BRPI1000354A2 - heat treatable coated article with infrared reflective layer including niobium, zirconium and hafnium, and production process thereof - Google Patents

Abstract

THERMALLY TREATABLE COATED ARTICLE WITH INFRARED RADIATION LAYER INCLUDING NIOBE, ZIRCINIUM AND HAPHONY, AND THE SAME PRODUCTION PROCESS. The present invention relates to a coated article which is provided to include a solar control coating, having a reflective layer of infrared (IR) radiation interspersed between at least a pair of dielectric layers. The reflective layer IV includes NbZr and / or NbZrO ~ x ~, along with hafnium in certain embodiments of this invention. A protective overcoating of zirconium oxide (e.g., ZrO2 or other suitable stoichiometry) and hafnium can also be provided in certain exemplary embodiments. The use of these materials, as one or more reflective layers IV, allows the coated article to have a good resistance to corrosion to alkaline solutions, a good mechanical behavior such as scratch resistance, and / or a good color stability (this i.e., one or lower values of AE *), after heat treatment. The coated article may or may not be heat treated in the different embodiments of the invention.

Description

Report of the Invention Patent for "THERMOUSLY TREATABLE COATED ARTICLE WITH INFRARED RADIATION INCLUDING NIOBIUM, ZIRCONIUM AND HABNIUM, PRODUCTION PROCESS OF THE SAME".

FIELD OF INVENTION

Certain exemplary embodiments of this invention pertain to coated articles, which include at least one infrared (IR) reflective layer including niobium and zirconium oxide (NbZrOx) and hafnium (Hf), and / or a production process thereof. In certain exemplary embodiments, a protective zirconium oxide overlay (e.g., ZrO2 or other suitable stoichiometry) and hafnium may also be provided. These coated articles may be used in the context of monolithic windows, insulating glass (IG) window units, laminated windows and / or other suitable applications.

Background and Summary of Exemplary Embodiments of the Invention

Solar control coatings having a stack of glass / Si3N4 / NiCr / Si3N4 layers are known, in which the NiCr metallic layer is the only infrared (IR) reflective layer in the coating. In certain cases, the NiCr layer may be nitrified. Unfortunately, while these NiCr IR reflective layer piles provide efficient solar control and overall good coatings, they are sometimes lacking in terms of: (a) acid corrosion resistance (eg Boiling HCl); (b) mechanical behavior, such as risk resistance; and / or (c) color stability under heat treatment for noise, heat bending or the like (ie very high ΔΕ * value or values). For example, a known heat-treatable article having a glass / Si3N4 / NiCr / Si3N4 layer stack preferably has a high value of ΔΕ * reflection on the glass side above 5.0 after heat treatment (HT). at 625 or 650 ° C for about ten minutes. The high ΔΕ * reflectance value on the glass side means that the coated article when subjected to HT1 will not be approximately comparable to its counterpart without HT with respect to the reflective color on the glass side after such HT.

Accordingly, there is a need in the art for a coated article which has improved characteristics with respect to (a), (b) and / or (c) compared to a conventional glass / Si3N4 / NiCr / Si3N4 layer stack, but which is still capable of acceptable thermal behavior (eg blocking a reasonable degree of IR and / or UV radiation) and / or heat treatment. It is an aspect of certain exemplary embodiments of the invention to satisfy at least one of the needs listed above, and / or other needs that will be apparent to those of skill in the art, provided that the following description is provided.

A recent development by the assignee of the present invention, disclosed in US 6,994,910 (incorporated herein by reference), is the use of a stack of glass-Si3N4 / NbNx / Si3N4 layers, wherein NbNx It is used as the IR reflective layer. This layer stack is advantageous over the above-mentioned Siidro / Si3N4 / NiCr / Si3N4 layer stack because the articles coated with the NbNx IR reflective layer provide improved color stability (ie lower ΔΕ * values). ) and / or improved durability.

Although coated articles having a stack layer of Si3N4 / NbNx / Si3N4 layers represent improvements in the art, they are sometimes lacking in chemical durability. This is because, for example, NbNx is damaged when exposed to certain chemical substances, such as alkaline solutions, for example by exposure to a one hour NaOH boiling test for durability. In commercial use, microporosities may form on the outer layer of silicon nitride, thereby exposing NbNx in certain areas; If damaged by alkaline solutions, this can have consequences on durability. For example, certain photographs in US Patent 6,852,419 (incorporated herein by reference) illustrate that Nb and NbNx layers are often damaged by the one hour (one hour boiling solution) boiling test with NaOH. including approximately 0.1 normal NaOH solution - 0.4% NaOH in mix with water - at approximately 90.5 ° C (195 ° F) For boiling test see ASTM d 1308-87, incorporated by reference in the present descriptive report.

Another recent development is the use of CrNx as an IR reflective layer in this layer stack. Unfortunately, while CrNx provides exceptional chemical durability, its thermal behavior is not as good.

In addition, U.S. Patent 6,852,419 to the same requires the use of NbCr and NbCrN as IR reflective layers. While both NbCr and NbCrN provide excellent durability, there is a mismatch between chemical durability and thermal behavior in NbCr and NbCrN-based coatings. In particular, higher Cr alloys have excellent chemical durability, but better thermal behavior is attainable for lower Cr contents. Thus, a compromise has to be established between ΔΕ * and thermal behavior when using coatings using IRde NbCr or NbCrN reflective layers.

Accordingly, it will be apparent that there is a need in the art for coated articles which are capable of acceptable sun control behavior and which are also durable to exposure to certain chemicals such as acidic and / or alkaline solutions ( for example, boiling test with NaOH).

In certain exemplary embodiments of this invention, a coating or layer system is provided which includes an infrared (IR) reflective layer comprising niobium and zirconium (NbZr) and / or a niobium zirconium oxide (NbZrOx). ), interspersed between at least one substrate and one dielectric layer. Surprisingly, it has been found that the addition of Zr to Nb makes the coated articles provide excellent chemical and mechanical durability as well as excellent thermal behavior. Furthermore, it was surprisingly found that the oxidation of NbZr (to form NbZrOx) provides even better color stability during heat treatment (i.e. one or more lower ΔΕ * values) compared with situations where NbZr is not oxidized. Moreover, the inclusion of small amounts of hafnium has been found to further improve the durability of the NbZr coating.

In certain exemplary embodiments of NbZrOx, it has been unexpectedly found that oxidation (e.g., partial oxidation) is particularly beneficial with respect to lowering the ΔΕ values (). For example, in certain exemplary embodiments, partial oxidation of NbZr has been found to be particularly beneficial when a particular range of metal contents in the layer is obtained. For example, the oxygen layer atomic ratio for the combination of Nb and Zr may be represented, in certain exemplary embodiments, by (Nb + Zr) xOy, where the y / x ratio (i.e. the oxygen to Nb + Zr) is from 0.00001 to 1.0, particularly from 0.03 to 0.20, and especially from 0.05 to 0.15. It has been found that these oxygen / metal content ranges, for illustrative purposes only and without limitation, unless otherwise indicated, lead to one or more significantly improved ΔΕ * values combined with good durability. As mentioned above, the inclusion of small amounts of hafnium has been found to further improve the durability of NbZrOx coatings.

In certain exemplary non-limiting embodiments, it has been found that the flow of gaseous oxygen (O2) upon crackling of one or more NbZr targets can be about 0.5 to 6 m3 under normal temperature and pressure conditions ( CNTP) / kW, particularly about 1 to 4m3 on CNTP / kW (where kW is a crackling power unit). These oxygen flows, for exemplary purposes only and without limitation, unless otherwise claimed, to provide one or more improved ΔΕ * values.

For example, the use of NbZrOx in one or more IV reflective layers provides that one or more coated articles obtain at least one of: (a) improved corrosion resistance to alkaline solutions, such as NaOH (compared to batteries) glass layers / Si3N4 / Sb / Si3N4 and glass / Si3N4 / NbNx / Si3N4); (b) a good thermal behavior comparable to that of Nb and NbNx; (c) good mechanical behavior, such as scratch resistance; and / or (d) good color stability and heat treatment (for example, one or more lower ΔΕ * values than articles coated with glass / Si3N4 / NiCr / Si3N4 stacks).

Because of this spectral selectivity, niobium and zirconium oxide (NbZrOx) provides similar or better thermal behavior (eg IR block) than NiCr and NbNx, but is surprisingly more mature than both NiCr and NbNx. Furthermore, it has been surprisingly found that in certain exemplary cases, the use of NbZrOx in / with one or more IR reflective layers provides that the controlsolar coating has substantially improved color stability in HT (e.g., a lower ΔΕ * value with a certain time of HT) than the conventional coating mentioned above, in which NiCr is used as the IR reflective layer. In addition, the inclusion of small amounts of hafnium has been found to further improve the durability of NbZrOx coatings.

An article coated in accordance with an exemplary embodiment of this invention utilizes one or more Nb-ZrOx IR reflective layers, also including hafnium, interspersed between at least one dielectric layer of one or more materials, such as silicon nitride or some other suitable dielectric materials. In certain exemplary embodiments of this invention, the layer including NbZrOx - hafnium does not come into contact with any metallic IR reflective layer (e.g., not in contact with any Ag or Au layer).

In certain exemplary embodiments of this invention, heat-treated coated (HT) articles, including one or more IR reflector layers including NbZr and / or NbZrOx, which also include hafnium, have a reflection value of ΔΕ * due to the glass. heat treatment of not more than 4,0, particularly not more than 3,0, more particularly not exceeding 2,5, more particularly not exceeding 2,0, especially not more than 1.5, and sometimes not even higher than 1.0. For exemplary purposes, the heat treatment (HT) may be for at least 5 minutes at one or more temperatures of at least about 580 ° C (for example, ten minutes at about 625 or 650 ° C).

In certain exemplary embodiments of this invention, the ratio of Zr: Nb (atomic%) in one or more NbZre / or NbZrOx IR reflective layers may be from about 0.001 to 1.0, particularly from about 0.001 to 1.0. more particularly from about 0.001 to 0.60, and even more particularly from about 0.004 to 0.50, and especially from about 0.05 to 0.20 (e.g., 0.11). For exemplary purposes only, if a target of Nb / Zr 90/10 is used, the Zr: Nb ratio will be about 0.11. In certain exemplary embodiments, the reflective layer IV comprising NbZr and / or NbZrOx may include from about 0.1 to 60% Zr, preferably from about 0.1 to 40% Zr, particularly 0, 1 to 20%, more particularly from 0.1 to 15%, even more particularly from 0.4 to 15% of Zr, and especially from 3 to 12% of Zr (% atomic). Nitride gas may also be used to at least partially nitrate NbZrOx in certain alternative embodiments of this invention.

In certain exemplary embodiments, an IR reflective layer of NbZrOx, which also includes hafnium, generally includes about 10% Zr, 80-90% Nb, and 0-19% Ox. In certain other exemplary embodiments, NbZrOx, which also includes hafnium, generally includes about 10% Zr1 85 - 90% Nb and 0 - 5% Ox. The proportion of hafnium included in the layer (s) is small. For example, in certain exemplary embodiments, the NbZrOx reflective layer IV, which also includes hafnium, preferably has about 0.001 - 2% by weight of hafnium, particularly about 0.001 - 1.0%. of hafnium. Any intermediate range may also be used in certain exemplary embodiments. Suitable NbZrOx IR reflector layer, which also includes hafnium, can be deposed using a crackling target having an Nb / Zr ratio of about 90/10, particularly 95/5, in certain exemplary embodiments. Some exemplary embodiments include about 10-50 ppm hafnium, particularly 15-45 ppm hafnium, more particularly about 20-40 ppm hafnium, and especially about 30 ppm hafnium. Any intermediate range may also be used in certain exemplary embodiments.

Optionally, a protective overcoat of a material such as zirconium oxide may also be provided in certain exemplary embodiments. Like the Nb-ZrOx reflective layer (s) IV, which includes hafnium, the protective overcoating layer, which includes zirconium oxide, also preferably includes hafnium. However, the protective overcoat layer may include more hafnium than in the NbZrOx reflective layers IV. For example, in certain exemplary embodiments, the protective overcoat layer includes 0.001 - 5 wt% hafnium, particularly 0.003 - 4.5 wt% hafnium, and more particularly about 0.003 - 1.5% by weight of hafnium.

Any intermediate range may also be used in certain exemplary embodiments. A protective overcoating layer, which includes zirconium oxide and hafnium, may be deposited by cracking a crackling target, which includes about 1 - 1,000 ppm hafnium, preferably 50 - 1,000 ppm. hafnium, particularly 50-500ppm, more particularly 50-400ppm, even more particularly about 50-350 ppm, and especially about 50-300ppm. Any intermediate range may also be used in certain exemplary embodiments. In certain alternative embodiments, the protective overcoat layer, which includes zirconium oxide and hafnium, may be deposited by the crackling of a crackling target, which includes about 1-200 ppm hafnium, preferably 10-120 µm. ppm of hafnium. The diverter layer IV may be crackled deposited using a crackling target having the same proportions of hafnium indicated above in this paragraph together with the overcoat layer.

In certain exemplary embodiments of this invention, a coated article, including a substrate supported layer system, is provided, the layer system comprising: a first dielectric layer; a layer comprising a niobium zirconium oxide (NbZrOx) and hafnium provided on the substrate over at least the first dielectric layer; and a second dielectric layer provided on the substrate, over at least the layer comprising niobium ezirconium oxide, and hafnium. In certain exemplary embodiments, the layer comprising niobium zirconium oxide and hafnium will include from 0.001 - 1% by weight of hafnium.

In certain other exemplary embodiments of this invention, there is provided a process of producing a coated article, the process comprising: crackling a target comprising niobium, zirconium and hafnium, in an atmosphere including oxygen to form a "comprising" layer. a niobium and zirconium oxide, supported by a substrate, and repeating a dielectric layer over at least one layer comprising niobium and zirconium oxide. In certain exemplary embodiments, the target includes about 1 - 200 ppm hafnium, particularly about 10 -120 ppm, and possibly about 10 - 50 ppm hafnium.

In certain exemplary embodiments, an overcoat layer comprising hafnium and zirconium oxide is provided. In certain exemplary embodiments, the overcoat layer includes about 0.001 - 5% hafnium, particularly about 0.003 - 4.5%, and especially about 0.003 - 1.5% hafnium. In certain exemplary embodiments, a target used to produce the overcoat layer includes about 100-1000 ppm hafnium. In certain exemplary embodiments, the overcoat layer may comprise more hafnium than the reflective layer IV.

In certain exemplary embodiments of this invention, a coated article, including a substrate-supported layer system, is provided. The layer system comprises: a first dielectric layer; an infrared (IR) reflective layer comprising a niobium zirconium oxide (NbZr) and provided over at least the first dielectric layer, the IR reflective layer further comprising hafnium; a second dielectric layer provided on the substrate over at least reflective layer IV; and an overcoat layer comprising zirconium oxide over at least the second dielectric layer, the overcoat layer further comprising hafnium. The IR reflective layer comprises about 0.001-1 wt% hafnium and the overcoating layer may also comprise about 0.001-5 wt% hafnium.

The production processes thereof are also provided in certain exemplary embodiments, for example when some or all of the layers in the layer system are deposited by cracking.

In certain exemplary embodiments, the overcoat layer has more hafnium than the reflective layer IV. In certain exemplary embodiments, the overcoat layer is at least 10 times more hafn than the reflective layer IV, particularly at least 50 times more hafnium than the reflective layer IV. In certain exemplary embodiments, the overcoat layer is often more hafnier than the reflective layer IV, such as, for example, any proportion or range within a factor of 100 to 5,000 times.

In certain non-limiting exemplary embodiments, the first dielectric layer has a thickness of 70 - 440 Å, the reflecting layer IV has a thickness of 30 - 305 Å, the second dielectric layer has a thickness of 80 - 545 Å, and the overcoat layer has a thickness of 40 - 60 Å.

In a first exemplary case, the first dielectric layer has a thickness of 70 - 110 Å, the reflective layer IV has a thickness of 200 - 305 Å, the second dielectric layer has a thickness of 80-120 Å, and the overcoat layer has a thickness of 70-110 Å. 40 - 60 Á thickness.

In a second exemplary case, the first dielectric layer has a thickness of 180 - 280 Å, the reflective layer IV has a thickness of 135 - 205 Å, the second dielectric layer has a thickness of 230 - 350 Å, and the Overcoat layer has a thickness of 40 - 60 Â.

In a third exemplary case, the first dielectric layer has a thickness of 180 - 270 Å, the reflective layer IV has a thickness of 60 - 95 Å, the second dielectric layer has a thickness of 220 - 330 Å, and the overcoat layer has a thickness of 40 - 60 Á.

In a fourth exemplary case, the first dielectric layer has a thickness of 290 - 440 Å, the reflective layer IV has a thickness of 105 - 160 Å, the second dielectric layer has a thickness of 360-545 Å, and the Overcoat has a thickness of 40 - 60 Â.

In a fifth exemplary case, the first dielectric layer has a thickness of 125 - 195 Å, the reflective layer IV has a thickness of 30 - 47 Å, the second dielectric layer has a thickness of 170 - 225 Å, and the overcoat layer has a thickness of 125 Å. 40 - 60 À.

In the above-mentioned non-limiting exemplary embodiments, the coated article may be heat treated and may have a value of ΔΕ * (reflective on the glass side) of not more than 2.5 after and / or due to heat treatment. Additionally, the reflective layer IV may be interleaved between and come into contact with both the first and second dielectric layers in certain exemplary embodiments. Furthermore, the first and second dielectric layers may both comprise a nitride (e.g., a non-absorbent silicon nitride) and / or a metal oxide in certain exemplary embodiments.

In certain exemplary embodiments, a coated article including a layer system supported by a substrate is provided. The layer system comprises: a first dielectric layer, an infrared (IR) reflective layer comprising a niobium zirconium oxide (NbZr) provided over at least the first dielectric layer, said reflective layer IV further comprising niobium; and a second dielectric layer provided on the substrate over at least the reflective layer IV. The reflective layer IV comprises about 0.001 -1% by weight of hafnium. In certain exemplary embodiments, a coated article including a layer system supported by a substrate is provided. The layer system comprises: a first dielectric layer, an infrared (IR) reflective layer; a second dielectric layer provided on the substrate over at least the reflective layer IV; and a overcoat layer comprising zirconium oxide over at least the second dielectric layer, said overcoat layer further comprising hafnium. The overcoat layer comprises about 0.01 - 5% by weight of hafnium.

The features, aspects, advantages and exemplary embodiments described in this descriptive report may be combined to provide further embodiments.

BRIEF DESCRIPTION OF DRAWINGS

These and other features and advantages will be better understood more fully by reference to the following detailed description of the exemplary illustrative embodiments in conjunction with the drawing, in which Figure 1 is a partial cross-sectional view of an embodiment of a monolithic coated article (treated or non-thermally) according to an exemplary embodiment of this invention.

DETAILED DESCRIPTION OF EXEMPLIFICATION OF THE INVENTION

Certain embodiments of this invention provide resurfaced articles, which may be used on windows, such as monolithic windows (e.g., vehicle, residential and / or architectural windows), IG window units, and / or other suitable applications. Certain exemplary embodiments of this invention provide a layer system which is characterized by at least one of: (a) good resistance to corrosion to acids, and to alkaline solutions such as NaOH; (b) good thermal behavior such as blocking significant degrees of IR and / or UV radiation; (c) good mechanical behavior such as scratch resistance; and / or (d) good color stability in heat treatment (ie low value or values of ΔΕ *). With respect to color stability in heat treatment (HT), this means a low value of ΔΕ *, where Δ is indicative of a *, b * and L * variation in HT view, such as heat quenching, thermal bending or thermal reinforcement, monolithically and / or in the context of double panel physical media such as IG units or laminates.

Figure 1 is a side cross-sectional view of a coated garment according to an exemplary embodiment of this invention. The coated article includes at least one substrate 1 (e.g. light green, bronze, gray, blue or greenish blue substrate). about 1.0 to 12.0 mm thick), an optional first dielectric layer 2 (e.g., from or including silicon nitride (e.g. Si3N4 or other suitable stoichiometric), tin oxide, or some other dielectric such as a metal oxide and / or nitride), a reflective layer of infrared (IR) radiation 3 from or including niobium zirconium (NbZr) and / or a zirconium deniobium oxide (NbZrOx) together with hafnium, and a second dielectric layer 4 (e.g., from or including silicon nitride (e.g. Si3N4), tin oxide, or some other suitable dielectric such as a metal oxide and / or nitride). In certain alternative embodiments, the bottom dielectric layer 2 may be omitted such that the reflective layer IV 3 is located in contact with the glass substrate. Also, it is possible to nitrite the reflective layer IV of NbZrOx having hafnium to some degree in certain alternative embodiments of this invention.

Optionally, a protective overcoat of or including material such as zirconium oxide and hafnium 6 may be provided over layers 2-4 in certain exemplary embodiments of this invention. Protective overcoats comprising silicon nitride, zirconium oxide and / or chromium oxide, which may optionally be used in certain exemplary embodiments of this invention, are described in US Patent 7,147,924, the disclosure of which is incorporated by reference in this descriptive report.

In certain exemplary embodiments of this invention, coating 5 may optionally not include any reflective or IR-blocking Ag or Au layers. In these embodiments, one or more layers including NbZr and / or NbZrOx 3, which also include hafnium, may be only the reflective layer IV in coating 5, although many of these layers may be provided in certain cases. In certain exemplary embodiments of this invention, the NbZr and / or NbZrOx 3 reflective layer IV, which also includes hafnium, reflects at least part of the IR radiation.

In certain exemplary embodiments, the Nb-Zr and / or NbZrOx 3 layer, which also includes hafnium, may also include other materials, such as dopants. In any case, it has been determined that the inclusion of hafnium in the NbZr and / or NbZrOx 3 layer increases durability and is therefore advantageous.

Overall liner 5 includes at least layers 2-4. It should be noted that the terms "oxide" and "nitride" as used in the present disclosure include various stoichiometries. For example, the term silicon nitride includes stoichiometric Si3N4 as well as non-stoichiometric silicon nitride. Silicon nitride may be doped with Al, Zr and / or any other suitable metal. Similarly, a zirconium oxide overcoat layer 6, which also includes hafnium, may be doped with Si or other materials. Layers 2-4, which may be deposited on substrate 1 by magnetron crackling, any kind of crackling, or by any other different technique in different embodiments of this invention. In addition, the inclusion of hafnium has been found to improve the hardness of the zirconium oxide overcoating layer and is therefore advantageous.

Surprisingly, it has been found that the use of Zr and Nb, together with small proportions of hafnium in the IR 3 reflective layer, provides the resulting coated article to have excellent chemical and mechanical durability, as well as good thermal behavior. For example, the use of NbZr and / or NbZrOx in one or more IV 3 reflective layers, together with hafnium, allows the one or more resulting coated articles to have: (a) improved corrosion resistance to alkaline solutions such as deNaOH (compared to with the glass layer / Si3N4 / Nb / Si3N4 glass cells / Si3N4 / NbNx / Si3N4; (b) excellent thermal behavior comparable to that of Nb and NbNx; (c) good mechanical behavior such as resistance to and / or (d) good color stability in heat treatment (for example, one or more lower ΔΕ * values than with glass / Si3N4 / NiCr / Si3N4 layers). In certain exemplary cases, the use of NbZr together with hafnium instead of Nb provides one or more lower ΔΕ * values.

Moreover, in certain exemplary embodiments of hafnium Nb-ZrOx, it has unexpectedly been found that oxidation (e.g. partial oxidation) is particularly beneficial with respect to lowering one or more ΔΕ * values. . For example, in certain exemplary embodiments, the gaseous oxygen (O2) fluxes when cracking one or more NbZr targets, which include small proportions of hafnium, may be from 0.5 to 6 cm3 at CNTP / kw, particularly about 1 to 4 cm3 at CNTP / kW (where kW is an electrical power unit used in crackling). These oxygen flows are considered to provide one or more significantly improved ΔΕ * values.

As will be shown below, the one or more ΔΕ * values may be further decreased, due to the oxidation of the layer including NbZr, to form a layer comprising hafnium NbZrOx, as compared to non-oxidized NbZr and NbZrNx layers.

In certain exemplary embodiments, the Zr: Nb (atomic%) ratio of layer 3 may be from about 0.001 to 1.0, more particularly from about 0.001 to 0.60, and even more particularly about from 0.004 to 0.50, and especially from about 0.05 to 0.20 (e.g. 0.11).

In certain exemplary embodiments, with respect to the metallic content, the reflector bed IV may include from about 0.1 to 60% Zr, preferably from about 0.1 to 40% Zr, particularly from 0.1 to 40%. 20%, more particularly from 0.1 to 15%, even more particularly from 0.4 to 15% of Zr, and especially from 3 to 12% of Zr (% atomic). Surprisingly, durability improvement was observed, even at very low Zr levels, determined to be below 0.44% atomic (Zr / Nbde 0.00438 ratio), while at the same time the thermal behavior is comparable to that. when using Nb.

In embodiments in which the reflective layer IV 3 is or includes NbZrOx (i.e. an oxide of NbZr), the atomic ratio in the oxygen layer for the total combination of Nb and Zr may be represented in certain exemplary embodiments by ( Nb + Zr) xOy, where the ratio y / x (ie the oxygen to Nb + Zr ratio) is from 0.00001 to 1.0, particularly from 0.03 to 0.20, and especially from 0.05 to 0.15. This ratio is applicable before and / or after heat treatment. Thus, it may be noted that in certain exemplary embodiments of this invention, the layer including Nb-Zr is partially oxidized, although this oxidation is certainly material in that it results in significant advantages over non-oxidized versions.

In certain exemplary embodiments, an IR reflective layer of NbZrOx, which also includes hafnium, will generally include about 10% Zr, 80-90% Nb, and 0-19% Ox. In certain other exemplary embodiments, NbZrOx, which also includes hafnium, generally includes about 10% Zr, 85-90% Nb and 0-5% Ox. The proportion of hafnium included in the layer (s) is small. For example, in certain exemplary embodiments, the NbZrOx reflective layer IV, which also includes hafnium, preferably has about 0.001-1 wt% hafnium hafnium. Any intermediate range may also be used in certain exemplary embodiments. Suitable NbZrOx IR reflective layer, which also includes hafnium, can be deposited using a crackling target having an Nb / Zr ratio of about 90/10, particularly 95/5, in certain exemplary embodiments. These targets of certain exemplary embodiments include about 1 - 1,000 ppm hafnium, preferably 50 - 1,000 ppm hafnium, particularly about 50 - 500 ppm hafnium, more particularly about 50 - 350 ppm hafnium, and, especially about 50 - 300 ppm hafnium. In certain exemplary embodiments, targets may include from 1 - 200 ppm hafnium, possibly from about 10-120 ppm hafnium, possibly from 10 - 50 ppm hafnium, preferably 15-45 ppm hafnium, particularly about 20-40 ppm hafnium, and especially about 30 ppm hafnium. Any intermediate range may also be used in certain exemplary embodiments. Advantageously, the inclusion of hafnium in this and / or other ways has been verified as improving the durability of the NbZr and / or NbZrOx coating.

Although Figure 1 illustrates coating 5 in a manner in which the NbZr and / or NbZrOx layer with hafnium 3 is in direct contact with dielectric layers 2 and 4, and where layer 3 is the only diverter layer IV in the coating, The present invention is not thus limited. Other or other layers may be provided between layers 2 and 3 (and / or between layers 3 and 4) in certain other embodiments of this invention. Furthermore, another or other layers (not shown) may be provided between substrate 1 and layer 2 in certain embodiments of this invention; and / or other or other layers (not shown) may be provided on the substrate 1 on top of layer 4 in certain exemplary embodiments of this invention. Thus, although the coating 5 or its layers are "on" or "supported by" the substrate 1 (directly or indirectly), other or other layers may be provided therebetween.

Thus, for example, the layer system 5 and its layers shown in Figure 1 are considered "in" substrate 1, even when another or other layers (not shown) are provided between them (ie, the terms "in" and " "as used in this descriptive report are not limited to direct contact). Also, more than one NbZr and / or NbZrOx hafnium IR reflective layer may be provided in alternative embodiments of this invention.

In certain exemplary embodiments of this invention, anti-reflection dielectric layer 2 may have a "n" refractive index of 1.7 to 2.7, particularly from 1.9 to 2.5 in certain embodiments, while bed 4 may have an index of refraction. refraction "n" from about 1.4 to 2.5, particularly from 1.9 to 2.3. Meanwhile, layer 3, when comprising hafnium NbZr oxide, may have a "n" refractive index of about 2.0 to 3.2, particularly from 2.2 to 3.0, and especially of 2.4 to 2.9, may have an extinction coefficient "k" of 2.5 to 4, particularly from 3.0 to 4.0, and especially from 3.3 to 3.8. In embodiments of this invention, wherein layers 2 and / or 4 comprise silicon nitride (e.g. Si 3 N 4), crackling targets including Si employed to form these layers may or may not be mixed with up to 1 - 40% by weight of silicon nitride. aluminum, zirconium and / or stainless steel (eg SS 313), with this ratio approximately appearing in the layers thus formed. Even with these proportions of aluminum and / or stainless steel, layers 2 and 4 are still considered dielectric layers in the present descriptive report.

Furthermore, a protective overcoat of a material such as zirconium oxide 6 may also be provided in certain exemplary embodiments. Like the NbZrOx reflective layer (s) IV which includes hafnium, the protective overcoat layer, which includes zirconium oxide 6, also preferably includes hafnium. However, protective overcoat 6 may include more hafnium than the reflective layer (s) IV. For example, in certain exemplary embodiments, protective overcoat layer 6 preferably includes 0.001-5% by weight. hafnium, in particular 0.003 - 4.5 wt.%, and especially 0.003 - 1.5 wt.% hafnium. Any intermediate range may also be used in certain exemplary embodiments. A protective overcoat layer including hafnium zirconium oxide 6 may be deposited by crackling from a crackling target, which includes about 1 - 1,000 ppm hafnium, preferably 1 - 500 ppm hafnium, particularly 200 - 400 ppm hafnium, more particularly about 250 - 350 ppm hafnium, and especially about 300 ppm hafnium.

Any intermediate range may also be used in certain exemplary embodiments. In certain exemplary embodiments, the target may have from 1 - 200 ppm hafnium, particularly from about 10 - 120 ppm hafnium.

Although Figure 1 illustrates a coated article according to one embodiment of this invention in monolithic form, articles coated according to other embodiments of this invention may comprise IG (insulating glass) window units. In embodiments IG, the jacket 5 of the Figure may be provided on the inner wall of the outer substrate of the IG1 unit and / or on the inner wall of the inner substrate, or at any other suitable location in other embodiments of this invention.

Turning to Figure 1, various thicknesses may be used compatible with this invention. In accordance with certain non-limiting illustrative exemplary embodiments of this invention, the exemplary thicknesses and materials for the respective layers 2-4 on the glass substrate 1 are as shown in the following table.

Table 1: Nonlimiting Exemplary Thicknesses

<table> table see original document page 19 </column> </row> <table>

In certain exemplary embodiments, HT color stability may result in a substantial similarity between the heat treated or untreated versions of the coating or layer system. In other words, in monolithic and / or IG1 applications in certain embodiments of this invention, two glass substrates having the same coating system thereon (one HT after deposition and the other non-HT) appear to the naked eye to be substantially equal.

The AE * value (s) is important in determining whether or not there is similarity, or substantial color similarity after HT, in the context of certain embodiments of this invention (ie, the term AE * is important in determining color stability. after HT). The color in this descriptive report is described by reference to the conventional values dea * and b *. For example, the term Aa * is indicative of how much color value a * changes due to HT. The term AE * (and AE) is well understood in the art. The definition of EA * can be found, for example, in international patent application WO 02/090281 and / or U.S. Patent 6,475,626, the disclosure of which is incorporated by reference in this specification. In particular, AE * corresponds to L *, a * and b * of the CIE LAB scale, and is represented by:

AE * = {(AL *) 2 + (Ab *) 2)} 172 (1)

on what:

AL * = L * i - L * o (2)

Aa * = a * i - a * o (3)

Ab * = b * i - b * o (4)

wherein the subscript "0" represents the coating (or coated article) before heat treatment and the subscript "1" represents the coating (or coating) after the heat treatment, and the numbers employed (for example, a *, b *, L *) are those calculated by the coordinate technique L *, a *, b * (CIE LAB 1976) mentioned above. Similarly, AE can be calculated using equation (1) by replacing a *, b *, L * with Hunter Lab values ah, bh, Lh. Also within the scope of this invention and the quantification of AE * are equivalent numbers, if converted to those calculated by any other technique employing the same concept as AE * as defined above.

Prior to heat treatment (HT), such as tempering, in certain exemplary embodiments of this invention the coated articles have color characteristics as shown in Table 2 (monolithic unit and / or IG). It should be noted that the subscript "G" represents the mirror reflective color of the glass, the subscript "T" represents a transmissive color, and the subscript "F" represents the color on the film side. As is known in the art, the glass laden (G) means the reflective color when viewed from the glass (opposite edge of the layer / film) side of the coated article. The film side (F) means the corrector, when viewed from the coated article side, in which the coating 5 is provided. Table 3 below illustrates certain characteristics of coated articles according to certain illustrative exemplary embodiments of this invention after HT, such as thermal tempering (monolithic and / or IG units) - the characteristics below in Table 2 (without HT) are also applicable to the HT coated articles of the present invention, except for the additions shown in Table 3.

Table 2: Color / Optical Characteristics (without HT)

<table> table see original document page 21 </column> </row> <table>

Table 3: Color / Optical Characteristics (after HT; in addition to Ta-Bela 2)

<table> table see original document page 21 </column> </row> <table>

As explained in this report, the oxidation of the IR reflective layer including Nbzr, which has hafnium to form a layer comprising hafnium NbZrOx, is advantageous in that it unexpectedly provides an even lower AE * value to be obtained. In certain embodiments of hafnium NbZrOx, the coated article may have a reflection value AE * on the glass side due to heat treatment not exceeding 4.0, particularly not more than 3.0, more particularly not greater than 2,5 and especially not more than 2,0. Sometimes it will not exceed 1.5, and sometimes it will not exceed 1.0.

For exemplary purposes only, various examples representing different exemplary embodiments of this invention are set forth below.

EXAMPLES

Examples 1, 2 and 4 are non-oxidizing examples of this invention (i.e. NbZr reflective layers IV), while Examples 3 and 5 to 7, wherein the reflective layer IV is oxidized to include NbZrOx.

EXAMPLES 1 AND 2

Examples 1 and 2 were monolithic coated articles (both annealed and heat treated, although not all embodiments of the present invention need to be HT), with the layer stack, as shown in Figure 1, without the zirconium oxide overcoat with hafnium. Si3N4 layers 2 and 4 in all examples were deposited by crackling silicon target (doped with about 10% Al) in an atmosphere including nitrogen and argon gases. The reflective IV layer of hafnium NbZr in all examples was deposited by crackling a target of about 90% Nb and about 10% Zr in an atmosphere including argon gas. For Example 1, the decrepit process parameters shown in the following table were used in the deposition of the coat. The line velocity is in centimeters per minute (inches per minute - IPM) and gas flows (Ar, OeN) were in cm3 CNTP units.

Table 4: Example 1 Coating Process Parameters

<table> table see original document page 22 </column> </row> <table> <table> table see original document page 23 </column> </row> <table>

It should be noted that all examples can easily be transformed into an embodiment of hafnium NbZrNx by using an adequate amount of nitrogen gas flow during the process of repeating the IR 3 reflective layer. In addition, it is possible that the NbZr layer with hafnium 3 can be nitrified as a result of denitrogen diffusion during heat treatment, even though no nitrogen is intentionally added during crackling. NbZr with hafnium deposited on silicon nitride and / or NbZr with hafnium overcoated with silicon nitride may have some nitrogen in them due to diffusion even before heat treatment.

After crackling, Examples 1 and 2 showed the characteristics shown in the following table (annealed and without monolithic HT1) (grade III.C.2 observer)

Table 6: Characteristics (without HT)

<table> table see original document page 24 </column> </row> <table>

Both Examples 1 and 2 had a stack of layers as shown below, shown in Table 7. The thicknesses and stoichiometrics listed below in Table 7 for Examples 1 and 2 are inaccurate approximations. The glass substrates were clear and about 6 mm thick in both examples. TABLE 7: Coatings in the examples

<table> table see original document page 25 </column> </row> <table>

Both examples were then evaluated and tested for durability, showing excellent performance in usual equimetric mechanical tests, both coated and after HT. For example, the Teledyne risk test with a load of 500 g produced no significant risks in any of the samples. A wheel abrasion test after 500 revolutions was also done. A one hour NaOH boiling test was also conducted, although some color variations were observed. When a hafniophore zirconium oxide overcoating was provided, the boiling test with NaOH was conducted in an improved manner.

After cracking coating, Examples 1 and 2 (as in Tables 4-7 above with a ZrO overcoat) were heat treated for 10 minutes at about 625 or 650 ° C. Table 8 below shows certain color stability characteristics of Examples 1 and 2 during / after such heat treatment (HT).

TABLE 8: Reflection color stability on the glass side during HT

<table> table see original document page 25 </column> </row> <table>

As can be seen from Table 8, Examples 1 and 2 were characterized by satisfactory glass side reflection AE * values (the lower the better). These low values illustrate how little the optical reflection characteristics on the glass side of the coating vary with HT. This is indicative of good color stability during heat treatment. It has further been found in other examples of NbZr with Hf, similar to Examples 1 and 2, having a higher Zr content of about 10% in layer 3 that the glass side reflection AE * is about 1%. , 9a to 2.0.

For comparison purposes, consider the following layer stack: glass / Si3N4 / NiCr / Si3N4, which has a reflection value AE * above 5.0 after heat treatment (HT) at 625 or 650 ° C for ten minutes. Examples 1 and 2 above clearly illustrate the comparative advantage of using hafnium niobium zirconium, as opposed to NiCr1 for IR reflective layer (a much lower reflection of AE * on the glass side is obtainable).

EXAMPLES 3 - 7

Examples 3 to 7 illustrate the unexpected finding that oxidation of NbZr reflective layer IV with hafnium 3 further decreases or AE * values, according to certain embodiments of this invention. Hafnium NbZr 3 have good HT color stability, or even lower AE * values represent a significant commercial advantage. The human eye is able to notice slight differences in appearance between two samples having an EA * value of 2.0 (the first sample not being HT and the second sample having been subjected to HT). However, the human eye is typically not able to notice slight differences in appearance between two samples having an AE * value of less than about 1.5. For this reason, the possibility of finding a human eye capable of noticing slight differences in appearance between two samples having an AE * value of 1.5 or less would be an advantage in the art. It may be possible to find this or these very low AE * values using an NbN or NbZrOx IR reflective layer, although nitrides sometimes have noticeably worse thermal and / or optical performance than metallic materials.

Surprisingly, as will be shown in Examples 3 - 7, it has been found that partial oxidation of NbZr with hafnium layers (reactively deposited with low oxygen gas flows, the main gas being argon) provides significantly low AE * values, which will be obtained without any negative impact on spectral selectivity (eg thermal behavior). It has also been found to allow higher Zr content to be stable at lower oxygen flows, and alloys with higher oxygen content are generally more stable in transmission - depending on the film design. About 10% of Zr has been found to work very well in certain exemplary embodiments of this invention. Moreover, it has been found that the best results can be obtained by the use of oxygen gas (O2) flows when cracking one or more NbZr targets of about 0.5 to 6 cm3 on CNTPs, in particular, about 1 to 4 cm3 on CNTP / kW (where kW is an electrical power unit used for crackling) - see examples below.

Examples were monolithic coated articles (all basically annealed and heat treated, although not all embodiments of the present invention need to be HT), with the stack of layers, as shown in Figure 1 again, lacking oxode overcoating. zirconium with hafnium. The Si3N3 layers 2 and 4 in all Examples 3-7 were deposited by crackling a silicon target (doped with about 10% Al) in an atmosphere including nitrogen and argon gas. NbZrOx reflective layer IV with hafnium 3 in Examples 3 - 6 was depleted by crackling a target of about 90% Nb and about 10% Zr, whereas the reflective layer IV of NbZrOx with hafnium 3 in E-examples 7, was deposited by crackling a target of about 85% Nbe and about 15% Zr. In Example 3, the following parameters were used in the crackling process in the coating deposition. Inline velocity is in centimeters per minute (inches per minute -IPM), and gas flows (Ar, OeN) are in cm3 units on CNTP:

TABLE 9: Parameters of the Example 3 Coating Process

<table> table see original document page 27 </column> </row> <table> Thus, it can be noted that the reflective layer IV in Example 3 has been oxidized. After crackling, Example 3 had the following characteristics (annealed and without monolithic HT1) (III. C, second observer) TABLE 10. Characteristics of Example 3 (without HT)

<table> table see original document page 28 </column> </row> <table>

Example 3 presented a stack of layers as shown below, shown in Table 7. The thickness and stoichiometry are listed below in Table 11. The glass substrate was clear and about 6 mm thick.

TABLE 11: Coating in Example 3

<table> table see original document page 28 </column> </row> <table>

Example 3 was then evaluated and tested for durability, showing excellent performance in usual mechanical and chemical tests such as coated and after HT. For example, the Teledyne risk test with a 500 g load produced no significant risks on either sample. A wheel abrasion test after 500 revolutions was also conducted. A one hour NaOH boiling test was also conducted, although some color variations were observed.

After crackling, Example 3 was heat treated for about 10 minutes at about 625 or 650 ° C. Table 12 below shows certain color stability characteristics of Examples 3-7. Table 12 includes the amount of oxygen used in the IR 3 reflective layer crackle in all Examples 3-7, and also includes the values of AE * Reflection on the glass side due to HT (REF 3 reflecting layers for all Examples 3 - 7 were deposited using a 30 cm 3 gaseous Ar stream at CNTP and 1 kW power).

TABLE 12: Reflection color stability on the glass side during HT

<table> table see original document page 29 </column> </row> <table>

As can be seen from Table 8, Examples 1 and 2 were characterized by satisfactory glass side reflection AE * values (the lower the better). These low values illustrate how little the optical reflection characteristics on the glass side of the coating vary with HT. This is indicative of good color stability during heat treatment. It has further been found in other examples of NbZr with Hf, similar to Examples 1 and 2, having a higher Zr content of about 10% in layer 3 that the glass side reflection AE * is about 1%. , 9a to 2.0.

In addition, Table 12 illustrates that even the lowest AE * (glass side) values can be obtained by oxidizing the diverter layer IV including NbZr with hafnium 3 to form a layer comprising NbZrOx with hafnium. This is shown by the fact that the hafnium NbZrOx examples (Examples 3 and 5 to 7) were characterized by AE * (glass side) values equal to or less than that of unoxidized Example 4, as shown in Table 12. Furthermore , Table 12 illustrates that gaseous oxygen flows in the ranges described above unexpectedly provided that better (ie, lower) AE * (ie, lower) values were obtained.

EXAMPLES 8-18

Examples 8-18 also illustrate the unexpected finding that oxidation of NbZr reflective layer IV with hafnium 3 further decreases AE * values, according to certain embodiments of this invention. The layer stack for each of Examples 8-18 was glass / Si3N4 / NbZrO / Si3N4. In Examples 8-10,14-16e18 silicon nitride overcoating was about 280 to 330 Angstrons thick, and in Examples 11 - 13 and 17, desilicon nitride overcoating (doped with Al in all cases in these examples) was about 800 Angstrons thick and the silicon nitride overcoat was about 200 to 300 Angstrons thick. The only other variations between these examples were the variations in oxygen flow, used during crackling (gaseous O2 flow in cm3 nasCNTP units) of the NbZrOx layer with hafnium 3, and the variation in the Zr content of the alloy target. of ZrNb1 and their results are presented in the table below. Clear glass substrates were used, and the AE * data below are for monolithic heat treated articles. As shown in the table below, it was surprisingly found that a ratio of oxygen to metal atoms (eg Zr and Nb) in the NbZrOx layer with hafnium 3 (ie O / (Zr + Nb)) from 0.05 to 0.15 was unexpectedly found to be particularly beneficial. Examples 8-13 used crackle targets for layer 3 having a Zr content of 5%, while Examples 14-17 used crackling targets having a 10% Zr content, and Example 18 used a target with a Zr content. of Zr of 15%. The exemplary non-limiting heat treatment used in determining AE * data for Examples 8-18 was about ten minutes at about 625 or 650Â ° C (although other types of HT may naturally be used - the values AE * will be lower for shorter periods of HT and / or lower temperatures during HT). TABLE 13: Examples 8-18

<table> table see original document page 31 </column> </row> <table>

ANOTHER EXAMPLES

For exemplary purposes only, a number of other examples representing different exemplary embodiments of this invention are set forth below. Unlike the examples provided below, the other examples given below include a hafnium zirconium oxide overcoat. Accordingly, the following other examples are similar to the exemplary embodiment shown in Figure 1. The introduction of a zirconium oxide overcoat with hafnium increased the chemical and mechanical durability of the coatings beyond the levels discussed above in together with the examples of an overfilling of zirconium oxide with hafnium. Also unlike the examples provided above, the other examples presented below include small proportions of hafnium on or in the NbZr and / or NbZrOx layers. The inclusion of a small proportion of hafnium in the NbZr and / or NbZrOx layer or layers advantageously increases the durability of the layer in which it is located, with or without the inclusion of an overcoat of zirconium oxide and / or hafnium zirconium oxide.

Various thicknesses may be used consistent with the other exemplary embodiments, described in detail below and herein. According to certain non-limiting illustrative exemplary embodiments of this invention, the exemplary thicknesses and materials for the respective layers 2 - 4 and 6 on the glass substrate 1 are as follows:

TABLE 14: Exemplary Nonlimiting Thicknesses

<table> table see original document page 32 </column> </row> <table>

Prior to heat treating (HT), such as tempering, in certain exemplary embodiments of this invention, the coated articles have color characteristics as shown in Table 15 (monolithic unit and / or IG).

TABLE 15: Color / Optical and / or other characteristics (without HT)

<table> table see original document page 32 </column> </row> <table> <table> table see original document page 33 </column> </row> <table>

Similarly as explained above, oxidation of the diverter layer IV including hafnium NbZr to form a layer comprising hafnium is advantageous in that it unexpectedly provides an even greater value of AE *. low, while also increasing durability. In certain embodiments of NbZrOx with hafnium, the coated article may have a reflection value of AE * on the glass side due to heat treatment not exceeding 4.0, particularly not exceeding 3.0, more particularly not exceeding 2.5, and especially not more than 2.0. Sometimes it will not be over 1.5 and sometimes not over 1.0.

In certain exemplary embodiments, an IR reflective layer of NbZrOx, which also includes hafnium, generally includes about 10% Zr, 80-90% Nb, and 0-10% Ox. In certain exemplary embodiments, NbZrOx, which also includes hafnium, generally includes about 10% Zr, 85-90% Nb and 0-5% Ox. The proportion of hafnium included or in the layers is small. For example, in certain exemplary embodiments, the NbZrOx reflective layer IV, which also includes hafnium, is about 0.001-1 wt% hafnium. Any intermediate range may also be used in certain exemplary embodiments. NbZrOx IR reflective layer, which also includes hafnium, can be deposited using a crackling target having a Nb / Zr ratio of about 90/10, particularly 95/5 in certain exemplary embodiments. These targets of certain exemplary embodiments include about 1 - 200 ppm hafnium, preferably 10-120 ppm, particularly 10-50 ppm hafnium, more particularly 15-45 ppm hafnium, even more particularly about 20 - 40 ppm. ppm hafnium, and especially about 30 ppm hafnium. Any intermediate range may also be used in certain exemplary embodiments.

As with one or more IR reflective layers of NbZrOx, which include hafnium, the protective overcoat layer which includes tenirconium oxide also preferably includes hafnium. However, the protective overcoat layer may include more hafnium than one or more IR reflective layers. For example, in certain exemplary embodiments, the protective overcoat layer preferably includes 0.1 - 5 wt.% Hafnium, particularly 1 - 4.5 wt.% Hafnium, and especially 1 - 4% by weight of hafnium. Any intermediate range may also be used in certain exemplary embodiments. A suitable protective overcoat layer including silver oxide and hafnium may be deposited by crackling from a crackling target which includes about 1 - 1,000 ppm, preferably 100 - 1,000 ppm hafnium, particularly 100 - 500 ppm hafnium, more particularly 200 - 400 ppm hafnium, even more particularly about 250 - 350 ppm hafnium, and especially about 300 ppm hafnium.

Other examples given below are layer cells comprising glass / dielectric / NbZrOx + Hf / dielectric / ZrOx + Hf. Dielectrics may comprise materials such as, for example, non-absorbent silicon nitride (e.g. Si3Nx or other appropriate stoichiometry). All are advantageous in that they offer superior durability and transmission over their particular applications. They are all advantageous in that they offer color matching between the annealed and heat treated articles (eg, thermally tempered). Optical and other exemplary thicknesses and properties are provided for each additional example.

ADDITIONAL EXAMPLE 1

Table 16 shows the preferred and particularly preferred exemplary thicknesses for additional example 1, while Table 17 shows the preferred and particularly preferred optical and other exemplary properties for additional example 1.

Table 16 (Non-limiting exemplary thicknesses)

<table> table see original document page 35 </column> </row> <table>

Table 17: Color / Optical and / or Other Characteristics (Without HT)

<table> table see original document page 35 </column> </row> <table> <table> table see original document page 36 </column> </row> <table>

ADDITIONAL EXAMPLE 2

Table 18 shows the preferred and particularly preferred exemplary thicknesses for additional example 2, while Table 19 shows the preferred and particularly preferred exemplary optical and other properties for additional example 2.

Table 18 (Non-limiting exemplary thicknesses)

<table> table see original document page 36 </column> </row> <table>

Table 19: Color / Optical and / or other characteristics (without HT)

<table> table see original document page 36 </column> </row> <table> <table> table see original document page 37 </column> </row> <table>

ADDITIONAL EXAMPLE 3

Table 20 shows the preferred and particularly preferred exemplary thicknesses for additional example 3, while Table 21 shows the preferred and particularly preferred exemplary optical and other properties for additional example 3.

Table 20 (Non-limiting exemplary thicknesses)

<table> table see original document page 37 </column> </row> <table> Table 21: Color / Optical and / or other characteristics (without HT)

<table> table see original document page 38 </column> </row> <table>

ADDITIONAL EXAMPLE 4

Table 22 shows the preferred and particularly preferred exemplary thicknesses for additional example 4, whereas Table 23 shows the preferred and particularly preferred exemplary optical and other properties for additional example 4. Table 22 (Non-limiting exemplary thicknesses)

<table> table see original document page 39 </column> </row> <table>

Table 23: Color / Optical and / or other characteristics (without HT)

<table> table see original document page 39 </column> </row> <table> ADDITIONAL EXAMPLE 5

Table 24 shows the preferred and particularly preferred exemplary thicknesses for additional example 5, whereas Table 25 shows the preferred and particularly preferred exemplary optical and other properties for additional example 5.

Table 24 (Non-limiting exemplary thicknesses)

<table> table see original document page 40 </column> </row> <table>

Table 25: Color / Optical and / or other characteristics (without HT)

<table> table see original document page 40 </column> </row> <table> <table> table see original document page 41 </column> </row> <table>

Certain terms are predominantly used in the glass coating technique, particularly when defining the properties and characteristics of solar control of coated glass. These thermos are used in this specification according to their well-known meanings. For example, as used in this descriptive report:

light intensity of reflected visible wavelength, ie "reflectance", defined by its percentage and stated as RxY (ie Y-value cited below in ASTM E-308-85), where "X" is " G "for the glass seam or" F "for the film side. "Glass side" (for example, "G") means, as seen from the glass substrate side opposite that on which the coating is located, while "film side" (ie "F") means, as seen next to the glass substrate on which the coating is located.

Color characteristics are measured and recorded in the descriptive report using the coordinates and the a *, b * CIE LAB scale (that is, the a * b * CIE diagram, observer at 2nd ClE-C). Other similar coordinates may be used equivalently, such as by subscript "h", to mean the conventional use of the Hunter Lab Ladder, or 10 ° observer, CIE-C, or the u * v * CIE LUV coordinates. These scales are defined in the present descriptive report in accordance with ASTM D-2244-93 "Standard Test Method for Calculation of Color Differences From Instrumented Measured Color Coordinates" 9/15/93 as expanded by StandardAST E-308-85, ASTM Annual Standards Book, vol. 06.01 "Standard Me-thod for Computing the Colors of Objects by 10 Using the CIE System", and / or as indicated in the IES LIGHTING HANDBOOK reference volume.

The terms "emittance" and "transmittance" are well understood by nature and are used in this specification in accordance with their well-known meanings. Thus, for example, the terms visible light transmittance (TY) 1 infrared radiation transmittance and ultraviolet radiation transmittance (Tuv) are known in the art. Total solar energy transmittance (TS) is then usually characterized as a weighted average of these values from 300 to 2500 nm (UV, visible and near infrared). For these transmittances, visible transmittance (TY), as indicated in this descriptive report, is characterized by the standard CIE Illuminant, 2nd observer technique at 380 - 720 nm; near infrared is 750 - 2,500 nm; ultraviolet is 300 - 380 nm; and solartotal is 300 - 2500 nm. For emission purposes, however, a particular infrared range (ie 2,500 - 40,000 nm) is employed.

Visible transmittance can be measured using known conventional techniques. For example, by using a spectrophotometer, such as Perkin Elmer Lambda 90 or Hitachi U4001, the transmission spectral curve is obtained. Visible transmission is then calculated using the ASTM 308/2244 - 93 methodology mentioned above. Fewer wavelength points may be employed than indicated, if desired. Another technique for measuring visible transmittance is to employ a spectrometer, such as a commercially available Spectrogard spectrophotometer manufactured by Pacific Scientific Corporation. This device measures and directly records visible transmittance. As indicated and measured in the present invention, visible transmittance (i.e. the Y value in the CIE triple stimulus system, ASTM E-308-85) uses the 2nd III observer. Ç.

Another term used in this descriptive report is "sheet strength". Sheet strength (Rs) is a well-known technical term and is used in this specification in accordance with its well-known meaning. Enter this descriptive report in ohms per square units. Generally speaking, the term refers to the resistance in ohms for any square of a layered system in a glass substrate to an electrical current passed through the layer system. Sheet resistance is an indication of how well the layer or layer system is reflecting infrared energy, and is thus often used in conjunction with the emittance as a measure of this characteristic. "Sheet resistance" may, for example, be conveniently measured by use of a 4-point probe ohmmeter, such as a distributable 4-point resistivity probe, with a head from Magne-tron Instruments Corp., Model M- 800, produced by Signatone Corp. from Santa Clara, California.

The terms "heat treatment" and "heat treating" as used in this specification mean heating the article to a temperature sufficient to allow heat quenching, bending and / or thermal reinforcement of the article including glass. This definition includes, for example, heating a coated article to a temperature of at least about 580 or 600 ° C, for a period sufficient to provide for the heating and / or thermal reinforcement. In some exemplary cases, HT may be for at least about 4 or 5 minutes.

While the invention has been described in conjunction with what is currently considered to be the preferred and most practical embodiment, it is to be understood that the invention is not limited to the described embodiment, but rather is intended to cover various modifications and provisions. equivalents included within the spirit and scope of the appended claims.

Claims (30)

1. A coated article including a substrate supported layer system, the layer system comprising: a first dielectric layer, an infrared (IR) reflector layer comprising a niobium zirconium oxide (NbZr) 1 provided on the substrate alone; at least the first dielectric layer, said reflective layer IV further comprising hafnium, a second dielectric layer provided on the substrate over at least the reflective layer IV; In an overcoat layer comprising tenirconium oxide over at least the second dielectric layer, said overcoat layer further comprises hafnium, wherein the reflective layer IV comprises about 0.001-1% by weight of hafnium. The coated article of claim 1, wherein the overcoat layer comprises from about 0.001 to 5% by weight of hafnium, particularly from about 0.003 to 4.5% by weight of hafnium, and especially from 0.003 to 1.5% by weight of hafnium. A coated article according to claim 1, wherein the overcoat layer comprises hafnium having more hafnium than reflective layer IV. The coated article of claim 3, wherein the overcoat layer is at least 10 times more hafn than the reflective layer IV. The coated article of claim 1, wherein the coated article has no metallic infrared (IR) radiation reflective layer comprising Ag or Au. Coated article according to claim 1, wherein the reflective layer IV is interspersed between the contacts of both first and second dielectric layers. A coated article according to claim 1, wherein both first and second dielectric layers comprise a nitride and / or a metal oxide. A coated article according to claim 1, wherein both the first and second dielectric layers comprise silicon nitride. A coated article according to claim 8, wherein both the first and second dielectric layers comprise non-absorbent silicon nitride. A coated article according to claim 1, wherein a contact or nucleation layer is provided between the reflecting layer and the first dielectric layer. Coated article according to claim 1, wherein the reflective layer IV comprises from 0.05 to 10% oxygen. The coated article of claim 1, wherein the reflective layer IV comprises (Nb + Zr) xOy, wherein the oxygen ratio y / x to Nb-Zr ratio is 0.03 to 0.20. The coated article of claim 1, wherein the zirconium to niobium azazion (Zr / Nb) is about 0.004 to 0.500. A coated article according to claim 1, wherein the coated article is heat treated and has an AE * value of no more than 2.5 after and / or due to heat treatment. A coated article according to claim 1, wherein the coated article comprises an IG window unit, a monolithic window or a laminated window. The coated article of claim 1, wherein: the first dielectric layer has a thickness of 70-110 Å, the reflective layer IV has a thickness of 200 - 305 Å, the second dielectric layer has a thickness of 80-110 Å. 120 Å; and the overcoat layer has a thickness of 40 - 60 Å. The coated article of claim 1, wherein: the first dielectric layer has a thickness of 180 - 280 Å, the reflective layer IV has a thickness of 135 - 205 Å, the second dielectric layer has a thickness of 230 - 280 Å. 350Á; and the overcoat layer has a thickness of 40 - 60 Å. A coated article according to claim 1, wherein: the first dielectric layer has a thickness of 180 - 270 Å, the reflective layer IV has a thickness of 60 - 95 Å, the second dielectric layer has a thickness of 220 - 270 Å. 330A; and the overcoat layer has a thickness of 40 - 60 Å. The coated article of claim 1, wherein: the first dielectric layer has a thickness of 290 - 440 Å, the reflective layer IV has a thickness of 105 - 160 Å, the second dielectric layer has a thickness of 360 - 440 Å. 545Á; and the overcoat layer has a thickness of 40 - 60 Å. The coated article according to claim 1, wherein: the first dielectric layer has a thickness of 125 - 195 Å, the reflective layer IV has a thickness of 30 - 47 Å, the second dielectric layer has a thickness of 170 - 195 Å. 255Á; and the overcoat layer has a thickness of 40 - 60A. A process for producing a coated article including a substrate supported layer system, the process comprising: cracking a first dielectric layer on the substrate; cracking a reflective layer of infrared (IV) radiation comprising an oxide niobium and zirconium (NbZr) and hafnium, reflective layer IV further comprising hafnium, depositing by cracking a second dielectric layer over at least reflective layer IV; and crepitating an overcoat layer comprising zirconium oxide over at least the second dielectric layer, the overcoat layer further comprising hafnium, wherein the reflective layer IV comprises about 0.001 - 1% by weight of hafnium, and the The overcoat comprises about 0.001-5% by weight of hafnium. The process of claim 21, wherein the overcoat layer comprises from about 0.003 to 4.5% by weight of hafnium. The process of claim 21, wherein both first and second dielectric layers comprise silicon nitride. The process of claim 21, wherein the IR reflective layer comprises from 0.05 to 10% oxygen. The process of claim 21, wherein the reflective layer IV is crackled deposited using a crackling target, including about 1 - 200 ppm hafnium, particularly about 10 to 120 ppm hafnium. The process of claim 21, wherein the overcoat layer is crackled deposited using a decrepit target, including about 1 - 200 ppm hafnium, particularly about 10 to 120 ppm hafnium. The process according to claim 21, wherein: the first dielectric layer has a thickness of 70 - 440 Å, the reflective layer IV has a thickness of 30 - 305 Å, the second dielectric layer has a thickness of 80 - 545 Å. THE; and the overcoat layer has a thickness of 40 - 60 Å. A process according to claim 21, wherein the coated garment is heat treated and has an AE * (reflection on the glass side) value of not more than 2.5 after and / or due to heat treatment. 29. Coated article including a substrate supported layer system, the layer system comprising: a first dielectric layer, an infrared (IR) reflective layer comprising a niobium zirconium oxide (NbZr) provided on the substrate alone; at least the first dielectric layer, said reflective layer IV further comprising hafnium; a second dielectric layer provided on the substrate over at least reflective layer IV, wherein the reflective layer IV comprises about 0.001 - 1 wt.% hafnium. A coated article including a substrate supported layer system, the layer system comprising: a first dielectric layer, an infrared (IR) reflective layer, a second dielectric layer provided on the substrate, over at least the IR reflective layer; In an overcoat layer comprising tenirconium oxide, over at least the second dielectric layer, said overcoat layer further comprises hafnium, wherein the overcoat layer comprises about 0.001-5% by weight of hafnium.