PL204881B1

Heat treatable coated articles with metal nitride layer and methods of making same

Abstract

A heat treatable coated article comprising an infrared (IR) solar reflecting layer or the like sandwiched between a substrate and an overlying dielectric layer thereon. The underlying dielectric layer between the substrate and the solar control layer is optional. In some embodiments, the solar control layer may include NiCrNx, and the dielectric layer(s) may include a nitride such as silicon nitride. It was found that the coated product obtained by nitriding the sun protection layer has a more durable color after heat treatment (HT). For example, the coated article may have a ΔE* value (for glass-side transmission and/or reflection) of no more than 5.0, more preferably no more than 4.0, and most preferably no more than 3 ,0. The coated articles of the present invention may be used in the context of insulating glass (IG) window assemblies. insulating glass), vehicle windows, or the like.

PL204881B1, drawing sheet 1 — Sheet 1 of 21

Term

Term ended

Expired 2 May 2022, 4.4 years ago.

13 claims: 2 independent, 11 dependent

1
Wytwór powlekany obejmujący układ warstw (19), oparty na podłożu szklanym (11) który to układ warstw (19) obejmuje zawierającą azotek metalu warstwę (15), znamienny tym, że:zawierająca azotek metalu warstwa (15) jest umieszczona między podłożem szklanym (11) a co najmniej częściowo azotowaną warstwą dielektryczną (17);przy czym azotek metalu obejmuje co najmniej jeden spośród NiN x i CrN x i NiCrN x oraz jest w kontakcie z warstwą dielektryczną (17);a metal (e) Ni i/lub Cr zawierającej azotek metalu warstwy (15) jest(są) częściowo azotowane przed obróbką cieplną ze zmniejszeniem migracji N, Cr i/lub Ni podczas obróbki cieplnej;i wytwór powlekany ma wartość AE* T transmisyjnej nie większą niż 5,0 korzystnie nie większą niż 4,0, najkorzystniej nie większą niż 3,0 mierzoną po co najmniej 5 minutach obróbki cieplnej obejmującej odpuszczanie cieplne w temperaturze wynoszącej co najmniej 600°C.
2
Wytwór powlekany według zastrz. 1, znamienny tym, że układ warstw (19) zawiera dodatkową warstwę dielektryczną (13), przy czym warstwa zawierająca azotek metalu (15) znajduje się pomiędzy drugą, co najmniej częściowo azotowaną warstwą dielektryczną (17) a dodatkową warstwą dielektryczną (13).
3
Wytwór powlekany według zastrz. 1, znamienny tym, że wartość barwy a* transmisyjnej i/lub wartość barwy a* odbijanej po stronie szkła wyrobu jest ujemna zarówno przed jak i po obróbce cieplnej.
4
Wytwór powlekany według zastrz. 1, znamienny tym, że co najmniej częściowo azotowana warstwa dielektryczna (17) zawiera azotek krzemu.
5
Wytwór powlekany według zastrz. 2, znamienny tym, że dodatkowa warstwa dielektryczna (13) zawiera azotek krzemu i ma grubość od 3,0-25,0 nm, korzystnie od 5,0-12,0 nm, warstwa zawierająca azotek metalu (15) zawiera NiCrN x i ma grubość od 2,0-60,0 nm, korzystnie od 5,0-35,0 nm, a co najmniej PL 204 881 B1 częściowo azotowana warstwa dielektryczna (17) zawiera azotek krzemu i ma grubość od 10,0-50,0 nm, korzystnie od 21,0-31,0 nm.
6
Wytwór powlekany według zastrz. 1, znamienny tym, że przed obróbką cieplną wytwór cechują następujące parametry barwy transmisyjnej:a* 0,0 do -5,0, korzystnie 0,0 do -2,0;b* -2,0 do -15,0, korzystnie -3,0 do -9,0;L* 10,0 do 70,0, korzystnie 20,0 do 50,0.
7
Wytwór powlekany według zastrz. 1, znamienny tym, że po obróbce cieplnej ma opór arkusza (Rs) nie większy niż 500 omów/kw., korzystnie nie większy niż 250 omów/kw., a obróbka cieplna prowadzi do spadku oporu arkusza.
8
Wytwór powlekany według zastrz. 1, znamienny tym, że po odpuszczaniu cieplnym ma wartość Aa* odbijanej po stronie szkła nie większą niż 1,0, korzystnie nie większą niż 0,6, najkorzystniej nie większą niż 0,3.
9
Wytwór powlekany według zastrz. 1, znamienny tym, że ma wartość AE*G odbijanej po stronie szkła nie większą niż 5,0 korzystnie nie większą niż 4,0, najkorzystniej nie większą niż 3,0.
10
Wytwór powlekany według zastrz. 1, znamienny tym, że ma wartość Aa*T transmisyjnej nie większą niż 1,3, korzystnie nie większą niż 1,1, najkorzystniej nie większą niż 0,8.
11
Wytwór powlekany według zastrz. 1, znamienny tym, że ma wartość Ab*G odbijanej po stronie szkła nie większą niż 1,1, korzystnie nie większą niż 0,7, najkorzystniej nie większą niż 0,4.
12
Sposób wytwarzania wytworu powlekanego, znamienny tym, że obejmuje:dostarczenie podłoża szklanego;osadzenie metalu na podłożu w atmosferze zawierającej azot z wytworzeniem na podłożu szklanym warstwy zawierającej azotek metalu, przy czym otrzymana zawierająca azotek metalu warstwa zawiera co najmniej jeden spośród NiNx i CrNx i NiCrNx;osadzenie warstwy dielektrycznej zawierającej azotek na podłożu nad warstwą zawierającą azotek metalu;i obróbkę cieplną wytworu, przez co najmniej 5 minut w temperaturze wynoszącej co najmniej 600°C, przy czym warstwa zawierająca azotek metalu jest azotowana podczas jej nakładania przed obróbką cieplną ze zmniejszeniem migracji N, Cr i/lub Ni podczas obróbki cieplnej w takim stopniu, że po obróbce cieplnej wytwór ma wartość AE* wynoszącą nie więcej niż 5,0 i/lub wartość Aa* transmisyjnej nie większą niż 1,1.
13
Sposób według zastrz. 12, znamienny tym, że dodatkowo obejmuje osadzanie na podłożu dodatkowej warstwy dielektrycznej, tak, że warstwa zawierająca azotek metalu jest osadzana na podłożu nad dodatkową warstwą dielektryczną.

Independent claims13

329 paragraphs in 8 sections, as filed

The present invention relates to a coated article including a glass substrate layer system, the layer system including a metal nitride-containing layer, and a method of making such an article. Such a coated article may be used in insulating glass (IG) units, vehicle windows, and / or other suitable applications.

There is a known need for color consistency in coated articles (before heat treatment versus after heat treatment). Glass floors are often produced in large quantities and cut to size to meet the needs of a particular situation, such as new office buildings with multiple windows and doors, vehicle windows, etc. Often in such applications it is desirable that some of the windows and / or doors be heat treated (i.e., tempered, heat strengthened or bent) while others do not. Office buildings often use IG units and / or laminates for safety and / or thermal regulation reasons. It is often desirable for architectural and / or aesthetic reasons that assemblies and / or laminates that are heat treated (HT) heat treatment), generally matched their untreated counterparts (e.g., in terms of color, reflectance, and / or the like).

US Patent No. 5376455 corresponding to European Patent EP-0747329 discloses a coated article comprising: glass / Si3N4 / NiCr / Ag / NiCr / Si3N4 in which the nickel alloy, as explicitly stated in the specification, should not be nitrided. The coating system of the '455 Patent does not have sufficient color compatibility after heat treatment with its non-heat treated counterpart. In other words, the coating system of the '455 Patent has a fairly high ∆Ε value. In addition, for buyers who want their heat treated and untreated coated articles to have approximately matching colors as perceived by the naked eye, this means that two different coated articles with different coatings (one to be heat treated) have to be manufactured. , and another one to be untreated).

Referring to the '455 patent, stability has generally only been achieved by providing two different layer systems, one of which is heat treated (HT) and the other is not. The need to develop and use two different layer systems to achieve stability creates additional manufacturing costs and inventive needs which are undesirable.

However, jointly owned US Patent No. 5,688,585 discloses a sunscreen coated article comprising glass / Si3N4 / NiCr / Ag / NiCr / Si3N4 where constancy is achieved with a single layer system. As explained at column 9 of the '585 patent, it is a requirement of the' 585 invention that the NiCr layer be substantially free of any nitride. The object of the '585 patent is to produce a sputter-deposited layer system that is heat-treated in a color consistent with its non-heat-treated counterpart. However, the '585 patent employs a heat treatment (HT) of only three (3) minutes (col. 10 line 55). Longer heat treatments are often desired in order to achieve better tempering or HT performance. Unfortunately, as explained below, it has been found that at longer HT times, the coatings of the '585 Patent cannot maintain low ΔE values and thus lose color consistency. In particular, the present inventor has surprisingly found that in coatings such as in the '585 patent, ΔE values jump significantly upward after HT for 4-5 minutes at a temperature of about 600 to 800 degrees C.

Consider the following layer stack (see example 7 below): glass / Si3N4 / NiCr / Ag / NiCr / Si3N4, where the underlying Si3N4 layer is about 5.0-7.0 nm (angstroms), the NiCr layer is about 32. 5nm (the NiCr layer is not nitrided on deposition as can be seen in Fig. 15), and the overlying Si3N4 layer is about 21.0-31.0nm thick.

As explained in Example 7 below, this coated article has a fairly high ∆E * transmission value of about 5.9 after heat treatment (HT) at 625 degrees C for ten (10) minutes. This high transmission ΔE value means that the HT version of the '585 coated article after 10 minutes of HT does not even closely match its color to its non-heat-treated counterpart version in terms of transmission color. This is undesirable.

The present inventor believes that the high ΔE * value associated with the coating of Example 7 in the present specification is caused by at least the following reasons. Fig. 15 is an XPS graph illustrating the Example 7 coating before heat treatment (HT) and Fig. 16 illustrating the Example 7 coating after HT. As shown in Fig. 15, before the heat treatment, the three different layers are completely separated and different. For example, prior to HT, it can be seen that the Ni slopes 3 on either side of the NiCr layer are very steep, as are the Si and N slopes 5 and 7, respectively, on the lower side of the upper Si3N4 layer. Thus, the vast majority of the Ni is in the NiCr layer, and the vast majority of the Si and N of the upper Si3N4 layer are in this layer. However, Fig. 16 illustrates that when shown in Fig. 15 Example 7 coated article is heat treated (HT) for 10 minutes as discussed above, a significant portion of the Ni from the NiCr layer migrates to the upper Si3N4 layer. Additionally, after HT, a significant portion of the Si and N from the upper Si3N4 layer migrate to the NiCr layer. In other words, the interface between the metallic NiCr layer and the upper Si3N4 layer becomes blurry and blurry. This is shown in Fig. 16 by a less steep Ni slope 3a on the upper / outer side of the NiCr layer, and by a less steep slope 5a and 7a of Si and N on the lower side of the upper Si3N4 layer. Moreover, by comparing Figs. 15 and 16, it can be seen that HT causes a significant amount of Cr in the NiCr layer to migrate in this layer towards its upper side so that it is not distributed as evenly as before HT.

Unfortunately, the above-mentioned HT-induced migration of Si, N, Ni and Cr from their positions in Fig. 15 to their respective positions in Fig. 16 causes a significant color change to occur and thus explains the high transmission value of ΔΕ * associated with the coating of Example 7. that is, with the coatings of the '585 Patent when exposed to prolonged heat treatments.

JP 05124839 relates to a heat treatable coated glass, the glass comprising a glass substrate, a first silicon nitride layer, a functional metal nitride layer, and an outer silicon nitride layer, the functional layer comprising at least chromium nitride and an alloy thereof with nickel. . It also discloses that heat-treatable heat-insulating glass is produced by forming and laminating at least one layer of a thin metal film or metal nitride including Ti, Ta, Cr, Zr, Ni or alloys thereof. JP '839, however, does not disclose any particular advantage associated with the use of any particular material selected from the foregoing. Moreover, the selection of the metal film over the metal nitride or the selection of any material other than nickel, chromium and / or nickel chromate does not achieve the advantages indicated in the present invention. Moreover, from the content of JP '839, particular values of the parameters of the currently claimed product, ie AE, Δa and Ab, cannot be deduced or derived. Thus, JP '839 does not disclose an effective method and / or product that has the features desired in accordance with the present invention.

With the foregoing in mind, skilled artisans will be able to recognize that there is still a need for a coating or layer system that has a low AE (or AE *) value (transmissive and / or reflective on the glass side) and thus good color stability performance. after at least five (5) minutes of heat treatment (HT). It is an object of the present invention to meet the above-stated needs, and / or other needs that will become more apparent to those skilled in the art from the presentation of the following disclosure.

The present invention relates to a coated article having a layer system based on a glass substrate, the layer system including a metal nitride layer in which:

the metal nitride layer is interposed between the glass substrate and the at least partially nitrided dielectric layer;

wherein the metal nitride comprises at least one of NiNx and CrNx and NiCrNx and is in contact with the dielectric layer; and the metal (s) of Ni and / or Cr of the metal nitride-containing layer is (are) partially nitrided prior to heat treatment to reduce N, Cr and / or Ni migration during the heat treatment; and the coated article has a transmission AE * T of no greater than 5.0, preferably no greater than 4.0, most preferably no greater than 3.0, measured after at least 5 minutes of heat treatment including heat tempering at a temperature of at least 600 ° C.

Preferably, the layer system comprises an additional dielectric layer, the layer containing the metal nitride being located between the second, at least partially nitrided dielectric layer and the additional dielectric layer. Even more preferably, the additional dielectric layer comprises silicon nitride and has a thickness from 3.0-25.0 nm, preferably from 5.0-12.0 nm, the metal nitride layer comprises NiCrNx and has a thickness from 2.0-60.0 nm. , preferably from 5.0-35.0 nm and the at least partially nitrided dielectric layer comprises silicon nitride and has a thickness from 10.0-50.0 nm, preferably from 21.0-31.0 nm.

In a preferred embodiment of the invention, the transmission color a * value and / or the a * value reflected on the glass side of the article is negative both before and after the heat treatment.

PL 204 881 B1

According to a further preferred embodiment, the partially nitrided dielectric layer comprises silicon nitride.

Preferably, before heat treatment, the product has the following transmission color parameters: a * 0.0 to -5.0, preferably 0.0 to -2.0; b * -2.0 to -15.0, preferably -3.0 to -9.0;

L * 10.0 to 70.0, preferably 20.0 to 50.0.

In a preferred embodiment, the heat treated article has a sheet resistance (Rs) of no more than 500 ohms / sq., Preferably no more than 250 ohms / sq., And the heat treatment results in a decrease in sheet resistance.

According to another preferred embodiment of the invention, the fabrication after thermal tempering has a value

Δα * reflected on the glass side of not more than 1.0, preferably not more than 0.6, most preferably not more than 0.3.

According to yet another preferred embodiment of the invention, the product has a value of ΔE *G. reflected on the side of the glass not more than 5.0, preferably not more than 4.0, most preferably not more than 3.0, the value of Δa *T. transmission is not greater than 1.3, preferably not greater than 1.1, most preferably not greater than 0.8, and the value of Δb *G. reflected on the glass side of not more than 1.1, preferably not more than 0.7, most preferably not more than 0.4.

The invention also relates to a method of making a coated article, the method comprising:

providing a glass substrate;

depositing the metal on the substrate in a nitrogen-containing atmosphere to form a metal nitride-containing layer on the glass substrate, the resulting metal nitride-containing layer comprising at least one of NiNx and CrNx and NiCrNx;

depositing a dielectric layer including nitride on the substrate over the layer including metal nitride; and heat treating the article for at least 5 minutes at a temperature of at least 600 ° C, the layer containing the metal nitride being nitrided during its application prior to the heat treatment to reduce the migration of N, Cr and / or Ni during the heat treatment to such an extent, that the fabric after heat treatment has a ∆E * value of no more than 5.0 and / or a transmission ∆a * value of no more than 1.1.

According to a preferred embodiment, the method of the invention further comprises depositing an additional dielectric layer on the substrate such that a layer including metal nitride is deposited on the substrate over the additional dielectric layer.

The present invention will now be described with reference to certain preferred embodiments thereof, as illustrated in the following drawings, wherein:

Description of the drawings

Fig. 1 is a partial, side sectional view of an embodiment of a coated article (heat treated or not heat treated) according to an example embodiment of this invention.

Fig. 2 is a partial cross sectional view of an IG unit as contemplated in the present invention to which the coating or layer system of Fig. 1 may be used.

In fig. 3 is an X-ray photoelectron spectroscopy (XPS) graph illustrating the atomic% of the components N, O, Na, Al, Si, Ca, Cr, and Ni through the thickness of the layered system according to Example 1 of the present invention (before heat treatment), where the depth axis refers to to the depth in the coating and / or substrate from their outer surface compared to the depth in a conventional SiO2 layer that would be achieved over the same period of time (i.e., depth in nm does not mean the actual depth, but it does mean how deep the sputtering would reach the SiO2 reference layer in a given period of time).

Fig. 4 is an XPS graph illustrating the atomic% of N, O, Na, Al, Si, Ca, Cr, and Ni components through the thickness of the tier system according to Example 1 of the present invention after heat treatment at 625 degrees C for 10 minutes.

Fig. 5 is an X-ray photoelectron spectroscopy (XPS) graph illustrating the atomic% of the components N, O, Na, Al, Si, Ca, Cr, and Ni through the thickness of the layer system according to Example 2 of the present invention (before heat treatment), where the depth axis refers to the depth in the coating and / or substrate from their outer surface compared to the depth in a conventional SiO2 layer that would have been reached over the same period of time.

PL 204 881 B1

Fig. 6 is an XPS graph illustrating the atomic% of N, O, Na, Al, Si, Ca, Cr, and Ni components through the thickness of the tier system according to Example 2 of the present invention after heat treatment at 625 degrees C for 10 minutes.

Fig. 7 is an X-ray photoelectron spectroscopy (XPS) graph illustrating the atomic% of the components N, O, Na, Al, Si, Ca, Cr, and Ni through the thickness of the layer system according to Example 3 of the present invention (before heat treatment), where the depth axis refers to the depth in the coating and / or substrate from their outer surface compared to the depth in a conventional SiO2 layer that has been reached over the same period of time.

Fig. 8 is an XPS graph illustrating the atomic% of N, O, Na, Al, Si, Ca, Cr, and Ni components through the thickness of the tier system according to Example 3 of the present invention after heat treatment at 625 degrees C for 10 minutes.

Fig. 9 is an X-ray photoelectron spectroscopy (XPS) graph illustrating the atomic% of the components N, O, Na, Al, Si, Ca, Cr, and Ni through the thickness of the layer system according to Example 4 of the present invention (before heat treatment), where the depth axis refers to the depth in the coating and / or substrate from their outer surface compared to the depth in a conventional SiO2 layer that has been reached over the same period of time.

Fig. 10 is an XPS graph illustrating the atomic% of N, O, Na, Al, Si, Ca, Cr, and Ni components through the thickness of the tier system according to Example 4 of the present invention after heat treatment at 625 degrees C for 10 minutes.

Fig. 11 is an X-ray photoelectron spectroscopy (XPS) graph illustrating the atomic% of components N, O, Na, Al, Si, Ca, Cr, and Ni through the thickness of the layer system according to Example 5 of the present invention (before heat treatment). wherein the depth axis c refers to the depth in the coating and / or substrate from their outer surface compared to the depth in a conventional SiO2 layer that would be reached over the same period of time.

Fig. 12 is an XPS graph illustrating the atomic% of N, O, Na, Al, Si, Ca, Cr, and Ni components through the thickness of the tier system according to Example 5 of the present invention after heat treatment at 625 degrees C for 10 minutes.

Fig. 13 is an X-ray photoelectron spectroscopy (XPS) graph illustrating the atomic% of the components N, O, Na, Al, Si, Ca, Cr, and Ni through the thickness of the layer system according to Example 6 of the present invention (before heat treatment), where the depth axis refers to the depth in the coating and / or substrate from their outer surface compared to the depth in a conventional SiO2 layer that would have been reached over the same period of time.

Fig. 14 is an XPS plot illustrating the atomic% of N, O, Na, Al, Si, Ca, Cr, and Ni components through the thickness of the tier system according to Example 6 of the present invention after heat treatment at 625 degrees C for 10 minutes.

Fig. 15 is an X-ray photoelectron spectroscopy (XPS) graph illustrating the atomic% of components N, O, Na, Al, Si, Ca, Cr, and Ni through the thickness of the layered system according to Example 7 of the present invention (before heat treatment), where the depth axis refers to the depth in the coating and / or substrate from their outer surface compared to the depth in a conventional SiO2 layer that would have been reached over the same period of time.

Fig. 16 is an XPS plot illustrating the atomic% of N, O, Na, Al, Si, Ca, Cr, and Ni components through the thickness of the tier system according to Example 7 of the present invention after heat treatment at 625 degrees C for 10 minutes.

Fig. 17 is an X-ray photoelectron spectroscopy (XPS) graph illustrating the atomic% of components N, O, Na, Al, Si, Ca, Cr, and Ni through the thickness of a layer system according to Example 8 of the present invention (before heat treatment), where the depth axis refers to the depth in the coating and / or substrate from their outer surface compared to the depth in a conventional SiO2 layer that would have been reached over the same period of time.

Fig. 18 is an XPS graph illustrating the atomic% of N, O, Na, Al, Si, Ca, Cr, and Ni components through the thickness of the tier system according to Example 8 of the present invention after heat treatment at 625 degrees C for 10 minutes.

Fig. 19 is an X-ray photoelectron spectroscopy (XPS) graph illustrating the atomic% of components N, O, Na, Al, Si, Ca, Cr, and Ni through the thickness of the layered system according to Example 9 of the present invention (before heat treatment), where the depth axis refers to the depth in the coating and / or substrate from their outer surface compared to the depth in a conventional SiO2 layer that would have been reached over the same period of time.

PL 204 881 B1

Fig. 20 is an XPS graph illustrating the atomic% of N, O, Na, Al, Si, Ca, Cr, and Ni components through the thickness of the tier system according to Example 9 of the present invention after heat treatment at 625 degrees C for 10 minutes.

Fig. 21 is an X-ray photoelectron spectroscopy (XPS) graph illustrating the atomic% of components N, O, Na, Al, Si, Ca, Cr, and Ni through the thickness of a layer system according to Example 10 of the present invention (before heat treatment), where the depth axis refers to the depth in the coating and / or substrate from their outer surface compared to the depth in a conventional SiO2 layer that would have been reached over the same period of time.

Fig. 22 is an XPS graph illustrating the atomic% of N, O, Na, Al, Si, Ca, Cr, and Ni components through the thickness of the tier system according to Example 10 of the present invention after heat treatment at 625 degrees C for 10 minutes.

Certain embodiments of the present invention provide a coating or layer system that may be used in applications such as IG units, vehicle windows, architectural windows, and / or other useful applications. Certain embodiments of the present invention provide a layer system that has excellent color stability (i.e., low ΔΕ * value and / or low Δα * value; where Δ is the change with HT) upon heat treatment (e.g., heat tempering, bending). or heat curing) monolithic and / or in the context of a double glazing environment such as IG units or vehicle windshields. Such heat treatments often require heating the coated substrate to temperatures from about 600 ° C up to about 800 ° C for at least about 5 minutes.

Figure 1 is a side sectional view of a coated article according to an example embodiment of this invention. The coated article comprises a substrate 11 (e.g., a clear, green, brown, gray, blue, or cyan glass substrate from about 1.0 to 12.0 mm thick), an optional first dielectric layer 13 (e.g., consisting of or including silicon nitride (e.g., Si3N4), titanium dioxide, titanium nitride, zirconium nitride, silicon oxynitride, or the like), an IR reflecting layer comprising nickel (Ni) or nickel-chromium 15 that is nitrided (e.g., NiCrNx), and a second nitrided dielectric layer 17 (e.g., composed of or including silicon nitride (e.g., Si3N4), titanium nitride, zirconium nitride, silicon oxynitride, aluminum nitride, or the like). Thus, the coating system 19 comprises a metal nitride layer 15 sandwiched between (directly or indirectly) a pair of dielectric antireflection layers 13 and 17. The underlying layer 13 is optional and the upper dielectric layer 17 is preferably at least partially nitrided.

It has surprisingly been found that coatings of the present invention can be made with greater color consistency upon heat treatment (HT) if layer 15 is nitrided during the deposition process (e.g., the layer is nitrided so as to be deposited as NiCrN).x). It is believed that by at least partially nitriding layer 15 during the deposition process (i.e., so that it becomes nitrided to some significant extent prior to HT), migration of N, Cr, and / or Ni during HT can be reduced, thereby rendering that the resulting coated article may have a more constant color on HT (ie, have a low ΔE * value (s)). The metal in metal nitride layer 15 may or may not be fully nitrided in various embodiments of this invention. For example, the metal such as Cr in layer 15 may be at least about 40% nitrided in certain embodiments of this invention, more preferably at least about 50% nitrided, more preferably at least about 60% nitrided, and most preferably at least about 60% nitrided. about 75% nitrided. When layer 15 is NiCrNxthe layer is believed to include at least Ni and CrNx. In alternative embodiments of this invention, layer 15 may be an oxynitride (e.g., metal oxynitride) layer. Thus, metal nitride layer 15 may or may not include any amounts of oxide in various embodiments of this invention.

In certain preferred embodiments of this invention, for anti-reflection purposes, each of the dielectric anti-reflection layers 13 and 17 has a refractive index less than the refractive index of the metal nitride layer 15 (e.g., the silicon nitride layers 13 and 17 may have a refractive index n of about 1. 9 to 2.1, and the metal nitride layer 15 has an n-factor greater than that).

Also, layer (s) below or above the illustrated coating system of layers 19 may be provided. Thus, while the layer system 19 is on or supported on substrate 11 (directly or indirectly), other layer (s) may be provided therebetween. Thus, for example, the layer system 19 of Fig. 1 is considered to lie on the substrate 11 even when other layer (s) are provided therebetween.

PL 204 881 B1

In embodiments of this invention where layers 13 and 17 include silicon nitride (e.g., Si3N4), the Si-sputtering targets used to form the layers may be blended with up to 6-20% by weight of aluminum or stainless steel (e.g. SS # 316), and more or less this amount will then appear in the layers thus formed. Moreover, while layer 15 may be NiCrNx, NINx, or CrNx In certain embodiments of this invention, these materials are not limiting and other IR reflecting metal nitrides may be used instead. In the NiCrNx embodiments, any suitable Ni: Cr ratio may be used. For example, in some embodiments, the ratio of Ni: Cr in this layer may be 50:50, in other embodiments, it may be 80:20, and in still other embodiments, it may be 90:10 or any other suitable ratio.

Fig. 2 illustrates the coating or layer system 19 of Fig. 1 applied to face 2 of an insulating glass (IG) window assembly. To distinguish the inside of the IG unit from its outside, the sun 21 is schematically depicted on the outside. The IG unit comprises an outer glass pane or sheet 11 and an inner glass pane or sheet 23. The two glass substrates (e.g., 2mm to 12mm thick fleet glass) are sealed at their peripheral edges with a conventional sealant (not shown) and equipped with a conventional strip of desiccant (not shown). The panes are then attached to a conventional window or door mounting frame. By sealing the peripheral edges of the glass sheets and replacing the air in the insulating space (or chamber) with a gas such as argon, an IG unit with a high insulating value is formed. Optionally, in some alternative embodiments, the insulating space 25 may be at a pressure less than atmospheric pressure, although this is obviously not necessary in all IG embodiments. Coating 19 may be provided on the inner wall of substrate 11 in certain embodiments of this invention (as shown in FIG. 2), and / or on the inner wall of substrate 23 in other embodiments of this invention.

Returning to Fig. 1, while the various thicknesses may be used coherently for one or more of the purposes and / or needs discussed herein, according to certain example embodiments of this invention, the preferred thicknesses and materials for the respective layers on the glass substrate 11 are as follows:

Table 1 (Thickness)

<td>Layer</td><td>Favorable range (nm)</td><td>More preferred (nm)</td>

<td>Si3N4 (layer 13)</td><td> 3,0-25,0</td><td> 5,0-12,0</td>

<td>NiCrNx (layer 15)</td><td> 2,0-60,0</td><td> 5,0-35,0</td>

<td>Si3N4 (layer 17)</td><td> 10,0-50,0</td><td> 21,0-31,0</td>

In certain example embodiments, the color consistency with long term HT due to at least the nitriding of layer 15 results in substantial color consistency between heat treated and non-heat treated versions of the heat treated and non-heat treated coating or layer system. In other words, in monolithic and / or IG applications, in certain embodiments of this invention, two glass substrates having the same coating system thereon (one post-deposited heat treated and the other unheathed) appear to be substantially the same when viewed to the naked human eye.

The values of ΔE * and Δa * are important in the context of the present invention in determining whether or not there is a color stability or substantial consistency after HT. Color is described herein by reference to conventional a *, b * values. The term Δa * simply indicates how much the color value of a * changes as a result of HT.

The term ∆E * (and ∆E) is well understood in the art and is referenced, along with various techniques for determining it, in ASTM 2244-93, as well as described in Hunter et al., The Measurement of Appearance, ed. 2, chap. 9, page 162 et seq. [John Wiley & Sons, 1987]. As used in the art, ∆E * (and ∆E) is a way of adequately expressing the change (or lack thereof) in reflectance and / or transmittance (and thus also color appearance) in an article after or due to HT. ΔE can be calculated by ab technique or by Hunter technique (determined using the subscript h). ΔE corresponds to the Lab Hunter scale: L, a, b (or Lh, ah, bh). Similarly, ΔE * corresponds to the CIE LAB scale: L *, a *, b *. Both are considered useful and equivalent for the purposes of this inventory8

PL 204 881 B1. For example, as noted in the aforementioned Hunter et al. Publication, a rectangular coordinate / scale technique (CIE LAB 1976) known as the L *, a *, b * scale may be used, wherein:

L * is the units of the lightness scale (CIE 1976) and * the units of the red-green scale (CIE 1976) b * are the units of the yellow-blue scale (CIE 1976) and the distance ΔΕ * between L *about and*about b *about and L *1 and*1 b1 is:

AE * = [(AL *)2 + (Δα *)2 + (Ab *)2]1/2 (1) where:

AL * = L * 1 - L * o (2)

Aa * = a *1 - a *about (3)

Ab * = b *1 - b *about (4) where the subscript o is the coating (or coated article) before heat treatment and the subscript 1 is the coating (coated article) after heat treatment; and the numbers used (e.g., a *, b *, L *) are those calculated by the above-mentioned L *, a *, b * coordinate technique (CIE LAB 1976). In a similar way, AE can be calculated using equation (1) by replacing a *, b *, L * with the Hunter Lab values: a *, b *, L *.

Equivalent numbers are also within the scope of the present invention and for quantifying AE * if converted to those numbers calculated by any other technique using the same AE * concept as defined above.

In certain example non-limiting embodiments of this invention, the coatings or layer systems provided herein on transparent monolithic glass substrates as viewed from the glass side of the coated article (% RG) are reflective prior to heat treatment, as follows:

Table 2a:

Reflection color on the glass side (RG) before heat treatment

<td></td><td>Generally</td><td>Favorable</td>

With regard to transmission color, in certain non-limiting embodiments of the present invention, the coatings or layer systems provided herein on transparent monolithic glass substrates have a transmission color prior to heat treatment as follows.

Table 2b:

Transmission color before heat treatment

<td></td><td>Generally</td><td>Favorable</td>

After heat treatment (HT), in certain embodiments of this invention, the layer systems provided on transparent monolithic glass substrates have AE *, and Aa *, and Ab * color parameters as seen when viewed from the side of the glass (G) (opposite to the side of the glass). layers) of the coated article:

Table 3a:

Reflective color on the glass side (AE * G, Aa * G and Ab * G) after heat treatment

<td></td><td>Generally</td><td>Favorable</td><td>Most preferably</td>

PL 204 881 B1

With regard to transmission color parameters, in certain embodiments of this invention, the layer arrangements provided on post-HT transparent monolithic glass substrates have transmission color parameters ΔE *, Δa *, and Ab * as follows:

Table 3b:

Transmission color parameters (AE * t and Aa * T) after HT

<td></td><td>Generally</td><td>Favorable</td><td>Most preferably</td>

Accordingly, as shown in Table 3 above, coated articles according to certain embodiments of this invention have an AE * G (glass side) of no more than 5.0, more preferably no more than 4.0, and even more preferably no more than 5.0. more than 3.0; and have an Aa * G value (glass side) of no more than about 1.0, more preferably no more than 0.6, and most preferably no more than 0.3. Also, in certain example embodiments, and as shown in Table 3 above, coated articles according to certain embodiments of this invention have an AE * T (transmit) value of no greater than 5.0, more preferably no greater than 4.0, and even more preferably no more than 3.0; and have an Aa * T (transmitting) value of no more than about 1.3, more preferably no more than 1.1, and most preferably no more than 0.8. When one or more of these requirements are met, color consistency may result.

Examples 1-10

Coated articles were prepared according to the following ten examples (each finally annealed and heat treated), with Examples 1-6 and 8-10 were made in accordance with certain example embodiments of this invention, and Example 7 was produced for comparative purposes, wherein the NiCr layer was was not nitrided. For Examples 1-6 and 8-10, the layering on about 6.0 mm thick clear soda-lime-silica glass substrate was: silicon nitride / NiCrNx / silicon nitride (e.g., see Figure 1). For Comparative Example 7, the layering on about 6.0 mm thick clear soda-lime-silica glass substrate was: silicon nitride / NiCr / silicon nitride (i.e., the NiCr layer was not nitrided in Comparative Example 7). The coater / process settings for the examples were as follows.

For each example, a Leybold Terra-G six-chamber sputter coating machine was used to sputter the coatings onto glass substrates. There were five cathodes in each chamber, so there were a total of 30 cathode targets in the sputter coater (not all were used). Cathode numbering uses the first digit to refer to the coater chamber and the second digit to refer to the cathode position in that chamber. For example, cathode # 42 was the second (second digit) cathode in the fourth (first digit) chamber of the coater. Cathodes 42, 55 and 61 were double C-Mag type cathodes; and cathodes # 44 and 45 were flat cathodes. Below, * means an Al content of approximately 10%. The line speed for Examples 5-10 was 3.5 meters per minute (m / min), approximately 2.5 m / min for Examples 1-4. All gas flows in Table 4 (e.g., Ar and N) are shown in normal cm3. Voltage is measured in volts and frequency in kHz. Pressure is measured in hPa and power in kW. T-gas refers to the equalizing gas used to individually adjust the gas flows along the cathode length to allow for corrections to layer thickness uniformity (total T-gas flow was 100 normal cm3). % C refers to the percentage (%) of the equalizing gas introduced at the center,% PS refers to the percentage of the equalizing gas introduced at the pump side, and% VS refers to the percentage of the equalizing or tuning gas introduced at the observer side. The NiCr targets were approximately 80/20 NiCr.