阅读说明：本技术 具有含氮化硅和/或氧氮化硅的保护涂层的涂覆制品 (Coated article having a protective coating comprising silicon nitride and/or silicon oxynitride ) 是由 A·甘珠 S·纳拉亚南 J·J·芬利 P·A·梅德维克 于 2019-02-13 设计创作，主要内容包括：一种涂覆制品。所述涂覆制品包括基底,在所述基底的至少一部分上方的功能层,以及在所述功能层的至少一部分上方的保护涂层,其中所述功能层的最上层是金属氧化物层,并且其中所述保护涂层包括金属氮化物和金属氧氮化物层,所述金属氮化物和金属氧氮化物层被设置在所述金属氮化物层的至少一部分和所述功能层的金属氧化物层之间并与之接触。(A coated article. The coated article includes a substrate, a functional layer over at least a portion of the substrate, and a protective coating over at least a portion of the functional layer, wherein an uppermost layer of the functional layer is a metal oxide layer, and wherein the protective coating includes a metal nitride and metal oxynitride layer disposed between and in contact with at least a portion of the metal nitride layer and the metal oxide layer of the functional layer.)

1. A coated article, comprising: a substrate, a first functional layer over at least a portion of the substrate, and a protective coating over at least a portion of the functional layer,

wherein the uppermost layer of the functional layer is a metal oxide film, and

wherein the protective coating comprises one or more layers of metal nitrides, metal oxynitrides, or combinations thereof.

2. The coated article of claim 1, wherein the metal nitride, metal oxynitride or combination thereof is at least one of silicon nitride, silicon oxynitride or combination thereof.

3. The coated article of claim 1, wherein the protective coating comprises a metal oxynitride film over and in contact with at least a portion of the metal oxide film of the uppermost layer of the first functional layer; and

a metal nitride film over and in contact with at least a portion of the metal oxynitride film.

4. The coated article of any of claims 1-3, wherein the protective coating comprises a graded metal oxynitride film over and in contact with at least a portion of the metal oxide film of the uppermost layer of the first functional layer, wherein the amount of oxygen in the metal oxynitride film decreases with increasing distance from the uppermost layer of the first functional layer, wherein the metal oxynitride of the graded layer is optionally silicon oxynitride.

5. The coated article of any of claims 1-4, wherein the metal oxide film of the uppermost dielectric layer of the first functional layer comprises zinc stannate.

6. The coated article of any of claims 1-5, wherein the first functional layer comprises: a dielectric layer over at least a portion of the substrate, a metallic layer over at least a portion of the dielectric layer, and an uppermost layer over at least a portion of the metallic layer.

7. The coated article of claim 6, wherein the first functional layer further comprises a primer layer over the metallic layer and under at least a portion of the topmost layer.

8. The coated article of claim 7, wherein the primer layer comprises titanium or titanium and aluminum, and wherein at least a portion of the titanium or titanium and aluminum is optionally oxidized after the titanium or titanium and aluminum is deposited over the metallic layer.

9. The coated article of claim 6, wherein the dielectric layer comprises zinc oxide and/or zinc stannate, the metallic layer comprises Ag, Cu, Au, and/or Pd, and/or the uppermost layer comprises zinc stannate.

10. The coated article of any of claims 1-9, wherein the topmost layer does not comprise zinc oxide.

11. The coated article of any of claims 1-9, further comprising a second functional layer below at least a portion of the first functional layer and above at least a portion of the substrate.

12. The coated article of any of claims 1-11, further comprising a second protective film disposed at least partially over the one or more layers of metal nitride, metal oxynitride, or combinations thereof, and

wherein the second protective film comprises at least one of the following: titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, alloys of any one or more of the foregoing, or mixtures of any of the foregoing.

13. The coated article of claim 1, comprising:

a glass substrate;

a first zinc stannate layer over at least a portion of the glass substrate;

a zinc oxide layer over at least a portion of the zinc stannate layer;

a silver layer over at least a portion of the zinc oxide layer;

a primer layer comprising Ti, TiAl, and/or an oxide thereof over at least a portion of the silver layer;

a second zinc stannate or zinc oxide layer over at least a portion of the primer layer;

a metal oxynitride layer comprising SiON directly over at least a portion of the second zinc stannate layer;

a metal nitride layer comprising silicon directly over at least a portion of the metal oxynitride layer; and

a second protective layer over at least a portion of the metal nitride layer, the second protective layer comprising Ti, TiAl, and/or an oxide of any of the foregoing.

14. The coated article of claim 1, comprising a functional layer comprising:

a glass substrate;

a first zinc stannate layer directly over at least a portion of the glass substrate;

a zinc oxide layer directly over at least a portion of the zinc stannate layer;

a silver layer directly over at least a portion of the zinc oxide layer;

a primer layer directly over at least a portion of the silver layer, the primer layer comprising Ti, TiAl, and/or an oxide of any of the foregoing;

a second zinc stannate layer directly over at least a portion of the primer layer;

a metal oxynitride layer comprising silicon directly over at least a portion of the second zinc stannate layer;

a metal nitride layer comprising silicon directly over at least a portion of the metal oxynitride layer; and

a second protective layer comprising TiAlO directly over at least a portion of the metal nitride layer.

15. The coated article of claim 1, comprising a functional layer comprising:

a glass substrate;

over at least a portion of the glass substrate and having a thickness of

over at least a portion of the zinc stannate layer and having a thickness ofTo

over at least a portion of the zinc oxide layer and having a thickness ofTo

over at least a portion of the silver layer and having a thickness ofToA Ti-containing primer layer of (a);

over at least a portion of the primer layer and having a thickness ofTo

directly over at least a portion of the second zinc stannate layer and having a thickness ofToA metal oxynitride layer containing SiON;

directly over at least a portion of the metal oxynitride layer and having a thickness of

over the metal nitride layer and having a thickness ofToThe second protective layer comprising TiAlO.

Technical Field

The invention according to the present disclosure generally relates to solar control coatings having a top coat comprising a metal nitride layer and/or a metal oxynitride layer disposed over a metal oxide layer.

Technical considerations

The coating stack of the coated article may corrode over time. To prevent this, a protective coating may be applied to the coating stack. For example, the titanium dioxide films disclosed in US4,716,086 and US4,786,563 are protective films that provide chemical resistance to the coating. The silicon oxides disclosed in canadian patent CA 2,156,571, the aluminum oxides and silicon nitrides disclosed in U.S. patents 5,425,861, US 5,344,718, US 5,376,455, US 5,584,902 and US 5,532,180 and PCT international patent publication No. WO 95/29883 are also protective films that provide chemical resistance to the coating. This technique can be enhanced by a chemically and/or mechanically more durable coating.

Another known problem with coating stacks including protective coatings occurs in silver-based coating stacks. In certain coated articles, the top layer of the functional coating comprises a metal oxide layer, such as a layer of zinc oxide, positioned over the terminal metal primer layer of the functional coating. This may lead to corrosion or flash defects in the stack when exposed to a condensation moisture environment for a long time. Therefore, there is a further need to reduce or avoid these defects in the coating stack.

Background

Disclosure of Invention

According to one aspect of the present invention, a coated article is provided. The coated article includes a substrate, a first functional layer over at least a portion of the substrate, and a protective coating over at least a portion of the functional layer, wherein the uppermost layer of the functional layer is a metal oxide film, and wherein the protective coating includes one or more layers of metal nitrides, metal oxynitrides, or combinations thereof.

In one aspect, the coated article comprises: a glass substrate; a first zinc stannate layer over at least a portion of the glass substrate; a zinc oxide layer over at least a portion of the zinc stannate layer; a silver layer over at least a portion of the zinc oxide layer; a primer layer comprising Ti, TiAl, and/or an oxide thereof over at least a portion of the silver layer; a second zinc stannate layer over at least a portion of the primer layer; a metal oxynitride layer comprising silicon oxynitride directly over at least a portion of the second zinc stannate; a metal nitride layer comprising silicon directly over at least a portion of the metal oxynitride layer; and a second protective layer over at least a portion of the metal nitride layer, the second protective layer comprising Ti, TiAl, and/or an oxide of any of the foregoing.

In another aspect, a coated article is provided. The coated article comprises: a substrate, a functional layer having an uppermost layer over at least a portion of the substrate, and a protective coating layer over at least a portion of the functional layer, wherein the uppermost layer of the functional layer is a dielectric layer having a refractive index of at least 1.5 and not greater than 2.1.

In another aspect, there is provided a coated article comprising: a substrate, a functional layer over at least a portion of the substrate, and a protective coating over at least a portion of the functional layer, wherein the functional layer comprises at least one metallic layer and a primer layer at least partially disposed over and in contact with at least a portion of the at least one metallic layer, and wherein an uppermost layer of the functional layer is disposed over and in contact with at least a portion of the primer layer, and the uppermost layer of the functional layer does not comprise zinc oxide.

Drawings

The present invention will be described with reference to the following drawings, wherein like reference numerals refer to like parts throughout.

FIG. 1A is a side view (not to scale) of an insulated glass unit ("IGU") having a coating of the present invention.

FIG. 1B is a cross-sectional view of a transparency having a coating of the present invention.

FIGS. 2A and 2B are cross-sectional views (not to scale) of coatings of the present invention.

FIG. 3 is a cross-sectional view (not to scale) of a coating according to an embodiment of the invention.

FIGS. 4A and 4B are cross-sectional views (not to scale) of coatings according to embodiments of the invention.

FIG. 5 is a cross-sectional view (not to scale) of a coating according to an embodiment of the invention.

FIG. 6 is a cross-sectional view (not to scale) of a coating according to an embodiment of the invention.

Detailed Description

As used herein, spatial or directional terms, such as "left", "right", "inside", "outside", "above", "below", and the like, relate to the invention as it is shown in the drawings. It is to be understood, however, that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting. Moreover, as used herein, all numbers expressing dimensions, physical characteristics, processing parameters, quantities of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims can vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Further, it is to be understood that all ranges disclosed herein encompass the beginning and ending range values and any and all subranges subsumed therein. For example, a stated range of "1 to 10" should be considered to include any and all subranges between (and including) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1 to 3.3, 4.7 to 7.5, 5.5 to 10, and so on. "a" and "an" mean one or more.

Further, as used herein, the term "formed over," deposited over, ", or" provided over, ", refers to being formed, deposited, or provided on, but not necessarily in contact with, a surface. For example, a coating "formed over" a substrate does not preclude the presence of one or more other coatings or films of the same or different composition located between the formed coating and the substrate. Moreover, all documents (such as, but not limited to, issued patents and patent applications) referred to herein are to be considered to be "incorporated by reference" in their entirety. As used herein, the term "film" refers to a coating region of a coating composition that is desired or selected. A "layer" may comprise one or more "films" and a "coating" or "coating stack" may comprise one or more "layers". The term "asymmetric reflectivity" means that the coating visible reflectance from one side is different from the coating visible reflectance from the opposite side. The term "critical thickness" refers to a thickness above which the coating material forms a continuous, uninterrupted layer, and below which the coating material forms discrete regions or islands of coating material rather than a continuous layer. The term "subcritical thickness" refers to a thickness below the critical thickness such that the coating material forms isolated, unconnected regions of the coating material. The term "island-like" means that the coating material is not a continuous layer, but rather that the material is deposited to form isolated regions or islands.

For the purposes of the following discussion, the coated articles described herein may be discussed with reference to use with architectural transparencies, such as, but not limited to, Insulated Glass Units (IGUs). As used herein, the term "architectural transparency" refers to any transparency located on a building, such as, but not limited to, windows and skylights. However, it should be understood that the coated articles described herein are not limited to use with such architectural transparencies, but can be practiced with transparencies in any desired field, such as, but not limited to: laminated or non-laminated residential and/or commercial windows, insulating glass units, and/or transparencies for land vehicles, aircraft, spacecraft, marine and underwater vehicles. In one aspect or embodiment, the coated article described herein is a transparency for a vehicle, such as a window or sunroof. Therefore, it is to be understood that the specifically disclosed exemplary aspects or embodiments are provided merely to explain the general concepts of the invention and that the invention is not limited to these specific exemplary embodiments. Further, while a typical "transparency" may have sufficient visible light transmission such that the material can be viewed through the transparency, the "transparency" need not be transparent to visible light, but may be translucent or opaque. I.e., "transparent" means having a visible light transmission of greater than 0% up to 100%.

A non-limiting transparency 10 incorporating features of the present invention is shown in fig. 1A. The transparent member 10 may have any desired visible, infrared or ultraviolet radiation transmission and/or reflection.

The exemplary transparency 10 of fig. 1A is in the form of a conventional insulated glass unit and includes a first layer 12 having a first major surface 14 (1 st surface) and an opposing second major surface 16 (2 nd surface). In the non-limiting embodiment shown, the first major surface 14 faces the exterior of the building, i.e., the exterior major surface, and the second major surface 16 faces the interior of the building. The transparency 10 also includes a second layer 18 having an inner (first) major surface 20 (No. 3 surface) and an outer (second) major surface 22 (No. 4 surface) and spaced apart from the first layer 12. This numbering of the layer surfaces is consistent with conventional practice in the window alignment art. The first layer 12 and the second layer 18 can be connected in any suitable manner, such as by adhesive bonding to a conventional spacer frame 24. A gap or cavity 26 is formed between the two layers 12, 18. The chamber 26 may be filled with a selected atmosphere, such as air, or a non-reactive gas (such as argon or krypton). A solar control coating 30 (or any other coating described below) is formed over at least a portion of one of the layers 12, 18, such as but not limited to over at least a portion of the No. 2 surface 16, or over at least a portion of the No. 3 surface 20. However, the coating may also be on the 1 st or 4 th surface, if desired. Examples of insulating glass units can be found in, for example, US4,193,236, US4,464,874, US 5,088,258 and US 5,106,663.

The exemplary transparency of FIG. 1B is in the form of a conventional transparency 110 for a vehicle, such as a window or sunroof. For clarity, the seals, connectors and opening mechanisms are not shown, nor is the entire vehicle shown. The transparency includes a first layer 112 having a first major surface 114 (No. 1 surface) and an opposing second major surface 116 (No. 2 surface) that is mounted in the body of a vehicle 118. In the non-limiting embodiment shown, the first major surface 114 faces the exterior of the vehicle, and thus is the exterior major surface, and the second major surface 116 faces the interior of the vehicle. Non-limiting examples of vehicle bodies include: a vehicle roof in the case of a sunroof, a vehicle door or frame in the case of a vehicle window, or a fuselage of an aircraft. As is well known in the vehicle art, the transparency may be secured to a mechanism capable of opening and closing the transparency, such as a window or sunroof. The solar control coating 130, or any other coating described herein, is shown as being formed over the No. 1 surface 114, which may be formed over at least a portion of the No. 2 surface 116.

In the broad practice of the invention, the layers 12, 18, 112 of the transparent members 10, 110 may be of the same or different materials. The layers 12, 18, 112 may comprise any desired material having any desired characteristics. For example, one or more of the layers 12, 18, 112 may be transparent or translucent to visible light. By "transparent" is meant having a visible light transmission of greater than 0% up to 100%. Alternatively, one or more of the layers 12, 18, 112 may be translucent. By "translucent" is meant allowing electromagnetic energy (e.g., visible light) to pass through but diffusing that energy such that objects on the side opposite the viewer are not clearly visible. Examples of suitable materials include, but are not limited to, plastic substrates (e.g., acrylic polymers such as polyacrylates; polyalkylmethacrylates such as polymethylmethacrylate, polyethylmethacrylate, polypropylmethacrylate, and the like; polyurethanes; polycarbonates; polyalkyl terephthalates such as polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, and the like; polysiloxane-containing polymers; or copolymers of any of the monomers used to prepare these, or any mixtures thereof); a ceramic substrate; a glass substrate; or mixtures or combinations of any of the above. For example, one or more of the layers 12, 18, 112 may comprise conventional soda-lime-silicate glass, borosilicate glass, or lead glass. The glass may be a transparent glass. "clear glass" means glass that is uncolored or colorless. Alternatively, the glass may be tinted or otherwise colored glass. The glass may be annealed or heat-treated glass. As used herein, the term "heat treating" refers to tempering or at least partially tempering. The glass may be of any type, such as conventional float glass, and may have any composition possessing any optical properties, such as any value of visible light transmission, ultraviolet transmission, infrared transmission, and/or total solar energy transmission. By "float glass" is meant glass formed by a conventional float process in which molten glass is deposited onto a molten metal bath and controllably cooled to form a float glass ribbon. Examples of float glass processes are disclosed in U.S. Pat. Nos. 4,466,562 and 4,671,155.

The layers 12, 18, 112 may each comprise, for example, clear float glass or may be tinted or colored glass, or one layer 12, 18 may be clear glass while the other layer 12, 18 is colored glass. Although not limiting, examples of glasses suitable for use in the first layer 12 and/or the second layer 18 are described in U.S. Pat. nos. 4,746,347, 4,792,536, 5,030,593, 5,030,594, 5,240,886, 5,385,872 and 5,393,593. The layers 12, 18, 112 may have any desired dimensions, such as length, width, shape, or thickness. In an exemplary automotive transparency, the first layer and the second layer can each be 1mm to 10mm, such as 1mm to 8mm, such as 2mm to 8mm, such as 3mm to 7mm, such as 5mm to 7mm, such as 6 mm thick.

In the non-limiting embodiments of the coated articles described herein, the solar control coating 30, 130 of the present invention is deposited over at least a portion of at least one major surface of one of the glass plies 12, 18, 112. In the embodiment according to fig. 1A, the coating 30 is formed over at least a portion of the inner surface 16 of the outside glass layer 12, 112; additionally or alternatively, it should be understood that in non-limiting examples consistent with the present disclosure, a coating may be formed over at least a portion of the inner surface 20 of the inner glass layer 18. As used herein, the term "solar control coating" refers to a coating comprised of one or more layers or films that affect the solar performance of a coated article, such as, but not limited to, the amount of solar radiation, e.g., the amount of visible, infrared, or ultraviolet radiation reflected, absorbed, or transmitted from the coated article; a shading coefficient; emissivity, etc. The solar control coating 30 can block, absorb, or filter selected portions of the solar spectrum, such as, but not limited to, the IR, UV, and/or visible spectrum.

The coatings described herein, such as the solar control coatings 30, 130, can be deposited by any useful method, such as, but not limited to, conventional Chemical Vapor Deposition (CVD) and/or Physical Vapor Deposition (PVD) methods. Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam evaporation and vacuum sputtering (e.g., Magnetron Sputtering Vapor Deposition (MSVD)). Other coating methods may also be used, such as but not limited to sol-gel deposition. In one non-limiting embodiment, the coating 30, 130 is deposited by MSVD. Examples of MSVD coating apparatus and methods will be well understood by those of ordinary skill in the art and are described, for example, in U.S. patents US4,379,040, US4,861,669, US4,898,789, US4,898,790, US4,900,633, US4,920,006, US4,938,857, US 5,328,768, and US 5,492,750.

Fig. 2 schematically shows an example of a coated article 200 according to the present disclosure. The coated article includes a substrate 210. Substrate 210 may include any desired properties and may have any desired thickness. Substrate 210 may include any suitable transparent material or materials, such as, but not limited to, polymer, glass, and/or ceramic substrates described above in the context of layers 12, 18, and 112. In a non-limiting example, as shown in fig. 1A or 1B, substrate 210 may comprise a glass substrate as described above with reference to layers 12, 18, 112. However, it should be understood that the present invention may also be applied to other substrates, such as those used in solar cells.

The functional layer 220 is disposed over at least a portion of the substrate 210. As used in fig. 2-6, the functional layer 220, 320, 420, 520 may be any functional coating. For example, it may comprise one or more dielectric films and/or one or more metal films. Alternatively, the functional layers 220, 320, 420, 520 may comprise a Transparent Conductive Oxide (TCO), for example, but not limited to, as disclosed in U.S. patent application No. 15/669,414. The functional layers 220, 320, 420, 520 may comprise a stack as described in any one of or any portion of U.S. patent application publication US 2017/0341977, US 2014/0272453, US 2011/0236715, and/or U.S. patent application No. 15/669,414. These exemplary stacks of functional layers are schematically represented as elements 330, 430, 530 of fig. 3-6, except as specifically discussed below, and details of aspects of stacks 330 and 530 are depicted in fig. 3 and 6 and described with reference to fig. 3 and 6.

The functional layer may comprise one or more metallic layers. The one or more metallic films within the functional layers 220, 320, 420, 520 may be composed of silver, gold, palladium, copper, aluminum, and/or mixtures and/or alloys of any of the foregoing. Any metallic layer in the functional layers 220, 320, 420, 520 may be continuous or discontinuous.

The one or more metallic layers may be continuous layers. The thickness of the continuous metallic layer is within

ToWithin the range of (1), preferably

To

More preferablyTo

Most preferablyTo

Fig. 3, 4A and 4B depict an example in which the uppermost layer of the functional layer 320 comprises a dielectric layer, referred to as the uppermost dielectric layer 322, which is the uppermost film in the functional layer 320. An example of the uppermost dielectric layer 322 of the functional layer 320 may have a thickness of

ToWithin the range of (1), preferablyToMore preferably, for example

ToAnd most preferably isTo

As shown in fig. 4B, uppermost dielectric layer 322 may include a first film 324 shown over optional primer layer 328, and a second film 326 over the first film and in contact with protective overcoat 350. The first film 324 and the second film 326 of the uppermost dielectric layer 322 may be metal oxide, metal nitride, or metal oxynitride films. The metal of the first film 324 and the second film 326 may be titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum, silicon, and mixtures thereof.

In one non-limiting embodiment, the first film 324 of the uppermost dielectric layer 322 may be a zinc/tin alloy oxide. "zinc/tin alloy oxide" refers to both true alloys and mixtures of oxides. Zinc oxide can be deposited from a zinc cathode including other materials to improve the sputtering characteristics of the cathode. In this way, zinc/tin alloy oxides can be obtained from cathodes of zinc and tin by magnetron sputtering vacuum deposition. For example, the zinc cathode can include a small amount (e.g., up to 20 wt.%, up to 15 wt.%, up to 10 wt.%, or up to 5 wt.%) of tin to improve sputtering. In such a case, the resulting zinc oxide film will comprise a small percentage of tin oxide, for example up to 10% by weight tin oxide, for example up to 5% by weight tin oxide. A coating layer deposited from a zinc cathode having up to 10 wt% tin (added to enhance the conductivity of the cathode) is referred to herein as a "zinc oxide film" even though small amounts of tin may be present. One non-limiting cathode can comprise zinc and tin in a ratio of 5 to 95 weight percent zinc and 95 to 5 weight percent tin, such as 10 to 90 weight percent zinc and 90 to 10 weight percent tin. However, other zinc to tin ratios may be used.

One suitable metal alloy oxide that may be present in either the first film 324 or the second film 226 is zinc stannate. "Zinc stannate" means Zn_XSn_1-XO_2-X(formula 1), wherein "x" varies in the range of more than 0 to less than 1. For example, "x" can be greater than 0 and can be any fraction or decimal between greater than 0 and less than 1. For example, when x is 2/3, formula 1 is Zn_{2/ 3}Sn_1/3O_4/3It is often described as "Zn₂SnO₄". The zinc stannate-containing film has a major amount of one or more of the forms of formula 1 in the layer.

Fig. 4A discloses an embodiment of a coated article comprising a substrate 310, a functional layer 320 according to any aspect or embodiment described herein, and a protective coating 350 comprising a metal nitride film 356 over the functional layer 320, and a second protective film 360 over the metal nitride film 356. The functional layer comprises the uppermost dielectric layer, as shown, for example, in fig. 3 and 4B. In one non-limiting embodiment, the uppermost dielectric layer 322 may be comprised of a metal oxide (e.g., zinc stannate). In another non-limiting embodiment, the uppermost dielectric layer 322 may have a refractive index of not less than 1.5 and not more than 2.1. In another non-limiting embodiment, the refractive index of the uppermost dielectric layer 322 may be not less than 1.7, and not more than 1.9, and more preferably not less than 1.8, and not more than 1.85.

As shown in fig. 4B, in another non-limiting example including a substrate 310 and a functional layer 320, the functional layer 320 including an uppermost dielectric layer 322, an optional primer layer 328, and a stack 330, such as the stack described with reference to fig. 3, the uppermost dielectric layer 322 of the functional layer 320 may include a first film 324, the first film 324 including or consisting of a metal oxide (such as zinc oxide), the first film 324 being deposited over at least a portion of the optional primer layer 328. The second film 326 of the uppermost dielectric layer 322 of the functional layer 320 over at least a portion of the first film 324 may include zinc stannate.

As shown in fig. 3-4B, the functional layer 320 may also include an optional primer layer 328 disposed below the dielectric layer 322. Optional primer layer 328 can be a single film layer or multiple film layers. Optional primer layer 328 can include an oxygen-trapping material that can be sacrificed during the deposition process to prevent oxidation during or following the sputtering processDegradation or oxidation of the metallic layer 334 during the post heating process. Optional primer layer 328 is also capable of absorbing at least a portion of the electromagnetic radiation, such as visible light, that passes through coating 300. Examples of suitable materials for optional primer layer 328 include titanium, silicon dioxide, silicon nitride, silicon oxynitride, nickel-chromium alloys (e.g., Inconel), zirconium, aluminum, alloys of silicon and aluminum, alloys containing cobalt and chromium (e.g., cobalt and chromium alloys)) And mixtures of any of the foregoing. In non-limiting embodiments, optional primer layer 328 may comprise titanium, or titanium and aluminum, deposited as a metal, and at least a portion of the titanium, or titanium and aluminum, subsequently oxidized. The thickness of optional primer layer 328 may be inToWithin a range of, for example

ToFor exampleToFor example

To

For exampleTo

For exampleTo

For example fromTo

In another embodiment, the thickness of optional primer layer 328 may be inTo

Within a range of, for example

To

For example

To

For exampleTo

For exampleTo

As shown, optional primer layer 328, when present, is disposed under and in direct contact with first film 324 of dielectric layer 322. Although shown in the figures, it is to be understood that examples in accordance with the present invention do not necessarily include optional primer layer 328.

Referring to fig. 2A, a protective coating 250 is disposed over at least a portion of the functional layer 220 and is the uppermost layer of the coated article. The protective coating 250 may help protect underlying coating layers (e.g., the functional layer 220 and any constituent films and layers thereof) from mechanical and/or chemical attack. Fig. 2B is similar in structure to the coated article depicted in fig. 2A, showing a substrate 210 and a protective coating 250, but including a first functional layer 220 identical to the functional layer 220 of fig. 2A and a second functional layer 220' disposed below the first functional layer 220 and above the substrate 210. The first functional layer 220 may be the same as or different from the second functional layer 220'. For example, and without limitation, the first functional layer 220 includes a dielectric layer, a metallic layer over the dielectric layer, and optionally a primer layer over the metallic layer, and the uppermost dielectric layer includes a metal oxide film over the metallic layer and over the primer layer when present. The second functional layer 220' includes a second dielectric layer over the substrate 210, a second metallic layer over the second dielectric layer, and optionally a second primer layer over the second metallic layer. In one example, one of the first and/or second metallic layers is subcritical. In another example, neither is subcritical. In yet another example, the coated article includes a third functional layer (not shown) that is below the second functional layer 220 'and above the substrate 210, and that is the same as or different from either of the first or second functional layers 220, 220'. Note that multiple smaller functional layers may be layered to produce a larger functional layer that may or may not have properties specific to any particular combination of smaller functional layers, such as having single, double, and triple silver coatings, optionally including one or more subcritical silver layers.

In one embodiment of the present invention, referring to fig. 4A, protective layer 350 can comprise silicon oxide, silicon oxynitride, silicon nitride, a mixture of any two or more of the foregoing, and/or an alloy of any of the foregoing, and it can provide increased durability to functional layer 320. Protective layer 350 may comprise silicon oxide, silicon oxynitride and/or silicon nitride deposited with other materials having excellent conductivity to improve sputtering of silicon. For example, during deposition, the silicon cathode may include a small amount (e.g., up to 20 wt.%, up to 15 wt.%, up to 10 wt.%, or up to 5 wt.%) of aluminum to improve sputtering. In this case, the resulting protective layer will comprise a similar percentage of aluminium, for example at most 15 wt.% aluminium, for example at most 10 wt.% aluminium, for example at most 5 wt.% aluminium. A coating layer deposited from a silicon cathode having up to 10 wt.% aluminum (added to enhance the conductivity of the cathode) is referred to herein as a "silicon oxide", "silicon oxynitride" or "silicon nitride" layer or film, even though small amounts of aluminum may be present. It is believed that a small amount of aluminum (e.g., less than or equal to 15 wt.%, such as less than or equal to 10 wt.%, such as less than or equal to 5 wt.%) in the cathode forms aluminum nitride in the protective layer 350, which is primarily nitride. In the case of a silicon nitride layer, the protective layer 350 may be formed in a nitrogen atmosphere; however, it should be understood that other gases, such as oxygen, may be present in the atmosphere during deposition of protective layer 350.

In another embodiment, referring to fig. 4B, the protective coating 350 may comprise a film of metal nitride 356, such as silicon nitride, disposed over and in contact with a metal oxynitride film 354 (such as SiON) disposed over and in contact with the uppermost dielectric layer 322 of the functional layer 320. Examples of the metal oxynitride film 354 may also or alternatively include two or more metal nitrides and/or an alloy of one or more metal nitrides. Examples of the metal nitride film 356 may also or alternatively include a mixture of two or more metal oxynitrides and/or an alloy of one or more metal oxynitrides. Protective coating 350 can provide increased durability to functional layer 320. The protective coating 350 may be deposited with other materials having excellent conductivity to improve sputtering of the metal.

Protective coatingThe total thickness of the layers 250, 350 (i.e., the sum of all thicknesses of the layers or films within the protective coating 250, 350) is in the following range:

to

ToToToTo ToOrTo

The atomic ratio of oxygen and nitrogen in the metal oxynitride can vary from 0 wt% to 100 wt%, where wt% refers to the ratio of the mass of N or O to the total mass of N + O in the composition, excluding the metals in the metal oxynitride. Thus, referring to fig. 4B, the metal oxynitride film 354 contains more than 0% by weight of nitrogen, and not more than 100% by weight of nitrogen. The metal oxynitride film 354 contains more than 0 wt% oxygen, and not more than 15 wt% oxygen; not more than 10 wt.% oxygen; not more than 5% by weight of oxygen. Non-limiting examples of useful atomic ratios of oxygen and nitrogen in the metal oxynitride layer include, for example and without limitation: 0.1% to 99.9% O and 99.9% to 0.1% N; 1% to 99% O and 99% to 1% N; or 10% to 90% O and 90% to 10% N.

In one embodiment, the oxynitride is an oxynitride of the same metal as in the metal nitride layer 356 that contacts the metal oxynitride layer 354. In another embodiment, the metal oxynitride layer 354 is a graded layer in which the portion of the oxynitride closest to the uppermost dielectric layer 322 comprises a greater amount of oxygen and the opposing portion of the metal oxynitride layer 354 (e.g., the portion closest to the metal nitride layer 356) comprises a greater amount of nitrogen, such as in the atomic ratios described above. In one embodiment, metal oxynitride layer 354 and metal nitride layer 356 form a continuous single gradient layer. In another embodiment, the metal oxynitride layer 354 is applied over the metal oxide layer and/or between the metal oxide layer and the metal nitride layer. In another embodiment, the metal nitride layer 356 is not present and the metal oxynitride film 354 is a graded layer in which the amount of oxygen in the metal oxynitride film decreases with increasing distance from the uppermost dielectric layer. For example, the portion of the oxynitride layer closest to the uppermost dielectric layer 322 comprises a greater amount of oxygen, while the opposing portion of the oxynitride layer 354 comprises a greater amount of nitrogen, such as in the atomic ratios described above, such as, but not limited to: 0.1% to 99.9% O and 99.9% to 0.1% N; 1% to 99% O and 99% to 1% N; or 10% to 90% O and 90% to 10% N.

In the protective coating 350 according to the present disclosure, the metal oxynitride film 354, for example, a film composed of silicon oxynitride, may have a refractive index of at least 1.4 and not more than 2.3. In one embodiment, the metal oxynitride film 354 has a refractive index of at least 1.45 and not greater than 2.2. In another embodiment, the metal oxynitride film 354 has a refractive index of at least 1.75 and not greater than 2.1. In yet another embodiment, the metal oxynitride film 354 has a refractive index of at least 1.8 and not greater than 2.1. It should be appreciated that the refractive index of the metal oxynitride film 354 is at least partially dependent on the weight percentage of nitrogen present in the metal oxynitride film 354. The protective coating 350 can be the uppermost layer of the coated article.

The thickness of the metal oxynitride film 354 may range fromToFor exampleTo

ToTo

OrToIn embodiments where the metal oxynitride film 354 is a graded layer, it is the only film in the protective coating, or in embodiments where no metal nitride film is present in the protective coating, it may be of a thicknessTo

Preferably, it is

To

More preferably

To

Most preferablyTo

The thickness of the metal nitride film 356 may be inTo

Within a range of, for example

To

ToToToToTo

OrTo

In embodiments without a metal oxynitride layer and/or without a second protective film, goldThe thickness of the metal nitride film 356 may be inTo

Within the range of (1), preferablyTo

Most preferablyTo

In embodiments where the protective coating has a metal oxynitride film 354 and a second protective layer, the metal nitride film 356 may have a thickness of

To

Preferably, it isToMore preferably

ToMost preferably

To

In embodiments where the protective coating has both a metal nitride 356 film and a second protective film 360, the metal oxynitride film may have a thickness ofToPreferably, it isToMore preferablyToMost preferably

To

In certain embodiments, the present invention has a total thickness of the metal oxynitride film 354 (if present) and/or the metal nitride film 356 (if present). The total thickness can be withinAndin between, e.g.

ToToOr

To

The thickness of the combined layer of metal nitride, metal oxynitride, metal nitride and/or second protective film (e.g., TiAlO) may be atToWithin a range of, for example

To

Within the range of (A) and (B),

toToToTo

To

To

OrTo

Referring to fig. 3 and 4B, the metal oxynitride film 354 of the protective coating 350 creates a stronger bond between the metal nitride film 356 and the metal oxide of the second film 326 of the uppermost dielectric layer 322 of the functional layer 320. Examples consistent with the present disclosure include a silicon nitride film 356 disposed over and in contact with at least a portion of a silicon oxynitride film 354, the silicon oxynitride film 354 disposed over and in contact with at least a portion of a zinc stannate uppermost dielectric layer 322.

It is understood that in examples consistent with the present disclosure, the silicon in the metal nitride film 356 and/or the metal oxynitride film 354 may be at least partially replaced by other metals, respectively oxides, oxynitrides, and nitrides. These other metals may be the same or different between the films 354, 356. The metal may be titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum, silicon, and mixtures thereof.

Referring to fig. 4A and 4B, a coated article according to any aspect or embodiment of the coated article described herein may include a second protective film 360. The second protective film 360 is shown disposed over the metal nitride film 356 and may comprise, for example, a metal oxide or metal nitride layer. The second protective film 360 may be titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, tin oxide, a mixture thereof, or an alloy thereof. For example, the second protective film 360 may include a mixture of silicon oxide and aluminum oxide; a mixture of titanium oxide and aluminum oxide; or zirconia. An example of the second film 360 may include TiAlO. Non-limiting examples of the second protective film 360 may have the following thickness ranges: for example

To

For exampleToFor exampleToIt should be understood that second protective film 360 may be applied, for example, as the topmost layer to any other configuration of the topmost dielectric layer, metal nitride and metal oxynitride films consistent with the present disclosure. Alternatively, an additional functional or protective layer may be applied over the second protective film 360. Similarly, it should be understood that the coated article need not include the second protective film 360.

In a non-limiting example, the coated article may include an additional protective layer (not shown) over the second protective film 360. The additional protective layer may be any material used to form the protective coating 350 or the second protective film 360, or any material that can be used as a topcoat (topcoat).

A primer, such as the optional primer 328 described above, may be located over and/or in direct contact with any metallic layer of the functional layer 320 or any metallic layer as a continuous layer. In one non-limiting embodiment, the primer is not in direct contact with the non-continuous (subcritical) metal layer. In this embodiment, the primer is not applied directly over or in direct contact with the non-continuous layer. However, a primer layer may be located over and in direct contact with each continuous metallic layer. Additionally, the primer may be titanium, or a mixture or alloy of titanium and aluminum, such as, but not limited to, titanium aluminide.

Referring to fig. 5, a transparent article 400 may include a substrate 410, a functional layer 420, and a protective coating 450. Although not shown, it is understood that some examples may also include a second protective film 360 (fig. 4B) according to the present disclosure, although the second protective film 360 may also not be included. In the example depicted in fig. 5, protective coating 450 may comprise a second protective film consistent with second protective film 360 disclosed above, or any other construction or topcoat known in the art consistent with the present disclosure. The functional layer 420 may comprise a stack of metallic layers, dielectric layers, and primer layers consistent with the present disclosure.

With further reference to fig. 5, the functional layer 420 includes an uppermost dielectric layer 422. An uppermost dielectric layer 422 may be disposed at least partially over primer layer 428, consistent with the present disclosure. In a non-limiting example, the uppermost dielectric layer 422 is composed of a single layer, and may have a refractive index of at least 1.5 and not greater than 2.1, and more preferably a refractive index of at least 1.9 and not greater than 1.9, and still more preferably a refractive index of at least 1.8 and not greater than 1.85. In an example according to the present disclosure, the uppermost dielectric layer 422 may be composed of zinc stannate. The features of the uppermost dielectric layer 422 may be identical to the features of the uppermost dielectric layer 322. In other examples, the uppermost dielectric layer 322, 422 does not include zinc 90 (90% zinc oxide with 10% tin oxide).

It was found by diligent testing that under such conditions, uppermost dielectric layer 322 comprising zinc stannate improves the durability of the stack and reduces corrosion/flash defects. In addition, the use of the uppermost dielectric layer 322 composed of zinc stannate disposed on the uppermost primer layer 328 of the functional layer 320 does not affect color control. Alternatively, zinc oxide or zinc 90 may be used at the uppermost dielectric layer. Alternatively, the uppermost dielectric layer may have two films, wherein the bottom film is a zinc oxide film and the top film is a zinc stannate film.

Referring to fig. 6, a coated article 500 includes: a substrate 510 according to any embodiment or aspect described herein; a functional layer 520 over the substrate 510; and a protective coating 550 over the functional layer 520. The functional layer 520 includes a functional stack 530 comprising a metal oxide layer 531 according to any embodiment or aspect described herein, and over the metal oxide layer 531According to any embodiment or aspect described herein. An optional primer layer 528 according to any embodiment or aspect described herein is deposited over the metal layer 534. The functional layer 520 further comprises an uppermost dielectric layer 522 according to any aspect or embodiment described herein. The protective coating 550 is a protective coating according to any embodiment or aspect described herein. In one embodiment, substrate 510 is glass; metal oxide layer 531 is a dielectric layer, such as zinc oxide layer 532 and a second zinc stannate layer 533 over the zinc oxide layer; the metallic layer 534 includes or consists of Ag; primer layer 528 comprises or consists of Ti or TiAl; the dielectric layer 522 comprises or consists of zinc oxide and/or zinc stannate; the protective coating 550 comprises a metal nitride layer comprising one or more layers of SiON, or Si over the metal oxide layer 522₃N₄And a second protective film 560 over the metal nitride layer 552. In one embodiment, for example, referring to fig. 6, metal nitride layer 552 of protective coating 550 comprises a silicon oxynitride layer 554 over and in contact with metal oxide layer 522 and a silicon nitride layer 556 over and in contact with silicon oxynitride layer 554.

Tables 1-6 provide examples of coated articles useful according to the present disclosure, including thicknesses and preferred thicknesses of the various layers.

TABLE 1 SiN over Zinc stannate

TABLE 2 SiN over dielectric layer and Zinc stannate over Zinc oxide layer

TABLE 3 SiN over SiON over dielectric layer

TABLE 4 SiN and TiAlO protective layers over SiON over dielectric layers

TABLE 5 SiON and TiAlO protective layers over dielectric films

TABLE 6 SiON gradient films and TiAlO protective layers over dielectric films

Range of% by weight N, excluding Si content, from Zn₂SnO₄Film to TiAlO

Examples of coated articles according to the present disclosure are provided below. It should be understood, however, that the intention is not to limit the invention to the particular embodiments described.