CN114430732A - Low-E matchable coated articles with absorbent films and corresponding methods - Google Patents

Abstract

The present invention provides a low E coating with good color stability (low ΔE* value) upon heat treatment (HT). Thermal stability can be improved by providing a crystalline or substantially crystalline layer as deposited having or comprising zinc oxide doped with at least one dopant (eg, Sn) immediately after having or comprising under an infrared (IR) reflective layer of silver; and/or by providing at least one dielectric layer having or comprising zirconium oxide. These have the effect of significantly improving the thermal stability of the coating (ie reducing the ΔE* value). Absorptive films can be designed to adjust visible light transmission and provide desired coloration while maintaining durability and/or thermal stability. Dielectric layers (eg, with or containing Zr oxide) can be sputter deposited to have a monoclinic phase to improve thermal stability.

Description

Low E matchable coated article with absorbent film and corresponding method

This application claims the benefit of US Application Serial No. 16/596,632, filed October 8, 2019, which is a continuation-in-part of US Application Serial No. 16/355,966, filed March 18, 2019 ( CIP), which US Application Serial No. 16/355,966 is a continuation-in-part (CIP) of US Application No. 16/220,037, filed on December 14, 2018, which was filed on July 16, 2018 A continuation-in-part of US Application Serial No. 16/035,810 (now US Patent No. 10,031,215), the disclosures of which are hereby incorporated by reference in their entirety.

The present invention relates to low-E coated articles having approximately the same color characteristics as observed with the naked eye, both before and after heat treatment (eg, thermal tempering), and corresponding methods. In certain exemplary embodiments, such articles may incorporate two or more of: (1) desirable visible light transmission properties, (2) good durability before and/or after heat treatment, (3) indicative of heat treatment (HT) low ΔE* values for color stability, and/or (4) absorbing films designed to adjust visible light transmission and provide desired coloration to coated articles while maintaining durability and/or thermal stability. Such coated articles can be used monolithically in windows, insulating glass (IG) window units, laminated window units, vehicle windshields, and/or other vehicle or architectural or residential window applications.

Background technique

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 new multi-window office buildings, vehicle window requirements, etc.). In such applications, it is often desirable that some of the windows and/or doors be heat treated (ie, tempered, heat strengthened, or heat bent), while others are not. Office buildings often employ IG units and/or laminates for security and/or thermal control. For architectural and/or aesthetic purposes, it is desirable that heat-treated (HT) units and/or laminates are substantially identical to their non-heat-treated counterparts (e.g., at least on the side viewed from the exterior of the building, on the Color, reflectivity, transmission, etc.) matching.

Commonly owned US Patent _5,688,585 discloses a solar control coated article comprising: glass/ _{Si3N4 /} NiCr/Si3N4 _. One object of the '585 patent is to provide a sputter coating system that, after heat treatment (HT), can be color matched to its non-heat treated counterpart. While the coating systems of the '585 patent are excellent for their intended purpose, they suffer from certain disadvantages. In particular, they tend to have relatively high emissivity and/or sheet resistance values (eg, because silver (Ag) layers are not disclosed in the '585 patent).

In the prior art, in systems other than those of the aforementioned '585 patent, compatibility can be achieved between two different layer systems, one heat treated and the other unheat treated. The necessity to develop and use two different layer systems for matching creates undesired additional manufacturing overhead and inventory requirements.

US Patents 6,014,872 and _5,800,933 (see Example B) disclose heat treatable low E layer systems comprising: Glass/ _TiO2 /Si3N4/NiCr/ _Ag / _NiCr /Si3N4 _. Unfortunately, when heat treated, this low E layer system is not approximately color matchable with its unheat treated counterpart (as viewed from the glass side). This is because this low-E layer system has a ΔE* (glass side) value greater than 4.1 (ie, for Example B, Δa* _G is 1.49, Δb*G is 3.81, and ΔL* (glass side) was not measured; using Equation (1) below, then the ΔE* on the glass side must necessarily be greater than 4.1 and may be much higher).

US Patent 5,563,734 discloses a low E coating system comprising: substrate/ _TiO2 / _NiCrNx / _Ag / _NiCrNx /Si3N4. Unfortunately, it has been found that when high nitrogen (N) flow rates are used in forming the _NiCrNx layer (see the high N flow rate of 143 seem in Table 1 of the '734 patent; translates to about 22 seem/kW), the resulting coated article Colors are not stable upon heat treatment (ie, they tend to have high ΔE* (glass side) values greater than 6.0). In other words, if subjected to HT, the '734 patent low E layer system would not be able to approximately color match its non-heat treated counterpart (as viewed from the glass side).

Furthermore, it is sometimes desirable for coated articles to have desirable visible light transmission properties and/or good (mechanical and/or chemical) durability. Unfortunately, certain known steps taken to adjust or improve visible light transmission properties and/or pre-HT durability tend to reduce post-HT durability and thermal stability. Therefore, 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 is a need for a low E coating or layer system that is color and/or reflective (as observed by the human eye) after HT substantially matched to its unheat-treated counterpart. In other words, there is a need in the art for a low E matching coating or layered system. There is also a need in the art for a heat treatable system that can incorporate one or more of: (1) a desired visible light transmission characteristic (eg, about 30%-75% measured on a single sheet, and/or a IG units measured as 30%-70%), (2) good durability before and/or after heat treatment, (3) low ΔE* values indicating color stability upon heat treatment (HT), and/or (4) Absorbent films designed to adjust visible light transmission and provide desired coloration to coated articles while maintaining durability and/or thermal stability.

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

SUMMARY OF THE INVENTION

An exemplary object of the present invention is to provide a low E coating or layer system with good color stability (low ΔE* value) upon heat treatment (HT). Another exemplary object of the present invention is to provide a low E matchable coating or layering system. In certain exemplary embodiments, another exemplary object is to provide an absorbing film in a low E coating that is designed to adjust visible light transmission and provide a desired coloration to the coated article, While maintaining durability and/or thermal stability.

Exemplary embodiments of the present invention relate to low-E coated articles having approximately the same color characteristics as observed with the naked eye, both before and after heat treatment (eg, thermal tempering), and corresponding methods. In certain exemplary embodiments, such articles may incorporate two or more of: (1) desirable visible light transmission properties, (2) good durability before and/or after heat treatment, (3) indicative of heat treatment (HT) low ΔE* values for color stability, and/or (4) absorbing films designed to adjust visible light transmission and provide desired coloration to coated articles while maintaining durability and/or thermal 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 having or comprising NiCr (NiCrO _x ) which is partially or fully oxidizable of the second layer. Thus, in certain exemplary embodiments, such a multilayer absorber film may be composed of a layer sequence of Ag/ _NiCrOx . This sequence of layers may be repeated in some illustrative examples. The silver base layer in the absorbing 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 functioning primarily as an IR reflective layer). NiCr or _NiCrOx is placed 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 present invention, a single layer of NiCr (or other suitable material) may also be used as an absorber film in a low E coating. However, it has surprisingly been found that the use of silver in absorber films (single or multi-layer absorber films) provides several unexpected advantages compared to single layer NiCr as absorber. First, it has been found that a single layer of NiCr as an absorber tends to cause a yellowish tint in certain low E coating 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 this yellowish coloration and/or instead provides a more desirable neutral coloration of the resulting coated article. Accordingly, the use of silver in absorbing films has been found to provide improved optical properties. Second, using a single layer of NiCr as an absorber often also involves providing a silicon nitride base layer on both sides of the NiCr so that the NiCr is directly sandwiched between and in contact with it. It has been found that providing silicon nitride at certain locations in the coating stack may result in compromised thermal stability during HT. In contrast, it has been surprisingly found that when silver is used in the absorber film, a pair of immediately adjacent silicon nitride layers is not required, thereby improving thermal stability at HT. Accordingly, the use of silver in absorber films has been found to provide improved thermal stability, including lower ΔE* values, and thus improved matching between HT and non-HT versions of the same coating. The use of silver in absorber films can also provide improved manufacturability in some cases.

In certain exemplary embodiments, it has been found, surprisingly and unexpectedly, that an infrared (IR) reflective layer having or comprising silver in the low E coating is disposed with or comprising at least one dopant As-deposited crystalline or substantially crystalline (eg, at least 50% crystalline, more preferably at least 60% crystalline) layers of zinc oxide of impurities (eg, Sn) have significantly improved thermal stability of the coating (ie, reduced ΔE* value). In various embodiments of the present invention, one or more such crystalline or substantially crystalline (eg, at least 50% crystalline, more preferably at least 60% crystalline, for example, at least 50% crystalline, more preferably at least 60% crystalline) may be disposed beneath one or more corresponding silver-containing IR reflective layers. % crystalline) layer. Thus, in various embodiments of the present invention, a crystalline or The substantially crystalline layer can 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, one example of which is about 10% Sn (in wt %). Zinc oxide doped with Sn is in the as-deposited crystalline or substantially crystalline phase (as opposed to amorphous or nanocrystalline), such as via sputter deposition techniques from at least one sputter target having or comprising Zn and Sn. The as-deposited crystalline phase doped zinc oxide based layer combination with silver and glass allows the coated article to achieve improved thermal stability (reduced ΔE* value) with optional HT. It is believed that the combination of the as-deposited crystalline phase of the doped zinc oxide based layer (eg, at least 50% crystalline, more preferably at least 60% crystalline) with the layer between the IR reflective layer and the glass allows the silver of the IR reflective layer to have improved A crystal structure that is textured but has some randomly oriented grains such that its refractive index (n) changes less with optional HT, allowing improved thermal stability to be achieved.

In certain exemplary embodiments, it has also been surprisingly and unexpectedly discovered that arrangements having or comprising silicon oxide, zirconium oxide, zirconium oxynitride, silicon zirconium oxide, and/or silicon zirconium oxynitride (eg, SiZrO _x , zirconium oxynitride, etc.) Dielectric layers of ZrO ₂ , SiO ₂ and/or SiZrO _x N _y ) also provide improved thermal stability of the coated article and thus lower ΔE* values during thermal treatment (HT) such as thermal tempering. In certain exemplary embodiments, silicon oxide, zirconium oxide, silicon zirconium oxide, and/or silicon zirconium oxynitride (eg, SiZrO _x , ZrO ₂ , SiO ₂ , and/or SiZrO _x N _y ) may be provided that have or include At least one dielectric layer: (i) in the bottom dielectric portion of the coating below all silver-based IR reflective layers, and/or (ii) in the middle dielectric portion of the coating between a pair of silver-based IR reflective layers middle. For example, in certain exemplary embodiments of the present invention, a dielectric layer having or comprising silicon oxide, zirconium oxide, silicon zirconium oxide, and/or silicon zirconium oxynitride may be disposed directly below the lowermost doped zinc oxide based layer and in contact therewith, and/or disposed between a pair of zinc oxide containing layers in the intermediate dielectric portion of the low E coating.

In various exemplary embodiments of the present invention, a dielectric layer having or comprising silicon oxide, zirconium oxide, silicon zirconium oxide, and/or silicon zirconium oxynitride may or may not be associated with as-deposited crystalline or A substantially crystalline (eg, at least 50% crystalline, more preferably at least 60% crystalline) layer combination is disposed immediately below the infrared (IR) reflective layer, the zinc oxide doped with at least one dopant ( such as Sn).

In certain exemplary embodiments, it has been surprisingly and unexpectedly discovered that the initial sputter deposition has or comprises zirconium oxide (eg, ZrO ₂ ), zirconium oxynitride, zirconium silicon oxide, and/or zirconium silicon oxynitride ( Dielectric layers such as SiZrO _x , ZrO ₂ , SiO ₂ and/or SiZrO _x N _y ) to comprise a monoclinic crystal structure are advantageous as it results in the coated article having improved thermal stability upon thermal treatment (HT) (lower ΔE* values) and/or reduced visible transmittance (eg T _vis or TY ) changes. In certain exemplary embodiments, a dielectric layer (eg, ZrO ₂ ) can be achieved by using a very high oxygen flow rate for the layer during sputter deposition of the layer, and using a metal sputter target (eg, a Zr target) the monoclinic phase. For example, when sputter depositing layers 2 and/or 2" to form a layer having a monoclinic phase, the sputtering process for this layer may achieve at least 5ml/kW, more preferably at least 6ml/kW, more preferably An oxygen flow of at least 8 ml/kW, most preferably at least 10 ml/kW, where ml represents the total oxygen flow in the chamber and kW represents the power to the target. It should be noted that in certain exemplary embodiments of this Such high oxygen flow rates as desired are counterintuitive and generally undesirable because they reduce deposition rates and thus create increased time and expense in making coated articles. Although certain types of sputtering equipment are used In certain exemplary embodiments, high oxygen flow rates are used to achieve the monoclinic phase associated with the metal target, but the invention is not so limited as it has been found that for certain types of sputtering equipment, the monoclinic phase It can also be achieved with low or lower oxygen flow.

It has been found that the significant partial or complete phase transition of the layer from monoclinic to tetragonal or cubic structure upon HT and the corresponding change in density tend to compensate for the change in the crystal structure of the silver layer upon HT, which appears to result in coating Articles have improved thermal stability (lower ΔE* values) and/or reduced changes in visible light transmittance (T _vis or TY ) at HT. Surprisingly, it has been found that initial sputter deposition of zirconium oxide, zirconium oxynitride, silicon zirconium oxide and/or silicon zirconium oxynitride (eg SiZrO _x , ZrO ₂ , SiO ₂ and/or SiZrO _x N _y ) It is advantageous for the dielectric layer to contain a monoclinic phase crystal structure because it results in at least about 0.25 g/cm ³ , more preferably at least about 0.30 g/cm ³ and most preferably at least about 0.35 g/cm ³ at HT ( A high layer density variation of, for example, about 5.7 g/cm ³ to about 6.1 g/cm ³ ), which in turn compensates for the change in the crystal structure of the silver layer at the HT, resulting in the coated article having upon heat treatment (HT) Improved thermal stability (lower ΔE* values) and/or reduced visible transmittance (eg T _vis or TY ) changes. In certain exemplary embodiments, this results in no more than 1.2%, more preferably no more than 1.0%, and most preferably no more than 0.5% reduction in visible light transmittance (T _vis or TY) of the coated article due to HT changes, and/or decreased ΔE* values.

It has also been surprisingly and unexpectedly found that between the glass substrate and the lowermost silver layer, the silicon nitride layer not disposed directly under and in contact with the lowermost doped zinc oxide layer, has no difference with the as-deposited crystalline phase. The combination of doped zinc oxide based layers allows for improved thermal stability (reduced ΔE* values) upon thermal processing. It was also surprisingly and unexpectedly found that not providing a silicon nitride based layer in the middle section of the stack between two silver based IR reflective layers allows for improved thermal stability (lower ΔE) upon thermal processing. *value).

In certain exemplary embodiments measured monolithically and/or measured with an IG unit with dual panes, the coated article is configured to achieve one or more of the following: (i) at a temperature of about 650°C Transmission ΔE* values (in the case of measuring transmission optics) at 8 minutes, 12 minutes and/or 16 minutes under HT of not greater than 3.0 (more preferably not greater than 2.8 and most preferably not greater than 2.5 or 2.3), (ii) Glass side reflection ΔE* values (in the case of measuring glass side reflection optics) at a temperature of about 650°C for 8 minutes, 12 minutes and/or 16 minutes of HT not greater than 3.0 (more preferably not greater than 2.5, more preferably no greater than 2.0, and most preferably no greater than 1.5, no greater than 1.0, and/or no greater than 0.6), and/or (iii) HT at a temperature of about 650°C for 8 minutes, 12 minutes, 16 minutes Film side reflection ΔE* values at minutes and/or 20 minutes (in the case of measuring film side reflection optics) not greater than 3.5 (more preferably not greater than 3.0 and most preferably not greater than 2.0, or not greater than 1.5 or 1.3). Of course, in commercial practice, bake times may be used for different/other time periods, and these time periods are for reference purposes. In certain exemplary embodiments measured monolithically, the coated article is constructed to have at least about 30%, more preferably at least about 40%, and most preferably at least about 50% ( For example, about 45%-60%) visible light transmittance (T _vis or Y). The coated articles herein may have, for example, about 30%-75% visible light transmittance measured monolithically, and/or 30%-70% visible light transmittance measured in IG units. Among them, the thickness, composition and/or number of layers of the absorber can be adjusted to adjust the visible light transmittance. In certain exemplary embodiments measured monolithically, the coated article is constructed to have a glass side visible light reflection ( _RgY or RGY) of no greater than about 20% measured monolithically before or after any optional HT .

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 coating comprising a dopant disposed on the glass substrate A crystalline or substantially crystalline layer of zinc oxide doped with about 1% to 30% Sn (wt %); a first infrared (IR) reflective layer comprising silver 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; %-30% Sn zinc oxide directly below and in contact with a first crystalline or substantially crystalline layer; at least one dielectric layer having a monoclinic phase and comprising zirconium oxide; wherein said having a monoclinic phase and At least one dielectric layer comprising zirconium oxide is located at: (1) at least the glass substrate and the first crystalline or substantially crystalline layer comprising zinc oxide doped with about 1%-30% Sn (wt %) between, and/or (2) between at least the first IR reflective layer comprising silver and the second IR reflective layer comprising silver of the coating; an optional absorbing film comprising a layer, wherein the ratio of the physical thickness of the first silver-containing IR reflective layer of the absorber film to the physical thickness of the silver-containing layer is at least 5:1 (more preferably at least 8:1, even more preferably at least 10:1, and most preferably at least 15:1); and wherein the coated article is constructed to have at least two of the following measured in a single piece: (i) due to at a temperature of about 650°C a transmission ΔE* value of not greater than 3.0 due to the reference heat treatment for 12 minutes, (ii) a glass side reflection ΔE* value of not greater than 3.0 due to the reference heat treatment performed at a temperature of about 650°C for 12 minutes, and (iii) A film side reflection ΔE* value of not greater than 3.5 due to the reference heat treatment at a temperature of about 650° C. for 12 minutes.

Such coated articles can be used monolithically on windows, insulated glass (IG) window units (eg, on Surface #2 or Surface #3 in IG window unit applications), laminated window units, vehicle windshields and/or or other vehicle or architectural or residential window applications.

The present invention will now be described with respect to certain embodiments of the invention as shown in the following drawings, wherein:

Description of drawings

Figure 1(a), Figure 1(b), Figure 1(c), Figure 1(d), Figure 1(e), Figure 1(f), Figure 1(g), Figure 1(h) and Figure 1 (i) is a cross-sectional view of a coated article according to an exemplary embodiment of the present invention.

2 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 1 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(a).

3 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 2 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(a).

4 is a graph showing the optical characteristics of Example 1: as coated (annealed) before heat treatment, after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes in the leftmost data column (HTX) and after heat treatment at 650°C for 24 minutes in the far right data column (HTXXX).

5 is a graph showing the optical characteristics of Example 2: as coated (annealed) before heat treatment, after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes in the leftmost data column (HTX) and after heat treatment at 650°C for 24 minutes in the far right data column (HTXXX).

6 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 3 on a 3.1 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(a).

7 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 4 on a 3.1 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(a).

Figure 8 is a graph showing the optical properties of Examples 3-4: as-coated (annealed) before heat treatment, after heat treatment at 650°C for 8 minutes (FIT), HT at 650°C for 12 minutes in the leftmost data column After (HTX) and after heat treatment at 650°C for 20 minutes in the far right data column (HTXXX).

9 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 5 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(a).

10 is a graph showing the optical characteristics of Example 5: as coated (annealed) before heat treatment, after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes in the leftmost data column (HTX) and after heat treatment at 650°C for 24 minutes in the far right data column (HTXXX).

11 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 6 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(a).

12 is a graph showing the optical characteristics of Example 6: as coated (annealed) before heat treatment, after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes in the leftmost data column (HTX) and after heat treatment at 650°C for 24 minutes in the far right data column (HTXXX).

13 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 7 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(a).

14 is a graph showing the optical characteristics of Example 7: as coated (annealed) before heat treatment, after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes in the leftmost data column (HTX) and after heat treatment at 650°C for 24 minutes in the far right data column (HTXXX).

15 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 8 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(a).

16 is a graph of wavelength (nm) versus refractive index (n) showing the change in refractive index of the silver layer of Example 8 from the as-coated (AC) state to the heat-treated (HT) state.

17 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 9 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(a).

18 is a graph showing the optical properties of Example 9: as coated (annealed) before heat treatment in the leftmost data column, after heat treatment at 650°C for 12 minutes (HT) and at 650°C in the rightmost data column After 16 minutes of HT (HTX).

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

20 is a cross-sectional view of a coated article according to one embodiment of the present invention, showing the coatings of Examples 1-10.

21 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 10 on a 3.1 mm thick glass substrate, where the low E coating is generally represented by FIGS. 1( a ) and 10 out.

22 is a graph of 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.

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

24 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 11 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(b).

25 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 12 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(b).

26 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 13 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(b).

Figure 27 is a graph showing the optical properties of Examples 11-13: as coated (annealed) before heat treatment, after heat treatment at 650°C for 12 minutes (HT), HT 16 at 650°C in the respective leftmost data column After minutes (HTX) and after heat treatment at 650°C for 24 minutes (HTXXX) in the respective rightmost data column.

28 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Example 14 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. 1(b).

29 is a graph showing the optical characteristics of Example 14: as coated (annealed) before heat treatment, after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes in the leftmost data column (HTX) and after heat treatment at 650°C for 24 minutes in the far right data column (HTXXX).

FIG. 30 is a graph showing sputter deposition conditions for the sputter deposition of the low E coatings of Examples 15 and 16 with a bottommost dielectric layer of ZrO2 _on a 6 mm thick glass substrate. This is generally shown by Figure 1(b).

31 is a graph showing the optical characteristics of Examples 15 and 16: as-coated (annealed) before heat treatment in the leftmost data column, after heat treatment at 650° C. for 12 minutes (FIT) and in the rightmost data column After 16 min HT at 650°C (HTX).

32 is a graph showing sputter deposition conditions for the sputter deposition of the low E coatings of Example 17 and Example 18 on a 6 mm thick glass substrate having a ) The low-E coating of the bottom-most dielectric layer of SiO ₂ is generally shown in Figure 1(b).

33 is a graph showing the optical properties of Examples 17 and 18: as-coated (annealed) before heat treatment in the leftmost data column, after heat treatment at 650° C. for 12 minutes (HT) and in the rightmost data column After 16 min HT at 650°C (HTX).

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

Figure 35 is a graph showing the optical properties of Comparative Example 2 (CE 2): as coated (annealed) before heat treatment, after heat treatment at 650°C for 12 minutes (HT), HT at 650°C in the leftmost data column After 16 minutes (HTX) and in the far right data column after heat treatment at 650°C for 24 minutes (HTXXX).

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

Figure 37 shows, at the top, sputter deposition conditions for sputter deposition of the low E coating of Example 20 on a 6 mm thick glass substrate, where the low E coating is generally shown in Figure 1(e) and in The bottom shows the optical properties of Example 20: as coated before heat treatment (annealed; AC), after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes (HTX) and at 650°C After heat treatment for 24 minutes (HTXXX).

FIG. 38 shows at the top sputter deposition conditions for sputter deposition of the low E coating of Example 21 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. The bottom shows the optical properties of Example 21: as coated before heat treatment (annealed; AC), after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes (HTX) and at 650°C After heat treatment for 24 minutes (HTXXX).

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

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

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

42 shows at the top sputter deposition conditions for sputter deposition of the low E coating of Example 25 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. The bottom shows the optical properties of Example 25: as coated before heat treatment (annealed; AC), after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes (HTX) and at 650°C After heat treatment for 24 minutes (HTXXX).

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

44 shows at the top sputter deposition conditions for sputter deposition of the low E coating of Example 27 on a 6 mm thick glass substrate, where the low E coating is generally shown in FIG. The bottom shows the optical properties of Example 27: as coated before heat treatment (annealed; AC), after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes (HTX) and at 650°C After heat treatment for 24 minutes (HTXXX).

Figure 45 shows, at the top, sputter deposition conditions for sputter deposition of the low E coating of Example 28 on a 6 mm thick glass substrate, where the low E coating is generally shown in Figure 1(e), and in The bottom shows the optical properties of Example 28: as coated before heat treatment (annealed; AC), after heat treatment at 650°C for 12 minutes (HT), after heat treatment at 650°C for 16 minutes (HTX) and at 650°C After heat treatment for 24 minutes (HTXXX).

Figure 46 shows at the top sputter deposition conditions for the sputter deposition of the low E coating of Example 29 on a 6 mm thick glass substrate, where the low E coating is generally shown in Figure 1(h), with different Layer 2" is not provided in Example 29, and the optical properties of Example 29 are shown at the bottom: as coated (annealed; AC) before heat treatment, after heat treatment at 650°C for 12 minutes (HT), at 650°C After heat treatment at 650° C. for 16 minutes (HTX) and after heat treatment at 650° C. for 24 minutes (HTXXX).

Figure 47 shows at the top sputter deposition conditions for sputter deposition of the low E coating of Example 30 on a 6 mm thick transparent glass substrate, wherein the low E coating is generally shown in Figure 1(i), and The optical properties of Example 30 measured monolithically are shown at the bottom: as-coated before heat treatment (annealed; AC), after heat treatment at 650°C for 12 minutes (HT) and after HT at 650°C for 16 minutes (HTX) .

Figure 48 shows at the top sputter deposition conditions for sputter deposition of the low E coating of Example 31 on a 6 mm thick transparent glass substrate, wherein the low E coating is generally shown in Figure 1(i), and The optical properties of Example 31 measured monolithically are shown at the bottom: as-coated (annealed; AC) before heat treatment, after heat treatment at 650°C for 12 minutes (HT) and after HT at 650°C for 16 minutes (HTX) .

49 shows at the top sputter deposition conditions for sputter deposition of the low E coating of Example 32 on a 6 mm thick transparent glass substrate, where the low E coating is generally shown in FIG. 1(i), and The optical properties of Example 32 measured monolithically are shown at the bottom: as-coated (annealed; AC) before heat treatment, after heat treatment at 650°C for 12 minutes (HT) and after HT at 650°C for 16 minutes (HTX) .

Figure 50 shows at the top sputter deposition conditions for sputter deposition of the low E coating of Example 33 on a 6 mm thick transparent glass substrate, where the low E coating is generally shown in Figure 1(i), and The optical properties of Example 33 measured monolithically are shown at the bottom: as-coated (annealed; AC) before heat treatment, after heat treatment at 650°C for 12 minutes (HT) and after HT at 650°C for 16 minutes (HTX) .

Figure 51 shows graphs of sputter deposition of a ZrO2 layer using a metallic Zr target (upper image) and a ceramic _ZrOx target (lower image ₎ before and after HT, and showing that the layer comprises a monoclinic crystal when a metal target is used phase (see peak at m _- ZrO2), while the layer does not include the monoclinic phase when a ceramic target is used in this particular case.

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 the layer stacks of Examples 34-42 and Comparative Examples (CE) 43-47.

Figure 53 shows the optical data for Examples 34-42: as coated (AC; annealed) before heat treatment in the leftmost data column of each example and after heat treatment at 650°C for 12 minutes (HT) in the right data column of each example ), Examples 34-42 have coating stacks as shown in Figures ₁ (i) and 52, in which the monoclinic ZrO2 layer was deposited with a metal target and the layer thicknesses of Examples 34-42 are shown in Figure 55 where sample 7982 is embodiment 34, sample 8077 is embodiment 35, sample 8085 is embodiment 36, sample 8090 is embodiment 37, sample 8091 is embodiment 38, sample 8097 is embodiment 39, and sample 8186 is embodiment 40, Sample 8187 is Example 41, and Sample 8202 is Example 42.

Figure 54 shows optical data for Comparative Examples (CE) 43-47: as coated (AC; annealed) prior to heat treatment in the leftmost data column of each example and heat treated at 650°C for 12 minutes in the right data column of each example After (HT), Examples 43-47 had the coating stacks shown in Figure 1(i) and Figure 52, in which a non _- monoclinic ZrO2 layer was deposited with a ceramic target, and the layer thicknesses of Examples 43-47 As shown in Figure 56; where sample 8392 is CE 43, sample 8394 is CE 44, sample 8395 is CE45, sample 8396 is CE 46, and sample 8397 is CE 47.

55 is a graph showing deposition process conditions and layer thicknesses for Example 37 with monoclinic _ZrO layers, where the total oxygen flow ₍ ml ₎ during the sputtering process for each layer is set by O , O _The sum of the conditioning and O offset indicates that the high oxygen flow during sputter deposition of the ZrO layer helps to provide the monoclinic phase of the _ZrO layer of Example 37 ₍ monoclinic Examples 34-36 and 38- 42 with similar process conditions).

Figure 56 is a graph showing deposition process conditions and layer thicknesses for Comparative Example (CE) 44 with non _- monoclinic ZrO layers, where the total oxygen flow (ml ₎ during the sputtering process for each layer was set by O _The sum of the value, O adjustment, and O offset indicates that the low oxygen flow during sputter deposition of the ZrO layer, together with the ceramic target, helps to provide the non _- monoclinic phase (non _- monoclinic ₎ of the ZrO layer of Example 44. Crystal Examples 43 and 45-47 had similar process conditions).

57 is a graph showing deposition process conditions and layer thicknesses for Example 48 with a monoclinic ZrO ₂ layer deposited via a ceramic target.

FIG. 58 is a graph showing ΔE* values for Example 48 with different heat treatment times.

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

Detailed ways

Reference is now made more particularly to the drawings, wherein 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 coated articles that can be used monolithically on windows, insulating glass (IG) window units (eg, IG surface #2 or surface #3 in window unit applications), laminated window units, vehicle windshields, and/or other vehicle or architectural or residential window applications. Certain embodiments of the present invention provide layer systems that combine one or more of high visible light transmission, good durability (mechanical and/or chemical) before and/or after HT, and good color stability upon heat treatment . This article will show how certain layer stacks surprisingly achieve this unique combination.

With regard to color stability, certain embodiments of the present invention have excellent color stability in the case of monolithic heat treatments (eg, thermal tempering or thermal bending) and/or dual pane environments (such as IG units or windshields) (ie, low ΔE* values; where Δ indicates the change due to heat treatment). Such heat treatment (HT) typically requires heating the coated substrate to at least about 1100°F (593°C) and at most 1450°F (788°C) [more preferably about 1100°F to 1200°F, and most preferably 1150°F-1200°F °F] for a sufficient period of time to ensure the final result (eg, tempering, bending, and/or heat strengthening). Certain embodiments of the present invention combine one or more of (i) color stability under heat treatment and (ii) use of a silver-containing layer for selective IR reflection.

Exemplary embodiments of the present invention relate to low-E coated articles having approximately the same color characteristics as observed with the naked eye, both before and after heat treatment (eg, thermal tempering), and corresponding methods. In certain exemplary embodiments, such articles may incorporate one or more of: (1) desirable visible light transmission characteristics, (2) good durability before and/or after heat treatment, (3) indicative of heat treatment ( low ΔE* values for color stability at HT), and/or (4) absorbing films designed to adjust visible light transmittance and provide the desired coloration to the coated article while maintaining durability and/or thermal stability.

厚，更优选地不大于约

厚，更优选地不大于约

厚，并且最优选地不大于约

厚，并且可能不大于约

厚。在某些示例性实施方案中，吸收膜的NiCr基层59可为约

厚，更优选地约

厚，并且最优选地约

厚。In certain exemplary embodiments, the absorber film may be a multilayer absorber film that includes a first layer 57 having or comprising silver (Ag), and a second layer having or comprising NiCr (NiCrO _x ) which is partially or fully oxidizable 59 on the second floor. See eg Figure 1(i). Thus, in certain exemplary embodiments, such multilayer absorber films 57, 59 may be composed of a layer sequence of Ag/ _NiCrOx . Elements from one layer can diffuse into adjacent layers due to HT or other factors. In certain example embodiments, the NiCr base layer 59 of the absorber may be deposited initially 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 base layer 57 of the absorbing 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 functioning primarily as an IR reflective layer). NiCr or NiCrO _x 59 is placed over and in contact with the silver 57 of the absorber film in order to protect the silver and also to aid in absorption. In certain exemplary embodiments, the silver-based layer 57 of the absorber film may, in certain exemplary embodiments of the present invention, be no greater than about

thick, more preferably no greater than about

thick, more preferably no greater than about

thick, and most preferably no greater than about

thick, and may not be greater than approx.

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

thick, more preferably about

thick, and most preferably about

thick.

In certain exemplary embodiments of the present invention, a single layer of NiCr (or other suitable material) may also be used as an absorber film in a low E coating. See, for example, absorber film 42 in Figures 1(d) and 1(f). However, it has been surprisingly found that the use of silver 57 in absorber films (single or multilayer absorber films) provides several unexpected advantages compared to single layer NiCr as absorber. First, it has been found that a single layer of NiCr as an absorber tends to cause a yellowish tint in certain low E coating coated articles, which may be undesirable in certain circumstances. In contrast, it has been surprisingly found that the use of silver 57 in the absorbent film tends to avoid this yellowish coloration and/or instead provides a more desirable neutral coloration of the resulting coated article. Accordingly, the use of silver 57 in the absorber film has been found to provide improved optical properties. Second, using a single layer of NiCr 42 as the absorber often also involves providing a silicon nitride base layer on both sides of the NiCr so that the NiCr is directly sandwiched between and in contact with it. See, for example, Figures 1(d) and 1(f). It has been found that providing silicon nitride at certain locations in the coating stack may result in compromised thermal stability during HT. In contrast, it has been surprisingly found that when silver is used in the absorber film, a pair of immediately adjacent silicon nitride layers is not required, thereby improving thermal stability at HT. Accordingly, the use of silver 57 in the absorber film has been found to provide improved thermal stability, including lower ΔE* values, and thus improved matching between HT and non-HT versions of the same coating. The use of silver in absorber films can also provide improved manufacturability in some cases.

Surprisingly and unexpectedly, it has been found that the infrared (IR) reflective layer 7 (and/or 19 ) in the low E coating 30 with or comprising silver is disposed with or doped with at least one dopant. As-deposited crystalline or substantially crystalline layers 3, 3" (and/or 13) (eg, at least 50% crystalline, more preferably at least 60% crystalline) of zinc oxide of impurities (eg, Sn) and in direct contact therewith have The effect of significantly improving the thermal stability of the coating (ie, reducing the ΔE* value). As used herein, "substantially crystalline" means at least 50% crystalline, more preferably at least 60% crystalline, and most preferably at least 70% crystalline Crystalline. In various exemplary embodiments of the invention, one or more such crystalline or substantially crystalline layers 3, 3", 13 may be provided over one or more corresponding IR reflective layers comprising silver 7, 19 below. Thus, in various embodiments of the present invention, the infrared (IR) reflective layers 7 and/or 19 with or containing silver directly below the Crystalline or substantially crystalline layers 3 (or 3") and/or 13 of zinc oxide may be used for single silver low E coatings, double silver low E coatings (eg, such as shown in Figure 1 or Figure 20) or triple silver Low E coating. In certain exemplary embodiments, 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, one example of which is about 10% Sn (by weight %). Zinc oxide doped with Sn can be obtained from materials having or containing Zn and At least one sputtering target of Sn is in the as-deposited crystalline phase or substantially crystalline phase (as opposed to amorphous or nanocrystalline) on layers 3 and/or 13. The as-deposited crystalline phase of the doped zinc oxide base layer 3 and/or Or 13 in combination with layers between silver 7 and/or 19 and glass 1, allowing the coated article to achieve improved thermal stability (reduced ΔE* value) upon optional HT. It is believed that the doping of the as-deposited crystalline phase A hybrid zinc oxide base layer 3 and/or 13 and a layer combination between silver and glass, allowing the silver 7 and/or 19 deposited thereon to have an improved crystal structure that is textured but with some random orientation grains so that their refractive index (n) changes less with optional HT, allowing for improved thermal stability.

It was also surprisingly and unexpectedly found that the arrangement has or contains silicon oxide, zirconium oxide, silicon zirconium oxide and/or silicon zirconium oxynitride (eg, SiZrO _x , ZrO ₂ , SiO ₂ and/or SiZrO _x N _y ) The dielectric layers (eg, 2 and/or 2") also provide improved thermal stability of the coated article, as shown, for example, in Figures 1(b)-1(i), and thus during thermal processing (HT) such as thermal reclamation Fire reduces the ΔE* value. In certain exemplary embodiments, there may be provided with or comprising silicon oxide, zirconium oxide, silicon zirconium oxide, and/or silicon zirconium oxynitride (eg, SiZrO _x , ZrO ₂ , SiO ₂ and/or or _SiZrOxNy ) at least one dielectric layer (eg, 2 and/or 2"): ( _i ) in the bottom dielectric portion of the coating below all silver-based IR reflective layers (eg, see Figure 1(b) )-1(i)), and/or (ii) in the intermediate dielectric portion of the coating between a pair of silver-based IR reflective layers (see, eg, Figures 1(e)-1(i)) . For example, in certain exemplary embodiments of the present invention, a dielectric layer (eg, 2 and/or 2") having or comprising silicon oxide, zirconium oxide, silicon zirconium oxide, and/or silicon zirconium oxynitride may be disposed at the most directly below and in contact with the underlying doped zinc oxide based layer (eg, 3), and/or disposed between a pair of zinc oxide-containing layers (eg, between 11 and 11 ) in the intermediate dielectric portion of the low-E coating between 13, or between 11 and 3").

_In various exemplary embodiments of the present invention, a dielectric layer (eg, ₂ and/or 2") may or may not be combined with as-deposited crystalline or substantially crystalline (eg, at least 50% crystalline, more preferably at least 60% crystalline) layers (eg, 3 and/or 13) in combination immediately below the infrared (IR) reflective layer, the zinc oxide doped with at least one dopant (eg Sn). The two methods that can be used together but do not need to be used together improve For example, when using dielectric layers having or containing silicon oxide (eg, SiO ₂ ), zirconium oxide (eg, ZrO ₂ ), silicon zirconium oxide, and/or silicon zirconium oxynitride (eg, , 2 and/or 2"), the contact/seed layer immediately below one or both silvers may have or may comprise zinc oxide doped with aluminum (rather than Sn), and The contact/seed layer need not be crystalline (eg, see Figures 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 comprises zirconium oxide, zirconium oxynitride, zirconium silicon oxide, and/or zirconium silicon oxynitride (eg, SiZrO _x , ZrO ₂ , SiO ₂ and/or SiZrO _x N _y ) dielectric layers 2 and/or 2 ″ to contain a monoclinic phase crystal structure are advantageous as it leads to improved thermal stability of the coated article upon thermal treatment (HT) (lower ΔE* values) and/or reduced visible light transmittance (eg, T _vis or TY). See, for example, Figures 1(a)-1(i), Figures 51-53, and Figure 55. In a certain In some example embodiments, the dielectric layers 2 and/or 2" may also include other materials such as Ti and/or Nb. In certain exemplary embodiments, the monoclinic phase of the dielectric layer (eg, ZrO ₂ ) 2 and/or ₂ ″ (eg, see m-ZrO peak in the upper panel of FIG. 51 ) may pass through the layer The sputter deposition process for this layer uses very high oxygen flow rates for this layer, and uses a metal sputter target (eg, a metal Zr or SiZr target) (see, eg, Figure 55). It should be noted that in certain Such high oxygen flow rates, which are desired in some exemplary embodiments, are counterintuitive for zirconia-based layers and are generally undesirable because they reduce deposition rates and thus create increased time in the manufacture of coated articles. and cost. It has been found that upon HT, layers 2 and/or ₂ " go from a monoclinic phase (see the m-ZrO peak in the upper panel of Figure 51) to a tetragonal or cubic structure (see c-ZrO2 in Figure 51). The significant partial or complete phase transition and corresponding density change of ZrO ₂ ) tend to compensate for the change in the crystal structure of the silver base layers 7, 57 and/or 19 upon HT, which appears to result in coated articles with improved HT upon HT Thermal stability (lower ΔE* values) and/or reduced visible light transmittance (T _vis or TY ) changes. In Figure 51, note how the monoclinic phase (see m _- ZrO peak in the top panel of Figure 51) is present in the top panel (high oxygen flow during deposition, and metallic Zr target), but not in the bottom panel Pictured (low oxygen flow during deposition, and ceramic ZrO _x target). And, also in the top panel of Figure 51, it can be seen how the monoclinic phase (see m _- ZrO2 peak) is higher before HT and lower after HT. Surprisingly, it has been found that initial sputter deposition of zirconium oxide, zirconium oxynitride, silicon zirconium oxide and/or silicon zirconium oxynitride (eg SiZrO _x , ZrO ₂ , SiO ₂ and/or SiZrO _x N _y ) It is advantageous for the dielectric layers 2 and/or 2" to contain a monoclinic phase crystal structure as it results in at least about 0.25 g/cm ³ , more preferably at least about 0.30 g/cm ³ and most preferably at least about 0.35 g/cm 3 due to HT The high layer 2 and/or 2" density variation in g/cm ³ (eg, about 5.7 g/cm ³ to about 6.1 g/cm ³ ), which in turn compensates for the Changes in crystal structure resulting in improved thermal stability (lower ΔE* values) and/or reduced changes in visible light transmittance (eg Tvis or TY) of the coated article upon heat treatment (HT). In certain exemplary embodiments, this results in no more than 1.2%, more preferably no more than 1.0%, and most preferably no more than 0.5% reduction in visible light transmittance (T _vis or TY) of the coated article due to HT changes, and/or decreased ΔE* values.

更优选地约

并且最优选地约

的物理厚度。It has also surprisingly been found that the increase has or comprises silicon oxide, zirconium oxide, zirconium oxynitride, silicon zirconium oxide and/or silicon zirconium oxynitride (eg SiZrO _x , ZrO ₂ , SiO ₂ and/or SiZrO _x N _y ) The thickness of the dielectric layers 2 and/or 2" tends to result in smaller changes in sheet resistance (Rs) and visible light transmittance at HT, and thus lower ΔE* values for the coated articles. In certain exemplary In embodiments, a dielectric layer ₂ having or comprising silicon oxide, zirconium oxide, zirconium oxynitride, silicon zirconium oxide, and/or silicon zirconium oxynitride (eg, _SiZrOx , _ZrO2 , _SiO2 , and/or _SiZrOxNy ) and/or one or both of 2" may each have approximately

More preferably about

and most preferably about

physical thickness.

It was also surprisingly and unexpectedly found that between the glass substrate 1 and the lowermost silver base layer 7, no silicon nitride base layer (for example, a silicon nitride base layer (eg, Si ₃ N ₄ , optionally doped with 1%-10% Al, etc.), in combination with the doped zinc oxide base layer 3 of the as-deposited crystalline phase or substantially crystalline phase, allows to achieve improved thermal stability during heat treatment (reduced ΔE* value). See, for example, the coatings of Figures 1(a)-1(d) and Figure 1(i). Furthermore, in certain exemplary embodiments, there is no amorphous or substantially amorphous layer located between the glass substrate 1 and the first IR reflective layer 7 comprising silver. It was also 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 reflective layers 7 and 19 allows for improved thermal stability upon thermal treatment (compared to low ΔE* values) (see, eg, Figures 1(a)-1(i)).

In certain exemplary embodiments, it has also been found in glass substrates with or containing silicon oxide, zirconium oxide, silicon zirconium oxide, and/or silicon zirconium oxynitride (eg, SiZrO _x , ZrO ₂ , SiO ₂ , and/or SiZrO _{x )} Disposing an absorber layer (eg, NiCr, _NiCrNx , _NbZr and/or _NbZrNx ) 42 between the dielectric layers 2 of Ny) can advantageously reduce the glass-side visible light reflection ( _RgY ) of the coated article in a desired manner, And allows the visible light transmittance to be adjusted in a desired manner. For example, in certain exemplary embodiments, such as shown in FIGS. 1(d) and 1(f), absorber layer 42 may be disposed on a pair of silicon nitride based layers 41 and 43 (eg, having or comprising Si3N _{) 4} (optionally doped with 1%-10% Al etc. and optionally containing 0%-10% oxygen) between and in contact with a pair of silicon nitride based layers. See also, eg, FIG. 39 and Example 22. In other exemplary embodiments, the stack of absorber layer 42 between nitride-based dielectric layers 41 and 43 may be located elsewhere within the stack.

In certain exemplary embodiments of monolithic measurements, in view of the structures described above (eg, see Figures 1(a)-1(i)), the coated article is configured to achieve one or more of the following: (i ) transmission ΔE* values (in the case of measuring transmission optics) at a temperature of about 650°C for 8 minutes, 12 minutes and/or 16 minutes HT of not greater than 3.0 (more preferably not greater than 2.8 or 2.5, and most Preferably not greater than 2.3), (ii) glass side reflection ΔE* values (in the case of measuring glass side reflection optics) at a temperature of about 650°C for 8 minutes, 12 minutes and/or 16 minutes of HT are not greater than 3.0 (more preferably not greater than 2.5, more preferably not greater than 2.0, more preferably not greater than 1.5, and most preferably not greater than 1.0 or 0.6), and/or (iii) HT at a temperature of about 650°C for 8 minutes, Film side reflection ΔE* values at 12 minutes and/or 16 minutes (in the case of measuring film side reflection optics) not greater than 3.5 (more preferably not greater than 3.0, more preferably not greater than 2.0, more preferably not greater than 1.5, and most preferably no more than 1.2).

In certain exemplary embodiments measured monolithically, the coated article is constructed to have at least about 30%, more preferably at least about 35%, more preferably at least about 40%, before or after any optional HT, More preferably at least about 50% visible light transmittance (T _vis or Y). In certain exemplary embodiments, before and/or after the optional thermal treatment, the low E coating has 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 sheet resistance (SR or _Rs ) of 2.2 ohms/square. In certain exemplary embodiments, the low E coating has a hemispheric specific emissivity/emissivity (E _h ) of no greater than 0.08, more preferably no greater than 0.05, and most preferably no greater than 0.04.

In the context of the present invention, the ΔE* value is important in determining whether the heat treatment (HT) is matched or substantially matched. 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 the desired substantially neutral color toward the blue-green quadrant range of colors. For the purpose of example, the term Δa* only indicates the degree of change in color value a* due to heat treatment.

In ASTM 2244-93 and in Hunter et al., The Measurement of Appearance, 2 ^nd Ed. Cptr. 9, page 162 et seq. [John Wiley & Sons, 1987] (Measurement of Appearance, 2nd Edition, Chapter 9, p. 162 and below, John Wiley Press, 1987), the term ΔE* (and ΔE), along with various techniques for determining it, are well known and reported in the art. As used in the art, ΔE* (and ΔE) is a way to adequately express the change (or lack thereof) in reflectance and/or transmittance (and thus color appearance) in an article after or due to heat treatment. ΔE can be calculated by the "ab" technique or by the Hunter technique (denoted by the use of the subscript "H"). ΔE corresponds to the Hunter Lab L, a, b scale (or L _h , a _h , b _h ). Similarly, ΔE* 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 Cartesian coordinate/scale technique known as L*, a*, b* scaling (CIE LAB 1976) can be used, where:

L* is the (CIE 1976) unit of luminance

a* is the (CIE 1976) red-green unit

b* is (CIE 1976) yellow-blue unit

And the distance ΔE* between L* _o a* _o b* _o and L* _l a* _l b* _l is:

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

in:

ΔL*=L* _l -L* _o (2)

Δa*=a* _l -a* _o (3)

Δb*=b* _l -b* _o (4)

where the subscript "o" refers to the coated article before heat treatment, and the subscript "l" refers to the coated article after heat treatment; LAB 1976) Numbers calculated by L*, a*, b* coordinate techniques. In a similar manner, ΔE can be calculated using equation (1) by replacing a*, b*, L* with the Hunter Lab values a _h , b _h , L _h . Also within the scope of the present invention, and if converted to a number calculated by any other technique employing the same concept of ΔE* as defined above, the quantification of ΔE* is an equivalent number.

In certain exemplary embodiments of the present invention, the low-E coating 30 includes two silver-based IR reflective layers (eg, see Figures 1(a)-1(i)), although the present invention is not in all cases So defined (eg, three silver-based IR reflective layers may be used in some cases). It should be appreciated that the coated articles of Figures 1(a)-1(i) are shown in monolithic form. However, these coated articles can also be used, for example, in IG window units.

Baking at high temperatures (eg, 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 reactions, resulting in 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. IR materials such as Ag have also changed. Typically, Ag materials undergo crystallization, grain growth, or even orientation changes upon thermal treatment. These changes often cause changes in conductivity, especially in refractive index n/k, which have a large impact on the optical and thermal properties of low-E coatings. In addition, dielectric and dielectric changes also have significant effects on IR reflective layers such as silver that undergo thermal treatment. Furthermore, silver can have more variation in one layer stack than in other layer stacks simply because of the material and the layer stack itself. If the silver changes beyond a certain limit, it may not be aesthetically acceptable after heat treatment. We have found that in order to obtain the thermal stability of the low E coating, a doped zinc oxide crystalline material with a thin modified layer directly or indirectly on the glass can be used under the silver of the IR reflective layer. It has been found that crystalline or substantially crystalline doped zinc oxide in these positions changes less during heat treatment and results in less change in properties of silver such as refractive index (eg n and/or k) and thus upon heat treatment Minor changes in overall color.

FIG. 1( a ) is a side cross-sectional view of a coated article according to an exemplary non-limiting embodiment of the present invention, wherein the low E coating 30 has two silver-based IR reflective layers 7 and 19 . The coated article includes a substrate 1 (eg, a transparent, green, bronze or blue-green glass substrate about 1.0 mm to 10.0 mm thick, more preferably about 3.0 mm to 8.0 mm thick), and is disposed directly or indirectly on the substrate 1 A low-E coating (or layer system) 30 on. In Figure 1(a), a coating (or layer system) 30 includes, for example, a dielectric layer 3 having or comprising zinc oxide doped with at least one metal dopant (eg, Sn and/or Al), so The dielectric layer is a crystalline or substantially crystalline layer in the as-deposited state; an infrared (IR) reflective layer 7 with or containing silver located above and in direct contact with layer 3; above and in direct contact with the IR reflective layer 7 Contact layer 9 having or comprising Ni and/or Cr (eg, NiCr, NiCrO _x , NiCrN _x , NiCrON, NiCrM, NiCrMoO _x etc.), Ti or other suitable material; having or comprising zinc stannate (eg ZnSnO, Dielectric layer ₁₁ of _Zn2SnO4 , or other suitable stoichiometry) or other suitable material, which may be amorphous or substantially amorphous as deposited; having or comprising doping with at least one dopant Another dielectric layer 13 of zinc oxide of impurities (eg, Sn), the dielectric layer being a crystalline or substantially crystalline layer in the as-deposited state; another layer 13 having or containing silver located above and in direct contact with layer 13 Infrared (IR) reflective layer 19; having or comprising Ni and/or Cr (eg, NiCr, NiCrO _x , NiCrN _x , NiCrON, NiCrM, NiCrMoO _x , etc.), Ti or Another contact layer 21 of other suitable material _; another dielectric layer 23 having or containing zinc stannate (eg, ZnSnO, _Zn2SnO4 , or other suitable stoichiometry) or other suitable material such as tin oxide, so The dielectric layer may be an as-deposited amorphous or substantially amorphous layer; and an amorphous or substantially amorphous dielectric layer having or comprising silicon _nitride (eg, _Si3N4 or other suitable stoichiometry) 25. The silicon nitride may be optionally doped with Al and/or O. The layers shown in Figure 1(a) may be deposited by sputtering or in any other suitable manner.

As explained herein, it has been found that the infrared (IR) reflective layers 7 and/or 19 in the low-E coating 30 directly below and in direct contact with or containing silver have or contain a dopant doped with at least one The presence of as-deposited crystalline or substantially crystalline layers 3 and/or 13 of zinc oxide of dopant (eg, Sn) has the effect of significantly improving the thermal stability of the coating (ie reducing the ΔE* value). In certain exemplary embodiments, 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 about 10% Sn (by weight %) being an example.

In certain exemplary embodiments, dielectric zinc stannate (eg, ZnSnO ₄ , Zn ₂ SnO ₄ , etc.) base layers 11 and 23 may be deposited in an amorphous or substantially amorphous state (which/they may become crystalline upon thermal treatment or substantially crystalline). It has been found that having similar amounts of Zn and Sn in the layer, or having more Sn in the layer than Zn, 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 may 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 (wt % excluding oxygen in the layer). Thus, for example, in certain exemplary embodiments of the present invention, amorphous or substantially amorphous can be sputter deposited using a metal target comprising about 52% Zn and about 48% Sn, or about 50% Zn and about 50% Sn Zinc stannate base layer 11 and/or 23. Optionally, the zinc stannate base layers 11 and 23 may be doped with other metals, such as Al or 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 the incorporation of good optical properties such as acceptable transmission, color and reflection) to achieve improved thermal stability. It should be noted that zinc stannate layers 11 and/or 23 may be replaced by corresponding layers of other materials, such as tin oxide, zinc oxide, zinc oxide doped with 1%-20% Sn (as discussed elsewhere herein for layers 11, 13 )Wait.

In certain embodiments of the present invention, the dielectric layer 25, which may be an overcoat, may be a dielectric layer having or comprising silicon _nitride (eg, _Si3N4 or other suitable stoichiometry) in order to improve coated articles heat treatability and/or durability. In certain exemplary embodiments, the silicon nitride may be optionally doped with Al and/or O, and may also be replaced in certain exemplary embodiments with other materials such as silicon oxide or zirconium oxide.

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

Other layers may also be provided below or above the coating shown in Figure 1 . Thus, when a layer system or coating is "on" or "supported by" the substrate 1 (directly or indirectly), one or more other layers may be disposed therebetween. Thus, for example, the coating of Figure 1(a) can be considered "on substrate 1" and "supported by" even if one or more other layers are disposed between layer 3 and substrate 1 . Furthermore, in certain embodiments certain layers of the coatings shown may be removed, while in other embodiments of the present invention other layers may be added between layers, or layers may be associated with separation sections Additional layers are added separately without departing from the overall essence of certain embodiments of the invention.

While various thicknesses and materials may be used in the layers in different embodiments of the invention, exemplary thicknesses and materials for the corresponding layers on the glass substrate 1 in the embodiment of Figure 1(a) are as follows, from the glass substrate outward :

Table 1 Exemplary Materials/Thicknesses; Figure 1(a) Embodiment

厚、更优选地约

厚并且最优选地约

厚。以上针对图1(a)实施方案的厚度也可适用于图1(b)-1(i)。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 also includes a doped zinc oxide based layer 3 Substantially transparent material having or comprising silicon zirconium oxide, silicon oxide and/or silicon zirconium oxynitride (eg SiZrO _x , ZrO ₂ , SiO ₂ , SiAlO ₂ and/or SiZrO _x N _y ) below and in direct contact therewith Dielectric layer 2. It has been found that this additional layer 2 provides further improved thermal stability of the coated article, and thus lower ΔE* values (eg, lower glass side reflection ΔE*) even upon thermal treatment (HT) such as thermal tempering value). In certain exemplary embodiments of the invention, there is or comprises zirconium silica, zirconia, silicon oxide, and/or zirconium oxynitride (eg, _SiZrOx , ZrO2, _SiO2 , _SiAlO2 , and/or _{SiZrOx )} . A dielectric layer 2 of N _y ) may be disposed directly below and in contact with the bottommost doped zinc oxide base layer 3 , as shown in FIG. 1( b ). In certain exemplary embodiments of the invention, there is or comprises zirconium silica, zirconia, silicon oxide, and/or zirconium oxynitride (eg, _SiZrOx , ZrO2, _SiO2 , _SiAlO2 , and/or _{SiZrOx )} . The dielectric layer 2 of N _y ) may be about

thick, more preferably about

thick and most preferably about

thick. The thicknesses above for the embodiment of Figure 1(a) may also apply to Figures 1(b)-1(i).

When layer 2 (or 2', or 2") has or comprises _SiZrOx and/or _SiZrOxNy , _it has been found that from an optical point of view, providing more Si than Zr in this layer advantageously has a low Refractive index (n) and improved antireflection and other optical properties. For example, in certain exemplary embodiments, when layer 2 ₍ or 2', or 2") has or comprises _SiZrOx and/or _SiZrOxNy , the metal content of the layer may comprise 51%-99% Si, more preferably 70%-97% Si and most preferably 80%-90% Si, and 1%-49% Zr, more preferably 3%-30% Zr, and most preferably 10%-20% Zr (atomic %). In an exemplary embodiment, the transparent _dielectric layer 2 having or comprising _SiZrOx and/or _SiZrOxNy may have a measurement at 550 nm of about 1.48 to 1.68, more preferably about 1.50 to 1.65, and most preferably about 1.50 Refractive index (n) to 1.62.

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 also includes a dielectric layer between the glass substrate 1 and the dielectric layer. ₂ with or in contact with silicon nitride (eg, Si3N4, optionally doped with ₁ %-10% Al, etc. and optionally containing 0%-10% oxygen, or other suitable stoichiometry) and/or a substantially transparent dielectric layer 2' of silicon zirconium oxynitride. Layer 2' may also have or contain aluminum nitride (eg, AlN).

厚，更优选地约

厚。在某些示例性实施方案中，氮化硅基层41和43可为约

厚，更优选地约

厚。例如，在实施例22和图39中，吸收层42为NiCr的氮化物，并且为约1.48nm厚。在其他示例性实施方案中，由氮化物基电介质层41和43之间的吸收层42构成的叠堆可位于叠堆内的其他位置处。The FIG. 1(d) 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(d) embodiment also includes an interposed silicon nitride based layer. Metallic or substantially in contact between 41 and ₄₃ (eg, Si3N4, optionally doped with ₁ %-10% Al, etc., and optionally containing 0%-10% oxygen) Absorber layer 42 of metal. In certain exemplary embodiments, dielectric layers 41 and/or 43 may also have or include aluminum nitride (eg, AlN). In exemplary embodiments of the present invention, absorber layer 42 may have or include NiCr, NbZr, Nb, Zr or their nitrides or other suitable materials. The absorber layer 42 preferably contains 0% to 10% oxygen (atomic %), more preferably 0% to 5% oxygen. In certain exemplary embodiments, it has been found that glass substrates have or contain zirconium silica, zirconia, silica, and/or zirconium oxynitride (eg, _SiZrOx , ZrO2, _SiO2 , _SiAlO2 , and/or zirconium oxynitride ₎ . or SiZrO _x N _y ) between the dielectric layers 2, an absorber layer (eg, NiCr, NiCrN _x , NbZr and/or NbZrN _x ) 42 advantageously reduces the glass-side visible light reflection (R _g Y ) of the coated article in a desired manner , and allows the visible light transmittance to be tuned in a desired manner. See, eg, Figure 39 and Example 22. In certain exemplary embodiments, the absorber layer 42 may be about

thick, more preferably about

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

thick, more preferably about

thick. For example, in Example 22 and Figure 39, the absorber layer 42 is a nitride of NiCr and is about 1.48 nm thick. In other exemplary embodiments, the stack of absorber layer 42 between nitride-based dielectric layers 41 and 43 may be located elsewhere within the stack.

Referring to Figures 1(a)-1(d), another transparent dielectric layer (not shown ₎ having or comprising _ZrO2 , _SiZrOx and/or _SiZrOxNy may be disposed between layers 11 and 13. In certain exemplary embodiments, the zinc _stannate -containing layer 11 may be omitted, or may be replaced with such another transparent dielectric layer having or comprising _ZrO2 , _SiZrOx , and/or _SiZrOxNy . The doped zinc oxide layer 13 may also be separated from such another layer transparent _dielectric layer having or containing _ZrO2 , _SiZrOx and/or _SiZrOxNy . For example, in certain exemplary embodiments, when such an additional layer is an additional layer having or comprising _SiZrOx and/or _SiZrOxNy , the metal content of the layer may comprise 51% _-99 % Si, more preferably 70%-97% Si, and most preferably 80%-90% Si, and 1%-49% Zr, more preferably 3%-30% Zr, and most preferably 10%-20% Zr (atomic % ), and may contain 0%-20% nitrogen, more preferably 0%-10% nitrogen and most preferably 0%-5% nitrogen (atomic %). For example, at least one dielectric may be provided with or comprising silicon oxide, zirconium oxide, zirconium oxynitride, silicon zirconium oxide, and/or silicon zirconium oxynitride (eg, _SiZrOx , _ZrO2 , _SiO2 , and/or _{SiZrOxNy )} Layers (eg, 2 and/or 2"): (i) in the bottom dielectric portion of the coating below all silver-based IR reflective layers (eg, see Figures 1(b)-1(i)), and/ or (ii) in the intermediate dielectric portion of the coating between a pair of silver-based IR reflective layers (eg, see Figures 1(e)-1(i)).

更优选地约

更优选地约

并且最优选地约

或约

或

的物理厚度。电介质层2、2”优选地为氧化物基电介质层，并且优选地含有极少的氮或不含氮。例如，电介质层2、2”可各自包含0％-20％的氮、更优选地0％-10％的氮、并且最优选地0％-5％的氮(原子％)。As explained above and shown in the drawings, the coated article may include a dielectric layer 2, ₂ " (eg, ZrO2 or SiZrOx) as shown in Figures 1(b)-( _i ), which may be located in There is about 1%-30% Sn under and in direct contact with the first crystalline or substantially crystalline layer 3 of zinc oxide, and or under the zinc oxide-containing layer 3". Dielectric layer 2 (and ₂ ") may have or include silicon oxide, zirconium oxide (eg, ZrO2), zirconium oxynitride, silicon zirconium oxide, and/or silicon zirconium oxynitride (eg, SiZrO) optionally doped with Al _x , ZrO ₂ , SiO ₂ , and/or SiZrO _x N _y ). The dielectric layer 2 (or 2 ″) may be in direct contact with the glass substrate 1 (eg, see FIG. 1( b ), FIG. 1( e ), FIG. 1 (g), Figure 1 (h)). The dielectric layers 2, 2" may each have approximately

More preferably about

More preferably about

and most preferably about

or about

or

physical thickness. 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 (atomic %).

The embodiment of Figure 1(i) is based on the embodiments of Figures 1(a)-(b), Figures 1(e) and 1(h) discussed herein, and the layer and performance descriptions for these embodiments also apply to Figure 1(i). However, the embodiment of Figure 1(i) also includes an absorber film comprised of layers 57 and 59, wherein 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 present invention. Layer 2" is as described above, and may have or contain optionally doped zinc oxide. Al-doped silicon oxide, zirconium oxide (eg ZrO ₂ ), silicon zirconium oxide and/or silicon zirconium oxynitride (eg SiZrO _x , ZrO ₂ , SiO ₂ and/or SiZrO _x N _y ).

In the embodiment of Figure 1(i), the absorber film may be a multilayer absorber film comprising a first layer 57 having or comprising silver (Ag), and having or comprising a partially or fully oxidizable (NiCrO _x ) and possibly Second layer 59 of slightly nitrided NiCr. Thus, in certain exemplary embodiments, such multilayer absorber films 57, 59 may be composed of a layer sequence of Ag/ _NiCrOx . This sequence of layers may be repeated in some illustrative examples. For example, in certain exemplary embodiments of the invention, the absorber film may be composed of a layer sequence of Ag/ _NiCrOx /Ag/ _NiCrOx or Ag/ _NiCrOx /Ag/ _NiCrOx /Ag/ _NiCrOx in which The layers contribute to light absorption. Elements from one layer can diffuse into adjacent layers due to HT or other factors. In certain example embodiments, the NiCr base layer 59 of the absorber may be deposited initially 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 present invention relate to at least the embodiment of Figure 1(i) (see Figures 47-56). Furthermore, as explained herein, in certain exemplary embodiments, it has been surprisingly and unexpectedly discovered that the initial sputter deposition has or comprises silicon oxide, zirconium oxide, zirconium oxynitride, silicon oxide zirconium, and Dielectric layer ₂ and/or 2" of silicon zirconium oxynitride (eg _SiZrOx , _ZrO2 , _SiO2 and/or _SiZrOxNy ) to contain the monoclinic phase (see m- ZrO peak ₎ is advantageous as it results in coated articles with improved thermal stability (lower ΔE* values) and/or reduced visible transmittance (eg T _vis or TY ) changes upon heat treatment (HT) .

厚，更优选地不大于约

厚，并且最优选地不大于约

厚，并且可能不大于约

厚。在某些示例性实施方案中，吸收膜的NiCr基层59可为约

厚，更优选地约

厚，并且最优选地约

厚。在某些示例性实施方案中，吸收膜中的Ag/NiCrO_x比可以为1:Z(其中0.1<Z<20，更优选地其中2<Z<15，最优选地其中3<Z<12)，例如为约1:5。The silver base layer 57 of the absorbing 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 functioning primarily as an IR reflective layer). NiCr or NiCrO _x 59 is placed over and in contact with the silver 57 of the absorber film in order to protect the silver and also to aid in absorption. In certain exemplary embodiments, the silver-based layer 57 of the absorber film may, in certain exemplary embodiments of the present invention, be no greater than about

thick, more preferably no greater than about

thick, and most preferably no greater than about

thick, and may not be greater than approx.

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

thick, more preferably about

thick, and most preferably about

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

For the silver base layer 57 of the absorbing film to be thin enough that its primary function is to absorb visible light and provide the desired coloration (as opposed to being much thicker and primarily functioning as an IR reflective layer), the IR reflective layer 7 (eg silver) is physically thicker than silver The ratio of physical thicknesses of base layer 57 is preferably at least 5:1, more preferably at least about 8:1, even more preferably at least about 10:1, and even more preferably at least about 15:1. Likewise, the ratio of the physical thickness of the IR reflective layer 19 (eg, silver) to the physical thickness of the silver base layer 57 is preferably at least 5:1, more preferably at least about 8:1, even more preferably at least about 10:1 , and even more preferably at least about 15:1.

Although in certain exemplary embodiments of the present invention, a single layer of NiCr (or other suitable material) may also be used as an absorber film in a low-E coating (eg, see Figures 1(d) and 1(f) absorber film 42), but it has surprisingly been found that the use of silver 57 in the absorber film (single or multilayer absorber film) of Figure 1(i) provides several advantages compared to single layer NiCr as absorber an unexpected advantage. First, it has been found that a single layer of NiCr as an absorber tends to cause a yellowish tint in certain low E coating coated articles, which may be undesirable in certain circumstances. In contrast, it has been surprisingly found that the use of silver 57 in the absorbent film tends to avoid this yellowish coloration and/or instead provides a more desirable neutral coloration of the resulting coated article. Accordingly, the use of silver 57 in the absorber film has been found to provide improved optical properties. Second, using a single layer of NiCr 42 as the absorber often also involves providing a silicon nitride base layer on both sides of the NiCr so that the NiCr is directly sandwiched between and in contact with it. See, for example, Figures 1(d) and 1(f). It has been found that providing silicon nitride at certain locations in the coating stack may result in compromised thermal stability during HT. Conversely, it has been surprisingly found that when silver is used in the absorber film, as shown for example in Fig. 1(i), a pair of immediately adjacent silicon nitride layers is not required, leading to improved thermal stability during HT . Accordingly, the use of silver 57 in the absorber film has been found to provide improved thermal stability, including lower ΔE* values, and thus improved matching between HT and non-HT versions of the same coating. The use of silver in absorber films can also provide improved manufacturability in some cases.

Although the absorbing films 57, 59 in Fig. 1(i) are provided in the central part of the layer stack between the IR reflective layers 7 and 19, it is also possible to provide absorbing films 57, 59 which are in the bottom IR reflective layer 7 in the lower portion of the underlying layer stack, or in another suitable location. For example, the embodiment of Figure 1(i) can 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 are in contact with each other and layers 59 and 3 are in contact with each other touch. As another example, the embodiment of Figure 1(i) can 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 Figure 1(i) , so 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 absorber films 57, 59 in the central portion of the layer stack as shown in Figure 1(i), optical properties such as SHGC and glass side reflectivity can be improved.

Figure 1(i) shows a layer 59 with or comprising an absorber film of NiCrOx (partially or fully oxidized). However, layer 59 of the absorber film may have or contain other metal-based materials (eg, NiCr, Ni, Cr, _NiCrOx , _NiCrNx , NiCrON, NiCrM, _NiCrMoOx , Ti, or other suitable materials).

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

While various thicknesses and materials may be used in the layers in different embodiments of the present invention, exemplary thicknesses and materials for the corresponding layers on the glass substrate 1 in the embodiment of Figure 1(i) are as follows, from the glass substrate outward :

Table 1' Exemplary Materials/Thickness; Embodiment of Figure 1(i)

In certain embodiments of the present invention, a layer system herein (eg, See Figure 1(a)-(i)) with the following colors (RG%) before heat treatment ( _Ill.C , 2 degree viewer):

Table 2: Reflection/Color (R _G ) before and/or after heat treatment

Comparative Examples 1 and 2

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 that for the first comparative example (CE), the A relatively large 166% change in Ag(111) peak height was observed.

The difference between the first comparative example coating (see Figure 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 _{Zn2SnO4 .} layer and a zinc oxide base layer doped with aluminum. _The metal content of the zinc stannate layer ( _Zn2SnO4 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 amorphous form. The overall thickness of the lowermost dielectric stack in the first CE is about 400-500 angstroms, with the zinc stannate layer accounting for the majority of this thickness. Figure 23 shows the relatively large 166% change in Ag(111) peak height due to heat treatment at about 650°C for the first comparative example (CE), which indicates a significant change in silver layer structure during heat treatment , and this is consistent with the ΔE* value over 4.0 achieved by this comparative example. Therefore, the first CE is undesirable due to the significant change in the Ag(111) peak, and the high ΔE* value over 4.0 due to thermal treatment. Compared to the first comparative example, the following examples 1-24, 27-28 and 30-33 have metal contents directly below and in contact with silver 7, 19 of 90(Zn)/10(Sn) or 85( Zn)/15(Sn) crystalline or substantially crystalline layers 3, 13 and achieve significantly improved/reduced ΔE* values.

The second comparative example (CE 2) is shown in Figures 34-35. 34 is a graph showing sputter deposition conditions for sputter deposition of the low E coating of Comparative Example 2 (CE 2) on a 6 mm thick glass substrate. The layer stack of CE 2 is the same as that shown in Figure 1(b) of this application, except that the lowermost dielectric layer in CE 2 is made of silicon nitride (doped with about 8% aluminum) instead of Figure 1(b). of SiZrO _x shown in 1(b). Therefore, the bottom dielectric stack in CE 2 consists only of this silicon nitride based layer and the zinc oxide layer 3 doped with about 10% Sn. The thickness of the CE 2 coating is in the far right column of Figure 34. For example, the bottom silicon nitride base layer doped with Al (sputtered from a SiAl target in an Ar and _N2 gas atmosphere) is 10.5 nm thick in CE 2, and the bottom layer is doped with about 10% Sn just below the silver Zinc oxide layer 3 is 32.6 nm thick in CE 2, etc.

As can be seen in Figure 35, CE 2 has relatively high glass side reflection ΔE* values (ΔE*R _g ) and film side reflection ΔE* values (ΔE over 4.0 due to the 12 minute, 16 minute and 24 minute heat treatment) *R _f ). For example, Figure 35 shows that CE has a relatively high glass side reflection ΔE* value (ΔE*R _g ) of 4.9 and a relatively high film side reflection ΔE* value (ΔE*R _f ) of 5.5 due to heat treatment for 12 minutes . Figure 35 is a graph showing the optical properties of Comparative Example 2 (CE 2): as coated (annealed) before heat treatment, after heat treatment at 650°C for 12 minutes (HT), HT at 650°C in the leftmost data column After 16 minutes (HTX) and in the far right data column after heat treatment at 650°C for 24 minutes (HTXXX). These relatively high ΔE* values for CE2 are undesirable.

Therefore, Comparative Example 2 (CE 2) in FIGS. 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 under the bottom silver layer 7, when Undesirably high ΔE* values are also achieved when the only layer between layer 3 and glass substrate 1 is a silicon nitride based layer. The difference between the CE2 coating and the following Examples 1-24, 27-28 and 30-33 is that the following Examples 1-24, 27-28 and 30-33 were doped with about 10% or 15% by not having The silicon nitride base layer directly below and in contact with the crystalline or substantially crystalline zinc oxide layer 3 of % Sn, using a crystalline or substantially crystalline zinc oxide layer 3 doped with about 10% or 15% Sn can make the Surprisingly and unexpectedly, greatly improved (reduced) ΔE* values were achieved.

Examples 11-14, 19-21 and 26-33 below also show that replacing the bottom silicon nitride based layer of CE2 with _SiZrOx or ZrO2 layer ₂ significantly improves/decreases the ΔE* value in an unexpected manner.

Examples 1-48

It was surprisingly and unexpectedly found that when the lowermost dielectric stacks 5, 6 of Comparative Example (CE) in FIG. The crystalline or substantially crystalline Sn-doped zinc oxide layer 3 is replaced (the rest of the stack remains substantially the same) without the silicon nitride base layer directly below and in contact with the crystalline or substantially crystalline layer 3 The result is a much more thermally stable product with significantly lower ΔE* values and a much smaller change in Ag(111) peak height due to heat treatment at about 650°C. The crystalline or substantially crystalline Sn-doped zinc oxide layer 3 of Examples 1-24, 27-28 and 30-48 had a metal content of about 90% Zn and 10% Sn (wt %) (see also, 85% Zn and 15% Sn, relative to "85" of layer 13 in Example 19), which helps to allow Sn doped zinc oxide layers in Examples 1-24, 27-28, 30-48 3, 13 Sputter deposition in crystalline or substantially crystalline form (as opposed to amorphous form in CE). For example, FIG. 20 shows the layer stack of Example 10, FIG. 21 shows the sputter deposition conditions and layer thicknesses of Example 10, and FIG. 22 shows the result of heat treatment at about 650°C for Example 10. The much smaller 66% change in the Ag(111) peak height of , which is consistent with the much lower ΔE* values achieved for Examples 1-24, 27-28 and 30-33. Figure 16 also shows that for Example 8, the relatively small shift in refractive index (n) upon heat treatment.

The coated articles of the Examples (each annealed and heat treated), Examples 1-48, were prepared in accordance with certain exemplary embodiments of the present invention. The exemplary coating 30 shown is sputter deposited via sputter conditions (eg, gas flow, voltage, and power), sputter target, and deposited to Figures 2, 3, 6, 7, 9, 11, Layer thicknesses (nm) shown in Figures 13, 15, 21, 24-26, 28, 30, 32 and 36-57. For example, FIG. 2 shows sputtering conditions, sputtering targets and layer thicknesses for the coating of Example 1, and FIG. 3 shows sputtering conditions, sputtering, and layer thicknesses for the coating of Example 2. Sputtering targets and layer thicknesses for sputter deposition, Figure 6 shows sputtering conditions, sputtering targets and layer thicknesses for the coatings used in Example 3, Figure 7 shows sputtering targets and layer thicknesses for Example 4 Sputtering conditions for coatings, sputtering targets and layer thicknesses for sputter deposition, etc. Also, the examples shown include visible light transmittance (TY or T _vis ), glass side visible light reflectance (R _g Y or RGY), film side visible light reflectivity (R _f Y or RFY), a* and b* colors values, L* values and sheet resistance (SR or R _s ) data are shown in Figure 4, Figure 5, Figure 8, Figure 10, Figure 12, Figure 14, Figure 18, Figure 27, Figure 29, Figure 31, Figure 4 33 and Figures 36-56. As described above, for a given example, the ΔE* values were calculated using the L*, a* and b* values obtained before and after heat treatment. For example, for a given embodiment, glass side reflection ΔE* values (ΔE* _G or ΔE*R _g ) are calculated using glass side reflection L*, a* and b* values obtained before and after heat treatment. As another example, the film side reflection ΔE* values (ΔE* _F or ΔE*R _f ) are calculated using the glass side reflection L*, a* and b* values obtained before and after heat treatment for a given example. As another example, for a given embodiment, the transmission ΔE* value (ΔE* _T ) is calculated using the glass side reflection L*, a* and b* values obtained before and after heat treatment.

For the embodiments in Figures 4, 5, 8, 10, 12, 14 and 18 having glass substrates about 3 mm thick, "EGG" means heat treated at 650 degrees for about 8 minutes, "HTX" " means heat treatment at 650 degrees for about 12 minutes, "HTXXX" means heat treatment at 650 degrees for about 20 minutes. And for the glass substrates with about 6mm thick glass substrates in Figs. Examples, "HT" refers to heat treatment at 650 degrees for about 12 minutes, "HTX" refers to heat treatment at 650 degrees for about 16 minutes, and "HTXXX" refers to heat treatment at 650 degrees for about 24 minutes. Heat treatment temperatures and times are for reference purposes only (eg, to simulate examples of different tempering and/or heat bending processes).

For example, Figures 4 and 5 show the ΔE* values for Examples 1 and 2, respectively. The data of Example 1 is explained in detail below for purposes of illustration and explanation, and this discussion also applies to the data of Examples 2-33.

As shown in Figure 4, Example 1 as coated (before heat treatment) had a visible light transmittance (TY or _Tvis ) of 74.7%, a transmittance L* value of 89.3, a transmittance a* color value of -4.7, a transmittance of 5.8 Transmission b* color value, 9.6% glass side reflectance (R _g Y), 37.1 glass side reflection L* value, -1.1 glass side reflection a* color value, -10.1 glass side reflection b* color value, Film side reflectance (R _f Y ) of 9.9%, film side reflectance L* value of 37.7, film side reflectance a* color value of -1.5, film side reflectance b* color value of -5.7, and thin film side reflectance of 2.09 ohms/square layer resistance (SR). FIG. 2 shows the thicknesses of the layers in Example 1. FIG. Specifically, Figure 2 shows that the layer thicknesses of Example 1 are as follows: glass/crystalline Sn-doped ZnO (47.0 nm)/Ag (15.1 nm)/ _NiCrOx (4.1 nm)/amorphous zinc stannate (73.6 nm) /Crystalline Sn-doped ZnO (17.7nm)/Ag (23.2nm)/ _NiCrOx (4.1nm)/amorphous zinc stannate (10.8nm)/Aluminium-doped silicon nitride (19.1nm).

The coated article of Example 1 with a 6 mm thick glass substrate 1 was then heat treated. As shown in Figure 4, after heat treatment at 650°C for about 12 minutes, Example 1 had a visible light transmittance (TY or _Tvis ) of 77.0%, a transmittance L* value of 90.3, a transmittance a* color value of -3.5, 4.9 Transmission b* color value of 9.8%, glass side reflectance (R _g Y) of 9.8%, 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 , 10.2% film side reflectance (R _f Y), 38.1 film side reflection L* value, -1.4 film side reflection a* color value, -8.0 film side reflection b* color value, 1.75 sheet resistance (SR), transmission ΔE* value of 1.8, glass side reflection ΔE* value of 0.7, and film side reflection ΔE* value of 2.4.

It should be understood that these ΔE* values of Example 1 (as well as those of Examples 2-48) are in excess of 4.0 with those of the prior art discussed in the Background and with the Comparative Example (CE) discussed above. values are greatly improved (significantly lower). Thus, data from the Examples indicate that, for example, when the lowermost dielectric stack of the Comparative Example is replaced with a similar thickness of at least crystalline or substantially crystalline Sn-doped zinc oxide layer (the remainder of the stack remains substantially the same) , in the absence of a silicon nitride base 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 ΔE * value and much smaller change in Ag(111) peak height due to heat treatment.

The other examples show these same unexpected results compared to the comparative examples. In general, these examples show that crystalline or substantially crystalline Sn-doped zinc oxide layers and/or layers 2, ₂ " with or comprising _SiZrOx , _ZrOx , SiO2 significantly improve ΔE* values. For example, Examples 1-10 have the layer stack shown generally by Figure 1(a), where the only dielectric layer under the bottom silver is a crystalline or Substantially crystalline Sn-doped zinc oxide layer 3. In Examples 11-14, 19-24, 27-28, a crystalline or substantially crystalline Sn-doped zinc oxide layer directly over SiZrO _x layer 2 The metal content of 3 is about 90% Zn and 10% Sn (wt %), where the metal content of layer 2 is about 85% Si and 15% Zr (at %). In Examples 30-48, the crystalline or substantially crystalline The Sn-doped zinc oxide layer 3 is about 90% Zn and 10% Sn (wt %) and is disposed directly on the ZrO ₂ layer 2 as shown in Figure 1(i) and Figure 52. In Examples 15-16 , the metal content of the crystalline or substantially crystalline Sn-doped zinc oxide layer 3 directly above the ZrO ₂ layer 2 is about 90% Zn and 10% Sn (wt %); and in Examples 17-18, The crystalline or substantially crystalline Sn-doped zinc oxide layer 3 directly above the SiO ₂ layer 2 doped with about 8% Al (at %) has a metal content of about 90% Zn and 10% Sn (wt %) These examples surprisingly and unexpectedly achieve greatly improved ΔE* values compared to Comparative Examples 1-2.

The layer stacks of Examples 1-10 are generally shown in Figure 1(a). The layer stacks of Examples 11-14, 19 and 27 are generally shown in Figure 1(b), where layer 2 is _SiZrOx . The layer stack of Examples 15-16 is shown generally in Figure 1(b), where layer ₂ is ZrO2. The layer stack of Examples 17-18 is generally shown in Figure 1(b), where layer 2 is _SiO2 . The layer stacks of Examples 20-21 and 28 are generally shown in Figure 1(e), where layers 2 and 2" are _SiZrOx . The layer stacks of Examples 23-24 are generally shown in Figure 1(f) out, where layers 2 and 2" are _SiZrOx . The layer stack of Example 25 is generally shown in Figure 1(g), where layers 2 and 2" are _SiZrOx . The layer stack of Example 22 is generally shown in Figure 1(d), where layer 2 is _SiZrOx . The layer stack of Example 26 is generally shown in Figure 1(h), where layers 2 and 2" are _SiZrOx , oxide layer 3' has a metal content of 90% Zn and 10% Sn, and is oxidized The material layers 3, 13 are zinc oxide doped with about 4%-8% Al. The layer stack of Example 29 is generally shown in Figure 1(h), except that in Example 29 layer 2" is absent and layer 2 is _SiZrOx and oxide layer 3' has 90% Zn and 10% The metal content of Sn, and the oxide layers 3, 13 are zinc oxide doped with about 4%-8% Al. The layer stacks of Examples 30-48 are generally shown in Figures 1(i) and 52, Wherein layers 2 and ₂ " are ZrO2. These Examples surprisingly and unexpectedly achieve greatly improved ΔE* values compared to Comparative Examples 1-2. These examples show that crystalline or substantially crystalline Sn-doped zinc oxide layers (eg layer 3 and/or layer 13) and/or dielectric layers 2, ₂ " with or comprising _SiZrOx , _ZrOx , SiO2" Significantly improved/decreased ΔE* values.

For example, combining Examples 23-24 ( _SiZrOx layer 2" added to the central dielectric portion of the coating, as shown in Figure 1(f)) with Example 22 (no such layer 2" in the central dielectric portion, A comparison as shown in Figure 1(d) shows and demonstrates that the addition of a SiZrO _x layer 2" in Examples 23-24 unexpectedly improves/decreases at least the glass side reflection ΔE* value. Therefore, it should be understood that SiZrO The addition of _x -layer 2" provided unexpected results.

In addition, Example 28 ( _SiZrOx layer 2" added to the central dielectric portion of the coating, as shown in Fig. 1(e)) was combined with Example 27 (no such layer 2" in the central dielectric portion, as shown in Fig. 1(b)), it is further shown and demonstrated that the addition of the _SiZrOx layer 2" in Example 28 unexpectedly improves/decreases the glass side reflection ΔE* value. Therefore, it should be understood again that _SiZrOx or ZrO The addition of ₂ layers 2" provided unexpected results regarding improved thermal stability.

Examples 30-48 are generally shown in Figures 1(i) and 52, which include absorber films 57, 59, in which layers 2 and ₂ " are ZrO2. These examples are surprising and unexpected Significantly improved ΔE* values were unexpectedly achieved compared to Comparative Examples 1-2. Examples 30-48 demonstrate that crystalline or substantially crystalline Sn-doped zinc oxide layers (eg, layers 3 and/or 13) and Dielectric layers 2, ₂ " with or containing ZrO2 significantly improve/reduce ΔE* values in an unexpected manner. Examples 30-48 further demonstrate that providing an absorber film including a silver-containing layer 57 and a _NiCrOx -containing layer 59 allows the visible light transmittance to be adjusted to a desired value without sacrificing thermal stability or desired color of the resulting coated article. For example, Examples 30-48 with Ag/NiCrO _x absorber films (57, 59) as shown in Figure 1(i) are surprisingly more efficient than Examples 23-24 using a single NiCr layer absorber Neutral glass side reflection b* value (Rg b* or R-out b*).

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 contains silicon oxide, zirconium oxide, oxynitride Dielectric layers 2 and/or 2" of zirconium, silicon zirconium oxide, and/or silicon zirconium oxynitride ( _SiZrOx , ZrO2, _SiO2 , and/or _SiZrOxNy ) to include _monolayers in Examples _34-42 and 48 The oblique phase crystal structure is advantageous as it results in coated articles with improved thermal stability (lower ΔE* values) and/or reduced visible light transmittance (eg T _vis or TY ) upon heat treatment (HT) Variations. In general, compared to Examples 34-42 and 48, which have monoclinic ZrO layers ₂ , 2" and thus have improved/lower ΔE* values, some examples of the invention may still be in accordance with the present invention. Exemplary embodiments CE 43-47 have less preferred (higher) ΔE* values due to non-monoclinic ZrO layers ₂ , 2". In certain exemplary embodiments, with certain sputtering equipment Relatedly, the monoclinic phase of the dielectric layer (eg, ZrO ₂ ) 2 and/or ₂ ″ (eg, see the m-ZrO peak in the upper panel of FIG. This layer was achieved using a high oxygen flow rate and using a metal sputter target (eg, a metal Zr or SiZr target) (eg, see Figure 55), as in Examples 34-42. In this regard, Figure 51 shows graphs of sputter deposition of ZrO2 layers using a metallic Zr target (top panel) and a ceramic _ZrOx target (bottom panel ₎ before and after HT, and shows when a metal target is used with high gas The layer includes a monoclinic phase (see peak at m-ZrO ₂ ) at flow rate (see, eg, Figure 55 ), and does not include a monoclinic phase when a ceramic target is used in some cases. It should be noted, however, that it has been found that layers 2 and/or 2" can indeed be achieved when sputter deposition uses a ceramic target as in Example 48 with low or high oxygen flow rates (depending on the type of sputter equipment used) the monoclinic phase.

Figure 52 (see also Figure 1(i)) is a cross-sectional view of coated articles according to Examples 34-42, 48 and Comparative Examples (CE) 43-47. Figure 53 shows the optical data for Examples 34-42: as coated (AC; annealed) before heat treatment in the leftmost data column of each example and after heat treatment at 650°C for 12 minutes (HT) in the right data column of each example ), Examples 34-42 have the coating stacks shown in Figures 1(i) and 52 in which monoclinic ZrO2 layers ₂ and 2" were deposited with a metallic Zr target, and the layers of Examples 34-42 The thickness is shown in Figure 55; wherein sample 7982 is embodiment 34, sample 8077 is embodiment 35, sample 8085 is embodiment 36, sample 8090 is embodiment 37, sample 8091 is embodiment 38, sample 8097 is embodiment 39, Sample 8186 is Example 40, sample 8187 is Example 41, and sample 8202 is Example 42. Figure 55 is a graph showing deposition process conditions and layer thicknesses for Example 37 with a monoclinic _ZrO layer, where each _The total oxygen flow (ml ₎ during the sputtering process of the layer is represented by the sum of the O setpoint, the O _trim and the O offset, the high oxygen flow during the sputter deposition of the _ZrO layer helps to provide examples Monoclinic phase of ZrO2 layers ₂ and 2" of 37 (monoclinic examples 34-36 and 38-42 had similar process conditions). In the embodiment of Figure 52 and Figure 1(i), it should be noted that, for example, the central ZrO ₂ layer 2" may be omitted in certain illustrative examples.

57 is a graph showing the deposition process conditions and layer thicknesses of Example 48 having a monoclinic ZrO layer ₂ (layer ₂ " omitted), wherein the ZrO layer having a monoclinic phase was sputter deposited using a ceramic ZrO target 2. The layer stack of Example 48 is shown in Figures 1(i) and 52 (layer 2" omitted), and the corresponding layer thicknesses are provided in Figure 57. 58 shows ΔE* values for coatings according to Example 48 after various heat treatment times, and FIG. 59 shows optical data and sheet resistance data for coatings according to Example 48.

Figure 54 shows optical data for Comparative Examples (CE) 43-47: as coated (AC; annealed) prior to heat treatment in the leftmost data column of each example and heat treated at 650°C for 12 minutes in the right data column of each example After (HT), Examples 43-47 had the coating stacks shown in Figure 1(i) and Figure 52, in which a non _- monoclinic ZrO2 layer was deposited with a ceramic target, and the layer thicknesses of Examples 43-47 As shown in Figure 56; where sample 8392 is CE 43, sample 8394 is CE 44, sample 8395 is CE45, sample 8396 is CE 46, and sample 8397 is CE 47. Figure 56 is a graph showing deposition process conditions and layer thicknesses for Comparative Example (CE) 44 with non-monoclinic ZrO layers ₂ and 2" where the total oxygen flow (ml) during the sputtering process for each layer is given by _The sum of the O setpoint, O _trim , and O offset indicates that the low oxygen flow during sputter deposition of the _ZrO layer, together with the ceramic _ZrO target, helps to provide the non _- monoclinic of the _ZrO layer of Example 44 Crystal Phase (Non-monoclinic Examples 43 and 45-47 had similar process conditions).

Comparing Examples _34-42 , 48 with Comparative Examples (CE) 43-47, it can be seen that the as-deposited state of Examples 34-42, 48 of monoclinic ZrO ₂ layers 2 and 2" achieved lower/better ΔE* values and thus improved thermal stability and color matching at HT.

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

The intensity of reflected visible wavelength light, "reflectance" is defined by its percentage and reported as R _x Y or R _x (i.e. the Y value quoted below in ASTM E-308-85), where "X" for glass "G" for the side or "F" for the membrane side. "Glass side" (eg, "G" or "g") refers to viewing from the opposite side of the glass substrate from the side where the coating is located, while "film side" (ie, "F" or "f") refers to viewing from The coated side of the glass substrate is viewed.

Color properties are measured and reported herein using the CIE LAB a*, b* coordinates and scale (ie, CIE a*b* diagram, Ill. CIE-C, 2 degree viewer). Other similar coordinates (such as by the subscript "h" to denote conventional use of the Hunter Lab scale) or Ill. CIE-C 100 viewer or CIE LUV ^u *v* coordinates may equally be used. These scales are defined herein in accordance with ASTM D-2244-93 "Standard Test Method for Calculation of Color Differences From Instrumentally Measured Color Coordinates" 9/15/93, as described by ASTM E-308-85, Annual Book of ASTM Standards, No. 06.01 Volume, "Standard Method for Computing the Colors of Objects by 10 Using the CIE System" expanded and/or as reported in the IES LIGHTING HANDBOOK 1981 reference volume.

Visible light transmittance can be measured using known conventional techniques. For example, by using a spectrophotometer, such as a Perkin Elmer Lambda 900 or Hitachi U4001, a spectral curve of transmission is obtained. Visible light transmittance was then calculated using the aforementioned ASTM308/2244-93 method. If desired, a smaller number of wavelength points than specified may be used. Another technique for measuring visible light transmittance is to use a photometer, such as the commercially available Spectrogard spectrophotometer manufactured by Pacific Scientific Corporation. The device directly measures and reports visible light transmittance. As reported and measured herein, the visible light transmittance (ie, the Y value in the CIE tristimulus system, ASTM E-308-85) as well as the a*, b*, and L* values and glass/film side reflectance values are used herein Ill.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. In general, the term refers to the resistance (in ohms) of any square of a layer system on a glass substrate to current flow through the layer system. Sheet resistance is an indication of how well a layer or layer system reflects infrared energy and is therefore often used along with emissivity as a measure of this property. "Sheet resistance" can be conveniently measured, for example, by using a 4-point probe ohmmeter such as a distributable 4-point resistivity probe with a Magnetron Instruments Corp. head, model M-800, manufactured by Signatone Corp. (Santa Clara, California) .

As used herein, the terms "heat treatment" and "heat treating" mean heating an article to a temperature sufficient to effect thermal tempering, thermal bending and/or thermal strengthening of a glass-containing coated article. This definition includes, for example, heating the coated article in an oven or furnace at a temperature of at least about 580°C, more preferably at least about 600°C (including 650°C) for a sufficient period of time to allow tempering, bending and/or thermal strengthening . In some cases, the thermal treatment can 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 coating comprising a dopant disposed on the glass substrate A crystalline or substantially crystalline layer of zinc oxide doped with about 1% to 30% Sn (wt %); a first infrared (IR) reflective layer comprising silver 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; %-30% Sn, directly below and in contact with a first crystalline or substantially crystalline layer of zinc oxide; at least one dielectric layer having a monoclinic phase and comprising zirconium oxide (eg ZrO ₂ ), and optionally The ground also contains other elements, such as Si; wherein the at least one dielectric layer comprising zirconium oxide is located at: (1) at least the glass substrate and the between a first crystalline or substantially crystalline layer of zinc oxide, and/or (2) between at least the first IR reflective layer comprising silver and the second IR reflective layer comprising silver of (2) the coating; any A selected absorber film comprising a layer comprising silver, wherein the ratio of the physical thickness of the first IR reflective layer comprising silver to the physical thickness of the layer comprising silver of the absorber film is at least 5: 1 (more preferably at least 8:1, even more preferably at least 10:1, and most preferably at least 15:1); and wherein the coated article is constructed to have at least two of the following measured in a single piece : (i) a transmission ΔE* value of not greater than 3.0 due to the reference heat treatment at a temperature of about 650°C for 12 minutes, (ii) due to the reference heat treatment at a temperature of about 650°C for 12 minutes A glass side reflection ΔE* value of not greater than 3.0, and (iii) a film side reflection ΔE* value of not greater than 3.5 due to the reference heat treatment at a temperature of about 650°C for 12 minutes.

The coated article described in the preceding paragraph can be constructed to have all three of the following measured monolithically: (i) a transmission ΔE* of not greater than 3.0 due to a reference heat treatment at a temperature of about 650°C for 12 minutes value, (ii) a glass side reflection ΔE* value of not greater than 3.0 due to the reference heat treatment at a temperature of about 650°C for 12 minutes, and (iii) due to the reference heat treatment at a temperature of about 650°C Film side reflection ΔE* value of not more than 3.5 due to heat treatment for 12 minutes.

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

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

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

In the coated article of any of the preceding five paragraphs, the at least one dielectric layer may comprise or consist essentially of zirconium oxide and/or oxides of silicon and zirconium (eg, SiZrO _x ). For example, a dielectric layer comprising oxides of silicon and zirconium may have a metal of 51%-99% Si and 1%-49% Zr, more preferably 70%-97% Si and 3%-30% Zr (atomic %) content.

In the coated article of any of the preceding six paragraphs, the at least one dielectric layer can 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 as sputter deposited .

A coated article according to any of the preceding nine paragraphs may be constructed to have a monolithic measurement of all of: (i) not greater than 2.5 due to a reference heat treatment at a temperature of about 650°C for 12 minutes The transmission ΔE* value of (ii) a glass side reflection ΔE* value of not greater than 2.5 due to the reference heat treatment at a temperature of about 650°C for 12 minutes, and (iii) due to a temperature of about 650°C A film side reflection ΔE* value of not more than 3.0 due to performing the reference heat treatment for 12 minutes.

A coated article according to any one of the ten preceding paragraphs may be constructed to have at least two of the following, measured on a single piece: (i) invariance due to a reference heat treatment at a temperature of about 650°C for 16 minutes A transmission ΔE* value greater than 2.3, (ii) a glass side reflection ΔE* value of not greater than 2.0 due to the reference heat treatment at a temperature of about 650°C for 16 minutes, and (iii) due to a ΔE* value at about 650°C A film side reflection ΔE* value of not greater than 3.0 due to the reference heat treatment at temperature for 16 minutes.

The coated article of any of the preceding eleven paragraphs may be constructed such that the coating may have no greater than 20 ohms/square, more preferably no greater than 10 ohms/square, and most preferably no greater than Sheet resistance (R _s ) of 2.5 ohms/square.

A coated article according to any one 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 may further include a tin-containing coating on the glass substrate over at least the first IR-reflective layer containing silver A first amorphous or substantially amorphous layer of zinc oxide. 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 may further comprise a contact layer overlying and in direct contact with the silver-containing IR reflective layer. The contact layer may contain Ni and/or Cr, and may or may not be oxidized and/or nitrided.

In the coated article of any one of the preceding fifteen paragraphs, the coating may further comprise: a silver-containing film on the glass substrate over at least the first silver-containing IR reflective layer A second IR reflective layer, a second crystalline or substantially crystalline comprising zinc oxide doped with about 1%-30% Sn (wt %) below and in direct contact with the second IR reflective layer comprising silver layer. And there is no need for a silicon nitride based layer between the glass substrate and the second IR reflective layer comprising silver.

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

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

The coated article of any of the preceding eighteen paragraphs may further include a metallic or substantially metallic absorbing layer between the glass substrate and the first IR reflective layer. The absorber layer may be sandwiched between and in contact with the first and second layers comprising silicon nitride. The absorber layer may contain Ni and Cr (eg, NiCr, NiCrMo) or any other suitable material such as NbZr. A dielectric layer comprising at least one of (a), (b) and (c) may 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 preceding nineteen 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%-5% nitrogen (atomic %).

In the coated article of any of the twenty preceding paragraphs, the absorbent film may further comprise a Ni and/or Cr-containing layer over and in direct contact with the silver-containing layer of the absorbent film oxide layer.

In the coated article of any of the preceding twenty-one paragraphs, the absorbing film may be positioned over the first IR reflective layer such that the first IR reflective layer is positioned between at least the absorbing film and the between glass substrates.

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

厚，更优选地小于

厚，并且甚至更优选地小于

厚。In the coated article of any of the preceding twenty-three paragraphs, the silver-containing layer of the absorbent film may be less than

thick, more preferably less than

thick, and even more preferably less than

thick.

In the coated article of any of the preceding twenty-four 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 phase and comprising zirconium oxide may comprise two such layers comprising zirconium oxide and may be located below 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 reflective layer comprising silver and the absorbing 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% to 5% nitrogen (atomic %).

In the coated article of any of the preceding twenty-seven paragraphs, the at least one dielectric layer having a monoclinic phase may include zirconium oxide (eg, ZrO ₂ ), and may optionally further include Si.

In the coated article of any of the preceding twenty-seven paragraphs, the at least one dielectric layer having a monoclinic phase can 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 can be configured to achieve a density change ^of at least 0.25 g/cm upon the reference heat treatment , more preferably a density change of at least 0.30 g/cm ³ is achieved at the reference heat treatment, and most preferably a density change of at least 0.35 g/cm ³ is achieved at the reference heat treatment.

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

更优选地

并且最优选地

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

more preferably

and most preferably

thickness of.

In the coated article of any one of the preceding thirty-one paragraphs, the coated article may be configured to have two or three of the following, measured on a single sheet: (i) at about 650°C a transmission ΔE* value of not greater than 3.0 for a reference heat treatment at a temperature of 12 minutes, (ii) a glass side reflection ΔE* value of not greater than 1.5 for the reference heat treatment at a temperature of about 650°C for 12 minutes, and (iii) A film side reflection ΔE* value of not greater than 1.5 when the reference heat treatment was performed at a temperature of about 650°C 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, before and/or after the reference heat treatment, the at least one dielectric layer comprising a monoclinic phase may also comprise a tetragonal phase.

In an exemplary embodiment, there is provided a method of making a coated article comprising a coating on a glass substrate, the method comprising: sputter depositing a layer comprising zinc on the glass substrate; sputter-deposited on a substrate a first infrared (IR) reflective layer comprising silver over and in contact with a layer comprising zinc oxide; sputter-deposited on the glass substrate having a monoclinic phase at least one dielectric layer (eg, zirconium _oxide , such as ZrO2), wherein the dielectric layer having a monoclinic phase comprises zirconium oxide (and which may also comprise other elements, such as Si); wherein the monoclinic phase At least one dielectric layer of oblique phase and comprising zirconium oxide is located: (1) between at least the glass substrate and the layer comprising zinc oxide, and/or (2) at least the silver comprising layer of the coating and wherein the coated article is constructed to have at least two of the following measured monolithically: (i) at a temperature of about 650°C A transmission ΔE* value of not greater than 3.0 when the reference heat treatment was performed for 12 minutes, (ii) a glass side reflection ΔE* value of not greater than 3.0 when the reference heat treatment was performed at a temperature of about 650°C for 12 minutes, and (iii) at a temperature of about 650°C. A film side reflection ΔE* value of not more than 3.5 when the reference heat treatment was performed at a temperature of 650° C. for 12 minutes. T

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

In the method of either of the preceding two paragraphs, the at least one dielectric layer having a monoclinic phase may include ZrO ₂ , and may also include Si.

In the method of any of the preceding three paragraphs, the coated article can be constructed to have at least two or all three of the following measured on a single sheet: (i) at a temperature of about 650°C a transmission ΔE* value of not greater than 3.0 at a reference heat treatment for 12 minutes, (ii) a glass side reflection ΔE* value of not greater than 1.5 at a temperature of about 650°C for 12 minutes of the reference heat treatment, and (iii) at a temperature of about 650°C A film side reflection ΔE* value of not more than 1.5 when the reference heat treatment is performed at a temperature of °C for 12 minutes.

The method of any of the preceding four paragraphs may further include thermally treating the coated article via the reference heat treatment such that the at least one dielectric layer having a monoclinic phase achieves at least 0.25 g at the reference heat treatment A density change of at least 0.30 g/cm ³ , more preferably at least 0.30 g/cm ³ , and most preferably at least 0.35 g/cm ³ .

In the method of any of the preceding five paragraphs, the sputter deposition of 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 heat treatment.

In the method of any of the preceding seven paragraphs, the at least one dielectric layer comprising a monoclinic phase may be configured such that its monoclinic peak decreases upon the reference heat 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 to be a part of this invention, the scope of which is to be determined 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 about 1% -30% Sn (wt%), disposed on the glass substrate;

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

wherein no silicon nitride based layer is directly beneath 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 the zirconium oxide is located: (1) at least between 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 between 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 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 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 greater than 3.5 when subjected to the reference heat treatment at a temperature of about 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 any preceding claim, 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 any preceding claim, 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 any preceding claim, 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 any preceding claim, 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 any preceding claim, wherein the thickness of the layer comprising silver of the absorber film is less than

8. The coated article of any preceding claim, wherein the thickness of the layer comprising silver of the absorber film is less than

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

10. The coated article of any preceding claim, wherein the coated article is configured to have a single measurement of all three of: (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 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 greater than 3.5 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes.

11. The coated article of any preceding claim, 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 about 1% -30% Sn (wt%).

12. The coated article of any preceding claim, 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 any preceding claim, wherein the first crystalline or substantially crystalline layer comprising zinc oxide is doped with about 1% -20% Sn (wt%).

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

15. The coated article of any preceding claim, 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 any preceding claim, wherein the coated article is configured with all of the following measured monolithically: (i) a transmission Δ Ε value of not greater than 2.5 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 2.5 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 3.0 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes.

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

18. The coated article of any preceding claim, wherein the coating has a sheet resistance (Rg) of not greater than 10 ohms/square_s)。

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

20. The coated article of any preceding claim, 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 about 40% -60% Zn and about 40% -60% Sn (wt%).

22. The coated article of any preceding claim, 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 any preceding claim, 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 about 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 either of the first and second IR reflecting layers.

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

25. The coated article of any preceding claim, wherein the at least one dielectric layer comprising a monoclinic phase and comprising zirconium oxide is 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.

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 any preceding claim, wherein the at least one dielectric layer comprising a monoclinic phase comprises ZrO₂。

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

29. The coated article of any preceding claim, 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 treatment³The density of (a).

30. The coated article of any preceding claim, 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 treatment³The density of (a).

31. The coated article of any preceding claim, 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 treatment³The density of (a).

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

Is measured.

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

35. The coated article of any preceding claim, wherein the coated article is configured to have at least two 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.

36. The coated article of any preceding claim, wherein the coated article is configured to have a single measurement of all three of: (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.

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 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 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 greater than 3.5 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes.

38. The coated article of claim 35, wherein the coated article is not thermally tempered.

39. The coated article of any one of claims 35-36, 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 any of claims 35-37, wherein the at least one dielectric layer comprising a monoclinic phase comprises 0% -5% nitrogen (at%).

41. The coated article of any one of claims 35-38, wherein the at least one dielectric layer comprising a monoclinic phase and comprising the zirconium oxide further comprises Si.

42. The coated article of any of claims 35-38, wherein the at least one dielectric layer comprising a monoclinic phase consists essentially of zirconium oxide.

43. The coated article of any of claims 35-40, 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 treatment³Is changed 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 any of claims 35-41, 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 treatment³The density of (a).

45. The coated article of any of claims 35-42, 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 treatment³The density of (a).

46. The coated article of any of claims 35-43, 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 any of claims 35-44, wherein the at least one dielectric layer comprising a monoclinic phase has

Is measured.

48. The coated article of any of claims 35-45, wherein the at least one dielectric layer comprising a monoclinic phase further comprises a tetragonal phase.

49. The coated article of any one of claims 35-46, wherein the coated article is configured to have at least two 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.

50. The coated article of any one of claims 35-47, wherein the coated article is configured to have 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.

51. A method of making a coated article comprising a coating on a glass substrate, 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 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 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 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 greater than 3.5 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes.

52. The method of claim 49, 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.

53. The method of any one of claims 49-50, 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.

54. The method of any one of claims 49-51, wherein the at least one dielectric layer comprising a monoclinic phase comprises ZrO₂。

55. The method of any one of claims 49-52, wherein the coated article is configured to have a monolithic measurement of all three of: (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.

56. The method of any one of claims 49-53, 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 time of the reference heat treatment³The density of (a).

57. The method of any one of claims 49-54, wherein the sputter depositing the at least one dielectric layer comprising a monoclinic phase on the glass substrate uses a metal target.

58. The method of any one of claims 49-55, wherein the sputter depositing at least one dielectric layer comprising a monoclinic phase on the glass substrate uses an oxygen flow of at least 6 ml/kW.

59. The method of any one of claims 49-54, wherein the sputter depositing the at least one dielectric layer comprising a monoclinic phase on the glass substrate uses a ceramic target.

60. The method of any one of claims 49-57, wherein the at least one dielectric layer comprising a monoclinic phase further comprises a tetragonal phase.

61. The method of any one of claims 49-58, wherein the at least one dielectric layer comprising a monoclinic phase is configured to have its monoclinic peak reduced upon the reference thermal treatment.

62. 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

Wherein the coated article is configured to have at least two 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 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 greater than 3.5 when subjected to the reference heat treatment at a temperature of about 650 ℃ for 12 minutes.

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