Coated article with low-e coating having absorbing layer over functional layer designed to increase outside reflectance.

(54) Title: ARTICLE COATED WITH LOW-E COATING THAT HAS AN ABSORBING LAYER ON TOP OF A FUNCTIONAL LAYER DESIGNED TO INCREASE EXTERNAL REFLECTANCE.

(54) Title: COATED ARTICLE WITH LOW-E COATING HAVING ABSORBING LAYER OVER FUNCTIONAL LAYER DESIGNED TO INCREASE OUTSIDE REFLECTANCE.

(57) Summary

A coated article includes a low-E coating that has an absorbent layer located on top of a functional layer (IR reflective layer) and designed to cause the coating to have increased external reflectance (for example, in an IG window unit ) and good selectivity. In certain embodiments, the absorbent layer is metallic, or substantially metallic, and is provided directly on top of and contacting a bottom layer of the two IR reflective layers. In certain exemplary embodiments, a nitride-based layer (eg, silicon nitride or the like) may be located directly on top of and contacting the absorbent layer for the purpose of reducing or preventing oxidation thereof during heat treatment (eg, thermal tempering, heat bending, and / or heat setting) thereby allowing predictable coloration to be achieved, high values ​​of external reflectance and / or good selectivity. Articles coated in accordance with certain exemplary embodiments of this invention can be used in the context of insulating glass (IG) window units, vehicle windows, other types of windows, or in any other suitable application. The most representative figure of the invention is number 1.

(57) Abstract

A coated article ineludes a low-E coating having an absorbing layer located over a functional layer (IR reflecting layer) and designed to cause the coating to have an increased outside reflectance (eg, in an IG window unit) and good selectivity. In certain embodiments, the absorbing layer is metallic, or substantially metallic, and is provided directly over and contacting a lower of two IR reflecting layers. In certain example embodiments, a nitride based layer (eg, Silicon nitride or the like) may be located directly over and contacting the absorbing layer in order to reduce or prevent oxidation thereof during heat treatment (eg, thermal tempering, heat bending, and / or heat strengthening) thus permitting predictable coloration, high outside reflectance values, and / or good selectivity to be achieved. Coated articles according to certain example embodiments of this invention may be used in the context of insulating glass (IG) window units, vehicle Windows, other types of Windows, or in any other suitable application.

Institute

Mexican Property

Industrial

PATENT TITLE NO. 340550 _SE_

SiíWMA «ECONOMY

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Headlines):

Home:

D nomination:

Classification:

Inventor (M) c

GUARDIAN INDUSTRIES CORP.

2300 Harmon Road, Auburn Hills, Michigan, 48326-1714, USA

ARTICLE COATED WITH LOW-E COATING THAT HAS AN ABSORBING LAYER ON TOP OF A FUNCTIONAL LAYER DESIGNED TO INCREASE EXTERNAL REFLECTANCE.

lnt.CI.8: C03C17 / 34; C03C17 / 36; E06B3 / 67

KEVIN O'CONNOR, JJNGYU LAO; JOHN WOLFF

REQUEST

Number:

MX / a / 2014/004334 fi

Country:

US agency: Twenty years

Date:

October 2011

International filing datex September 2012]

PRIORITY

Number 3

13/317,176^

Expiration Date: September 14, 2032, the reference patent ^ and is granted based on articles 1, 2 'section V, 6 ° section llt, and 59d® (Industrial Property Law.

In accordance with article 23 of the Industrial Property Law, this patent is valid from the date of filing of the international application and will be subject to. payment of rights.

Twenty Unprofitable years, to keep the

Who subscribes to the presoite title jo does on the basis of the provisions of the aucutoe 6® * faccto κ »lll and 7 ° bis 2 the Industrial Property Law (DÍjjrio OficiMde de la Federación. (DOF) 06/27/1901, amended et 08/02/1004, 10/28/1996, 12/26/19 7, 05/17/1999

01/26/2004, 06/16/2005 01/25/2 (subsection a), 4th and 12th fractions I OI / 07/2002, 07/15/2004 ^ 07/07/2 (from Propij

06/05 / 2009,06 / 01/2010, t8 / t¡6 / 2Q10, 06/28/201 '311 of the Regulation of Insert ji I and 7/09/2007); 1st articles,

I Industrial (DOF 12/27/1999, amended

MHMHlMHil

04/01/2012), articles 3rd fraction V istrlal (DOF 12/14/199 reformed the Organic Act Ί 0/2002, 07/29/2004, 08/04/2004 and 09/13/2007); 1st, 3rd ^^^ IM ^ lMMtt ^ mM'itulars of the

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fractions I and lll and 30 of the Ei

Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).

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Arenal No. 550. Floor 1 Pueblo Sania María Tepepan, Xochimiico. CP 1S020.

Mexico City&gt;) 53 34 07 00 www.irrpi qob.m *

Issue Date: July 14, 2016

THE DIVISIONAL DIRECTOR OF PATENTS

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NAHANNY CANAL REYES

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MX / 2016/54853

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ARTICLE COATED WITH BA COATING

AN ABSORBING LAYER ON TOP OF A DESIGNED FUNCTIONAL LAYER

TO INCREASE EXTERNAL REFLECTANCE

FIELD OF THE INVENTION

This invention relates to a coated article that includes a low-E coating. In certain exemplary embodiments, an absorbent layer of the low-E coating is located on top of a functional layer (IR reflective layer) and is designed to cause the coating to have increased exterior reflectance (for example, in a window unit of GI) and / or increased glass side visible reflectance (eg, measured monolithically) and good selectivity. In certain exemplary embodiments, the absorbent layer is metallic, or substantially metallic, and is provided directly on top of and contacting a bottom layer of the two IR reflective layers. In certain exemplary embodiments, a nitride-based layer (eg, silicon nitride or the like) is located directly on top of and contacting the absorbent layer for the purpose of reducing or preventing oxidation thereof during heat treatment ( for example, thermal tempering, heat bending and / or heat hardening) thereby allowing

I jM jh i achieve a predictable coloration, valo^tr^s^ tAP * «^ &amp; s ^

FNCfJSTtUAl. ** external reflectance and / or good selectivity after

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heat treatment. Articles coated in accordance with certain exemplary embodiments of this invention can be used in the context of insulating glass window (IG) units, vehicle windows, other types of windows, or in any other suitable application.

BACKGROUND OF THE INVENTION

Coated articles are known in the field for use in window applications such as insulating glass (IG) window units, vehicle windows, and / or the like. It is known that in certain cases it is desirable to heat treat (eg heat temper, heat bend and / or heat cure) these coated articles for the purpose of tempering, bending or the like in certain exemplary cases.

In certain situations, designers of coated articles frequently strive to achieve a combination of high exterior reflectance for aesthetic purposes combined with good selectivity, desirable visible transmission, low emissivity (or emittance), and low sheet resistance (R_s). The characteristics of low emissivity (low-E) and low laminar resistance allow that /?

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.i'Va. . &lt;7 .'l τ tNSI (TUTO \¹

Dt LA ^Ί&lt; ) ...

Block these significant IR radiation coated items with the -e-in-do — reduce for example undesirable heating of vehicle or building interiors. However, heat treatment of coated articles typically requires the use of a temperature (s) of at least 580 ° C, more preferably of at least about 600 ° C, and even more preferably of at least 62 0 ° C. Use of these high temperatures (for example, for 5-10 minutes or more) frequently causes coatings to disintegrate, have an undesirably low external visible reflectance, and / or cause one or more of the desirable characteristics mentioned above to deteriorate significantly. in an undesirable way.

The United States Patent Document

2005/0202254, commonly owned and thus incorporated herein by reference, discloses a coated article having the following layers on a glass substrate, from the glass substrate outward.

Cap

Glass Substrate

Uncle₂

Yes₃N₄

ZnO

Ag

NiCrO_x

SnO₂

Yes₃N₄

SnO₂

ZnO

Ag

NiCrOx

SnO₂

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Yes₃N₄

While the aforementioned coated article can be heat treated and has many desirable and good characteristics, it has problems regarding its undesirably low external visible reflectance when the coated article is used in an IG window unit. In particular, US 2005/0202254 states that IG window units having the coating are only capable of realizing a visible reflectance of the outer glass side of 112%.

As another example, while the coated article of US Patent No. 8,017,243 has many desirable and good characteristics, it has problems with respect to its undesirably low external or glass side reflective reflectance. In

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INSTITUTO MÍXiCAKO In particular, the tables in the '243 IG window unit patent having snln coating are capable of performing a visible reflectance on the outside glass side of 1-14% (see RgY values).

As another example, while the coated article of United States Patent No. 7,419,725 has many desirable and good characteristics, it has problems with respect to its undesirably low external or glass-side reflective reflectance. In particular, Examples 1-2 in the '725 patent show that IG window units having the coating are only capable of performing a visible reflectance on the outside glass side of 16.9 to 17.7% (see RgY values) .

In view of the foregoing, it will be apparent to those skilled in the field that there is a need in the field for a coated article with more desirable optical characteristics (eg, higher external glass side visible reflectance in a GI combined with low emissivity and desirable visible transmission).

BRIEF SUMMARY OF EXEMPLARY MODALITIES OF THE INVENTION

This invention relates to a coated article that includes a low-E coating. In certain

JL ^;· ^: ί ^{, vf} &gt;&gt;

exemplary modalities, one layer. absorbent low-E coating is located on top of a functional layer (IR reflective layer) and is designed to cause the coating to have increased external visible reflectance (for example, in an IG window unit) and / or reflectance Increased glass side visible (eg, measured monolithically), along with transmission, desired visible selectivity, low SHGC, and low emissivity. In certain exemplary embodiments, the absorbent layer is metallic, or substantially metallic, and is provided directly on top of and contacting a bottom layer of the two IR reflective layers. In certain exemplary embodiments, the metallic or substantially metallic absorbent layer (eg, NiCr) is approximately 25-50 angstroms (Á) thick. Unexpectedly, it has been surprisingly found that it increases the external visible reflectance in IG window unit applications and / or has a visible reflectance of the

0 glass side increased when measured monolithically, while still allowing for desirable visible transmission and low emissivity. In certain exemplary embodiments, a nitride based layer (eg, silicon nitride or the like) is located directly on top of and contacting the absorbent layer with the ·&gt; .Λ. .....; . - ·, χ ', .Λ £ purpose of reducing or preventing oxidation · of; mj ^ mcL · ^^ during heat treatment (for example, thermal tempering, heat bending and / or heat hardening) allowing thereby achieving predictable coloration, high exterior reflectance values ​​and / or good selectivity after heat treatment. Articles coated in accordance with certain exemplary embodiments of this invention can be used in the context of insulating glass (IG) window units, vehicle windows, other types of windows, or in any other suitable application.

In certain exemplary embodiments of this invention, a coated article is provided that includes a coating supported by a glass substrate, the coating comprising: a first and a second reflective infrared radiation (IR) layer comprising silver, where the first IR reflective layer is located closer to the glass substrate than the second IR reflective layer and where the first IR reflective layer which comprising silver is located on top of and directly contacting a layer comprising zinc oxide; a substantially metallic absorption layer located on top of and directly contacting the first IR reflective layer; a layer comprising nitride located on top of and making

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oxide-comprising layer of the layer comprising: localized dielectric water directly contacting substantially metallic; a metal located on top of nitride; at least one on top of the second IR reflective layer; and wherein the coating has a sheet resistance less than or equal to 3.0 ohms / square and the monolithically measured coated article has a visible transmission of approximately 20-70% and a visible glass-side reflectance of at least 20% . In certain exemplary embodiments, the coated article may be heat treated (eg, heat tempered so that tempering occurs when the coating is on the glass substrate). In certain exemplary embodiments, the coated article may be provided in an IG window unit.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGURE 1 is a cross-sectional view of a coated article according to an exemplary embodiment of this invention.

FIGURE 2 is a cross-sectional view of a GI unit in accordance with an exemplary embodiment of this invention.

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DesciiLus coated articles in ¹ This * document can be used in applications such as IG window units, vehicle windows, monolithic architectural windows, residential windows and / or any other suitable application including single or multiple glass substrates.

In certain exemplary embodiments of this invention, the coating includes a double silver battery, although this invention is not limited in this way in all cases.

For example, in certain exemplary embodiments of this invention, heat treated (HT) and / or non-HT coated articles having multiple IR reflective layers (eg, two separate silver-based layers) are capable of developing laminar strength (R_s) less than or equal to 3.0 (more preferably less than or equal to 2.5, even more preferably less than or equal to 2.0, and much more preferably less than or equal to 1.7). In certain exemplary modalities, after and / or before heat treatment (HT) and measured in monolithic form, the coated articles described herein are capable of developing a visible transmission (111. C, 2 degrees) of approximately 20-70 %, more preferably of about of

Lv;:. . . ._h about 30-60%, even more preferably.) about 35-55% and much more preferably about 40-50%. On the other hand, in certain exemplary embodiments (HT or non-HT), when coupled to another glass substrate to form an IG window unit, articles coated with window units of

IGs according to certain exemplary embodiments of this invention are capable of developing a visible transmission of about 20-70%, more preferably about 30-60%, even more preferably 35-55%, more preferably about 40-50%, and much more preferably about 41-46%. In certain exemplary modalities, after and / or before heat treatment (HT) and measured in monolithic form, the visible reflectance on the glass side (% RgY) is significantly higher (for example, at least about 5% more high, more preferably at least about 10% or 15% higher than the visible reflectance of the film side (% RfY). For example, where 24% is the glass side visible reflectance and 12% is the film side visible reflectance, the glass side visible reflectance is 12% higher than the film side visible reflectance (24 % - 12% = 12%). In certain exemplary embodiments of this invention, after and / or before

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* Γ heat treated (HT) and measured in monolithic form, the coated articles described herein are preferably approximately approximately preferably preferably preferably of capable of developing a visible glass-side reflectance (% RgY) of at least 2 0%, more than 20-50%, more

20-40%, more

20-35% even more about 22-35% and much more preferably about 24-30%. On the other hand, in certain exemplary embodiments (HT or non-HT), when coupled to another glass substrate to form an IG window unit, the IG window unit coated articles according to certain exemplary embodiments of this invention are capable of developing a visible glass-side reflectance (% RgY) of at least 20%, more preferably of about 20-50%, about 20-40%, about 20-35%, still about 22-35% , about 23-30% or about 24-29% and much more preferably about 25-27%). In certain exemplary embodiments, the coating also makes it possible for the IG units to have an SHGC value of less than 0.27, more preferably less than 0.25, and much more preferably preferably preferably preferably of from more than more more less than 0.24 in combination with «» · * · - ..... any '

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modalities described in this document.

The terms heat treatment and heat treatment used herein mean heating the article to a temperature sufficient to achieve thermal tempering, heat bending and / or heat hardening of the glass inclusive article. This definition includes, for example, heating a coated article in an oven or incinerator at a temperature of at least about 580 ° C, more preferably at least about 600 ° C, for a period sufficient to allow tempering, bending and / or hardening with heat. In certain cases, the HT can be for at least about 4 to 5 minutes. The coated article may or may not be heat treated in different embodiments of this invention.

FIG. 1 is a side, cross-sectional view of an article coated in accordance with an exemplary, non-limiting embodiment of this invention. The coated article includes substrate 1 (eg, a clear, green, bronze, or teal colored glass substrate approximately 1.0 to 10.0 mm thick, more preferably approximately 1.0 mm to 7.0 mm thick, even more preferably of approximately 5-7 mm thick, where a thickness is

AA approximately 6 mm) and a low-E coating (or layer system) 30 provided on the substrate 1 either directly or indirectly. The coating (or layer system) 3 0 includes, for example: a layer based on and / or inclusive of bottom dielectric silicon nitride 3 which may be Si₃N₄ (which may or may not be doped with other material (s) such as aluminum in certain exemplary cases) of the Si-rich type for the reduction of opacity or any other silicon nitride of suitable stoichiometry in different modalities of this invention, a first lower dielectric contact layer 7 (which contacts the bottom IR reflective layer 9), a first conductive and preferably metallic infrared (IR) reflective layer 9, a metallic or substantially metallic absorbent layer 4 (eg, of or including NiCr or the like) which is located on top of and directly contacts the reflective IR layer 9), a nitride-based and / or inclusive layer of dielectric silicon 14 which is located on top of and makes direct contact with the absorbent layer 4, an intermediate layer based on and / or inclusive of tin oxide 15, a second lower dielectric contact layer 17 (which contacts the IR reflective layer 19), a second IR reflective layer ίί ·:

JL ± - '^:i.-i.

. . „. ÍN'-r- ·. ·:¹ conductive and preferably metallic 19, ^:a layer &lt;

upper contact 21 (which contacts the IR reflective layer 19), a dielectric layer 23 and finally a protective dielectric layer 25. The contact layers 7, 17 and 21 each contact at least one reflective layer IR (for example, Ag-based layer). The aforementioned layers 3-25 constitute the low-E (i.e. low emissivity) coating 30 that is provided on the glass or plastic substrate 1. In certain exemplary embodiments, there is no high dielectric index layer (for example, TiO layer₂) between the lower IR reflective layer 9 and the glass substrate 1 (high index layer means a layer having a refractive index n greater than about 2.15).

In certain exemplary embodiments, the problem that has now been solved is creating a coating that has a high differential between glass-side reflection (RgY) and film-side reflection (RfY), which includes for example post-processing heat treatment (eg thermal tempering). Typically with double silver coating designs the difference between the magnitude of the glass and film side visible reflections is low. A high differential is aesthetically desired for certain markets such as

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certain portions of the commercial market. Of^C'this. In order to illustrate certain exemplary embodiments of this invention, the coated articles have been designed to have high glass-side visible reflection, like a mirror, while maintaining low film-side visible reflection. While certain individual silver coatings have been able to do this in the past, certain exemplary embodiments of this invention relate to a multiple silver coat capable of doing this. A disadvantage of these individual silver coatings is that they tend to have a fairly high solar heat gain coefficient (SHGC) of 0.29 and cannot meet the proposed SHGC &lt;0.25 energy code standard where high solar loads are common. Certain exemplary embodiments of this invention meet energy code standards by providing an SHGC of approximately 0.23 while maintaining the high reflection differential aesthetics set forth in this document. In certain exemplary embodiments of this invention, by using a metallic or substantially metallic absorbent NiCr layer instead of a transparent NiCrOx layer above the bottom silver, a high RgY / RfY differential can develop after heat treatment . In certain exemplary modalities, significant oxidation of the lower silver during the

layer of directly on the part in order to avoid a

NiCr in NiCrOx Above the heating process a silicon nitride is deposited on top of the absorbent NiCr layer. Additionally, in certain exemplary modalities, in order to minimize or reduce the transmitted opacity and to maintain the optical properties during heating, a small amount of nitrogen (50 mL) can be introduced into the absorbent layer directly on top of the lower plate. Nitrogen has little impact on NiCr's immediate optical properties but enables it to remain metallic or substantially metallic during heating.

In monolithic cases, the coated article includes only a glass substrate 1 as illustrated in Figure 1. However, the monolithic coated articles described herein can be used in devices such as laminated vehicle windshields, window windows units IG and the like. As far as IG window units are concerned, an IG window unit can include two separate glass substrates. An exemplary IG window unit is illustrated and described, for example, in United States Patent No. 7,189,458, the disclosure of which is hereby incorporated in this document by way of. · '&lt;Reference. An exemplary IG window unit may include, for example, the coated glass substrate 1 shown in Figure 1 coupled to another glass substrate via a spacer (s), sealer (s) or the like, wherein an opening is defined between them. This opening between the substrates in the IG unit modalities can in some cases be filled with a gas such as argon (Ar). An exemplary GI unit may comprise a pair of separate clear glass substrates each approximately 3-7 mm (eg 6 mm) thick, one of which is coated with a coating 30 described herein in certain cases exemplary, where the opening between the substrates can be from about 5 to 30 mm, more preferably from about 10 to 20 mm, and much more preferably from about 12 mm. In certain exemplary cases, the coating 30 may be provided on the inner surface of either the substrate that is oriented toward the opening, however in preferred embodiments the coating 30 is provided on the inner surface of the outer glass substrate 1 as shown in Figure 2. A windowed IG unit unit eg is also shown in Figure 2 and may include, for example, the coated glass substrate 1 shown in

Figure 1 coupled to another glass substrate &lt;9 ^^Tg. ; ppr. v £ .a of;

a spacer (s), sealant (s) or the like 4 wherein an opening 6 is defined therebetween. This opening 6 between the substrates in the IG unit modalities can in some cases be filled with a gas such as argon (Ar). The opening 6 may or may not be at a pressure less than atmospheric pressure in different embodiments of this invention.

Still referring to Figure 2, an exemplary GI unit may comprise a pair of separate glass substrates (1 and 2) each approximately 6 mm thick, one of which is coated with a coating 30 described herein. in certain exemplary cases, where the opening 6 between the substrates can be from about 5 to 3 0 mm, more preferably from about 10 to 20 mm, and much more preferably from about 12-16 mm. In certain exemplary embodiments, the coating 30 is provided on the inner surface of the outer glass substrate 1 as shown in Figure 2 (i.e., on surface # 2 from the outside), although it may be provided on the other substrate 2 in alternative embodiments of this invention.

In certain exemplary embodiments of this invention, Absorption Layer 4 is located on top of and directly contacting the lower IR Retaining Layer 9. In certain exemplary embodiments, Layer 14 is located directly on top of and contacting the Absorption Layer. 4 is a nitride based layer and is not substantially or completely oxidized. This is advantageous in that it helps to prevent (or reduce the probability of) the absorption layer from being oxidized during heat treatment, thereby allowing the absorption layer to better perform one of its proposed functions, in particular absorption of at least some amount (eg, at least 5%, more preferably at least 10%) of visible light. It will be appreciated that if a layer becomes too oxidized during heat treatment or the like, it can no longer function as a suitable absorption layer.

In certain exemplary embodiments of this invention, the absorption layer 4 can be of or can include Ni and / or Cr (eg, NiCr with any suitable Ni: Cr ratio). In certain exemplary embodiments, it is desirable that the absorption layer 4 comprise 0-10% oxygen, more preferably 0-5% oxygen, and much more preferably 0-2% oxygen (atomic%). On the other hand, 0-20% nitrogen, more preferably 1-15% nitrogen and much more preferably 1-10% nitrogen (atomic%) can be provided in the absorbent layer 4. While NiCr ( eg possibly nitrided in certain exemplary embodiments) is a preferred material for absorption layer 4, it is possible that other materials may be used in place of or in addition to Ni and / or Cr. For example, in certain exemplary embodiments of this invention, the absorption layer 4 can be of or can include Ni, Cr, NiCrN_x, CrN, ZrN or the like. In non-heat treatable embodiments, any of the materials mentioned above can be used for the absorbent / absorbent layer 4, as well as other materials such as Ti, Zr, NiOx or the like.

The absorbent layer 4 of the low-E coating is designed to cause the coating and / or coated article (which includes an IG unit in certain embodiments) to have increased external (and / or glass side) visible reflectance (by example, in a IG window unit), along with a desired visible transmission, selectivity, low SHGC, and low emissivity. In certain exemplary embodiments, the metallic or substantially metallic absorbent layer (eg NiCr) 4 is thinner than the top contact layer 21 and is about 25-80 angstroms, more preferably about 25-50 angstroms (Á) of thick, more preferably about 30-40 angstroms (Á) thick and much more preferably about 3337 angstroms (Á) thick (eg, about 35 angstroms thick). On the other hand, in certain exemplary embodiments, the absorbent layer 4 is either metallic or only slightly oxidized, while the top contact layer 21 is significantly oxidized (eg oxidized by at least about 50%). In this way, layer 4 functions as an absorbent layer and surprisingly results in an exterior or glass-side reflectance of the coated article that is significantly increased, while upper contact layer 21 does not function as an absorbent layer.

In certain exemplary embodiments, the metallic or substantially metallic absorbent layer 4 is located directly between and contacting the metallic or substantially metallic IR reflective layer 9 and the nitride layer 14 for the purpose of reducing or preventing oxidation of layer 4 during heat treatment (for example, thermal tempering, heat bending and / or heat hardening) thereby allowing reflectance and visible transmission to be achieved after heat treatment (HT).

Furthermore, in certain exemplary embodiments, a metal oxide based and / or inclusive layer 15 of or including tin oxide can be provided between the nitride based layer "3.4. .and the upper reflecting infrared (IR) radiation layer 19 and in particular, in certain exemplary embodiments, enter and directly contact the nitride based layer 14 and the zinc oxide inclusive and / or inclusive contact layer 17 . For example, it has been discovered that the use of this tin oxide inclusive intermediate layer 15 results in a coated article which is capable of developing desired optical characteristics.

Dielectric layers 3, 14, and 25 can be of or can include silicon nitride in certain embodiments of this invention. Silicon nitride layers 3, 14 and 25 can improve, among other things, the heat-treating ability of coated articles, for example, such as thermal tempering or the like. The silicon nitride in these layers can be of the stoichiometric type (i.e.₃N₄), or alternatively of the Si-rich type in different embodiments of this invention. For example, Si 3 (and / or 14) rich silicon nitride combined with zinc oxide and / or tin oxide under a silver-based IR reflective coating can allow silver to be deposited (for example, via of the ion spray or the like) in a way which causes its laminar resistance to be decreased compared to the supposed case that other material (s)

<img file="MX340550B_D0019.tif" />

was (are) under the money. On the other hand, the *^Np ^ es ^ ricia 4e Si free in an inclusive layer of Si 3-rich silicon nitride can allow certain atoms such as sodium (Na) which migrate out of glass 1 during HT to be more efficiently stopped by the inclusive layer Si rich silicon nitride before they can reach silver and can damage it. In this way, it is believed that the Si_xN_and rich in Si can reduce the amount of damage done to the silver layer (s) during HT in certain exemplary embodiments of this invention thereby allowing laminar strength (R_s) decrease or remain approximately the same in a satisfactory manner. Furthermore, it is believed that the Si_xN_and Rich in Si in layer 3 can help reduce the amount of damage (eg, oxidation) done to absorbent layer 4 during HT in certain optional embodiments of this invention. In certain exemplary embodiments, when Si-rich silicon nitride is used in layer 3 and / or 14, the Si-rich silicon nitride layer as deposited may be characterized by Si layer (s)_xN_and, where x / y can be from 0.76 to 1.5, more preferably from 0.8 to 1.4, even more preferably from 0.85 to 1.2. On the other hand, in certain exemplary modalities, before and / or after HT, the Si layer (s)_xN_andrich in Si can (n) have a refractive index n of at least 2.05, more preferably of less ^ 2 or j2 ^ 07 /.

and sometimes at least 2.10 (eg 632nm) (note: if₃N₄ stoichiometric which can also be used has an index n of 2.02-2.04). In certain exemplary embodiments, it has been surprisingly discovered that improved thermal stability can be developed especially when the Si layer (s)_xN_and Rich in Si as deposited it has a refractive index n of at least 2.10, more preferably of at least 2.20 and much more preferably of 2.2 to 2.4.

Any and / or all of the silicon nitride layers discussed herein can be doped with other materials such as stainless steel or aluminum in certain exemplary embodiments of this invention. For example, any and / or all of the silicon nitride layers discussed herein (eg, 3, 14, and / or 25) may optionally include from about 0-15% aluminum, more preferably from about 1 to 10 % aluminum, in certain exemplary embodiments of this invention. Silicon nitride can be deposited by ion spraying a Si or SiAl target in certain embodiments of this invention. Oxygen can also be provided in certain cases in one or more of the silicon nitride layers. Because layer 14 is provided to protect the absorbent layer 4 from oxidation during the process,

ΙίιίηΓ - · 7 ·.;!

exemplary modalities, the layer based on^¡'nitride-

<img file="MX340550B_D0020.tif" />

silicon 14 is at least thin, more preferably at least about 100 angstroms thinner, than one or both of the silicon nitride 3 and / or 25 based layers. In certain exemplary embodiments, the silicon nitride based layer 14 is by at least about 100 angstroms thinner than silicon nitride-based layer 25 and is at least about 50 angstroms thinner than silicon nitride-based layer 3. While silicon nitride is a preferred material for layers 3, 14, and 25 in certain exemplary embodiments of this invention, it will be recognized that other materials may be used in place of or in addition to one or more of those layers in alternative embodiments thereof. invention.

<img file="MX340550B_D0021.tif" />

Reflective infrared (IR) radiation layers 9 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 radiation reflective material. Reflective IR radiation layers 9 and 19 help allow the coating to have low-E and / or good solar control characteristics. However, reflective layers of IR radiation can be slightly oxidized in certain modes of this JLuÉvenCÍóh., In '&lt;

^lf'⁵ In certain exemplary embodiments, the reflective layer of * upper IR radiation 19 is thicker (for^,,T5 ^ í ^ TOr '^ ST ”¹W^SKiaee· Less than about 5 angstroms thicker, more preferably at least about 10 or 15 angstroms thicker) than the lower IR reflective layer 9.

The top contact layer 21 can be of or can include nickel (Ni) oxide, chromium / chromium (Cr) oxide or a nickel alloy oxide such as nickel-chromium oxide (NiCrO_x) or other suitable material (s), in certain exemplary embodiments of this invention. For example, the use of NiCrO_x at layer 21 allows durability to be improved. NiCrO_x The layer 21 may be fully (or substantially completely) oxidized in certain embodiments of this invention (ie, it may be fully stoichiometric) or it may only be partially oxidized. In certain cases, the NiCrO layer_x 21 can be oxidized by at least about 50%. Contact layer 21 (eg, of or including a Ni and / or Cr oxide) may or may not have a degree of oxidation in different embodiments of this invention. Oxidation graduation means that the degree of oxidation in the layer changes in the thickness of the layer so that for example a contact layer can have a graduation in order to

<img file="MX340550B_D0022.tif" />

{/ Τ ρ τ &lt;30 which is less oxidized in the interface area £ of contact with the immediately adjacent IR reflective layer 19 than in a portion of the further contact layer or

<td>more much more</td><td>distant from</td><td>the</td><td>cap</td><td>reflective</td><td>TO GO</td>

<td>immediately</td><td>adjacent 19.</td><td>The</td><td>cap</td><td>contact 21</td><td>(by</td>

<td>example of or</td><td>which includes a</td><td colspan="2">oxide</td><td>Ni and / or Cr) can</td><td>to be</td>

or does not continue in different embodiments of this invention through substantially the entire IR reflective layer 19.

Dielectric layer 15 can be of or can include tin oxide in certain exemplary embodiments of this invention. However, as with other layers described in this document, other materials can be used in different cases.

In certain embodiments of this invention, the lower contact layers 7 and / or 17 are of or include zinc oxide (eg, ZnO). The zinc oxide in layers 7 and 17 can also contain other materials such as Al (for example to form ZnA10_x) and / or tin. For example, in certain exemplary embodiments of this invention, one or more of the zinc oxide based layers 7, 17 can be doped with from about 1 to 10% Al, more preferably from about 1 to 5% Al, and much more preferably about 1 to 4% of

To the.

The dielectric layer 23 may fit or - may include tin oxide in certain exemplary embodiments - of this invention. Like otTa'S '^' n ^ apsiS ..... del · -¹- · - coating, layer 23 is optional and need not be provided in certain exemplary embodiments of this invention. The dielectric layer 25, which may be an outer coating in certain exemplary cases, may be of or may include silicon nitride (eg Si₃N₄) or any other suitable material in certain exemplary embodiments of this invention. Optionally, other layers (eg, a layer of or including zirconium oxide) may be provided on top of layer 25. Layer 25 is provided for durability purposes and to protect the underlying layers during heat treatment and / or environmental use. In certain exemplary embodiments, layer 25 may have a refractive index (n) of from about 1.9 to 2.2, more preferably from about 1.95 to 2.05.

Another layer (s) may also be provided under or above the illustrated coating. In this way, while the layer or coating system 30 is on or is supported by the substrate 1 (directly or indirectly), another layer (s) can be provided between them. In this way, for example, the coating of Figure 1 can be considered over and supported by the substrate 1 even if chi? cpapa (s): * &lt;&amp; «&lt;·.

(n) is provided between layer 3 and substrate 1. other part, certain layers of coating Xja ..., iXuat ^ tadQ., ^ S ^_KMeTO«Can be removed in certain modalities, while other layers not illustrated can be added between the different layers in different exemplary modalities, or the diverse layer (s) can be divided with another layer (s) aggregate (s) between sections divided into other embodiments of this invention without departing from the full spirit of certain embodiments of this invention.

While various thicknesses and materials can be used in layers in different embodiments of this invention, the exemplary thicknesses and materials for the respective layers spray-deposited onto the glass substrate 1 in the embodiment of Figure 1 are as follows, from the glass substrate outwards:

Exemplary Materials / Thicknesses: Mode of Fig. 1 Preferred Interval Layer (Á) Most Preferred (A) Example (Á)

Glass (1-10mm thick)

<td>Yes_xN_and (layer 3)</td><td>40-250 A</td><td>50-200 A</td><td>120 A</td>

<td>ZnO_x (layer 7)</td><td>10-300 Á</td><td>40-150 Á</td><td>100 A</td>

<td>Ag (layer 9)</td><td>90-200 A</td><td>130-170 A</td><td>151 A</td>

<td>NiCr (layer 4)</td><td>25-80 A</td><td>30-40 A</td><td>35Á</td>

<td>Yes_xN_and (layer 14)</td><td>20-250 A</td><td>25-80 A</td><td>43 A</td>

<td>SnO₂ (layer 15)</td><td>300-950 A</td><td>500-900 A</td><td>I '' 'Í50 Á</td><td>--✓ • and '¹ . «·</td>

<td>ZnO_x (layer 17)</td><td>10-300 A</td><td>40-150 A</td><td>100 A '</td><td></td>

<td>Ag (layer 19)</td><td>100-250 A</td><td>140-200 A</td><td></td><td></td>

<td>NiCrOx (layer 21)</td><td>20-60 A</td><td>30-50 A</td><td>40 A</td><td></td>

<td>SnO₂ (layer 23)</td><td>0-750 A</td><td>40-250 A</td><td>120 A</td><td></td>

<td>Yes₃N₄ (layer 25)</td><td>80-750 A</td><td>100-320 A</td><td>225 A</td><td></td>

In certain exemplary embodiments of this invention, the coated articles described herein may have the following optical and solar characteristics set forth in Table 2 when measured monolithically (prior to any optional HT). The relevant optical characteristics are in accordance with 111. C 2 °, but it should be noted that the L * values ​​are Hunter.

Lamellar resistors (R_s) described in this document take into account all IR reflective layers (eg silver based layers 9, 19).

Optical / Solar Characteristics (Monolithic; pre-HT and / or post-HT)

<td>Characteristic</td><td>general</td><td>Most Preferred</td><td>Much More Preferred</td>

<td>R_s (ohms / square):</td><td> &lt;=3.0</td><td> &lt;=2.0</td><td> &lt;=1.7</td>

<td>RgY:</td><td> 20-40%</td><td> 22-35%</td><td> 24-30%</td>

<td>Kis.</td><td> 20-70%</td><td> 30-60%</td><td> 40-50%</td>

Furthermore, in certain exemplary embodiments of this invention, the coated articles described herein which may have been optionally heat treated to a sufficient degree for tempering and which may have been coupled to another glass substrate to form a unit of IG, may have the following optical / solar characteristics of

<td>units of</td><td>IG. Must be</td><td>note that when</td><td>the</td>

<td>covering</td><td>30 is about I</td><td colspan="2">unit surface # 2</td>

<td colspan="2">IG window as it</td><td>shown in Figure 2,</td><td>the</td>

<td colspan="2">external visible reflectance</td><td>window unit</td><td>IG</td>

<td colspan="2">is represented by R_gAnd in the</td><td>following table.</td><td></td>

<td></td><td colspan="2">Exemplary Optical Characteristics (GI Unit)</td><td></td>

<td>Characteristic</td><td>general</td><td>Most Preferred</td><td></td>

<td>Tvis (or TY) (III. C 2 °):</td><td> 30-60%</td><td> 35-55%</td><td></td>

<td>a *, (III. C 2 °):</td><td>-15 to-1</td><td>-10 to-3</td><td></td>

<td>b '_t (III. C 2 °):</td><td>-4 to +8.0</td><td>-1 to +4</td><td></td>

<td>L * (III. C 2 °):</td><td> 58-80</td><td> 61-74</td><td></td>

<td>R_FAnd (III. C, 2 degrees):</td><td> 9-15%</td><td> 11-14%</td><td></td>

<td>to'_F (III. C, 2 °):</td><td>-10 to + 2.0</td><td>-4 to -1</td><td></td>

<td>b *_F (III. C, 2 °):</td><td>-14 to + 4</td><td>-12 to-4</td><td></td>

<td>L * (III. C 2 °):</td><td> 30-55</td><td> 35-47</td><td></td>

<td></td><td></td><td></td><td></td>

<td>RgY (III. C, 2 degrees):</td><td> 20-40%</td><td> / 24-29%</td><td></td>

<td>to*_g(HI. C, 2 °):</td><td>-12 to + 2.0</td><td>-10 to-1</td><td></td>

<td>b * g (lll. c, 2 °):</td><td>-10 to + 5</td><td>-7 to-1</td><td></td>

<td>L * (III. C 2 °):</td><td> 34-65</td><td> 40-60</td><td></td>

<td>SHGC (surface # 2):</td><td> &lt;=0.27</td><td> &lt;= 0.25, &lt;=0.24, &lt;=0.23</td><td></td>

On the other hand, in certain modalities' éjemplarejsg ^

2i. Λ ·. '

... - - ....... .. · · .ΛΛ-Οη the coated article is thermally stable heat treatment (eg thermal tempering). characterized in that it has a reflective ΔΕ * value on the glass side due to HT not greater than about 5.0, more preferably not greater than about 4.5, when measured monolithically.

The following examples are provided for exemplary purposes only and are not intended to be limiting unless specifically claimed.

EXAMPLES

Example 1 below was made by sputtering onto 6mm thick clear glass substrates in order to have the layer stack subsequently exposed. Example 1 is in accordance with the exemplary embodiments of this invention as shown in Figure 1. Example 1 had the following stack of layers, where the thicknesses are in units of angstroms (Á).

<td>Cap</td><td>Thickness(</td>

<td>Glass (6mm thick)</td><td></td>

<td>Yes_xN_and (layer 3)</td><td>120 A</td>

<td>ZnO_x (layer 7)</td><td>100 A</td>

<td>Ag (layer 9)</td><td>151 A</td>

<td>NiCr (layer 4)</td><td>35Á</td>

<td>Yes_xN_and (layer 14)</td><td>43 A</td>

<td>SnO₂ (layer 15) ZnO_x (layer 17)</td><td>750 A 100 A</td><td>INSTITUT 0 4 υε ls rp.c; ; .toad;. '·· »N Dt 'S'f R1AL</td>

<td>Ag (layer 19)</td><td>172 A</td><td></td>

<td>NiCrO_x (layer 21)</td><td>40 A</td><td></td>

<td>SnO₂ (layer 23)</td><td>120 A</td><td></td>

<td>Yes₃N₄ (layer 25)</td><td>225 A</td><td></td>

<td>Example 1 was warmed up</td><td colspan="2">thermally and calculated</td>

<td>which had approximately</td><td>following</td><td>characteristics</td>

measured monolithically after HT.

<td>Characteristic</td><td>Ex. 1 (HT)</td>

<td>Tvis (0 TY) (III. C 2 °)</td><td> 47.7%</td>

<td>a * (III. C 2 °):</td><td> -4.5</td>

<td>b * (III. C 2 °):</td><td> 1.0</td>

<td>R_tAnd (III. C, 2 degrees):</td><td> 7.0%</td>

<td>a * (III. C, 2 °):</td><td> -3.0</td>

<td>b *_F (III. C, 2 °):</td><td> -14.5</td>

<td>RgY (III. C, 2 degrees):</td><td> 25.0%</td>

<td>to*_g (III. C, 2 °):</td><td> -1.5</td>

<td>b *_g (III. C, 2 °):</td><td> -6.5</td>

<td>ΔΕ * (transmlslvo):</td><td> &lt;=4.5</td>

<td>ΔΕ * (glass side reflective):</td><td> &lt;=4.5</td>

The tempered coated substrate of Example 1 was then coupled to another 6mm clear glass substrate, with a 12mm air gap therebetween, to form an IG window unit as shown -ex .'- A rm A -.- or Figure 2 and it was simulated that it had approximate Tehte Ias '' ^ following characteristics. -

<td>Characteristic</td><td>Ex. 1 (IG Unit)</td>

<td>T ^_s (or TY) (III. C 2 °)</td><td> 42.7%</td>

<td>a * (III. C 2 °):</td><td> -5.5</td>

<td>b *_t (III. C 2^and):</td><td> 1.0</td>

<td>R_FAnd (III. C, 2 degrees):</td><td> 13.0%</td>

<td>to*_F(lll. C, 2 °):</td><td> -2.5</td>

<td>b '_F(IH. C, 2 °):</td><td> -8.0</td>

<td>RgY (III. C, 2 degrees):</td><td> 26%</td>

<td>to'₀(HI. C, 2 °):</td><td> -2.0</td>

<td>b *_and(lll. C, 2 °):</td><td> -6.0</td>

<td>SHGC (surface # 2):</td><td> 0.23</td>

<td>Transmission Opacity (%):</td><td> &lt;=0.80</td>

While the invention has been described in relation to what is currently considered to be the most practical and preferred embodiment, it should be understood that the invention is not limited to the disclosed embodiment, but rather is intended to cover various modifications and equivalent arrangements that are included within the spirit and scope of the appended claims. Any modality described in this document may or may not be used in combination with any other modality described in this document.

1.