%</td><td>= &lt;1% (for example, 0.35%)</td>

<td rowspan="2"></td><td colspan="3">Table 2: Ni_xCryMo_z</td><td rowspan="2">(for example,</td><td rowspan="2">B3) - Elementary composition</td>

<td>in</td><td>% in</td><td>weight</td>

<td></td><td colspan="2">Element</td><td>Favorite</td><td>Most Preferred</td><td>Example</td>

<td></td><td>Neither</td><td></td><td> 50-80%</td><td> 60-70%</td><td>63-67% (for example, 65%)</td>

<td> 5</td><td>Cr</td><td></td><td> 0-15%</td><td> 0-5%</td><td>1-2% (for example, 1.5%)</td>

<td></td><td>Mo</td><td></td><td> 10-50%</td><td> 20-40%</td><td>25-30% (for example, 28.5%)</td>

<td></td><td>Faith</td><td></td><td> 0-10%</td><td> 0-5%</td><td>1 -4% (for example, 3%)</td>

<td></td><td>W</td><td></td><td> 0-15%</td><td> 0-10%</td><td>1-5% (for example, 3%)</td>

<td></td><td>Co</td><td></td><td> 0-15%</td><td> 0-10%</td><td>1-5% (for example, 3%)</td>

<td> 10</td><td>Yes</td><td></td><td> 0-2%</td><td> 0-1%</td><td>= &lt;0.2% (for example, 1%)</td>

<td></td><td>Mn</td><td></td><td> 0-15%</td><td> 0-10%</td><td>1-5% (for example, 3%)</td>

<td></td><td>C</td><td></td><td> 0-1%</td><td> 0-0.5%</td><td>= &lt;0.1% (for example, 0.01%)</td>

<td></td><td>To the</td><td></td><td> 0-3%</td><td> 0-2%</td><td>= &lt;1% (for example, 0.5%)</td>

<td></td><td>You</td><td></td><td> 0-2%</td><td> 0-1%</td><td>= &lt;0.5% (for example, 0.2%)</td>

<td> 15</td><td colspan="2">Table 3</td><td>: Neither_xCryMo_z</td><td>(for example,</td><td>BC1) - Elementary composition</td>

<td></td><td>in</td><td>% in</td><td>weight</td><td></td><td></td>

<td></td><td colspan="2">Element</td><td>Favorite</td><td>Most Preferred</td><td>Example</td>

<td></td><td>Neither</td><td></td><td> 50-80%</td><td> 60-70%</td><td>60-65% (for example, 62%)</td>

<td></td><td>Cr</td><td></td><td> 5-30%</td><td> 10-20%</td><td>12-17% (for example, 15%)</td>

<td> 20</td><td>Mo</td><td></td><td> 10-40%</td><td> 15-25%</td><td>20-25% (for example, 22%)</td>

<td></td><td>Faith</td><td></td><td> 0-10%</td><td> 0-5%</td><td>1-3% (for example, 2%)</td>

<td></td><td>Yes</td><td></td><td> 0-2%</td><td> 0-1%</td><td>= &lt;0.2% (for example, 0.08%)</td>

<td></td><td>Mn</td><td></td><td> 0-5%</td><td> 0-2%</td><td>= &lt;0.5% (for example, 0.25%)</td>

<td></td><td>C</td><td></td><td> 0-1%</td><td> 0-0.5%</td><td>= &lt;0.1% (for example, 0.01%)</td>

<td> 25</td><td>To the</td><td></td><td> 0-3%</td><td> 0-2%</td><td>= &lt;1% (for example, 0.5%)</td>

The dielectric layers 5, 13 and 17 may be of or may include silicon nitride (eg, Si₃N₄) or any other suitable material in certain exemplary embodiments of this invention such as silicon oxynitride. These layers are provided for durability purposes and to protect the underlying layers and / or for anti-reflective purposes. The silicon nitride based layer 13 provides good adhesion between the underlying IR reflective portion of the coating and the overlying metallic or substantially metallic layer 15 of the protective outer coating. In certain exemplary embodiments, the silicon nitride layer 17 may be rich in nitrogen (ie, it contains more nitrogen than Si₃N₄), which has been found to improve optical characteristics. In contrast, the silicon nitride layer 5 can be rich in silicon (that is, it contains more Si than Si₃N₄), which has been found to improve durability. In certain exemplary embodiments of this invention, the silicon nitride based layer 17 is substantially thicker (eg, at least 4 nm (approximately 40 angstroms) thicker, more preferably at least 7.5 nm (75 angstroms) thicker and much more preferably at least 10 nm (approximately 100 angstroms) thicker) than the silicon nitride based layer 13, in order to provide a lower SHGC, improved durability and good aesthetics. In certain exemplary embodiments, each of layers 5, 13 and 17 may have a refractive index (n) of about 1.9 to 2.2, more preferably of about 1.95 to 2.05. Silicon nitride layers 5, 13 and / or 17 may be impurified with aluminum (for example, from about 1-15% of Al, more preferably from about 1-12% or 1-5% of Al) in certain cases and can be oxidized slightly in certain exemplary embodiments of this invention. It will be appreciated that in alternative embodiments of this invention, a different silicon nitride material may be used for one or more of layers 5, 13 and / or 17. For example, Figure 2 emphasizes that a material other than silicon nitride for one or more of the dielectric layers 5, 13 and / or 17 in certain exemplary embodiments of this invention.

It has been found that the use of Zr, and in particular NbZr, in or for the protective barrier layer 15 allows the resulting coated article which has a low-E coating to develop excellent chemical and mechanical durability and also good performance. thermal if desired. For example, the use of NbZr in the protective layer 15 allows the resulting coated article (s) to achieve improved corrosion resistance to alkaline solutions such as NaOH (as compared to piles of layers where the multilayer outer coating that includes layer 15 is not present), good thermal performance, Improved mechanical performance such as scratch resistance (compared to piles of layers where the multilayer outer coating that includes layer 15 is not present). In certain exemplary embodiments of this invention, the NbZr or Zr 15 based layer may be 1-10 nm (approximately 10-100 angstroms) thick, more preferably 1-5 nm (approximately 10-50 angstroms) thick and more preferably 1-3 nm (approximately 10-30 angstroms) thick. An exemplary thickness for layer 15 is approximately 2 nm (approximately 20 angstroms). The protective layer 15 is thick enough to provide the improvement in durability, but is thin enough not to adversely affect the optical performance of the coated article. For example, if the layer 15 is very thick, the visible transmission of the coated article could descend undesirably and / or the desired coloration of the coated article could no longer develop. This is because layer 15 is more preferably 1-3 nm (approximately 10-30 angstroms) thick.

When the metallic (or substantially metallic) layer 15 of the outer coating is or includes NbZr (which can be oxidized and / or lightly nitrided in certain exemplary embodiments), the ratio of Zr / Nb (atomic%) in the layer based JflbZr may be from about 0.001 to 1.0, more preferably from about 0.001 to 0.60, more preferably from about 0.004 to 0.50 and even more preferably from about 0.05 to 0.2, where an exemplary ratio of Zr / Nb is approximately 0.1. In certain exemplary embodiments, the NbZr 15 based layer may include from about 0.1 to 60% Zr, more preferably from about 0.1 to 40% Zr, even more preferably from 1 to 20% Zr, even more preferably from 2 to 15% Zr, more preferably about 5 to 15% Zr and much more preferably 8 to 12% Zr (atomic%). For example, layer 15 can be deposited by ionic spraying using an ionic spray target containing 90% Nb and 10% Zr in certain exemplary embodiments. These Zr intervals have application for both NbZr-based layers, both metallic and slightly oxidized and / or nitrated. The NbZr or Zr 15 layer preferably contains no more than about 20% oxygen, more preferably no more than about 15% oxygen and much more preferably no more than about 10% or 5% oxygen. The NbZr or Zr 15 layer may be slightly oxidized (sub-oxidized) in certain exemplary embodiments of this invention, for example that includes about 1-20% oxygen, more preferably about 1-10% or 1-5% of oxygen Surprisingly it has been found that oxidizing layer 15 slightly as deposited by ionic spraying is originally beneficial because it allows the thermal stability of the HT coated article (for example, thermal tempering) to be improved. In this respect, in certain exemplary embodiments of this invention, when heat treated (for example, when it is thermally tempered), the coated article is capable of developing a ΔΕ * (reflective and / or transmissive glass side) value not greater than approximately 4.0, more preferably not greater than approximately 3.0, evidencing the thermal stability (see the technique for calculating ΔΕ * set forth in US Patent Document 2009/0324967, which is incorporated by this act in this document by way of reference).

The protective barrier layer 15 may be of or may alternatively include NiCrMo, for example, in the amounts and formulations set forth above in relation to the contact layers. In these alternative embodiments, layer 15 is still metallic or substantially metallic in preferred embodiments of the invention.

It has been found that layer 19 of or which includes zirconium oxide improves durability and can improve thermal stability if the coated article is heat treated. In certain exemplary embodiments, the use of a layer in the highest inclusive position of zirconium oxide 19 in combination with the silicon nitride inclusive layer 17 and the protective layer 15 can result in a coated article which has excellent durability and it can be treated with heat significantly (for example, thermally tempered) without suffering from significant mottle damage or other damage from heat treatment (for example, the coated article may develop an acceptable visible transmission, values ​​a * and / or * after heat treatment such as thermal tempering). In certain exemplary embodiments, the index n of the zirconium oxide layer 19 is about 2.1 to 2.25, more preferably about 2.16 (at 550 nm).

Without layers 15, 17 and 19, the test (for example, 2 0% NaOH test and 8 0% HCI test, Taber test with CASS classification in 26d) has shown that the coating (the underlying layers 5, 7, 9, 11, 13) is destroyed due to poor durability. However, when layers 15, 17 and 19 are added to those same underlying layers, the durability improves markedly and the coating survives these same tests.

While Figure 1 illustrates the coating 3 in a manner where the protective layer 15 is in direct contact with the dielectric layers 13 and 17 and where the layer 9 is the only IR-reflective layer based on Ag in the coating, the present invention It is not limited in this way. Another layer (s) may be provided between layers 13 and 15 (and / or between layers 15 and 17 and / or between layers 17 and 19) in certain other embodiments of this invention. On the other hand, another layer (s) (which are not shown) can be provided between the substrate 1 and the layer 5 in certain embodiments of this invention. In this way, while the coating 3 or layers thereof is (n) on or supported by the substrate 1 (directly or indirectly), another layer (s) can be provided between them. Thus, for example, the system of layers 3 and layers thereof shown in Figures 1-2 are considered on the substrate 1 even when another layer (s) (which are not shown) are provided between the themselves (that is, the terms on and sustained by how it is used in this document are not limited to making contact directly). Also, more than one Ag-based IR reflective layer can be provided in alternative embodiments of this invention.

On the other hand, in different embodiments of this invention, layers 15, 17 and 19 as described herein and as shown in Figures 1-2 can be provided on top of any of the various low-E coatings in the United States Patent Nos. 6,686,050, 6,749,941, 6,863,928, 7,166,359, 7,390,572, 7,462,398, 7,534,496, 7,597,962, 7,597,963, 7,655,313, 7,771,830, 7,858,191, 7,879,448, 7,897,260, 7,998,320 and / or all of which are incorporated in this way. The precise stack of the low-E coating under the outer coating is not particularly limiting in certain exemplary embodiments of this invention.

While Figures 1-2 illustrate a coated article according to an embodiment of this invention in monolithic form, coated articles according to other embodiments of this invention may comprise IG window units (insulating glass) as shown in the Figure 3. Figure 3 illustrates an IG window unit that includes the coated article of Figure 1 and / or Figure 2. As shown in Figure 3, the coated substrate 1 can be coupled to (after HT in certain cases) another glass substrate 20 via at least one separator and / or seal 22 in order to form a unit of IG window. The space or opening 24 between the substrates may or may not be evacuated at a pressure lower than atmospheric pressure in different exemplary embodiments. On the other hand, the space or opening 24 may or may not be filled with a gas (for example, Ar) in different embodiments of this invention. In embodiments of IG, the coating 3 of Figure 1 and / or Figure 2 may be provided on the inner wall of the outer substrate of the IG unit as shown in Figure 3 and / or on any major surface of the inner substrate

0 or in any other suitable location in other embodiments of this invention. The coating 3 can be located in similar locations in laminated window applications.

Returning to Figures 1-2, several thicknesses consistent with this invention can be used. In accordance with certain exemplary non-limiting embodiments of this invention, the exemplary thicknesses and materials for the respective layers on the glass substrate 1 are as shown in Table 4. Before and / or after heat treatment (HT) such as thermal tempering, in certain exemplary embodiments of this invention the coated articles have the following color characteristics shown in Table 5 (monolithic). It is observed that in Table 5 the subscript G represents the reflective color of the glass side, the subscript T represents the transmissive color and the subscript F represents the color of the film side. As is known in the field, the glass side (G) means the reflective color when viewed from the glass side (opposite the layer / film side) of the coated article. The side of the film (F) means the reflective color when viewed from the side of the coated article on which the coating 3 is provided.

Table 4 (Exemplary non-limiting thicknesses)

<td>Cap</td><td colspan="2">Exemplary Interval (nm)</td><td colspan="2">Preferred (nm) Best (nm)</td>

<td>silicon nitride (layer 5):</td><td></td><td>5-90 nm</td><td>30-60 nm</td><td>45 nm</td>

<td>bottom contact (layer 7):</td><td></td><td>1-5 nm</td><td>1-3 nm</td><td>2 nm</td>

<td>silver (layer 9):</td><td></td><td>3-15 nm</td><td>4-8 nm</td><td>6 nm</td>

<td>upper contact (layer 11):</td><td></td><td>1-5 nm</td><td>1-3 nm</td><td>2 nm</td>

<td>silicon nitride (layer 13):</td><td></td><td>5-70 nm</td><td>20-40 nm</td><td>30 nm</td>

<td>NbZr, ZroC22 (layer 15):</td><td></td><td>1-10 nm</td><td>1-3 nm</td><td>2 nm</td>

<td>silicon nitride (layer 17):</td><td></td><td>5-100 nm</td><td>30-60 nm</td><td>45 nm</td>

<td>Zirconium oxide (layer 19):</td><td></td><td>2-12 nm</td><td>3-8 nm</td><td>4 or 5 nm</td>

<td colspan="4">Table 5: Color / Optical Characteristics</td><td>Copies</td>

<td>(Monolithic)</td><td>general</td><td>Favorite</td><td colspan="2">Most Preferred</td>

<td>Tvis (TY):</td><td> &gt;=30%</td><td> 40-60%</td><td> 45-55%</td><td></td>

<td>L *_T</td><td> 68-84</td><td> 73-79</td><td> 74-78</td><td></td>

<td>^to* T</td><td>+4 to-7</td><td>0a-5</td><td>-1 to-3</td><td></td>

<td>b *_T</td><td>-10 to + 12</td><td>-3 to +8</td><td>0 to +5</td><td></td>

<td>R_gAnd (glass side):</td><td> 16-29%</td><td> 18-25%</td><td> 20-23%</td><td></td>

<td>L *_G</td><td> 46-63</td><td> 50-58</td><td> 53-55</td>

<td>to * G</td><td>-6 to +5</td><td>-4a + 1</td><td>-2a0</td>

<td>b * c</td><td>-10 to + 20</td><td>0a + ​​10</td><td>+2 to +4</td>

<td>RfY (film side):</td><td> 6-20%</td><td> 6-12%</td><td> 7-9%</td>

<td>L * f</td><td> 27-40</td><td> 29-38</td><td> 31-35</td>

<td>to*_F</td><td>-5 to + 10</td><td>-1 to + 6</td><td>0 to +4</td>

<td>b *_F</td><td>+10 to-50</td><td>-10 to-40</td><td>-20 to -30</td>

The color characteristics are measured and reported in this document using the coordinates and scale a *, b * of CIE LAB (ie the diagram a * b * of CIE, and 111, CIE-C, observer at 2 degrees). The terms transmittance transmittance are well understood in the field and are used in this document according to its well-known meaning. Thus, for example, the terms visible light transmittance (TY), infrared radiation transmittance and ultraviolet radiation transmittance (T_uv) are known in the field. The total solar energy transmittance (TS) is then usually characterized as a weighted average of those values ​​from 300 to 2500 nm (UV, visible and near IR). With respect to these transmittances, the visible transmittance (TY), as reported in this document, is characterized by the standard CIE C Illuminator, observer at 2 degrees, technique at 380 - 720 nm; near infrared is 720 - 2500 nm; ultraviolet is 300- 380 nm; and total solar is 300

2500 nm. For emittance purposes, however, a particular infrared range (ie 2,500-40,000 nm) is used.

Visible transmittance can be measured using conventional, known techniques. For example, by using a spectrophotometer, such as Perkin Elmer Lambda 900 or Hitachi U4 001, a transmission spectral curve is obtained. The visible transmission is then calculated using the ASTM 308 / 2244-93 methodology mentioned above. A smaller number of wavelength points may be used than those prescribed, if desired. Another technique for measuring visible transmittance is to employ a spectrometer such as a commercially available Spectrogard spectrophotometer manufactured by Pacific Scientific Corporation. This device directly measures and reports visible transmittance. As reported and measured in this document, the visible transmittance (ie the Y value in the three-stimulus CIE system, ASTM E-308-85) uses 111, C., observer at 2 degrees.

Another term used in this document is sheet resistance. Laminar resistance (R_s) is a well known term in the field and is used in this document according to its well known meaning. This document reports in ohms per square units. In general terms, this term refers to the resistance in ohms for any square of a layer system on a glass substrate at an electric current passed through the layer system. Laminar resistance is an indication of how well the layer or layer system is reflecting infrared energy and thus is often used together with the emittance as a measure of this characteristic. The sheet resistance can be conveniently measured, for example by the use of a 4-point probe ohmmeter, such as a disposable 4-point resistivity probe with a Magnetron Instruments Corp. head, Model M-800 produced by Signatone Corp. of Santa Clara, California.

The terms heat treatment and heat treatment (HT) as used herein mean heating the article to a temperature sufficient to make possible the thermal tempering, bending and / or heat straightening of the glass inclusive article. This definition includes, for example, the heating of a coated article at a temperature of at least about 580 or 600 degrees Celsius for a period sufficient to make tempering and / or heat straightening possible. In some cases, the HT may be for at least about 4 or 5 minutes.

In certain embodiments of this invention, a coated article is provided that includes a layer system supported by a glass substrate, the layer system comprises: a first dielectric layer on a glass substrate; an IR reflective layer comprising silver on the glass substrate above at least the first dielectric layer; a contact layer on the glass substrate on top of and making contact directly with the IR reflective layer; a second dielectric layer on the glass substrate above at least the contact layer; a layer comprising niobium-zirconium on the glass substrate above and making contact directly with the second dielectric layer; a third dielectric layer on the glass substrate above and making contact directly with the layer comprising niobium-zirconium; and a layer comprising zirconium oxide on the glass substrate above at least the third dielectric layer.

<td></td><td>In the article covered in the previous paragraph,</td><td>the</td>

<td>first</td><td>dielectric layer can comprise nitride</td><td>from</td>

<td>silicon.</td><td></td><td></td>

<td></td><td>In the coated article of any of the</td><td>two</td>

In the preceding paragraphs, the second dielectric layer may comprise silicon nitride.

In the coated article of any of the three preceding paragraphs, the third dielectric layer may comprise silicon nitride.

In the coated article of any of the four preceding paragraphs, each of the first and second dielectric layers may comprise silicon nitride.

In the coated article of any of the five preceding paragraphs, the coated article may further include a contact layer below and directly contacting the IR reflective layer.

In the coated article of any of the six preceding paragraphs, the layer comprising niobiozirconium may be substantially metallic.

In the coated article of any of the seven preceding paragraphs, the layer comprising niobiozirconium may be metallic.

In the coated article of any of the eight preceding paragraphs, the coated article may have a visible transmission of approximately 40 to 60%.

In the coated article of any of the nine preceding paragraphs, the coated article may be a window.

In the coated article of any of the ten preceding paragraphs, the layer system may have a sheet resistance (R_s) less than about 20 ohms / square.

In the coated article of any of the eleven preceding paragraphs, the layer system may contain only a silver-based or gold-based IR reflective layer.

<td>In the article</td><td>coated</td><td>from</td><td>anyone</td><td>of the</td>

<td>twelve previous paragraphs,</td><td>the layer</td><td>what</td><td>understands</td><td>niobium-</td>

<td>Zirconium can oxidize.</td><td></td><td></td><td></td><td></td>

<td>In the article</td><td>coated</td><td>from</td><td>anyone</td><td>of the</td>

<td>thirteen previous paragraphs,</td><td colspan="3">in the layer that comprises</td><td>niobium-</td>

<td>zirconium the relationship of</td><td>zirconium</td><td>with</td><td>about</td><td>niobium</td>

(Zr / Nb) may be from about 0.001 to 0.60, more preferably from about 0.004 to 0.50.

In the coated article of any of the fourteen preceding paragraphs, the layer comprising niobiozirconium may consist essentially of niobium-zirconium.

In the coated article of any of the fifteen preceding paragraphs, the layer comprising niobiozirconium may comprise about 1 to 20% Zr, more preferably 2 to 15% Zr (atomic%).

In the coated article of any of the sixteen preceding paragraphs, the coated article may comprise an IG window unit, a monolithic window or a laminated window.

In the coated article of any of the seventeen preceding paragraphs, the layer comprising niobium-zirconium need not make contact with any reflective IR layer comprising Ag or Au.

In the coated article of any of the eighteen preceding paragraphs, the coated article may be heat treated.

In the coated article of any of the nineteen preceding paragraphs, the contact layer may comprise one or more of: (a) NiCr, (b) Ni and Mo and / or (c) Ni, Cr and Mo.

In certain embodiments of this invention a coated article is provided that includes a layer system supported by a glass substrate, the layer system comprises: a first dielectric layer on the glass substrate; an IR reflective layer comprising silver on the glass substrate above at least the first dielectric layer; a contact layer on the glass substrate on top of and making contact directly with the IR reflective layer; a second dielectric layer on the glass substrate above at least the contact layer; a substantially metallic layer comprising zirconium or NiCrMo on the glass substrate above and making contact directly with the second dielectric layer; and a third dielectric layer on the glass substrate above and making contact directly with the substantially metallic layer.

In the coated article of the immediately preceding paragraph, the coated article may further include a dielectric layer comprising zirconium oxide on the glass substrate above at least the third dielectric layer.

In the coated article of any of the two preceding paragraphs, the second dielectric layer may comprise silicon nitride.

In the coated article of any of the three preceding paragraphs, the third dielectric layer may comprise silicon nitride.

In the coated article of any of the four preceding paragraphs, each of the first and second dielectric layer and / or the second and third dielectric layer, may comprise silicon nitride.

In the coated article of any of the five preceding paragraphs, the substantially metallic layer may consist essentially of Zr or NbZr.

In the coated article of any of the six preceding paragraphs, the substantially metallic layer may be metallic.

In the. coated article of any of the seven preceding paragraphs, the coated article may have a visible transmission of approximately 40 to 60%.

In the coated article of any of the eight preceding paragraphs, the layer system may contain only one silver-based or Au-based IR reflective layer.

In the coated article of any of the nine preceding paragraphs, the substantially metallic layer contains no more than about 20% oxygen.

In the coated article of any of the ten preceding paragraphs, the coated article may comprise an IG window unit, a monolithic window or a laminated window.

In the coated article of any of the eleven preceding paragraphs, the substantially metallic layer need not make contact with any reflective IR layer comprising Ag or Au.

In the coated article of any of the twelve preceding paragraphs, the contact layer may be of or may include one or more of: (a) NiCr, (b) Ni and Mo and / or (c) Ni, Cr and Mo.

Once the above description is provided, many other qualities, modifications and improvements will become apparent to the skilled artisan. Therefore, it is considered that these other qualities, modifications and improvements are part of this invention, the scope of which should be determined by means of the following claims.