CN114430732B - Low-E matchable coated articles with absorbent films and corresponding methods - Google Patents

Abstract

The present invention provides a low E coating having good color stability (low Δ Ε value) upon Heat Treatment (HT). The thermal stability can be improved by: by providing an as-deposited crystalline or substantially crystalline layer of or comprising zinc oxide doped with at least one dopant (e.g., sn) immediately beneath an Infrared (IR) reflecting layer of or comprising silver; and/or by providing at least one dielectric layer with or comprising zirconium oxide. These have the effect of significantly improving the thermal stability of the coating (i.e. reducing the Δ Ε value). The absorber film can be designed to adjust visible light transmittance and provide desired coloration while maintaining durability and/or thermal stability. A dielectric layer (e.g., with or comprising Zr oxide) may be sputter deposited to have a monoclinic phase to improve thermal stability.

Description

Low-E matchable coated articles with absorbent films and corresponding methods

This application claims the benefit of U.S. application serial No. 16/596,632, filed on 8.10.2019, which is a continuation-in-part application (CIP) of U.S. application serial No. 16/355,966, filed on 18.3.18.2019, which is a continuation-in-part application (CIP) of U.S. application No. 16/220,037, filed on 14.12.2018, which is a continuation-in-part application of U.S. application serial No. 16/035,810 (now U.S. patent No. 10,031,215), filed on 16.7.16.2018, the disclosures of which are hereby incorporated by reference in their entirety.

The present invention relates to low E coated articles having substantially the same color characteristics as observed by the naked eye both before and after heat treatment (e.g., thermal tempering), and corresponding methods. In certain exemplary embodiments, such articles may incorporate two or more of the following: (1) desirable visible light transmission characteristics, (2) good durability before and/or after heat treatment, (3) low Δ Ε values indicating color stability upon Heat Treatment (HT), and/or (4) absorbing films designed to adjust visible light transmission and provide desirable coloration to the coated article while maintaining durability and/or heat stability. Such coated articles may be used monolithically in windows, insulated Glass (IG) window units, laminated window units, vehicle windshields, and/or other vehicle or architectural or residential window applications.

Background

Substantial matching (before and after heat treatment) is required. Glass substrates are typically mass produced and cut to size to meet the needs of a particular situation, such as a new multi-window office building, window requirements, etc. In such applications, it is often desirable that some of the windows and/or doors be heat treated (i.e., tempered, heat strengthened, or heat bent), while others do not. Office buildings typically employ IG units and/or laminates for safety and/or thermal control. For architectural and/or aesthetic purposes, it is desirable that the Heat Treated (HT) cells and/or laminates substantially match their non-heat treated counterparts (e.g., in terms of color, reflectance, transmission, etc., at least on the side viewed from outside the building).

Commonly owned U.S. patent 5,688,585 discloses a solar control coated article comprising: glass/Si ₃ N ₄ /NiCr/Si ₃ N ₄ . It is an object of the' 585 patent to provide a sputter-coated layer system that is color-matched to its non-heat treated counterpart after Heat Treatment (HT). While the coating systems of the' 585 patent are excellent for their intended purposes, they have certain disadvantages. In particular, they tend to have relatively high emissivity and/or sheet resistance values (e.g., because the silver (Ag) layer is not disclosed in the' 585 patent).

In prior art systems other than those of the' 585 patent, matching can be achieved between two different layer systems, one heat treated and the other not. The necessity of developing and using two different layer systems to achieve matching creates undesirable additional manufacturing costs and inventory requirements.

Us patents 6,014,872 and 5,800,933 (see example B) disclose a heat treatable low E layer system comprising: glass/TiO ₂ /Si ₃ N ₄ /NiCr/Ag/NiCr/Si ₃ N ₄ . Unfortunately, when heat treated, the low E layer system is not substantially color-matchable to its non-heat treated counterpart (as viewed from the glass side). This is because the low E layer system had a Δ E (glass side) value greater than 4.1 (i.e., Δ a for example B) _G 1.49, Δ b × G3.81, and Δ L (glass side) was not measured; using equation (1) below, the Δ E of the glass side must necessarily be greater than 4.1 and possibly much higher than it).

Us patent 5,563,734 discloses a low E coating system comprising: substrate/TiO ₂ /NiCrNx/Ag/NiCrN _x /Si ₃ N ₄ . Unfortunately, it has been found that when NiCrN is formed _x When high nitrogen (N) flow rates are used for the layers (see high N flow rate of 143sccm in table 1 of the' 734 patent; conversion to about 22 sccm/kW), the resulting coated articles are color unstable upon thermal treatment (i.e., they tend to have high Δ E (glass side) values greater than 6.0). In other words, if subjected to HT, the low E layer system of the' 734 patent will not substantially color match its non-heat treated counterpart (as viewed from the glass side).

Furthermore, it is sometimes desirable for the coated article to have desirable visible light transmission characteristics and/or good (mechanical and/or chemical) durability. Unfortunately, certain known steps taken to adjust or improve visible light transmission characteristics and/or pre-HT durability tend to reduce post-HT durability and thermal stability. Thus, it is often difficult to obtain the desired combination of visible light transmittance values, thermal stability of the color, and good durability.

In view of the above, it will be apparent to those skilled in the art that there exists a need for a low E coating or layer system that substantially matches its non-heat treated counterpart in color and/or reflectance (as viewed by the human eye) after HT. In other words, there is a need in the art for low E-matching coatings or layered systems. There is also a need in the art for a heat treatable system that may incorporate one or more of the following: (1) desirable visible light transmission characteristics (e.g., about 30% -75% as measured on a single sheet, and/or 30% -70% as measured on an IG unit), (2) good durability before and/or after heat treatment, (3) low Δ Ε value indicating color stability upon Heat Treatment (HT), and/or (4) absorbing films designed to adjust visible light transmission and provide desired coloration to the coated article while maintaining durability and/or thermal stability.

It is an object of the present invention to meet one or more of the above listed needs, and/or other needs that will become more apparent to the skilled person once the following disclosure is given.

Disclosure of Invention

An exemplary object of the present invention is to provide a low E coating or layer system having good color stability (low Δ Ε value) upon Heat Treatment (HT). It is another exemplary object of the present invention to provide a low E matable coating or layered system. In certain exemplary embodiments, another exemplary object is to provide an absorbing film in a low E coating designed to adjust visible light transmittance and provide desired coloration to the coated article while maintaining durability and/or thermal stability.

Exemplary embodiments of the present invention are directed to low E coated articles having substantially the same color characteristics as observed by the naked eye both before and after heat treatment (e.g., thermal tempering), and corresponding methods. In certain exemplary embodiments, such articles may incorporate two or more of the following: (1) desirable visible light transmission characteristics, (2) good durability before and/or after heat treatment, (3) low Δ Ε -value indicating color stability upon Heat Treatment (HT), and/or (4) an absorber film designed to adjust visible light transmission and provide a desired coloration to the coated article while maintaining durability and/or heat stability.

In certain exemplary embodiments, the optional absorber film may be a multilayer absorber film comprising a first layer having or comprising silver (Ag), and a second layer having or comprising partially or fully oxidizable NiCr (NiCrO) _x ) The second layer of (2). Thus, in certain exemplary embodiments, such a multilayer absorber film may be made of Ag/NiCrO _x Is formed by the layer sequence of (a). The layer sequence may be repeated in some illustrative examples. The silver-based layer in the absorbing film is preferably sufficiently thin so that its primary function is to absorb visible light and provide the desired coloration (as opposed to being much thicker and acting primarily as an IR reflecting layer). NiCr or NiCrO _x Is disposed over and in contact with the silver of the absorber film to protect the silver and also to aid in absorption.

In certain exemplary embodiments of the invention, a single layer of NiCr (or other suitable material) may also be used as the absorber film in the low E coating. However, it has been surprisingly found that the use of silver in an absorber film (single or multi-layer absorber film) provides several unexpected advantages over a single layer of NiCr as an absorber. First, it has been found that a single layer of NiCr as an absorber tends to cause yellowish coloration in certain low E coated articles, which may be undesirable in certain circumstances. In contrast, it has been surprisingly found that the use of silver in the absorbing film tends to avoid such yellowish coloration and/or instead provides a more desirable neutral coloration of the resulting coated article. Thus, it has been found that the use of silver in the absorbing film provides improved optical properties. Second, the use of a single layer of NiCr as an absorber often also involves providing silicon nitride based layers on both sides of the NiCr so as to sandwich the NiCr directly therebetween and in contact therewith. It has been found that providing silicon nitride at certain locations in the coating stack may result in impaired thermal stability at HT. In contrast, it has surprisingly been found that when silver is used in the absorber film, a pair of directly adjacent silicon nitride layers is not required, so that the thermal stability at HT can be improved. Thus, it has been found that the use of silver in the absorbing film provides improved thermal stability, including lower Δ Ε values, and thus improved matching between HT and non-HT forms of the same coating. The use of silver in the absorber film may also provide improved manufacturability in certain circumstances.

In certain exemplary embodiments, surprisingly and unexpectedly, it has been found that disposing an as-deposited crystalline or substantially crystalline (e.g., at least 50% crystalline, more preferably at least 60% crystalline) layer having or comprising zinc oxide doped with at least one dopant (e.g., sn) directly beneath an Infrared (IR) reflecting layer having or comprising silver in a low E coating has the effect of significantly improving the thermal stability (i.e., lowering the Δ Ε value) of the coating. In various embodiments of the present invention, one or more such crystalline or substantially crystalline (e.g., at least 50% crystalline, more preferably at least 60% crystalline) layers may be disposed below one or more corresponding IR reflecting layers comprising silver. Thus, in various embodiments of the invention, a crystalline or substantially crystalline layer having or comprising zinc oxide doped with at least one dopant (e.g., sn) directly beneath an Infrared (IR) reflective layer having or comprising silver may be used for a single-silver low E coating, a double-silver low E coating, or a triple-silver low E coating. In certain exemplary embodiments, the crystalline or substantially crystalline layer having or comprising zinc oxide is doped with about 1% -30% sn, more preferably about 1% -20% sn, most preferably about 5% -15% sn, with one example being about 10% sn (in wt%). The Sn-doped zinc oxide is in a as-deposited crystalline phase or substantially crystalline phase (as opposed to amorphous or nanocrystalline) from at least one sputtering target having or comprising Zn and Sn, such as via a sputter deposition technique. The combination of the as-deposited crystalline phase doped zinc oxide based layer with the layer between silver and glass allows the coated article to achieve improved thermal stability (reduced Δ Ε value) upon optional HT. It is believed that the combination of the doped zinc oxide based layer of the as-deposited crystalline phase (e.g., at least 50% crystalline, more preferably at least 60% crystalline) with the layer between the IR reflecting layer and the glass allows the silver of the IR reflecting layer to have an improved crystal structure with texture but with some randomly oriented grains such that its refractive index (n) changes less at optional HT, allowing for improved thermal stability.

In certain exemplary embodiments, it has also been surprisingly and unexpectedly discovered that a substrate having or including silicon oxide, zirconium oxynitride, zirconium oxide and/or zirconium oxynitride (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) The dielectric layer of (a) also provides improved thermal stability of the coated article and thus a reduction of Δ Ε value upon thermal treatment (HT), such as thermal tempering. In certain exemplary embodiments, silicon oxide, zirconium silicon oxide, and/or zirconium silicon oxynitride (e.g., siZrO) may be provided with or comprise _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) At least one dielectric layer of (a): (i) In a bottom dielectric portion of the coating under all of the silver-based IR reflecting layers, and/or (ii) in an intermediate dielectric portion of the coating between a pair of silver-based IR reflecting layers. For example, in certain exemplary embodiments of the invention, a dielectric layer having or comprising silicon oxide, zirconium oxide and/or zirconium oxynitride can be disposed directly beneath and in contact with the lowermost doped zinc oxide-based layer and/or between a pair of zinc oxide-containing layers in the middle dielectric portion of the low E coating.

In various exemplary embodiments of the present invention, a dielectric layer having or comprising silicon oxide, zirconium silicon oxide, and/or zirconium silicon oxynitride may or may not be disposed immediately below an Infrared (IR) reflective layer in combination with an as-deposited crystalline or substantially crystalline (e.g., at least 50% crystalline, more preferably at least 60% crystalline) layer having or comprising zinc oxide doped with at least one dopant (e.g., sn).

In certain exemplary embodiments, it has been surprising and unexpectedIt has been found that the initial sputter deposition has or includes zirconia (e.g., zrO) ₂ ) Zirconium oxynitride, zirconium silicon oxide and/or zirconium silicon oxynitride (e.g. SiZrO _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) The dielectric layer(s) of (a) to (b) to comprise a monoclinic crystalline phase crystal structure is advantageous as it results in a coated article having an improved thermal stability (lower Δ Ε value) and/or a reduced visible light transmission (e.g. T) upon Heat Treatment (HT) _vis Or TY) change. In certain exemplary embodiments, the dielectric layer (e.g., zrO) may be achieved by using a very high oxygen flow rate for the layer during sputter deposition of the layer, and using a metal sputtering target (e.g., zr target) ₂ ) Monoclinic phase of (a). For example, when sputtering a deposited layer 2 and/or 2 "to form a layer having a monoclinic crystalline phase, the sputtering process for that layer may achieve an oxygen flow of at least 5ml/kW, more preferably at least 6ml/kW, more preferably at least 8ml/kW, most preferably at least 10ml/kW, where ml represents the total oxygen flow in the chamber and kW represents the power to the target. It should be noted that such high oxygen flow rates, which are desirable in certain exemplary embodiments of this situation, are counterintuitive and are generally undesirable because they reduce the deposition rate and thus create increased time and expense in manufacturing the coated article. While high oxygen flow rates are used in certain exemplary embodiments to achieve the monoclinic phase associated with the metal target when certain types of sputtering apparatus are used, the present invention is not so limited, as it has been found that monoclinic phases can also be achieved with low or lower oxygen flow rates for certain types of sputtering apparatus.

It has been found that a significant partial or complete phase transition of the layer from a monoclinic to a tetragonal or cubic crystal structure at HT and the corresponding density change tend to compensate for said change of the crystal structure of the silver layer at HT, which seems to result in a coated article with improved thermal stability (lower Δ Ε value) and/or reduced visible light transmission (T) at HT (T · T of the coated article) _vis Or TY) change. It has been surprisingly found that the initial sputter deposition has or includes zirconium oxide, zirconium oxynitride, zirconium silicon oxide and/or zirconium silicon oxynitride (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) Is advantageous in that it results in at least about 0.25g/cm at HT ³ More preferably at least about 0.30g/cm ³ And most preferably at least about 0.35g/cm ³ (e.g., about 5.7 g/cm) ³ To about 6.1g/cm ³ ) Which in turn compensates for the change in the crystalline structure of the silver layer at said HT, resulting in a coated article having improved thermal stability (lower Δ Ε value) and/or reduced visible light transmission (e.g. T) at Heat Treatment (HT) _vis Or TY) change. In certain exemplary embodiments, this results in coated articles visible light transmittance (T) due to HT _vis Or TY) a reduced variation of not more than 1.2%, more preferably not more than 1.0% and most preferably not more than 0.5%, and/or a reduced value of Δ Ε.

It has also been surprisingly and unexpectedly found that a silicon nitride based layer, which is not disposed directly beneath and in contact with the lowermost doped zinc oxide based layer, between the glass substrate and the lowermost silver based layer, in combination with the as-deposited crystalline phase doped zinc oxide based layer, allows for improved thermal stability (reduced Δ Ε value) upon thermal treatment. It has also been surprisingly and unexpectedly found that not providing a silicon nitride based layer in the middle section of the stack between two silver based IR reflecting layers allows to achieve an improved thermal stability upon thermal treatment (lower Δ Ε values).

In certain exemplary embodiments of monolithic measurements and/or measurements with an IG unit having a dual pane, the coated article is configured to achieve one or more of the following: (ii) a transmission Δ Ε value (in the case of measurement of transmission optics) at a temperature of about 650 ℃ at HT8 minutes, 12 minutes, and/or 16 minutes of not more than 3.0 (more preferably not more than 2.8, and most preferably not more than 2.5 or 2.3), (ii) a glass side reflection Δ Ε value (in the case of measurement of glass side reflection optics) at a temperature of about 650 ℃ at HT8 minutes, 12 minutes, and/or 16 minutes of not more than 3.0 (more preferably not more than 2.5, more preferably not more than 2.0, and most preferably not more than 1.5, not more than 1.0, and/or not more than 0.6), and/or (iii) at a temperature of about 650 ℃ at HT8 minutes, 12 minutesThe value of the film side reflection Δ Ε at clock, 16 minutes, and/or 20 minutes (in the case of measurement of the film side reflection optics) is no greater than 3.5 (more preferably no greater than 3.0, and most preferably no greater than 2.0, or no greater than 1.5 or 1.3). Of course, in commercial practice, the baking time may be used for different/other time periods, and these time periods are used for reference purposes. In certain exemplary embodiments of the monolithic measurement, the coated article is configured to have a visible light transmittance (T) of at least about 30%, more preferably at least about 40%, and most preferably at least about 50% (e.g., about 45-60%) before or after any optional HT _vis Or Y). The coated articles herein can have, for example, a visible light transmission measured monolithically of about 30% to 75%, and/or a visible light transmission measured as an IG unit of 30% to 70%. Wherein the thickness, composition and/or number of layers of the absorber can be adjusted to adjust the visible light transmission. In certain exemplary embodiments of the monolithic measurement, the coated article is configured to have a glass side visible light reflection (R) of not greater than about 20% of the monolithic measurement before or after any optional HT _g Y or RGY).

In an exemplary embodiment of the present invention, there is provided a coated article comprising a coating on a glass substrate, wherein the coating comprises: a crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% Sn (wt%) disposed on the glass substrate; a first Infrared (IR) reflecting layer comprising silver, said first IR reflecting layer being located on said glass substrate and directly above and in contact with said first crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% Sn; wherein no silicon nitride based layer is directly below and in contact with the first crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% Sn; at least one dielectric layer having a monoclinic phase and comprising zirconium oxide; wherein the at least one dielectric layer having a monoclinic phase and comprising zirconium oxide is located: (1) At least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% sn (wt%), and/or (2) at least the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating; optionally an absorber film comprising a layer comprising silver, wherein the ratio of the physical thickness of the first IR reflecting layer comprising silver of the absorber film to the physical thickness of the layer comprising silver is at least 5:1 (more preferably at least 8:1, even more preferably at least 10, and most preferably at least 15; and wherein the coated article is configured to have at least two of the following measured monolithically: (ii) a transmission Δ Ε value of not greater than 3.0 resulting from 12 minutes of a reference heat treatment at a temperature of about 650 ℃, (ii) a glass side reflection Δ Ε value of not greater than 3.0 resulting from 12 minutes of the reference heat treatment at a temperature of about 650 ℃, and (iii) a film side reflection Δ Ε value of not greater than 3.5 resulting from 12 minutes of the reference heat treatment at a temperature of about 650 ℃.

Such coated articles may be used in a single sheet of window, an Insulated Glass (IG) window unit (e.g., on surface #2 or surface #3 in IG window unit applications), a laminated window unit, a vehicle windshield, and/or other vehicle or architectural or residential window applications.

The invention will now be described with respect to certain embodiments thereof as illustrated in the following drawings, in which:

drawings

Fig. 1 (a), fig. 1 (b), fig. 1 (c), fig. 1 (d), fig. 1 (e), fig. 1 (f), fig. 1 (g), fig. 1 (h), and fig. 1 (i) are cross-sectional views of coated articles according to exemplary embodiments of the present invention.

Fig. 2 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 1 on a 6mm thick glass substrate, wherein the low E coating is generally illustrated by fig. 1 (a).

Fig. 3 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 2 on a 6mm thick glass substrate, wherein the low E coating is generally illustrated by fig. 1 (a).

Fig. 4 is a graph showing the optical characteristics of example 1: as-coated before heat treatment (annealed), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) in the leftmost data column and after heat treatment at 650 ℃ for 24 minutes (HTXXX) in the rightmost data column.

Fig. 5 is a graph showing the optical characteristics of example 2: as-coated before heat treatment (annealed), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) in the leftmost data column and after heat treatment at 650 ℃ for 24 minutes (HTXXX) in the rightmost data column.

Fig. 6 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 3 on a 3.1mm thick glass substrate, wherein the low E coating is generally shown by fig. 1 (a).

Fig. 7 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 4 on a 3.1mm thick glass substrate, wherein the low E coating is generally shown by fig. 1 (a).

FIG. 8 is a graph showing optical characteristics of examples 3 to 4: the left-most data column is in the as-coated state before heat treatment (annealed), after heat treatment at 650 ℃ for 8 minutes (FIT), after HT 12 minutes at 650 ℃ for HTX, and after heat treatment at 650 ℃ for 20 minutes in the right-most data column (HTXXX).

Fig. 9 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 5 on a 6mm thick glass substrate, wherein the low E coating is generally illustrated by fig. 1 (a).

Fig. 10 is a graph showing the optical characteristics of example 5: as-coated before heat treatment (annealed), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) in the leftmost data column and after heat treatment at 650 ℃ for 24 minutes (HTXXX) in the rightmost data column.

Fig. 11 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 6 on a 6mm thick glass substrate, wherein the low E coating is generally shown by fig. 1 (a).

Fig. 12 is a graph showing the optical characteristics of example 6: as-coated before heat treatment (annealed), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) in the leftmost data column and after heat treatment at 650 ℃ for 24 minutes (HTXXX) in the rightmost data column.

Fig. 13 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 7 on a 6mm thick glass substrate, wherein the low E coating is generally illustrated by fig. 1 (a).

Fig. 14 is a graph showing the optical characteristics of example 7: as-coated before heat treatment (annealed), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) in the leftmost data column and after heat treatment at 650 ℃ for 24 minutes (HTXXX) in the rightmost data column.

Fig. 15 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 8 on a 6mm thick glass substrate, wherein the low E coating is generally shown by fig. 1 (a).

Fig. 16 is a graph of wavelength (nm) versus refractive index (n) illustrating the change in refractive index of the silver layer of example 8 from the coated state (AC) to the Heat Treated (HT) state.

Fig. 17 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 9 on a 6mm thick glass substrate, wherein the low E coating is generally shown by fig. 1 (a).

Fig. 18 is a graph showing the optical characteristics of example 9: as-coated before heat treatment (annealed) in the leftmost data column, after heat treatment at 650 ℃ for 12 minutes (HT) and after HT at 650 ℃ for 16 minutes (HTX) in the rightmost data column.

Fig. 19 is a cross-sectional view of a first comparative example coated article.

FIG. 20 is a cross-sectional view of a coated article according to an embodiment of the invention, showing the coatings of examples 1-10.

Fig. 21 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 10 on a 3.1mm thick glass substrate, wherein the low E coating is generally illustrated by fig. 1 (a) and 10.

FIG. 22 is an XRD Lin (cps) versus 2-theta-scale showing a relatively small 66% change in Ag (111) peak height due to HT for example 10.

FIG. 23 is a XRD Lin (cps) versus 2-theta-scale showing a relatively large 166% change in Ag (111) peak height due to HT for the first Comparative Example (CE).

Fig. 24 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 11 on a 6mm thick glass substrate, wherein the low E coating is generally shown by fig. 1 (b).

Fig. 25 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 12 on a 6mm thick glass substrate, wherein the low E coating is generally shown by fig. 1 (b).

Fig. 26 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 13 on a 6mm thick glass substrate, wherein the low E coating is generally shown by fig. 1 (b).

FIG. 27 is a graph showing optical characteristics of examples 11 to 13: as-coated before heat treatment (annealed), after heat treatment at 650 ℃ for 12 minutes (HT), after HT at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX) in the respective leftmost data columns.

Fig. 28 is a graph showing sputter deposition conditions for sputter depositing the low E coating of example 14 on a 6mm thick glass substrate, wherein the low E coating is generally shown by fig. 1 (b).

Fig. 29 is a graph showing the optical characteristics of example 14: as-coated before heat treatment (annealed), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) in the leftmost data column and after heat treatment at 650 ℃ for 24 minutes (HTXXX) in the rightmost data column.

FIG. 30 is a graph showing sputter deposition conditions for sputter depositing the low E coatings of examples 15 and 16 on a 6mm thick glass substrate with ZrO for these examples ₂ The low E coating of the bottommost dielectric layer of (a) is generally illustrated by fig. 1 (b).

Fig. 31 is a graph showing optical characteristics of example 15 and example 16: the coated state before heat treatment (annealed) in the leftmost data column, after heat treatment at 650 ℃ for 12 minutes (FIT) and after HT 16 minutes at 650 ℃ in the rightmost data column (HTX).

FIG. 32 is a sputter deposition condition showing sputter deposition of the low E coatings of example 17 and example 18 on a 6mm thick glass substrateWherein the SiO doped with about 8% Al (wt%) of these examples ₂ The low E coating of the bottommost dielectric layer of (a) is generally illustrated by fig. 1 (b).

Fig. 33 is a graph showing optical characteristics of example 17 and example 18: as-coated before heat treatment (annealed) in the leftmost data column, after heat treatment at 650 ℃ for 12 minutes (HT) and after HT at 650 ℃ for 16 minutes (HTX) in the rightmost data column.

Fig. 34 is a graph showing sputter deposition conditions for sputter depositing the low E coating of comparative example 2 (CE 2) on a 6mm thick glass substrate.

Fig. 35 is a graph showing the optical characteristics of comparative example 2 (CE 2): the leftmost data column is as-coated (annealed) before heat treatment, after heat treatment at 650 ℃ for 12 minutes (HT), after HT 16 minutes at 650 ℃ for 16 minutes (HTX) and the rightmost data column is after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 36 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 19 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (b), and the optical properties of example 19 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 37 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 20 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (E), and the optical properties of example 20 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 38 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 21 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (E), and the optical properties of example 21 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 39 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 22 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (d), and the optical properties of example 22 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 40 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 23 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (f), and the optical properties of example 23 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 41 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 24 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (f), and the optical properties of example 24 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 42 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 25 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (g), and the optical properties of example 25 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 43 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 26 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (h), and the optical properties of example 26 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 44 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 27 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (b), and the optical properties of example 27 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 45 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 28 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (E), and the optical properties of example 28 are shown at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 46 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 29 on a 6mm thick glass substrate, where the low E coating is generally shown by fig. 1 (h), except that no layer 2 "is provided in example 29, and the optical properties of example 29 are shown at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT), after heat treatment at 650 ℃ for 16 minutes (HTX) and after heat treatment at 650 ℃ for 24 minutes (HTXXX).

Fig. 47 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 30 on a 6mm thick transparent glass substrate, where the low E coating is generally shown by fig. 1 (i), and the optical properties of example 30 measured monolithically at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT) and after HT at 650 ℃ for 16 minutes (HTX).

Fig. 48 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 31 on a 6mm thick transparent glass substrate, where the low E coating is generally shown by fig. 1 (i), and the monolithically measured optical properties of example 31 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT) and after HT at 650 ℃ for 16 minutes (HTX).

Fig. 49 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 32 on a 6mm thick transparent glass substrate, where the low E coating is generally shown by fig. 1 (i), and the monolithically measured optical properties of example 32 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT) and after HT at 650 ℃ for 16 minutes (HTX).

Fig. 50 shows sputter deposition conditions at the top for sputter depositing the low E coating of example 33 on a 6mm thick transparent glass substrate, where the low E coating is generally shown by fig. 1 (i), and the monolithically measured optical properties of example 33 at the bottom: as coated before heat treatment (annealed; AC), after heat treatment at 650 ℃ for 12 minutes (HT) and after HT at 650 ℃ for 16 minutes (HTX).

FIG. 51 shows the use of a metallic Zr target (top) and ceramic ZrO before and after HT _x Target (lower panel) sputter deposited ZrO ₂ A graph of the layer and shows that the layer comprises a monoclinic phase when a metal target is used (see m-ZrO) ₂ Peaks at (c) while the layer does not include a monoclinic phase when a ceramic target is used in this particular case.

FIG. 52 is a cross-sectional view of a coated article according to an exemplary embodiment of the present invention, similar in some respects to FIG. 1 (i), including a laminated stack of examples 34-42 and Comparative Examples (CE) 43-47.

FIG. 53 shows the optical data of examples 34-42: examples 34-42 had coating stacks as shown in FIGS. 1 (i) and 52, with monoclinic ZrO deposited from a metal target, in the as-coated (AC; annealed) state prior to heat treatment in the leftmost data column for each example, and after heat treatment at 650 deg.C for 12 minutes (HT) in the right data column for each example ₂ Layer, and layer thicknesses for examples 34-42 are shown in FIG. 55; wherein sample 7982 is example 34, sample 8077 is example 35, sample 8085 is example 36, sample 8090 is example 37, sample 8091 is example 38, sample 8097 is example 39, sample 8186 is example 40, sample 8187 is example 41, andand sample 8202 was example 42.

FIG. 54 shows the optical data of Comparative Examples (CE) 43 to 47: examples 43-47 had coating stacks as shown in FIGS. 1 (i) and 52, with non-monoclinic ZrO deposited with a ceramic target, in the as-coated (AC; annealed) before heat treatment in the leftmost data column of each example, and after heat treatment at 650 deg.C for 12 minutes (HT) in the right data column of each example ₂ Layer, and layer thicknesses for examples 43-47 are shown in FIG. 56; where sample 8392 is CE 43, sample 8394 is CE 44, sample 8395 is CE 45, sample 8396 is CE 46, and sample 8397 is CE 47.

FIG. 55 is a graph showing a ZrO having monoclinic crystal ₂ Graph of deposition process conditions and layer thicknesses for example 37 of layers, where the total oxygen flow (ml) during the sputtering process for each layer was made of O ₂ Set value, O ₂ Regulation and O ₂ The sum of the offsets represents, zrO ₂ The high oxygen flow during sputter deposition of the layer helps to provide the ZrO of example 37 ₂ Monoclinic phase of the layer (monoclinic examples 34-36 and 38-42 have similar process conditions).

FIG. 56 is a view showing a ZrO having a non-monoclinic crystal ₂ Graph of deposition process conditions and layer thickness for comparative example of layers (CE) 44, where the total oxygen flow (ml) during the sputtering process of each layer was determined from O ₂ Set value, O ₂ Regulation and O ₂ Sum of offset representation, zrO ₂ The low oxygen flow during sputter deposition of the layer together with the ceramic target helps to provide the ZrO of example 44 ₂ The non-monoclinic phase of the layer (non-monoclinic examples 43 and 45-47 have similar process conditions).

FIG. 57 is a graph showing a single-monoclinic ZrO deposited via a ceramic target ₂ A graph of deposition process conditions and layer thicknesses for example 48 of layers.

Fig. 58 is a graph showing Δ E values of example 48 with different heat treatment times.

Fig. 59 is a graph showing optical data and sheet resistance data for the coating of example 48.

Detailed Description

Referring now more particularly to the drawings, in which like reference numerals refer to like parts/layers/materials throughout the several views.

Certain embodiments of the present invention provide a coating or layer system useful in a coated article that can be used monolithically in a window, an Insulated Glass (IG) window unit (e.g., on surface #2 or surface #3 in IG window unit applications), a laminated window unit, a vehicle windshield, and/or other vehicle or building or residential window applications. Certain embodiments of the present invention provide a layer system that combines one or more of high visible transmission, good durability (mechanical and/or chemical) before and/or after HT, and good color stability upon heat treatment. It will be shown here how certain layer stacks surprisingly achieve this unique combination.

With respect to color stability, certain embodiments of the present invention have excellent color stability (i.e., low Δ Ε values; where Δ indicates a change in view of the heat treatment) in the case of a single sheet heat treatment (e.g., heat tempering or heat bending) and/or a two-pane environment (such as an IG unit or windshield). Such Heat Treatment (HT) generally requires heating the coated substrate to a temperature of at least about 1100 ° f (593 ℃) and at most 1450 ° f (788 ℃) [ more preferably about 1100 ° f to 1200 ° f, and most preferably 1150 ° f to 1200 ° f ] for a sufficient period of time to ensure the final result (e.g., tempering, bending, and/or heat strengthening). Certain embodiments of the present invention combine one or more of (i) color stability under thermal treatment and (ii) the use of silver-containing layers for selective IR reflection.

Exemplary embodiments of the present invention are directed to low E coated articles having substantially the same color characteristics as observed by the naked eye both before and after heat treatment (e.g., thermal tempering), and corresponding methods. In certain exemplary embodiments, such articles may incorporate one or more of the following: (1) desirable visible light transmission characteristics, (2) good durability before and/or after heat treatment, (3) low Δ Ε -value indicating color stability upon Heat Treatment (HT), and/or (4) an absorber film designed to adjust visible light transmission and provide a desired coloration to the coated article while maintaining durability and/or heat stability.

In some casesIn an exemplary embodiment, the absorber film may be a multilayer absorber film comprising a first layer 57 having or comprising silver (Ag) and a second layer having or comprising NiCr (NiCrO) that may be partially or fully oxidized _x ) And a second layer 59. See, e.g., fig. 1 (i). Thus, in certain exemplary embodiments, such multilayer absorber films 57, 59 may be made of Ag/NiCrO _x Is formed by the layer sequence of (a). Elements from one layer may diffuse into an adjacent layer due to HT or other factors. In certain example embodiments, the NiCr base layer 59 of the absorber may be initially deposited in metallic form or as a suboxide. In certain exemplary embodiments, the silver-based layer 57 may be a continuous layer, and/or may be optionally doped. Furthermore, the silver-based layer 57 of the absorber film is preferably sufficiently thin so that its primary function is to absorb visible light and provide the desired coloration (as opposed to being much thicker and acting primarily as an IR reflecting layer). NiCr or NiCrO _x 59 are disposed over and in contact with the silver 57 of the absorber film to protect the silver and also to aid in absorption. In certain exemplary embodiments, the silver-based layer 57 of the absorber film may be no greater than about in certain exemplary embodiments of the invention

Thick, more preferably not greater than about

Thick, more preferably not greater than about

Is thick, and most preferably is not greater than about

Thick and may be no greater than about

Is thick. In certain exemplary embodiments, the NiCr base layer 59 of the absorber film may be about

Thick and betterChoosing land to offer

Is thick, and most preferably about

Is thick.

In certain exemplary embodiments of the invention, a single layer of NiCr (or other suitable material) may also be used as the absorber film in the low E coating. See, for example, the absorber film 42 in fig. 1 (d) and 1 (f). However, it has been surprisingly found that the use of silver 57 in an absorber film (single or multi-layer absorber film) provides several unexpected advantages over a single layer NiCr as absorber. First, it has been found that a single layer of NiCr as an absorber tends to cause yellowish coloration in certain low E coated articles, which may be undesirable in certain circumstances. In contrast, it has been surprisingly found that the use of silver 57 in the absorber film tends to avoid such yellowish coloration and/or instead provides a more desirable neutral coloration of the resulting coated article. Thus, it has been found that the use of silver 57 in the absorber film provides improved optical properties. Second, the use of a single layer of NiCr 42 as an absorber often also involves providing a layer of silicon nitride on both sides of the NiCr so that the NiCr is sandwiched directly between and in contact with them. See, for example, fig. 1 (d) and 1 (f). It has been found that providing silicon nitride at certain locations in the coating stack may result in impaired thermal stability at HT. In contrast, it has surprisingly been found that when silver is used in the absorber film, a pair of directly adjacent silicon nitride layers is not required, so that the thermal stability at HT can be improved. Thus, it has been found that the use of silver 57 in the absorber film provides improved thermal stability, including lower Δ Ε values, and thus improved matching between HT and non-HT forms of the same coating. The use of silver in the absorber film may also provide improved manufacturability in certain circumstances.

Surprisingly and unexpectedly, it has been found that disposing and directly contacting the as-deposited crystalline or substantially crystalline layer 3, 3 "(and/or 13) (e.g., at least 50% crystalline, more preferably at least 60% crystalline) of zinc oxide doped with at least one dopant (e.g., sn) directly beneath the Infrared (IR) reflective layer 7 (and/or 19) with or containing silver in the low-E coating 30 has the effect of significantly improving the thermal stability (i.e., lowering the Δ Ε value) of the coating. As used herein, "substantially crystalline" means at least 50% crystalline, more preferably at least 60% crystalline, and most preferably at least 70% crystalline. In various exemplary embodiments of the invention, one or more such crystalline or substantially crystalline layers 3, 3", 13 may be disposed below one or more corresponding IR reflecting layers comprising silver 7, 19. Thus, in various embodiments of the invention, crystalline or substantially crystalline layers 3 (or 3 ") and/or 13 having or comprising zinc oxide doped with at least one dopant (e.g., sn) directly beneath Infrared (IR) reflective layers 7 and/or 19 having or comprising silver may be used for single silver low E coatings, double silver low E coatings (e.g., such as shown in fig. 1 or fig. 20), or triple silver low E coatings. In certain exemplary embodiments, the crystalline or substantially crystalline layers 3 and/or 13 having or comprising zinc oxide are doped with about 1% -30% sn, more preferably about 1% -20% sn, more preferably about 5% -15% sn, with one example being about 10% sn (in weight%). The Sn-doped zinc oxide is in a crystalline or substantially crystalline phase (as opposed to amorphous or nanocrystalline) in the as-deposited state on layers 3 and/or 13, such as from at least one sputtering target having or comprising Zn and Sn via a sputter deposition technique. The combination of the doped zinc oxide based layers 3 and/or 13 with the layers between silver 7 and/or 19 and glass 1 in the as-deposited crystalline phase allows the coated article to achieve improved thermal stability (reduction of Δ Ε value) upon optional HT. It is believed that the combination of the doped zinc oxide based layer 3 and/or 13 of the as-deposited crystalline phase with the layer between silver and glass allows the silver 7 and/or 19 deposited thereon to have an improved crystal structure with texture but with some randomly oriented grains such that its refractive index (n) changes less at optional HT, thereby allowing improved thermal stability to be achieved.

It has also been surprisingly and unexpectedly found that providing a composition having or comprising oxidationSilicon, zirconium oxide, zirconium silicon oxide and/or zirconium silicon oxynitride (e.g., siZrO _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) The dielectric layer (e.g., 2 and/or 2 ") of (a) also provides improved thermal stability of the coated article, as shown, for example, in fig. 1 (b) -1 (i), and thus reduces the Δ E value upon thermal treatment (HT), such as thermal tempering. In certain exemplary embodiments, silicon oxide, zirconium silicon oxide, and/or zirconium silicon oxynitride (e.g., siZrO) may be provided with or comprise _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) At least one dielectric layer (e.g., 2 and/or 2 "): (i) In the bottom dielectric portion of the coating under all of the silver-based IR reflecting layers (see, e.g., fig. 1 (b) -1 (i)), and/or (ii) in the middle dielectric portion of the coating between a pair of silver-based IR reflecting layers (see, e.g., fig. 1 (e) -1 (i)). For example, in certain exemplary embodiments of the invention, a dielectric layer (e.g., 2 and/or 2 ") having or comprising silicon oxide, zirconium oxide and/or zirconium oxynitride can be disposed directly beneath and in contact with the lowermost doped zinc oxide based layer (e.g., 3) and/or disposed between a pair of zinc oxide containing layers (e.g., between 11 and 13, or between 11 and 3") in the middle dielectric portion of the low E coating.

In various exemplary embodiments of the invention, silicon oxide (e.g., siO) ₂ ) Zirconium oxide (e.g., zrO) ₂ ) Dielectric layers (e.g., 2 and/or 2 ") of zirconium silicon oxide and/or zirconium silicon oxynitride may or may not be disposed immediately below an Infrared (IR) reflective layer in combination with an as-deposited crystalline or substantially crystalline (e.g., at least 50% crystalline, more preferably at least 60% crystalline) layer (e.g., 3 and/or 13) having or containing zinc oxide doped with at least one dopant (e.g., sn). Both methods, which can be used together but need not be used together, improve thermal stability and thus reduce the Δ E value. For example, using a silicon oxide (e.g. SiO) with or in addition to ₂ ) Zirconium oxide (e.g. ZrO) ₂ ) Of a dielectric layer (e.g. 2 and/or 2') of zirconium silicon oxide and/or zirconium silicon oxynitrideIn certain embodiments, the contact layer/seed layer immediately below one or both silver may have or may comprise zinc oxide doped with aluminum (instead of Sn), and the contact layer/seed layer need not be crystalline (see, e.g., FIGS. 42, 43 and 46; and examples 25, 26 and 29).

In certain exemplary embodiments, it has been surprisingly and unexpectedly discovered that the initial sputter deposition has or includes zirconium oxide, zirconium oxynitride, zirconium silicon oxide, and/or zirconium silicon oxynitride (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) Is advantageous in that it results in a coated article having an improved thermal stability (lower Δ Ε value) and/or a reduced visible light transmission (e.g. T) upon Heat Treatment (HT), as a result of the dielectric layer 2 and/or 2 ″ comprising a monoclinic crystalline phase crystal structure _vis Or TY) change. See, for example, fig. 1 (a) -1 (i), fig. 51-53, and fig. 55. In certain example embodiments, the dielectric layers 2 and/or 2 "may also comprise other materials such as Ti and/or Nb. In certain exemplary embodiments, the dielectric layer (e.g., zrO) ₂ ) 2 and/or 2' (see, e.g., m-ZrO in the upper panel of FIG. 51) ₂ Peak) can be achieved by using a very high oxygen flow rate for the layer during sputter deposition of the layer, and using a metal sputtering target (e.g., a metallic Zr or SiZr target) (e.g., see fig. 55). It should be noted that such high oxygen flow rates that are desirable in certain exemplary embodiments of this case are counterintuitive to the zirconia-based layer and are generally undesirable because they reduce the deposition rate and thus create increased time and expense in manufacturing the coated article. It has been found that at HT layers 2 and/or 2' are in the monoclinic phase (see m-ZrO in the upper diagram of FIG. 51) ₂ Peak) to tetragonal or cubic structure (see c-ZrO in FIG. 51) ₂ ) Tends to compensate for said change in the crystalline structure of the silver-based layer 7, 57 and/or 19 at HT, which seems to result in a coated article having improved thermal stability (lower Δ Ε value) and/or reduced visible light transmission (T) at HT (T @) _vis Or TY) change. In FIG. 51, note that the monoclinic phase (see upper part of FIG. 51)m-ZrO in the figure ₂ Peaks) were present in the upper plot (high oxygen flow during deposition, and metallic Zr target), but not in the lower plot (low oxygen flow during deposition, and ceramic ZrO _x Target). Also, in the upper diagram of FIG. 51, a monoclinic phase (see m-ZrO) can be seen ₂ Peak) was higher before HT and lower after HT. It has been surprisingly found that the initial sputter deposition has or includes zirconium oxide, zirconium oxynitride, zirconium silicon oxide and/or zirconium silicon oxynitride (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) Is advantageous in that it results in at least about 0.25g/cm due to HT ³ More preferably at least about 0.30g/cm ³ And most preferably at least about 0.35g/cm ³ (e.g., about 5.7 g/cm) ³ To about 6.1g/cm ³ ) This in turn compensates for the change in the crystal structure of the HT silver-based layers 7, 19 and/or 57 due to the high layer 2 and/or 2 "density, which results in a coated article having improved thermal stability (lower Δ Ε value) and/or reduced change in visible light transmission (e.g. Tvis or TY) upon Heat Treatment (HT). In certain exemplary embodiments, this results in coated articles visible light transmittance (T) due to HT _vis Or TY) a reduced variation of not more than 1.2%, more preferably not more than 1.0% and most preferably not more than 0.5%, and/or a reduced value of Δ Ε.

It has also been surprisingly found that the addition of a material having or comprising silicon oxide, zirconium oxynitride, zirconium oxide and/or zirconium silicon nitride oxide (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) Tends to result in a smaller variation of the sheet resistance (Rs) and the visible light transmission at HT, and therefore in a lower Δ Ε value of the coated article, of the thickness of the dielectric layer 2 and/or 2 ″. In certain exemplary embodiments, having or comprising silicon oxide, zirconium oxynitride, zirconium oxide and/or zirconium silicon oxynitride (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) May each have about one or both of the dielectric layers 2 and/or 2 ″

More preferably about

And most preferably about

The physical thickness of (a).

It has also been surprisingly and unexpectedly found that between the glass substrate 1 and the lowermost silver-based layer 7, a silicon nitride-based layer (e.g., si) is not disposed directly beneath and in contact with the lowermost doped zinc oxide-based layer 3 ₃ N ₄ Optionally doped with 1-10% al etc.), in combination with the as-deposited crystalline phase or substantially crystalline phase of the doped zinc oxide based layer 3, allows to achieve an improved thermal stability (reduction of Δ E value) upon thermal treatment. See, for example, fig. 1 (a) -1 (d) and fig. 1 (i) for coatings. Further, in certain exemplary embodiments, there is no amorphous or substantially amorphous layer between the glass substrate 1 and the first IR reflecting layer 7 comprising silver. It has also been surprisingly and unexpectedly found that not providing a silicon nitride based layer in the middle section of the stack between the two silver based IR reflecting layers 7 and 19 allows to achieve an improved thermal stability (lower Δ Ε value) upon thermal treatment (see, e.g., fig. 1 (a) -1 (i)).

In certain exemplary embodiments, it has also been found that a glass substrate is formed with or includes silicon oxide, zirconium oxide and/or zirconium silicon oxynitride (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) With an absorption layer (e.g. NiCr, niCrN) arranged between the dielectric layers 2 _x NbZr and/or NbZrN _x ) 42 may advantageously reduce the glass side visible light reflection (R) of the coated article in a desired manner _g Y) and allows the visible light transmission to be adjusted in a desired manner. For example, in certain exemplary embodiments, such as shown in fig. 1 (d) and 1 (f), an absorber layer 42 may be disposed on a pair of silicon nitride-based layers 41 and 43 (e.g., with or comprising Si) ₃ N ₄ (optionally doped with 1% -10% Al or the like andoptionally containing 0% -10% oxygen) between and in contact with a pair of silicon nitride-based layers). See also, for example, figure 39 and example 22. In other exemplary embodiments, the stack of absorption layers 42 between nitride-based dielectric layers 41 and 43 may be located at other positions within the stack.

In certain exemplary embodiments of monolithic measurements, in view of the above-described structures (e.g., see fig. 1 (a) -1 (i)), the coated article is configured to achieve one or more of the following: (i) a transmission Δ Ε value at HT8 minutes, 12 minutes, and/or 16 minutes (in the case of measuring transmission optics) of no greater than 3.0 (more preferably no greater than 2.8 or 2.5, and most preferably no greater than 2.3), (ii) a glass side reflection Δ Ε value at HT8 minutes, 12 minutes, and/or 16 minutes (in the case of measuring glass side reflection optics) of no greater than 3.0 (more preferably no greater than 2.5, more preferably no greater than 2.0, more preferably no greater than 1.5, and most preferably no greater than 1.0 or 0.6) at a temperature of about 650 ℃, and/or (iii) a film side reflection Δ Ε value at HT8 minutes, 12 minutes, and/or 16 minutes (in the case of measuring film side reflection optics) of no greater than 3.5 (more preferably no greater than 3.0, more preferably no greater than 2.0, more preferably no greater than 1.5, and most preferably no greater than 1.5).

In certain exemplary embodiments of the monolithic measurement, the coated article is configured to have a visible light transmittance (T) of at least about 30%, more preferably at least about 35%, more preferably at least about 40%, more preferably at least about 50% before or after any optional HT _vis Or Y). In certain exemplary embodiments, the low E coating has a sheet resistance (SR or R) of no greater than 20 ohms/square, more preferably no greater than 10 ohms/square, and most preferably no greater than 2.5 ohms/square or 2.2 ohms/square before and/or after the optional heat treatment _s ). In certain exemplary embodiments, the low E coating has a hemispheric emissivity/emissivity (E) no greater than 0.08, more preferably no greater than 0.05 lower, and most preferably no greater than 0.04 _h )。

In the context of the present invention, the Δ Ε value is important in determining whether there is a match or substantial match upon Heat Treatment (HT). Colors herein are described by reference to conventional a, b values, both of which are negative in certain embodiments of the invention, in order to provide colors in the desired substantially neutral range of colors tending to the cyan quadrant. For the purposes of illustration, the term Δ a merely indicates the degree of change in color value a due to the heat treatment.

The Measurement of application in ASTM 2244-93 and in Hunter et al, 2 ^nd Ed.Cptr.9,page 162 et seq.[John Wiley&Sons,1987](measurement of appearance,2 nd edition, chapter 9, page 162 and below, john willi press, 1987), the terms Δ E (and Δ E), along with various techniques for determining the same, are well known and reported in the art. As used in the art, Δ E (and Δ E) is a means of adequately expressing the change (or lack thereof) in reflectance and/or transmittance (and thus color appearance) in an article after or as a result of heat treatment. Δ E can be calculated by the "ab" technique or by the Hunter technique (indicated by using the subscript "H"). Δ E corresponds to the Hunter Lab L, a, b scale (or L) _h 、a _h 、b _h ). Similarly, Δ E corresponds to the CIE LAB scale L, a, b. Both are considered useful and equivalent for the purposes of the present invention. For example, as reported by Hunter et al, cited above, a rectangular coordinate/scale technique known as the L, a, b scale (CIE LAB 1976) can be used, wherein:

l is (CIE 1976) luminance unit

a is (CIE 1976) red green unit

b is (CIE 1976) a yellow-blue unit

And L _o a* _o b* _o And L _l a* _l b* _l The distance Δ E between is:

ΔE*＝[(ΔL*) ² +(Δa*) ² +(Δb*) ² ] ^1/2 (1)

wherein:

ΔL*＝L* _l -L* _o (2)

Δa*＝a* _l -a* _o (3)

Δb*＝b* _l -b* _o (4)

wherein subscript "o" represents the coated article prior to heat treatment and subscript "l" represents the coated article after heat treatment; and the numbers used (e.g., a, b, L) are numbers calculated by the above-described (CIE LAB 1976) L, a, b coordinates technique. In a similar manner, equation (1) can be used by using the Hunter Lab value a _h 、b _h 、L _h And replacing a, b and L to calculate the delta E. Also within the scope of the invention, and if converted to a number calculated by any other technique that employs the same concept as Δ E defined above, the quantification of Δ E is an equivalent number.

In certain exemplary embodiments of the invention, the low E coating 30 comprises two silver-based IR reflecting layers (see, e.g., fig. 1 (a) -1 (i)), although the invention is not so limited in all cases (e.g., three silver-based IR reflecting layers may be used in some cases). It should be appreciated that the coated articles of fig. 1 (a) -1 (i) are shown in monolithic form. However, these coated articles may also be used in, for example, IG window units.

Baking at high temperatures (e.g., 580-650 c) can cause changes in the chemical composition, crystallinity, and microstructure or even phase of the dielectric layer material due to the stability of the material. High temperatures can also cause interfacial diffusion or even reaction, with resultant changes in composition, roughness, and refractive index at the interface location. Therefore, optical properties such as refractive index n/k and optical thickness change upon heat treatment. The IR material (e.g., ag) has also changed. Typically, ag materials undergo crystallization, grain growth, or even orientation changes upon heat treatment. These changes typically cause conductivity changes, especially refractive index n/k changes, which have a large impact on the optical and thermal properties of the low E coatings. In addition, the dielectric and the change in dielectric also have a significant effect on the IR reflecting layer, such as silver, that undergoes thermal processing. Furthermore, silver may have more variation in one layer stack than in the other layer stacks, simply due to the materials and the stack itself. If the silver changes beyond a certain limit, it may be aesthetically unacceptable after heat treatment. We have found that to achieve the thermal stability of the low E coating, a doped zinc oxide crystalline material with a thin modification layer directly or indirectly on the glass can be used under the silver of the IR reflecting layer. It has been found that crystalline or substantially crystalline doped zinc oxide in these locations changes less during heat treatment and results in less change in properties of the silver such as refractive index (e.g. n and/or k) and thus less change in overall color upon heat treatment.

FIG. 1 (a) is a side cross-sectional view of a coated article according to an exemplary non-limiting embodiment of the invention, wherein the low E coating 30 has two silver-based IR reflecting layers 7 and 19. The coated article includes a substrate 1 (e.g., a clear, green, bronze, or blue-green glass substrate that is about 1.0mm to 10.0mm thick, more preferably about 3.0mm to 8.0mm thick), and a low-E coating (or layer system) 30 disposed directly or indirectly on the substrate 1. In fig. 1 (a), the coating (or layer system) 30 comprises, for example: a dielectric layer 3 of or comprising zinc oxide doped with at least one metal dopant (e.g., sn and/or Al), the dielectric layer being a crystalline or substantially crystalline layer as deposited; an Infrared (IR) reflecting layer 7 with or comprising silver located over and in direct contact with layer 3; over and in direct contact with the IR reflecting layer 7, having or comprising Ni and/or Cr (e.g., niCr, niCrO) _x 、NiCrN _x 、NiCrON、NiCrM、NiCrMoO _x Etc.), a contact layer 9 of Ti or other suitable material; having or comprising zinc stannate (e.g. ZnSnO, zn) ₂ SnO ₄ Or other suitable stoichiometry) or other suitable material, which may be an amorphous or substantially amorphous layer as deposited; a further dielectric layer 13 of or comprising zinc oxide doped with at least one dopant (e.g. Sn), the dielectric layer being a crystalline or substantially crystalline layer in the as-deposited state; another Infrared (IR) reflective layer 19 with or comprising silver over and in direct contact with layer 13; over and in direct contact with the IR reflecting layer 19 having or comprising Ni and/or Cr (e.g., niCr, niCrO) _x 、NiCrN _x 、NiCrON、NiCrM、NiCrMoO _x Etc.), ti or other suitable materialThe other contact layer 21; having or comprising zinc stannate (e.g. ZnSnO, zn) ₂ SnO ₄ Or other suitable stoichiometry) or other suitable material such as tin oxide, which may be an amorphous or substantially amorphous layer as deposited; and with or comprising silicon nitride (e.g. Si) ₃ N ₄ Or other suitable stoichiometry) of an amorphous or substantially amorphous dielectric layer 25, which may optionally be doped with Al and/or O. The layers shown in fig. 1 (a) may be deposited by sputtering or in any other suitable manner.

As explained herein, it has been found that the presence of as-deposited crystalline or substantially crystalline layers 3 and/or 13 having or comprising zinc oxide doped with at least one dopant (e.g., sn) directly beneath and in direct contact with the Infrared (IR) reflecting layers 7 and/or 19 having or comprising silver in the low E coating 30 has the effect of significantly improving the thermal stability (i.e., reducing the Δ Ε value) of the coating. In certain exemplary embodiments, the crystalline or substantially crystalline layers 3 and/or 13 having or comprising zinc oxide are doped with about 1% -30% sn, more preferably about 1% -20% sn, more preferably about 5% -15% sn, with one example being about 10% sn (in weight%).

In certain exemplary embodiments, the dielectric zinc stannate (e.g., znSnO) ₄ 、Zn ₂ SnO ₄ Etc.) the base layers 11 and 23 may be deposited in an amorphous or substantially amorphous state (which/which may become crystalline or substantially crystalline upon heat treatment). It has been found that having similar amounts of Zn and Sn in the layer, or more Sn than Zn in the layer, helps to ensure that the layer is deposited in an amorphous or substantially amorphous state. For example, in certain exemplary embodiments of the present invention, the metal content of the amorphous zinc stannate-based layers 11 and 23 can include about 30% -70% zn and about 30% -70% sn, more preferably about 40% -60% zn and about 40% -60% sn, with examples being about 52% zn and about 48% sn, or about 50% zn and 50% sn (weight percent excluding oxygen in the layer). Thus, for example, in certain exemplary embodiments of the invention, a metal target comprising about 52% Zn and about 48% Sn, or about 50% Zn and about 50% Sn, may be usedAmorphous or substantially amorphous zinc stannate based layers 11 and/or 23 are sputter deposited. Optionally, the zinc stannate based layers 11 and 23 can be doped with other metals, such as Al and the like. It has been found that depositing layers 3 and 13 in a crystalline or substantially crystalline state while depositing layers 11 and 23 in an amorphous or substantially amorphous state advantageously allows for improved thermal stability in combination with good optical properties such as acceptable transmission, color and reflection. It should be noted that the zinc stannate layers 11 and/or 23 can be replaced by corresponding layers of other materials, such as tin oxide, zinc oxide doped with 1% -20% sn (as discussed elsewhere herein with respect to layers 11, 13), and the like.

In certain embodiments of the present invention, dielectric layer 25, which may be an overcoat, may be of or include silicon nitride (e.g., si) ₃ N ₄ Or other suitable stoichiometry) to improve the heat-treatability and/or durability of the coated article. In certain exemplary embodiments, the silicon nitride may optionally be doped with Al and/or O, and may also be replaced with other materials such as silicon oxide or zirconium oxide in certain exemplary embodiments.

The Infrared (IR) reflecting layers 7 and 19 are preferably substantially or completely metallic and/or electrically conductive, and may comprise or consist essentially of silver (Ag), gold, or any other suitable IR reflecting material. The IR reflecting layers 7 and 19 help to allow the coating to have low E and/or good solar control properties. However, in certain embodiments of the present invention, the IR reflecting layer may be slightly oxidized.

Other layers may also be provided below or above the coating shown in fig. 1. Thus, when a layer system or coating is "on" or "supported" (directly or indirectly) by the substrate 1, one or more other layers may be disposed therebetween. Thus, for example, the coating of fig. 1 (a) may be considered to be "on" and "supported by" substrate 1 even if one or more other layers are disposed between layer 3 and substrate 1. Furthermore, in certain embodiments, certain layers of the illustrated coating may be removed, while in other embodiments of the invention, other layers may be added between the various layers, or the various layers may be separated from other layers added between the discrete segments without departing from the overall spirit of certain embodiments of the invention.

Although various thicknesses and materials may be used in the layers in different embodiments of the present invention, exemplary thicknesses and materials of the respective layers on the glass substrate 1 in the fig. 1 (a) embodiment are as follows, from the glass substrate outward:

table 1 exemplary materials/thicknesses; FIG. 1 (a) embodiment

The fig. 1 (b) embodiment is the same as the fig. 1 (a) embodiment discussed above and elsewhere herein, except that the low-E coating 30 in the fig. 1 (b) embodiment further comprises a coating having or comprising zirconium silicon oxide, and/or zirconium silicon oxynitride (e.g., siZrO) beneath and in direct contact with the doped zinc oxide-based layer 3 _x 、ZrO ₂ 、SiO ₂ 、SiAlO ₂ And/or SiZrO _x N _y ) A substantially transparent dielectric layer 2. It has been found that this additional layer 2 provides a further improved thermal stability of the coated article and thus a lower Δ Ε value (e.g. a lower glass side reflection Δ Ε value) even upon thermal treatment (HT), such as thermal tempering. In certain exemplary embodiments of the invention, the material has or comprises zirconium silicon oxide, zirconium oxide, silicon oxide and/or zirconium silicon oxynitride (e.g., siZrO _x 、ZrO ₂ 、SiO ₂ 、SiAlO ₂ And/or SiZrO _x N _y ) May be disposed directly beneath and in contact with the lowermost doped zinc oxide base layer 3, as shown in figure 1 (b). In certain exemplary embodiments of the invention, the material has or comprises zirconium silicon oxide, zirconium oxide, silicon oxide and/or zirconium silicon oxynitride (e.g., siZrO _x 、ZrO ₂ 、SiO ₂ 、SiAlO ₂ And/or SiZrO _x N _y ) May be about

Thick, more preferably about

Is thick and most preferably about

Is thick. The thicknesses described above for the embodiment of fig. 1 (a) are also applicable to fig. 1 (b) -1 (i).

When the layer 2 (or 2' ) has or contains SiZrO _x And/or SiZrO _x N _y It has been found that providing more Si than Zr in this layer advantageously has a low refractive index (n) and improved anti-reflection and other optical properties from an optical point of view. For example, in certain exemplary embodiments, when layer 2 (or 2', or 2 ") has or comprises SiZrO _x And/or SiZrO _x N _y When the metal content of the layer may comprise 51% to 99% Si, more preferably 70% to 97% Si and most preferably 80% to 90% Si, and 1% to 49% Zr, more preferably 3% to 30% Zr, and most preferably 10% to 20% Zr (atomic%). In exemplary embodiments, with or containing SiZrO _x And/or SiZrO _x N _y May have a refractive index (n) of about 1.48 to 1.68, more preferably about 1.50 to 1.65, and most preferably about 1.50 to 1.62, measured at 550 nm.

The fig. 1 (c) embodiment is the same as the fig. 1 (b) embodiment discussed above and elsewhere herein, except that the low-E coating 30 in the fig. 1 (c) embodiment further comprises a coating having or comprising silicon nitride (e.g., si) disposed between and in contact with the glass substrate 1 and the dielectric layer 2 (e.g., si) ₃ N ₄ Optionally doped with 1% -10% Al or the like and optionally containing 0% -10% oxygen, or other suitable stoichiometry) and/or a substantially transparent dielectric layer 2' of zirconium silicon oxynitride. The layer 2' may also have or comprise aluminum nitride (e.g., alN).

The fig. 1 (d) embodiment is identical to the fig. 1 (b) embodiment discussed above and elsewhere herein, except that the low E coating 30 in the fig. 1 (d) embodiment further comprises an interlayer of silicon nitride based layers 41 and 43 (e.g., si ₃ N ₄ Optionally doped with 1% -10% Al, etc., and optionally containing 0% -10%Oxygen) between and in contact with the metal or substantially metal absorber layer 42. In certain example embodiments, dielectric layers 41 and/or 43 may also have or comprise aluminum nitride (e.g., alN). In exemplary embodiments of the present invention, the absorption layer 42 may have or comprise NiCr, nbZr, nb, zr or their nitrides or other suitable materials. The absorbing layer 42 preferably contains 0% to 10% oxygen (atomic%), more preferably 0% to 5% oxygen. In certain exemplary embodiments, it has been found that the glass substrate is formed with or includes zirconium silicon oxide, zirconium oxide, silicon oxide, and/or zirconium silicon oxynitride (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ 、SiAlO ₂ And/or SiZrO _x N _y ) An absorption layer (e.g., niCr, niCrN) is provided between the dielectric layers 2 _x NbZr and/or NbZrN _x ) 42 advantageously reduce the glass side visible light reflection (R) of the coated article in a desired manner _g Y) and allows the visible light transmittance to be adjusted in a desired manner. See, for example, fig. 39 and example 22. In certain exemplary embodiments, the absorbent layer 42 may be about

Thick, more preferably about

Is thick. In certain exemplary embodiments, silicon nitride based layers 41 and 43 may be about

Is thick, more preferably about

Is thick. For example, in embodiment 22 and fig. 39, the absorption layer 42 is nitride of NiCr, and is about 1.48nm thick. In other exemplary embodiments, the stack of absorber layers 42 between nitride-based dielectric layers 41 and 43 may be located at other locations within the stack.

Referring to FIGS. 1 (a) -1 (d), zrO or ZrO-containing layers 11 and 13 may be disposed between and may be included in ₂ 、SiZrO _x And/or SiZrO _x N _y Another transparent dielectric layer (not shown). In certain exemplary embodiments, the zinc stannate-containing layer 11 may be omitted, or such may be used with or comprising ZrO ₂ 、SiZrO _x And/or SiZrO _x N _y Is replaced by another transparent dielectric layer. The doped zinc oxide layer 13 can also be provided with or comprise ZrO ₂ 、SiZrO _x And/or SiZrO _x N _y Is separated by another transparent dielectric layer. For example, in certain exemplary embodiments, when such additional layers are with or comprise SiZrO _x And/or SiZrO _x N _y The metal content of the layer may comprise 51% to 99% si, more preferably 70% to 97% si, and most preferably 80% to 90% si, and 1% to 49% zr, more preferably 3% to 30% zr, and most preferably 10% to 20% zr (atomic%), and may comprise 0% to 20% nitrogen, more preferably 0% to 10% nitrogen, and most preferably 0% to 5% nitrogen (atomic%). For example, silicon oxide, zirconium oxynitride, zirconium oxide and/or zirconium oxynitride (e.g., siZrO) may be provided with or include _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) At least one dielectric layer (e.g., 2 and/or 2 "): (i) In the bottom dielectric portion of the coating under all of the silver-based IR reflecting layers (see, e.g., fig. 1 (b) -1 (i)), and/or (ii) in the middle dielectric portion of the coating between a pair of silver-based IR reflecting layers (see, e.g., fig. 1 (e) -1 (i)).

As explained above and shown in the drawings, the coated article may comprise dielectric layers 2, 2 "(e.g. ZrO) as shown in FIGS. 1 (b) - (i) ₂ Or SiZrO _x ) Which may underlie and be in direct contact with the first crystalline or substantially crystalline layer 3 comprising zinc oxide doped with about 1% -30% sn, and or the zinc oxide-containing layer 3 ". The dielectric layer 2 (and 2 ") may have or comprise silicon oxide, zirconium oxide (e.g. ZrO), optionally doped with Al ₂ ) Zirconium oxynitride, zirconium silicon oxide and/or zirconium silicon oxynitride (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ). The dielectric layer 2 (or 2') may be aligned with the glass substrate 1Contact (see, for example, fig. 1 (b), fig. 1 (e), fig. 1 (g), fig. 1 (h)). The dielectric layers 2, 2 "may each have about

More preferably about

More preferably about

And most preferably about

Or about

Or

The physical thickness of (a). The dielectric layers 2, 2 "are preferably oxide-based dielectric layers and preferably contain little or no nitrogen. For example, the dielectric layers 2, 2 "may each contain 0% -20% nitrogen, more preferably 0% -10% nitrogen, and most preferably 0% -5% nitrogen (at%).

The embodiment of fig. 1 (i) is based on the embodiments of fig. 1 (a) - (b), fig. 1 (e), and fig. 1 (h) discussed herein, and the layer and performance descriptions for these embodiments also apply to fig. 1 (i). However, the embodiment of fig. 1 (i) also includes an absorber film comprised of layers 57 and 59, where the absorber film is disposed in the central portion of the layer stack and on dielectric layers 11, 2", and 3" as described herein. Layer 3 "may be zinc stannate, zinc oxide, zinc aluminum oxide, or doped zinc oxide, as discussed in various embodiments of the invention. Layer 2 "is as described above and may have or be wrappedContaining silica, zirconia (e.g. ZrO) optionally doped with Al ₂ ) Zirconium silicon oxide and/or zirconium silicon oxynitride (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y )。

In the embodiment of fig. 1 (i), the absorber film may be a multilayer absorber film comprising a first layer 57 comprising or containing silver (Ag) and comprising or containing a partially or fully oxidizable (NiCrO) _x ) And possibly a slightly nitrided NiCr second layer 59. Thus, in certain exemplary embodiments, such multilayer absorber films 57, 59 may be made of Ag/NiCrO _x Is formed by the layer sequence of (a). The layer sequence may be repeated in some illustrative examples. For example, in certain exemplary embodiments of the invention, the absorber film may be made of Ag/NiCrO _x /Ag/NiCrO _x Or Ag/NiCrO _x /Ag/NiCrO _x /Ag/NiCrO _x The layers of (a) constitute a sequence of layers, each layer of said sequence contributing to light absorption. Elements from one layer may diffuse into an adjacent layer due to HT or other factors. In certain example embodiments, the NiCr-based layer 59 of the absorber may be initially deposited in metallic form or as a suboxide. In certain exemplary embodiments, the silver-based layer 57 may be a continuous layer, and/or may be optionally doped. Examples 30-47 of exemplary embodiments of the invention relate to at least the embodiment of fig. 1 (i) (see fig. 47-56). Furthermore, as explained herein, in certain exemplary embodiments, it has been surprisingly and unexpectedly discovered that the initial sputter deposition has or includes silicon oxide, zirconium oxynitride, zirconium oxide, and/or zirconium oxynitride (e.g., siZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) So as to contain a monoclinic phase (see m-ZrO in the upper diagram of FIG. 51) ₂ Peaks) are advantageous as they result in coated articles having improved thermal stability (lower Δ Ε value) and/or reduced visible light transmission (e.g. T) upon Heat Treatment (HT) _vis Or TY) change.

The silver-based layer 57 of the absorber film is preferably thin enough that its primary function is to absorb visible light and provide the desired coloration (as opposed to being much thicker and primarily useful)As opposed to an IR reflecting layer). NiCr or NiCrO _x 59 are disposed over and in contact with the silver 57 of the absorber film to protect the silver and also to aid in absorption. In certain exemplary embodiments, the silver-based layer 57 of the absorber film may be no greater than about in certain exemplary embodiments of the invention

Thick, more preferably not greater than about

Thick, and most preferably no greater than about

Thick, and may be no greater than about

Is thick. In certain exemplary embodiments, the NiCr base layer 59 of the absorber film may be about

Thick, more preferably about

Is thick, and most preferably about

Is thick. In certain exemplary embodiments, the Ag/NiCrO in the absorber film _x The ratio may be 1:Z (where 0.1<Z<20, more preferably 2 thereof<Z<15, most preferably 3 thereof<Z<12 For example, about 1:5.

With respect to the silver-based layer 57 of the absorber film being sufficiently thin so that its primary function is to absorb visible light and provide the desired coloration (as opposed to being much thicker and acting primarily as an IR reflecting layer), the ratio of the physical thickness of the IR reflecting layer 7 (e.g., silver) to the physical thickness of the silver-based layer 57 is preferably at least 5:1, more preferably at least about 8:1, even more preferably at least about 10, and even more preferably at least about 15. Also, the ratio of the physical thickness of the IR reflecting layer 19 (e.g., silver) to the physical thickness of the silver-based layer 57 is preferably at least 5:1, more preferably at least about 8:1, even more preferably at least about 10.

Although a single layer of NiCr (or other suitable material) may also be used as the absorber film in the low-E coating in certain exemplary embodiments of the present invention (see, e.g., absorber film 42 in fig. 1 (d) and 1 (f)), it has been surprisingly found that the use of silver 57 in the absorber film (single or multi-layer absorber film) of fig. 1 (i) provides several unexpected advantages over a single layer of NiCr as the absorber. First, it has been found that a single layer of NiCr as an absorber tends to cause yellowish coloration in certain low E coated articles, which may be undesirable in certain circumstances. In contrast, it has been surprisingly found that the use of silver 57 in the absorber film tends to avoid such yellowish coloration and/or instead provides a more desirable neutral coloration of the resulting coated article. Thus, it has been found that the use of silver 57 in the absorber film provides improved optical properties. Second, the use of a single layer of NiCr 42 as an absorber often also involves providing silicon nitride based layers on both sides of the NiCr so as to sandwich the NiCr directly therebetween and in contact therewith. See, for example, fig. 1 (d) and 1 (f). It has been found that providing silicon nitride at certain locations in the coating stack may result in impaired thermal stability at HT. In contrast, it has surprisingly been found that when using silver in the absorber film, for example as shown in fig. 1 (i), a pair of directly adjacent silicon nitride layers is not required, so that the thermal stability at HT can be improved. Thus, it has been found that the use of silver 57 in the absorber film provides improved thermal stability, including lower Δ Ε values, and thus improved matching between HT and non-HT forms of the same coating. The use of silver in the absorber film may also provide improved manufacturability in certain circumstances.

Although the absorbing films 57, 59 in fig. 1 (i) are provided in the central portion of the stack of layers between the IR reflecting layers 7 and 19, such absorbing films 57, 59 may also be provided: in the lower part of the layer stack below the bottom IR-reflecting layer 7, or in another suitable position. For example, the embodiment of fig. 1 (i) may be modified by moving directly adjacent and contacting layers 57 and 59 to a position between layers 2 and 3, such that layers 2 and 57 contact each other and layers 59 and 3 contact each other. As another example, the embodiment of fig. 1 (i) may be modified by moving the sequence of three layers 3"/57/59 from the central portion of the stack to a position between layers 2 and 3 in fig. 1 (i) such that layers 2 and 3" are in contact with each other and layers 59 and 3 are in contact with each other. However, it has surprisingly been found that by providing absorbing films 57, 59 in the central part of the layer stack as shown in fig. 1 (i), optical properties such as SHGC and glass side reflectivity can be improved.

Fig. 1 (i) shows layer 59 with or comprising an absorbing film of NiCrOx (partially or fully oxidized). However, layer 59 of the absorber film may have or comprise other metal-based materials (e.g., niCr, ni, cr, niCrO) _x 、NiCrN _x 、NiCrON、NiCrM、NiCrMoO _x Ti, or other suitable material).

It should be noted that in any of the embodiments herein, the zinc stannate layers 11 and/or 23 can be replaced by corresponding layers of other materials, such as tin oxide, zinc oxide doped with 1% -20% sn (as discussed elsewhere herein with respect to layers 3, 3", 13), and the like.

Although various thicknesses and materials may be used in the layers in different embodiments of the present invention, exemplary thicknesses and materials of the respective layers on the glass substrate 1 in the embodiment of fig. 1 (i) are as follows, outwardly from the glass substrate:

table 1' exemplary materials/thicknesses; FIG. 1 (i) embodiment

In certain embodiments of the present invention, the articles herein are disposed on a transparent monolithic glass substrate (e.g., a 6mm thick glass substrate for reference purposes) when viewed from the glass side of the coated articleThe layer system (see, for example, fig. 1 (a) - (i)) has the following color (R) before the heat treatment _G %) (il.c, 2 degree observer):

_G table 2: reflection/colour (R) before and/or after heat treatment

Comparative examples 1 and 2

Fig. 19 is a cross-sectional view of a first Comparative Example (CE) coated article, and fig. 23 is an XRD Lin (cps) versus 2-theta scale showing a relatively large 166% change in Ag (111) peak height due to heat treatment for the first Comparative Example (CE).

The difference between the first comparative example coating (see fig. 19) and examples 1-24, 27-28, and 30-33 below is that the lowermost dielectric stack of the coating in the first comparative example consists of Zn ₂ SnO ₄ The layer and the zinc oxide base layer doped with aluminum. Zinc stannate layer (Zn) ₂ SnO ₄ In the form of zinc stannate) is about 50% zn and about 50% sn (wt%); and thus the zinc stannate layer is sputter deposited in an amorphous form. The overall thickness of the lowermost dielectric stack in the first CE is about 400-500 a, with the zinc stannate layer accounting for the majority of this thickness. Fig. 23 shows a relatively large 166% change in Ag (111) peak height due to heat treatment at about 650 ℃ for the first Comparative Example (CE), indicating a significant change in silver layer structure during heat treatment, and this is consistent with the delta E values over 4.0 achieved by this comparative example. Thus, the first CE is undesirable due to the significant change in Ag (111) peak, and due to high Δ Ε values exceeding 4.0 resulting from the heat treatment. In comparison with the first comparative example, the following examples 1-24, 27-28 and 30-33 have crystalline or substantially crystalline layers 3, 13 with a metal content of 90 (Zn)/10 (Sn) or 85 (Zn)/15 (Sn) directly below and in contact with silver 7, 19, and a significantly improved/reduced Δ Ε value is achieved.

A second comparative example (CE 2) is shown in fig. 34 to 35. FIG. 34 is a view showing that a glass substrate having a thickness of 6mm is usedGraph of sputter deposition conditions for sputter depositing the low E coating of comparative example 2 (CE 2). The layer stack of CE2 is the same as that shown in fig. 1 (b) of the present application, except that the lowermost dielectric layer in CE2 is made of silicon nitride (doped with about 8% aluminum) instead of SiZrO as shown in fig. 1 (b) _x And (4) preparing. Thus, the bottom dielectric stack in CE2 consists only of the silicon nitride-based layer and the zinc oxide layer 3 doped with about 10% sn. The thickness of the CE2 coating is in the rightmost column of fig. 34. For example, doped with Al (in Ar and N) ₂ Sputtered from a SiAl target in a gas atmosphere) is 10.5nm thick in CE2, the zinc oxide layer 3 doped with about 10% sn directly below the bottom silver is 32.6nm thick in CE2, and so on.

As can be seen in fig. 35, CE2 has relatively high glass side reflectance Δ E values (Δ E R) of more than 4.0 due to the 12, 16 and 24 minute heat treatments _g ) And the film side reflection Δ E value (Δ E R) _f ). For example, fig. 35 shows that CE has a relatively high glass side reflection Δ E value (Δ E R) of 4.9 due to 12 minutes of heat treatment _g ) And a relatively high film side reflection Δ Ε value (Δ Ε R) of 5.5 _f ). Fig. 35 is a graph showing the optical characteristics of comparative example 2 (CE 2): the left-most data column is in the as-coated state before heat treatment (annealed), after heat treatment at 650 ℃ for 12 minutes (HT), after HT at 650 ℃ for 16 minutes (HTX), and the right-most data column is after heat treatment at 650 ℃ for 24 minutes (HTXXX). These relatively high Δ E values for CE2 are undesirable.

Thus, comparative example 2 (CE 2) in fig. 34-35 shows that even in the case where the crystalline or substantially crystalline zinc oxide layer 3 doped with about 10% sn is provided directly below the bottom silver layer 7, an undesirably high Δ E value is achieved when the only layer between the layer 3 and the glass substrate 1 is a silicon nitride based layer. The differences between CE2 coatings and the following examples 1-24, 27-28 and 30-33 are that the following examples 1-24, 27-28 and 30-33 enable surprisingly and unexpectedly a greatly improved (reduced) Δ E value to be achieved using a crystalline or substantially crystalline zinc oxide layer 3 doped with about 10% or 15% sn by not having a silicon nitride based layer directly below and in contact with the crystalline or substantially crystalline zinc oxide layer 3 doped with about 10% or 15% sn.

The following examples 11-14, 19-21 and 26-33 also show that SiZrO was used _x Or ZrO ₂ The bottom silicon nitride based layer of layer 2 replacing CE2 significantly improved/reduced the Δ E value in an unexpected manner.

Examples 1 to 48

It was surprisingly and unexpectedly found that when the lowermost dielectric stacks 5,6 of the Comparative Example (CE) in fig. 19, consisting essentially of as-deposited amorphous zinc stannate layers, were replaced with crystalline or substantially crystalline Sn-doped zinc oxide layers 3 of similar thickness contacting the silver-based layers (the remainder of the stack remained substantially the same), with no silicon nitride-based layers directly beneath and in contact with the crystalline or substantially crystalline layers 3, the result was a much more thermally stable product with significantly lower Δ Ε values and much smaller changes in Ag (111) peak heights due to heat treatment at about 650 ℃. The metal content of the crystalline or substantially crystalline Sn-doped zinc oxide layer 3 in examples 1-24, 27-28 and 30-48 was about 90% zn and 10% Sn (wt%) (see also, 85% zn and 15% Sn, relative to "85" of layer 13 in example 19), which helped to allow sputter deposition of the Sn-doped zinc oxide layer 3, 13 in examples 1-24, 27-28, 30-48 in a crystalline or substantially crystalline form (as opposed to the amorphous form in CE). For example, fig. 20 shows the stacked stack of example 10, fig. 21 shows the sputter deposition conditions and layer thicknesses of example 10, and fig. 22 shows a much smaller 66% change in Ag (111) peak height due to heat treatment at about 650 ℃ for example 10, consistent with the much lower Δ Ε values achieved by examples 1-24, 27-28, and 30-33. Fig. 16 also shows a relatively small refractive index (n) shift upon heat treatment for example 8.

The coated articles of the examples (each annealed and heat treated) were prepared according to certain exemplary embodiments of the present invention, i.e., examples 1-48. The exemplary coating 30 shown is sputter deposited via sputtering conditions (e.g., gas flow, voltage, and power), a sputter target, and deposited into fig. 2, 3, 6, 7, 9, 11, 13, 15, 21, 24-26, 28, 30, 32, and 36-57The indicated layer thicknesses (nm). For example, fig. 2 shows the sputtering conditions, sputtering deposition sputtering targets and layer thicknesses for the coating layer of example 1, fig. 3 shows the sputtering conditions, sputtering deposition sputtering targets and layer thicknesses for the coating layer of example 2, fig. 6 shows the sputtering conditions, sputtering deposition sputtering targets and layer thicknesses for the coating layer of example 3, fig. 7 shows the sputtering conditions, sputtering deposition sputtering targets and layer thicknesses for the coating layer of example 4, and so forth. Also, the illustrated embodiment includes visible light transmittance (TY or T) _vis ) Glass side visible reflectance (R) _g Y or RGY), film side visible light reflectance (R) _f Y or RFY), a and b color values, L value and sheet resistance (SR or R) _s ) The data of (a) are shown in fig. 4, fig. 5, fig. 8, fig. 10, fig. 12, fig. 14, fig. 18, fig. 27, fig. 29, fig. 31, fig. 33, and fig. 36 to fig. 56. As described above, for the given example, the values of L, a, and b taken before and after the heat treatment were used to calculate the value of Δ Ε. For example, for a given embodiment, the glass side reflection Δ Ε values (Δ Ε) were calculated using the glass side reflection L, a, and b values obtained before and after the heat treatment _G Or Δ E R _g ). As another example, for a given example, the glass side reflectance L, a, and b values obtained before and after heat treatment were used to calculate the film side reflectance Δ E value (Δ E) _F Or Δ E R _f ). As another example, for a given example, the transmission Δ E values (Δ E) were calculated using the glass side reflection L, a, and b values obtained before and after heat treatment _T )。

For the embodiments having a glass substrate of about 3mm thickness in fig. 4, 5,8, 10, 12, 14, and 18, "EGG" means heat treated at 650 degrees for about 8 minutes, "HTX" means heat treated at 650 degrees for about 12 minutes, "HTXXX" means heat treated at 650 degrees for about 20 minutes. And for the embodiments having a glass substrate of about 6mm thickness in fig. 4, 5,8, 10, 12, 14, 18, 27, 29, 31, 33, and 36-56, "HT" means heat treatment at 650 degrees for about 12 minutes, "HTX" means heat treatment at 650 degrees for about 16 minutes, and "HTXXX" means heat treatment at 650 degrees for about 24 minutes. The heat treatment temperature and time are for reference purposes only (e.g., to simulate examples of different tempering and/or hot bending processes).

For example, fig. 4 and 5 show Δ E values for examples 1 and 2, respectively. The data of example 1 is explained in detail below for purposes of example and explanation, and the discussion also applies to the data of examples 2-33.

As shown in FIG. 4, example 1 in the as-coated state (prior to heat treatment) had a visible light transmission (TY or T) of 74.7% _vis ) 89.3 transmission L value, -4.7 transmission a color value, 5.8 transmission b color value, 9.6% glass side reflectance (R) _g Y), a glass side reflection L value of 37.1, a glass side reflection a color value of 1.1, a glass side reflection b color value of 10.1, a film side reflectance (R) of 9.9% _f Y), a film side reflection L value of 37.7, a film side reflection a color value of-1.5, a film side reflection b color value of-5.7, and a Sheet Resistance (SR) of 2.09 ohms/square. Fig. 2 shows the thicknesses of the layers in example 1. Specifically, fig. 2 shows that the layer thicknesses of example 1 are as follows: glass/crystalline Sn-doped ZnO (47.0 nm)/Ag (15.1 nm)/NiCrO _x (4.1 nm)/amorphous zinc stannate (73.6 nm)/crystalline Sn doped ZnO (17.7 nm)/Ag (23.2 nm)/NiCrO _x (4.1 nm)/amorphous zinc stannate (10.8 nm)/aluminum doped silicon nitride (19.1 nm).

The coated article of example 1 having a 6mm thick glass substrate 1 was then heat treated. As shown in FIG. 4, example 1 had a visible light transmittance (TY or T) of 77.0% after heat treatment at 650 ℃ for about 12 minutes _vis ) Transmission L value of 90.3, transmission a color value of-3.5, transmission b color value of 4.9, glass side reflectance (R) of 9.8% _g Y), glass side reflection L value of 37.5, -glass side reflection a color value of 0.7, -glass side reflection b color value of 10.5, film side reflectance (R) of 10.2% _f Y), a film side reflection L value of 38.1, -a film side reflection a color value of 1.4, -a film side reflection b color value of 8.0, a Sheet Resistance (SR) of 1.75, a transmission Δ E value of 1.8, a glass side reflection Δ E value of 0.7, and a film side reflection Δ E value of 2.4.

It will be appreciated that these Δ E values for example 1 (and those of examples 2-48) are much improved (significantly lower) compared to those of the prior art discussed in the background and to the values over 4.0 of the Comparative Example (CE) discussed above. Thus, the data from the examples show that, for example, when the lowermost dielectric stack of the comparative example is replaced with an at least crystalline or substantially crystalline Sn-doped zinc oxide layer of similar thickness (the remainder of the stack remains substantially the same), without a silicon nitride-based layer directly beneath and in contact with the crystalline or substantially crystalline Sn-doped zinc oxide layer 3, the result is a much more thermally stable product with a significantly lower Δ Ε value and a much smaller change in Ag (111) peak height due to thermal treatment.

Other examples show these same unexpected results compared to comparative examples. Generally, these examples show crystalline or substantially crystalline Sn-doped zinc oxide layers and/or having or comprising SiZrO _x 、ZrO _x 、SiO ₂ The layers 2, 2 "of (a) significantly improved the Δ E value. For example, examples 1-10 have a layer stack generally shown by FIG. 1 (a) in which the only dielectric layer underlying the bottom silver is the crystalline or substantially crystalline Sn-doped zinc oxide layer 3 having a metal content of about 90% Zn and 10% Sn (wt%). In examples 11-14, 19-24, 27-28, in SiZrO _x The metal content of the crystalline or substantially crystalline Sn-doped zinc oxide layer 3 directly above the layer 2 is about 90% Zn and 10% Sn (wt%), wherein the metal content of the layer 2 is about 85% Si and 15% Zr (at%). In examples 30 to 48, the crystalline or substantially crystalline Sn-doped zinc oxide layer 3 was about 90% Zn and 10% Sn (wt.%), and was disposed directly on ZrO as shown in FIGS. 1 (i) and 52 ₂ On the layer 2. In examples 15 to 16, in ZrO ₂ The metal content of the crystalline or substantially crystalline Sn-doped zinc oxide layer 3 directly above layer 2 is about 90% zn and 10% Sn (wt%); and in examples 17 to 18, about 8% by weight of Al (atomic%) doped SiO ₂ The metal content of the crystalline or substantially crystalline Sn-doped zinc oxide layer 3 directly above the layer 2 is approximately 90% Zn and 10% Sn (wt%). These examples surprisingly and unexpectedly achieved greatly improved Δ Ε values compared to comparative examples 1-2.

The laminated stack of examples 1-10 is generally shown in fig. 1 (a). Layers of examples 11 to 14, 19 and 27The stack is shown generally in FIG. 1 (b), where layer 2 is SiZrO _x . The stacked stacks of examples 15-16 are shown generally in FIG. 1 (b), where layer 2 is ZrO ₂ . The stacked stacks of examples 17-18 are generally shown in FIG. 1 (b), where layer 2 is SiO ₂ . The stack of examples 20-21 and 28 is shown generally in FIG. 1 (e), where layers 2 and 2 "are SiZrO _x . The stack of examples 23-24 is shown generally in FIG. 1 (f), where layers 2 and 2 "are SiZrO _x . The stack of example 25 is shown generally in FIG. 1 (g), where layers 2 and 2 "are SiZrO _x . The stacked stack of example 22 is shown generally in FIG. 1 (d), where layer 2 is SiZrO _x . The stack of example 26 is shown generally in FIG. 1 (h), where layers 2 and 2 "are SiZrO _x The oxide layer 3' has a metal content of 90% Zn and 10% Sn, and the oxide layers 3, 13 are zinc oxide doped with about 4% to 8% Al. The layer stack of example 29 is shown generally in FIG. 1 (h), except that layer 2 "is not present in example 29, and layer 2 is SiZrO _x The oxide layer 3' has a metal content of 90% Zn and 10% Sn, and the oxide layers 3, 13 are zinc oxide doped with about 4% to 8% Al. The layer stack of examples 30-48 is generally illustrated by FIGS. 1 (i) and 52, where layers 2 and 2 "are ZrO ₂ . These examples surprisingly and unexpectedly achieved greatly improved Δ Ε values compared to comparative examples 1-2. These examples show crystalline or substantially crystalline Sn-doped zinc oxide layers (e.g., layer 3 and/or layer 13) and/or with or comprising SiZrO _x 、ZrO _x 、SiO ₂ The dielectric layers 2, 2 "of (a) significantly improve/reduce the value of Δ E.

For example, examples 23-24 (SiZrO added to the central dielectric portion of the coating) _x Comparison of layer 2", as shown in FIG. 1 (f), with example 22 (without such layer 2" in the central dielectric portion, as shown in FIG. 1 (d)) shows and demonstrates that the addition of SiZrO in examples 23-24 _x Layer 2 "unexpectedly improved/reduced at least the glass side reflection Δ Ε value. Therefore, it should be understood that SiZrO _x The addition of layer 2 "provides unexpected results.

Furthermore, examples 28 (A), (B)SiZrO added to the central dielectric portion of the coating _x Layer 2", as shown in fig. 1 (e) was compared to example 27 (without such layer 2" in the central dielectric portion, as shown in fig. 1 (b)) to further demonstrate and demonstrate the addition of SiZrO in example 28 _x Layer 2 "unexpectedly improved/reduced the glass side reflection Δ Ε value. Therefore, it should be understood again that SiZrO _x Or ZrO ₂ The addition of layer 2 "provides unexpected results with respect to improved thermal stability.

Examples 30-48 are generally illustrated by FIGS. 1 (i) and 52, and include absorbing films 57, 59, in these examples layers 2 and 2 "are ZrO ₂ . These examples surprisingly and unexpectedly achieved greatly improved Δ Ε values compared to comparative examples 1-2. Examples 30-48 show that crystalline or substantially crystalline Sn doped zinc oxide layers (e.g., layers 3 and/or 13) and with or containing ZrO ₂ The dielectric layer 2, 2 "of (a) significantly improves/reduces the Δ E value in an unexpected manner. Examples 30-48 further demonstrate the provision of a silver-containing layer 57 and a NiCrO-containing layer _x The absorbing film of layer 59 allows the visible light transmission to be adjusted to a desired value without sacrificing the thermal stability or desired color of the resulting coated article. For example, with Ag/NiCrO as shown in FIG. 1 (i) _x Examples 30-48 of the absorber films (57, 59) had surprisingly more neutral glass side reflectance values (Rg b or R-out b) than examples 23-24 using a single NiCr layer absorber.

Comparing examples 34-42 and 48 with Comparative Examples (CE) 43-47, it can be seen that it has been surprisingly and unexpectedly found that the initial sputter deposition has or includes silicon oxide, zirconium oxynitride, zirconium oxide and/or zirconium silicon oxynitride (SiZrO) _x 、ZrO ₂ 、SiO ₂ And/or SiZrO _x N _y ) The inclusion of the monoclinic phase crystal structure in dielectric layers 2 and/or 2 "of examples 34-42 and 48 is advantageous because it results in coated articles having improved thermal stability (lower delta E values) and/or reduced visible light transmission (e.g. T) upon Heat Treatment (HT) _vis Or TY) change. In general, with monoclinic ZrO ₂ Layers 2, 2 "and thus have improved/betterExamples 34-42 and 48, which have low Δ E values, CE 43-47, which may still be in accordance with certain exemplary embodiments of the present invention, are due to non-monoclinic ZrO ₂ The layers 2, 2 "have less preferred (higher) Δ E values. In certain exemplary embodiments, in connection with certain sputtering apparatus, a dielectric layer (e.g., zrO) ₂ ) 2 and/or 2' (see, e.g., m-ZrO in the upper panel of FIG. 51) ₂ Peaks) can be achieved by using a high oxygen flow rate for the layer during sputter deposition of the layer, and using a metal sputtering target (e.g., a metallic Zr or SiZr target) (see, e.g., fig. 55), as in examples 34-42. In this regard, fig. 51 shows the use of a metallic Zr target (top) and ceramic ZrO before and after HT _x Target (lower panel) sputter deposition of ZrO ₂ A graph of a layer and shows that the layer includes a monoclinic phase (see m-ZrO) when a metal target is used with a high gas flow (see, e.g., FIG. 55) ₂ Peaks at (a) while the layer does not include a monoclinic phase when a ceramic target is used in this certain case. It should be noted, however, that it has been found that the monoclinic phase of layers 2 and/or 2 "can indeed be achieved when sputter deposition uses a ceramic target as in example 48 with a low or high oxygen flow (depending on the type of sputtering equipment used).

FIG. 52 (see also FIG. 1 (i)) is a cross-sectional view of a coated article according to examples 34-42, 48 and Comparative Examples (CE) 43-47. FIG. 53 shows the optical data of examples 34-42: examples 34-42 had coating stacks as shown in FIGS. 1 (i) and 52, in the leftmost data column of each example, before heat treatment (AC; annealing) and after heat treatment at 650 deg.C for 12 minutes (HT) in the right data column of each example, where monoclinic ZrO was deposited with a metallic Zr target ₂ Layers 2 and 2", and the layer thicknesses for examples 34-42 are shown in FIG. 55; wherein sample 7982 is example 34, sample 8077 is example 35, sample 8085 is example 36, sample 8090 is example 37, sample 8091 is example 38, sample 8097 is example 39, sample 8186 is example 40, sample 8187 is example 41, and sample 8202 is example 42. FIG. 55 is a graph showing ZrO having monoclinic crystal ₂ Diagram of deposition process conditions and layer thicknesses for example 37 of layers, with sputtering process during each layerTotal oxygen flow (ml) from O ₂ Set value, O ₂ Regulation and O ₂ Sum of offset representation, zrO ₂ The high oxygen flow during sputter deposition of the layer helps to provide the ZrO of example 37 ₂ Monoclinic phase for layers 2 and 2 "(monoclinic examples 34-36 and 38-42 have similar process conditions). In the embodiments of fig. 52 and 1 (i), it should be noted that, for example, the central ZrO may be omitted in certain illustrative examples ₂ Layer 2".

FIG. 57 is a graph showing a ZrO having monoclinic crystal ₂ Graph of deposition process conditions and layer thicknesses for example 48 for layer 2 (layer 2 is omitted "), using ceramic ZrO ₂ The target sputter deposits a ZrO layer 2 having a monoclinic phase. The layer stack of example 48 is shown in fig. 1 (i) and 52 (layer 2 omitted "), and the corresponding layer thicknesses are provided in fig. 57. Fig. 58 shows Δ Ε values after various heat treatment times for the coating according to example 48, and fig. 59 shows optical data and sheet resistance data for the coating according to example 48.

FIG. 54 shows the optical data of Comparative Examples (CE) 43 to 47: examples 43-47 had coating stacks as shown in FIGS. 1 (i) and 52, with non-monoclinic ZrO deposited with a ceramic target, in the as-coated (AC; annealed) before heat treatment in the leftmost data column of each example, and after heat treatment at 650 deg.C for 12 minutes (HT) in the right data column of each example ₂ Layer, and layer thicknesses for examples 43-47 are shown in FIG. 56; where sample 8392 is CE 43, sample 8394 is CE 44, sample 8395 is CE 45, sample 8396 is CE 46, and sample 8397 is CE 47. FIG. 56 is a view showing a structure having non-monoclinic ZrO ₂ Graph of deposition Process conditions and layer thickness for Comparative Example (CE) 44 of layers 2 and 2", where the total oxygen flow (ml) during the sputtering Process of each layer was determined from O ₂ Set value, O ₂ Regulation and O ₂ Sum of offset representation, zrO ₂ Low oxygen flow and ceramic ZrO during layer sputter deposition _x The targets together contribute to provide ZrO of example 44 ₂ The non-monoclinic phase of the layer (non-monoclinic examples 43 and 45-47 have similar process conditions).

Comparing examples 34-42, 48 with Comparative Examples (CE) 43-47, it can be seen thatZrO having an oblique crystal phase ₂ Examples 43-47 of layers 2 and 2 "have monoclinic ZrO in the as-deposited state ₂ Examples 34-42, 48 of layers 2 and 2 "achieved lower/better Δ E values and thus improved thermal stability and color matching at HT.

Certain terms are commonly used in the glass coating art, particularly when defining the properties and solar management characteristics of the coated glass. Such terms are used herein according to their well-known meanings. For example, as used herein:

the intensity of the reflected visible wavelength light, i.e., "reflectance", is defined by its percentage and is reported as R _x Y or R _x (i.e., the Y values referenced below in ASTM E-308-85), where "X" is "G" for the glass side or "F" for the film side. "glass side" (e.g., "G" or "G") refers to the side of the glass substrate opposite the side on which the coating is located, while "film side" (i.e., "F" or "F") refers to the side of the glass substrate on which the coating is located.

Color characteristics are measured and reported herein using CIE LAB a, b coordinates and scales (i.e., CIE a b diagram, il. Other similar coordinates (such as conventional use of the Hunter Lab scale by subscript "h") or il.cie-C10 may be used equally well ⁰ Observer or CIE LUV v coordinates. These scales are defined herein according to ASTM D-2244-93"Standard Test Method for calibration of Color From instruments Measured Colors 9/15/93 as amplified by ASTM E-308-85, annual Book of ASTM Standards, volume 06.01," Standard Method for Computing the Colors of object by 10 Using the CIE System "and/or as reported in reference volume IES LIGHTING HANDBOOK 1981.

Visible light transmittance can be measured using known conventional techniques. For example, a spectral curve of the transmission is obtained by using a spectrophotometer such as a Perkin Elmer Lambda 900 or Hitachi U4001. The visible light transmittance is then calculated using the aforementioned ASTM 308/2244-93 method. If desired, a fewer number of wavelength points than specified may be employed. Another technique for measuring visible light transmission is to use a photometer, such as a commercially available spectrorogard spectrophotometer manufactured by Pacific Scientific inc. The device directly measures and reports the visible light transmittance. As reported and measured herein, the visible light transmittance (i.e., the Y value in the CIE tristimulus system, ASTM E-308-85) as well as the a, b, and L values and the glass/film side reflectance values herein were measured using the il.c.2 degree observer standard.

Another term used herein is "sheet resistance". Sheet resistance (Rs) is a term well known in the art and is used herein according to its well known meaning. Reported here in ohms/square. Generally, the term refers to the resistance (in ohms) of any square of the layer system on the glass substrate to current flow through the layer system. Sheet resistance is an indication of the degree to which a layer or system of layers reflects infrared energy and is therefore often used as a measure of this property together with emissivity. The "sheet resistance" can be conveniently measured, for example, by using a 4-point probe ohmmeter such as a dispensable 4-point resistivity probe with a magnon Instruments tip model M-800 produced by Signatone corp.

As used herein, the terms "heat treatment" and "heat treating" mean heating an article to a temperature sufficient to achieve thermal tempering, hot bending, and/or heat strengthening of a coated article comprising glass. This definition includes, for example, heating the coated article in an oven or furnace at a temperature of at least about 580 deg.C, more preferably at least about 600 deg.C (including 650 deg.C) for a sufficient period of time to allow tempering, bending, and/or heat strengthening. In some cases, the heat treatment may last for at least about 8 minutes or longer as discussed herein.

In an exemplary embodiment of the present invention, there is provided a coated article comprising a coating on a glass substrate, wherein the coating comprises: a crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% Sn (wt%) disposed on the glass substrate; a first Infrared (IR) reflecting layer comprising silver, located on the glass substrate and directly above and in contact with the first crystalline or substantially crystalline layer comprising zinc oxide doped with about 1-30% Sn(ii) a Wherein no silicon nitride based layer is located directly below and in contact with the first crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% Sn; at least one dielectric layer having a monoclinic phase and comprising zirconium oxide (e.g., zrO) ₂ ) And optionally also other elements, such as Si; wherein the at least one dielectric layer comprising zirconium oxide is located: (1) At least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% sn (wt%), and/or (2) at least the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating; optionally an absorber film comprising a layer comprising silver, wherein the ratio of the physical thickness of the first IR reflecting layer comprising silver of the absorber film to the physical thickness of the layer comprising silver is at least 5:1 (more preferably at least 8:1, even more preferably at least 10, and most preferably at least 15; and wherein the coated article is configured to have at least two of the following measured monolithically: (ii) a transmission Δ Ε value of not greater than 3.0 resulting from 12 minutes of a reference heat treatment at a temperature of about 650 ℃, (ii) a glass side reflection Δ Ε value of not greater than 3.0 resulting from 12 minutes of the reference heat treatment at a temperature of about 650 ℃, and (iii) a film side reflection Δ Ε value of not greater than 3.5 resulting from 12 minutes of the reference heat treatment at a temperature of about 650 ℃.

The coated article described in the previous paragraph can be configured to have all three of the following measured in a single piece: (ii) a transmission Δ Ε value of not greater than 3.0 resulting from 12 minutes of a reference heat treatment at a temperature of about 650 ℃, (ii) a glass side reflection Δ Ε value of not greater than 3.0 resulting from 12 minutes of the reference heat treatment at a temperature of about 650 ℃, and (iii) a film side reflection Δ Ε value of not greater than 3.5 resulting from 12 minutes of the reference heat treatment at a temperature of about 650 ℃.

In the coated article of any of the preceding two paragraphs, the at least one dielectric layer comprising zirconium oxide may be located at least between the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% sn (wt%).

In the coated article of any of the preceding three paragraphs, the at least one dielectric layer comprising zirconium oxide may be located at least between the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of at least the coating.

In the coated article of any of the preceding four paragraphs, the at least one dielectric layer comprising zirconium oxide can comprise a first layer comprising zirconium oxide and a second layer comprising zirconium oxide (each of which can also comprise one or more additional elements, such as Si); wherein the first layer may be located between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% Sn (wt%); and wherein the second layer may be located between at least the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating.

In the coated article of any of the preceding five paragraphs, the at least one dielectric layer may comprise zirconium oxide and/or oxides of silicon and zirconium (e.g., siZrO) _x ) Or consists essentially thereof. For example, a dielectric layer comprising oxides of silicon and zirconium may have a metal content of 51% -99% si and 1% -49% zr, more preferably 70% -97% si and 3% -30% zr (atomic%).

In the coated article of any of the preceding six paragraphs, the at least one dielectric layer may comprise ZrO ₂ 。

In the coated article of any of the preceding seven paragraphs, the first crystalline or substantially crystalline layer comprising zinc oxide may be doped with about 1% -20% sn, more preferably about 5% -15% sn (wt%).

In the coated article of any of the preceding eight paragraphs, the first crystalline or substantially crystalline layer comprising Sn-doped zinc oxide may be a crystalline or substantially crystalline layer in a sputter-deposited state.

The coated article of any of the preceding nine paragraphs may be configured to have all of the following measured monolithically: (ii) a transmission Δ Ε value of no greater than 2.5 resulting from a reference heat treatment conducted at a temperature of about 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of no greater than 2.5 resulting from the reference heat treatment conducted at a temperature of about 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of no greater than 3.0 resulting from the reference heat treatment conducted at a temperature of about 650 ℃ for 12 minutes.

The coated article of any of the preceding ten paragraphs can be configured to have at least two of the following measured monolithically: (ii) a transmission Δ Ε value of no greater than 2.3 resulting from a reference heat treatment performed at a temperature of about 650 ℃ for 16 minutes, (ii) a glass side reflection Δ Ε value of no greater than 2.0 resulting from the reference heat treatment performed at a temperature of about 650 ℃ for 16 minutes, and (iii) a film side reflection Δ Ε value of no greater than 3.0 resulting from the reference heat treatment performed at a temperature of about 650 ℃ for 16 minutes.

The coated article of any of the preceding eleven paragraphs can be configured such that the coating can have a sheet resistance (R) of no greater than 20 ohms/square, more preferably no greater than 10 ohms/square, and most preferably no greater than 2.5 ohms/square _s )。

The coated article according to any of the preceding twelve paragraphs may have a visible light transmittance of at least 35%, more preferably at least 50%, and more preferably at least 68%, measured monolithically.

In the coated article of any of the preceding thirteen paragraphs, the as-deposited coating can further comprise a first amorphous or substantially amorphous layer comprising zinc stannate on the glass substrate over at least the first IR reflecting layer comprising silver. The first amorphous or substantially amorphous layer comprising zinc stannate may have a metal content of about 40-60% Zn and about 40-60% Sn (wt%).

In the coated article of any of the preceding fourteen paragraphs, the coating can further comprise a contact layer over and in direct contact with the IR reflecting layer comprising silver. The contact layer may comprise Ni and/or Cr and may or may not be oxidized and/or nitrided.

In the coated article of any of the preceding fifteen paragraphs, the coating can further comprise: a second IR reflecting layer comprising silver on the glass substrate over at least the first IR reflecting layer comprising silver, a second crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% Sn (wt%) below and in direct contact with the second IR reflecting layer comprising silver. And wherein a silicon nitride based layer is not required to be located between the glass substrate and the second IR reflecting layer comprising silver.

In the coated article of any of the preceding sixteen paragraphs, the coating can further include an as-deposited amorphous or substantially amorphous layer comprising zinc stannate on the glass substrate over at least the second IR reflecting layer comprising silver. The amorphous or substantially amorphous layer comprising zinc stannate in the as-deposited state can have a metal content of about 40% -60% zn and about 40% -60% sn (wt%). In certain exemplary embodiments, the coating can further comprise a layer comprising silicon nitride over at least the amorphous or substantially amorphous layer comprising zinc stannate.

The coated article of any of the preceding seventeen paragraphs can be thermally tempered.

The coated article of any of the preceding eighteen paragraphs can further comprise a metallic or substantially metallic absorbing layer located between the glass substrate and the first IR reflecting layer. The absorber layer may be sandwiched between and in contact with a first layer comprising silicon nitride and a second layer. The absorption layer may comprise Ni and Cr (e.g., niCr, niCrMo) or any other suitable material such as NbZr. A dielectric layer comprising at least one of (a), (b), and (c) can be located between at least the absorber layer and the first crystalline or substantially crystalline layer comprising zinc oxide.

In the coated article of any of the nineteen preceding paragraphs, the at least one dielectric layer comprising zirconium oxide may comprise 0% to 20% nitrogen, more preferably 0% to 10% nitrogen, and most preferably 0% to 5% nitrogen (at%).

In the coated article of any of the twenty preceding paragraphs, the absorber film can further include a layer comprising an oxide of Ni and/or Cr located over and in direct contact with the layer comprising silver of the absorber film.

In the coated article of any of the twenty-one paragraphs immediately above, the absorbing film can be positioned over the first IR reflecting layer such that the first IR reflecting layer is positioned between at least the absorbing film and the glass substrate.

In the coated article of any of the preceding twenty-two paragraphs, the ratio of the physical thickness of the first IR reflecting layer comprising silver to the physical thickness of the layer comprising silver of the absorber film may be at least 8:1, more preferably at least 10, and even more preferably at least 15.

In the coated article of any of the preceding twenty-three paragraphs, the layer comprising silver of the absorber film may be less than

Is thick, more preferably less than

Is thick and even more preferably less than

Is thick.

In the coated article of any of the twenty-four preceding paragraphs, the coated article does not require thermal tempering.

In the coated article of any of the preceding twenty-five paragraphs, the at least one dielectric layer having a monoclinic crystalline phase and comprising zirconium oxide may comprise two such layers comprising zirconium oxide and may be located at both: (1) Between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with about 1% -30% sn (wt%), and (2) between at least the first IR reflecting layer comprising silver and the absorber film.

In the coated article of any of the preceding twenty-six paragraphs, the at least one dielectric layer having a monoclinic phase may comprise 0% -5% nitrogen (at%).

In the coated article of any of the preceding twenty-seven paragraphs, the at least one dielectric layer having a monoclinic phase may comprise zirconium oxide (e.g., zrO) ₂ ) And may optionally further comprise Si.

In the coated article of any of the preceding twenty-seven paragraphs, the at least one dielectric layer having a monoclinic phase may consist essentially of zirconium oxide.

In the coated article of any of the preceding twenty-eight paragraphs, the at least one dielectric layer having a monoclinic phase may be configured to achieve at least 0.25g/cm at the reference thermal treatment ³ More preferably at least 0.30g/cm at the time of said reference heat treatment ³ And most preferably at least 0.35g/cm at the reference thermal treatment ³ The density of (a).

In the coated article of any of the preceding twenty-nine paragraphs, the at least one dielectric layer having a monoclinic phase may comprise zirconium oxide and may have a metal content of at least 80% zr.

In the coated article of any of the foregoing thirty paragraphs, the at least one dielectric layer having a monoclinic phase may comprise zirconium oxide and/or may have a monoclinic phase

More preferably

And most preferably

Is measured.

In the coated article of any of the preceding thirty-one paragraphs, the coated article may be configured with two or three of the following measured monolithically: (i) a transmission Δ Ε value of not greater than 3.0 when subjected to a reference heat treatment at a temperature of about 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not greater than 1.5 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not greater than 1.5 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes.

The coated article of any of the preceding thirty-two paragraphs may be provided as a monolithic window, or as an IG window unit coupled to another glass substrate.

In the coated article of any of the preceding thirty-three paragraphs, the at least one dielectric layer comprising a monoclinic phase may further comprise a tetragonal phase before and/or after the reference thermal treatment.

In one exemplary embodiment, a method of making a coated article comprising a coating on a glass substrate is provided, the method comprising: sputter depositing a layer comprising zinc on the glass substrate; sputter depositing a first Infrared (IR) reflecting layer comprising silver on the glass substrate, the first IR reflecting layer being over and in contact with the layer comprising zinc oxide; sputter depositing at least one dielectric layer (e.g., zirconium oxide, such as ZrO) having a monoclinic phase on the glass substrate ₂ ) Wherein the dielectric layer having a monoclinic phase comprises zirconium oxide (and which may also comprise other elements, such as Si); wherein the at least one dielectric layer having a monoclinic phase and comprising zirconium oxide is located: (1) At least between the glass substrate and the layer comprising zinc oxide, and/or (2) between at least the first IR reflecting layer comprising silver and a second IR reflecting layer comprising silver of the coating; and wherein the coated article is configured to have at least two of the following measured monolithically: (ii) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of about 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 3.0 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 3.5 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes. T is

In the method of the preceding paragraph, the sputter depositing of the at least one dielectric layer having a monoclinic phase on the glass substrate may use an oxygen flow of at least 6ml/kW, more preferably an oxygen flow of at least 8ml/kW or 10 ml/kW.

In the method of any of the preceding two paragraphs, the at least one dielectric layer having a monoclinic phase may comprise ZrO ₂ And may further contain Si.

In the method of any of the preceding three paragraphs, the coated article may be configured to have at least two or all three of the following measured monolithically: (i) a transmission Δ Ε value of not greater than 3.0 when subjected to a reference heat treatment at a temperature of about 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not greater than 1.5 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not greater than 1.5 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes.

The method of any of the preceding four paragraphs may further comprise heat treating the coated article via the reference heat treatment such that the at least one dielectric layer having a monoclinic crystalline phase achieves at least 0.25g/cm at the time of the reference heat treatment ³ More preferably at least 0.30g/cm ³ And most preferably at least 0.35g/cm ³ The density of (a) varies.

In the method of any of the preceding five paragraphs, the sputter depositing the at least one dielectric layer having a monoclinic phase on the glass substrate may use a metal target or a ceramic target.

In the method of any of the preceding six paragraphs, the at least one dielectric layer comprising a monoclinic phase may further comprise a tetragonal phase before and/or after the reference thermal treatment.

In the method of any of the preceding seven paragraphs, the at least one dielectric layer comprising a monoclinic phase may be configured to have its monoclinic peak reduced upon the reference thermal treatment.

Numerous other features, modifications and improvements will become apparent to those skilled in the art once the above disclosure is given. Accordingly, such other features, modifications and improvements are considered part of this invention, the scope of which is defined by the following claims:

Claims (62)

1. a coated article comprising a coating on a glass substrate, wherein the coating comprises:

a first crystalline or substantially crystalline layer comprising zinc oxide doped with 1% -30% Sn (wt%), disposed on the glass substrate;

a first Infrared (IR) reflecting layer comprising silver, said first IR reflecting layer being located on said glass substrate and directly above and in contact with said first crystalline or substantially crystalline layer comprising zinc oxide doped with 1% -30% Sn;

wherein no silicon nitride based layer is directly below and in contact with the first crystalline or substantially crystalline layer comprising zinc oxide doped with 1% -30% Sn;

at least one dielectric layer having a monoclinic phase and comprising zirconium oxide;

wherein the at least one dielectric layer having a monoclinic phase and comprising the zirconium oxide is located: (1) At least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with 1% -30% sn (% by weight), and/or (2) at least the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating;

an absorber film comprising a silver-containing layer, wherein a ratio of a physical thickness of the first silver-containing IR reflecting layer to a physical thickness of the silver-containing layer of the absorber film is at least 5:1, and wherein the silver-containing layer of the absorber film does not directly contact the first IR reflecting layer; and is

Wherein the coated article is configured to have at least two of the following measured monolithically: (i) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 3.0 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 3.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

2. The coated article of claim 1, wherein the absorber film further comprises a layer comprising an oxide of Ni and/or Cr located over and in direct contact with the layer comprising silver of the absorber film.

3. The coated article of claim 1, wherein the absorbing film is positioned over the first IR reflecting layer such that the first IR reflecting layer is positioned between at least the absorbing film and the glass substrate.

4. The coated article of claim 1, wherein the ratio of the physical thickness of the first IR reflecting layer comprising silver to the physical thickness of the layer comprising silver of the absorber film is at least 8: 1.

5. The coated article of claim 1, wherein the ratio of the physical thickness of the first IR reflecting layer comprising silver to the physical thickness of the layer comprising silver of the absorber film is at least 10: 1.

6. The coated article of claim 1, wherein the ratio of the physical thickness of the first IR reflecting layer comprising silver to the physical thickness of the layer comprising silver of the absorber film is at least 15:1.

7. The coated article of claim 1, wherein the thickness of the layer comprising silver of the absorber film is less than

8. The coated article of claim 1, wherein the absorbent film isThe layer comprising silver has a thickness of less than

9. The coated article of claim 1, wherein the thickness of the layer comprising silver of the absorber film is less than

10. The coated article of claim 1, wherein the coated article is configured to have a single measurement of all three of: (i) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 3.0 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 3.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

11. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic phase is located at least between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with 1% -30% sn (wt%).

12. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic phase is located at least between at least the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating.

13. The coated article of claim 1, wherein the first crystalline or substantially crystalline layer comprising zinc oxide is doped with 1% -20% sn (wt%).

14. The coated article of claim 1, wherein the first crystalline or substantially crystalline layer comprising zinc oxide is doped with 5% -15% sn (wt%).

15. The coated article of claim 1, wherein the first crystalline or substantially crystalline layer comprising Sn-doped zinc oxide is sputter-deposited crystalline or substantially crystalline.

16. The coated article of claim 1, wherein the coated article is configured with all of the following measured monolithically: (i) a transmission Δ Ε value of not more than 2.5 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 2.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 3.0 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

17. The coated article of claim 1, wherein the coated article is configured to have at least two of the following measured monolithically: (i) a transmission Δ Ε value of not more than 2.3 when subjected to a reference heat treatment at a temperature of 650 ℃ for 16 minutes, (ii) a glass side reflection Δ Ε value of not more than 2.0 when subjected to the reference heat treatment at a temperature of 650 ℃ for 16 minutes, and (iii) a film side reflection Δ Ε value of not more than 3.0 when subjected to the reference heat treatment at a temperature of 650 ℃ for 16 minutes.

18. The coated article of claim 1, wherein the coating has a sheet resistance (R) of not greater than 10 ohms/square _s )。

19. The coated article of claim 1, wherein the coated article has a monolithically measured visible light transmission of at least 40%.

20. The coated article of claim 1, wherein the as-deposited coating further comprises a first amorphous or substantially amorphous layer comprising zinc stannate on the glass substrate over at least the first IR reflecting layer comprising silver.

21. The coated article of claim 20, wherein the first amorphous or substantially amorphous layer comprising zinc stannate has a metal content of 40% -60% zn and 40% -60% sn (wt%).

22. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic phase can be configured to have its monoclinic peak reduced upon the reference thermal treatment.

23. The coated article of claim 1, wherein the coating further comprises:

a second IR reflecting layer comprising silver on the glass substrate over at least the first IR reflecting layer comprising silver,

a second crystalline or substantially crystalline layer comprising zinc oxide doped with 1% -30% Sn (wt.%), located beneath and in direct contact with the second IR reflecting layer comprising silver;

wherein no silicon nitride based layer is located between the glass substrate and the second IR reflecting layer comprising silver; and is

Wherein the layer comprising silver of the absorber film does not directly contact any of the first and second IR reflecting layers.

24. The coated article of claim 1, wherein the coated article is not thermally tempered.

25. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic phase and comprising zirconia is located at both: (1) Between at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with 1% -30% sn (% by weight), and (2) between at least the first IR reflecting layer comprising silver and the absorbing film.

26. The coated article of claim 25, wherein the at least one dielectric layer comprising a monoclinic phase comprises 0% -5% nitrogen (at%).

27. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic phase comprises ZrO ₂ 。

28. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic phase consists essentially of the zirconium oxide.

29. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic crystalline phase is configured to achieve at least 0.25g/cm upon the reference thermal treatment ³ The density of (a).

30. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic crystalline phase is configured to achieve at least 0.30g/cm upon the reference thermal treatment ³ The density of (a).

31. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic crystalline phase is configured to achieve at least 0.35g/cm upon the reference thermal treatment ³ The density of (a) varies.

32. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic phase comprises zirconium oxide and has a metal content of at least 80% zr.

33. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic phase and comprising the zirconium oxide has

Is measured.

34. The coated article of claim 1, wherein the at least one dielectric layer comprising a monoclinic phase and comprising the zirconium oxide further comprises Si.

35. The coated article of claim 1, wherein the coated article is configured with at least two of the following measured monolithically: (i) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 1.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 1.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

36. The coated article of claim 1, wherein the coated article is configured to have all three of the following measured monolithically: (i) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 1.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 1.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

37. A coated article comprising a coating on a glass substrate, wherein the coating comprises:

a layer comprising zinc oxide disposed on the glass substrate;

a first Infrared (IR) reflecting layer comprising silver, the first IR reflecting layer being on the glass substrate and directly over and in contact with the layer comprising zinc oxide;

wherein no silicon nitride based layer is directly beneath and in contact with the layer comprising zinc oxide;

at least one dielectric layer comprising a monoclinic phase and comprising zirconium oxide;

wherein the at least one dielectric layer comprising a monoclinic phase and comprising the zirconium oxide is located: (1) At least between the glass substrate and the layer comprising zinc oxide, and/or (2) at least between the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating; and is

Wherein the coated article is configured to have at least two of the following measured monolithically: (i) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 3.0 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 3.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

38. The coated article of claim 37, wherein the coated article is not thermally tempered.

39. The coated article of claim 37, wherein the at least one dielectric layer comprising a monoclinic crystalline phase comprises two layers comprising zirconia, wherein one layer is located between (1) at least the glass substrate and the layer comprising zinc oxide, and wherein the other layer is located between (2) at least the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver.

40. The coated article of claim 37, wherein the at least one dielectric layer comprising a monoclinic phase comprises 0% -5% nitrogen (at%).

41. The coated article of claim 37, wherein the at least one dielectric layer comprising a monoclinic phase and comprising the zirconium oxide further comprises Si.

42. The coated article of claim 37, wherein the at least one dielectric layer comprising a monoclinic phase consists essentially of zirconium oxide.

43. The coated article of claim 37, wherein the at least one dielectric layer comprising a monoclinic crystalline phase is configured to achieve at least 0.25g/cm upon the reference thermal treatment ³ Is varied in density, and

wherein the at least one dielectric layer comprising a monoclinic phase can be configured to have its monoclinic peak reduced upon the reference thermal treatment.

44. The coated article of claim 37, wherein the at least one dielectric layer comprising a monoclinic crystalline phase is configured to achieve at least 0.30g/cm upon the reference thermal treatment ³ The density of (a).

45. The coated article of claim 37, wherein the at least one dielectric layer comprising a monoclinic crystalline phase is configured to achieve at least 0.35g/cm upon the reference thermal treatment ³ The density of (a).

46. The coated article of claim 37, wherein the at least one dielectric layer comprising a monoclinic phase has a metal content of at least 80% zr.

47. The coated article of claim 37, wherein the at least one dielectric layer comprising a monoclinic phase has

Is measured.

48. The coated article of claim 37, wherein the at least one dielectric layer comprising a monoclinic phase further comprises a tetragonal phase.

49. The coated article of claim 37, wherein the coated article is configured with at least two of the following measured monolithically: (i) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 1.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 1.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

50. The coated article of claim 37, wherein the coated article is configured to have a single measurement of all three of: (i) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 1.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 1.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

51. A coated article comprising a coating on a glass substrate, wherein the coating comprises:

a layer comprising zinc oxide disposed on the glass substrate;

a first Infrared (IR) reflecting layer comprising silver, the first IR reflecting layer being on the glass substrate and directly over and in contact with the layer comprising zinc oxide;

wherein no silicon nitride based layer is directly beneath and in contact with the layer comprising zinc oxide;

at least one dielectric layer comprising a monoclinic phase and comprising a metal oxide;

wherein the at least one dielectric layer comprising a monoclinic phase and comprising a metal oxide is located: (1) At least between the glass substrate and the layer comprising zinc oxide, and/or (2) at least between the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating; and is provided with

Wherein the coated article is configured to have at least two of the following measured monolithically: (i) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 3.0 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 3.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

52. A method of making a coated article comprising a coating on a glass substrate, the method comprising:

sputter depositing a layer comprising zinc oxide on the glass substrate;

sputter depositing a first Infrared (IR) reflecting layer comprising silver on the glass substrate, the first IR reflecting layer being over and in contact with the layer comprising zinc oxide;

sputter depositing at least one dielectric layer comprising a monoclinic phase on the glass substrate, wherein the dielectric layer comprising a monoclinic phase comprises zirconium oxide;

wherein the at least one dielectric layer comprising a monoclinic phase and comprising the zirconium oxide is located: (1) At least between the glass substrate and the layer comprising zinc oxide, and/or (2) at least between the first IR reflecting layer comprising silver and the second IR reflecting layer comprising silver of the coating; and is

Wherein the coated article is configured to have at least two of the following measured monolithically: (i) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 3.0 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 3.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

53. The method of claim 52, wherein the sputter depositing the at least one dielectric layer comprising a monoclinic phase on the glass substrate uses an oxygen flow of at least 6 ml/kW.

54. The method of claim 52, wherein the sputter depositing the at least one dielectric layer comprising a monoclinic phase on the glass substrate uses an oxygen flow of at least 8 ml/kW.

55. The method of claim 52, wherein the at least one dielectric layer comprising a monoclinic phase comprises ZrO ₂ 。

56. The method of claim 52, wherein the coated article is configured to have a single-sheet measurement of all three of: (i) a transmission Δ Ε value of not more than 3.0 when subjected to a reference heat treatment at a temperature of 650 ℃ for 12 minutes, (ii) a glass side reflection Δ Ε value of not more than 1.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes, and (iii) a film side reflection Δ Ε value of not more than 1.5 when subjected to the reference heat treatment at a temperature of 650 ℃ for 12 minutes.

57. The method of claim 52, further comprising heat treating the coated article via the reference heat treatment such that the at least one dielectric layer comprising a monoclinic crystalline phase achieves at least 0.25g/cm at the reference heat treatment ³ The density of (a).

58. The method of claim 52, wherein the sputter depositing the at least one dielectric layer comprising a monoclinic phase on the glass substrate uses a metal target.

59. The method of claim 58, wherein the sputter depositing the at least one dielectric layer comprising a monoclinic phase on the glass substrate uses an oxygen flow of at least 6 ml/kW.

60. The method of claim 52, wherein the sputter depositing the at least one dielectric layer comprising a monoclinic phase on the glass substrate uses a ceramic target.

61. The method of claim 52, wherein the at least one dielectric layer comprising a monoclinic phase further comprises a tetragonal phase.

62. The method of claim 52, wherein the at least one dielectric layer comprising a monoclinic phase is configured to have its monoclinic peak reduced upon the reference thermal treatment.

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