Articles with high visible light reflectance and neutral color

Abstract

The invention relates to articles having high visible light reflectance and neutral color. A coated article includes a substrate and a functional coating applied over at least a portion of the substrate. The functional coating includes a first dielectric layer, a first metallic layer, a first primer layer, a second dielectric layer, a second metallic layer, a second primer layer, a third dielectric layer, and an optional outermost protective coating. A coated article wherein the RgL * value is at least 35 and no greater than 55. The coated article has a total combined thickness of the metallic layers of at least 10 nanometers and no greater than 30 nanometers.

Description

[0001] This application is a divisional application of the Chinese invention patent application with application number 202080025360.0 filed on March 26, 2020 and invention name “Articles with high visible light reflection and neutral color”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application enjoys and claims priority to U.S. Provisional Application No. 62 / 976,645 filed on February 14, 2020 and U.S. Provisional Application No. 62 / 825,326 filed on March 28, 2019, the disclosures of which are incorporated by reference. Background of the Invention Field of the Invention

[0005] The present invention relates generally to vehicle transparencies, such as vehicle windshields, and in one particular embodiment, to windshields having high visible light reflectance and a neutral color.

[0006] Technical considerations

[0007] In the automotive market, vehicle styling is given great importance. The way a vehicle looks can be as important to vehicle sales as the mechanical reliability or safety rating of the vehicle. Therefore, automobile manufacturers go to great lengths to enhance vehicle styling. These styling enhancements include providing consumers with more color choices and also offering colors with metallic flakes to provide vehicles with a "photochromic effect."

[0008] While these styling enhancements have generally been well received by consumers, the current problem is that even with new vehicle paint finishes, automotive transparencies (such as, but not limited to, windshields, side windows, rear windows, sunroofs, and sunroofs) are still typically gray or neutral in color. While providing solar control properties, these conventional transparencies provide little enhancement to vehicle styling.

[0009] In the non-automotive field, it is known to provide coated articles in which the color is generated by the interference effect between the substrate and the coating. As will be understood by those skilled in the art, the term "interference effect" refers to the change in the amplitude of electromagnetic waves over distance or time, caused by the superposition of waves of electromagnetic radiation (e.g., visible light). These waves can be the result of reflection or transmission at the interface of one or more layers in an optical thin film coating. For example, U.S. Patent No. 6,164,777 discloses a plastic contact lens having an interference coating made of alternating materials of different refractive indices. U.S. Patent No. 5,923,471 discloses a "hot mirror" for a heating lamp having alternating layers of zirconium oxide and silicon oxide. U.S. Patent Application Publication No. 2003 / 0031842A1 discloses an article having a patterned appearance, the patterned appearance being provided by a contrast that can be visually observed between one or more generally transparent thin film coatings. Other examples of interference coatings and coated articles are discussed in U.S. Patent Nos. 5,619,059, 4,902,581 and 5,112,693 and Swiss Patent No. 339575.

[0010] While these disclosed coatings are suitable for their intended purposes, many other considerations must be addressed in attempting to incorporate interference coatings into automotive transparencies. For example, in the United States, government regulations require that all windshields must have a light (visible) transmittance (LTA) of at least 70%. In Europe, the required minimum LTA is 75%. The presence of an interference coating can adversely affect the light transmittance of a transparency.

[0011] It would be advantageous to provide methods of making automotive transparencies that are aesthetically pleasing and can be used to enhance vehicle styling. It would also be advantageous to provide automotive transparencies that provide the opportunity to coordinate or match the color of the transparencies with the paint color of the vehicle. It would also be advantageous if such transparencies also met government requirements for automotive transparencies. SUMMARY OF THE INVENTION

[0013] The present invention relates to a coated article. The coated article has a substrate and a functional coating on the substrate. The coating has a first dielectric layer located above at least a portion of the substrate. A first metallic layer is located above at least a portion of the first dielectric layer. A first primer layer is located above at least a portion of the first metallic layer. A second dielectric layer is located above at least a portion of the first primer layer. A second metallic layer is located above at least a portion of the second dielectric layer. The second primer layer is located above at least a portion of the second metallic layer. A third dielectric layer is located above at least a portion of the second primer layer. An optional outermost protective layer is located above at least a portion of the third dielectric layer or the functional coating. The coated article has an RgL of at least 35 and not more than 55. * value.

[0014] In another embodiment, the present invention relates to a coated article. The coated article has a substrate and a functional coating above the substrate. The coating has a first dielectric layer located above at least a portion of the substrate. The first metallic layer is located above at least a portion of the first dielectric layer. The first primer layer is located above at least a portion of the first metallic layer. The second dielectric layer is located above at least a portion of the first primer layer. The second metallic layer is located above at least a portion of the second dielectric layer. The second primer layer is located above at least a portion of the second metallic layer. The third dielectric layer is located above at least a portion of the second primer layer. The optional outermost protective layer is located above at least a portion of the third dielectric layer or the functional coating. The total combined thickness of the metallic layers is at least 10nm and not more than 30nm. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The present invention will be described with reference to the following drawings, wherein like reference numerals refer to like parts throughout.

[0017] Figure 1 is a cross-sectional view (not to scale) of a non-restrictive windshield.

[0018] Figure 2 is a cross-sectional view (not to scale) of a non-limiting coating according to the present invention.

[0019] Figure 3 is a cross-sectional view (not to scale) of a non-limiting coating according to the present invention.

[0020] Description of the invention

[0021] As used herein, spatial or directional terms, such as "left", "right", "inside", "outside", "upper", "lower", etc., refer to the present invention as shown in the accompanying drawings. However, it should be understood that the present invention can take a variety of alternative orientations, and therefore such terms should not be considered restrictive. In addition, as used herein, all numerical values ​​used in the specification and claims to represent dimensions, physical properties, processing parameters, the amount of ingredients, reaction conditions, etc. should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical values ​​listed in the following specification and claims may vary depending on the desired properties sought to be obtained by the present invention. At a minimum, 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 interpreted in accordance with the number of reported significant figures and by applying ordinary rounding techniques. In addition, all ranges disclosed herein should be understood to include starting and ending range values ​​and any and all subranges contained therein. For example, the range of "1 to 10" should be considered to include any and all subranges between a minimum of 1 and a maximum of 10 (and including a minimum of 1 and a maximum of 10); that is, all subranges starting with a minimum of 1 or greater and ending with a maximum of 10 or less, such as 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. In addition, as used herein, the term "formed above", "deposited above" or "provided above" means formed, deposited or provided on a surface but not necessarily in contact with the surface. For example, a coating "formed above a substrate" does not exclude the presence of one or more other coatings or films of the same or different composition located between the formed coating and the substrate. As used herein, the term "polymer" or "polymeric" includes oligomers, homopolymers, copolymers and terpolymers, such as polymers formed from two or more types of monomers or polymers. The term "visible region" or "visible light" refers to electromagnetic radiation with a wavelength in the range of 380 nanometers (nm) to 800 nm. The term "infrared region" or "infrared radiation" refers to electromagnetic radiation with a wavelength in the range of greater than 800nm ​​to 100,000nm. The term "ultraviolet region" or "ultraviolet radiation" means electromagnetic energy with a wavelength in the range of 300nm to less than 380nm. The visible (light) transmittance (LTA) value (Y, x, y) herein is that which can be determined using a λ9 spectrophotometer commercially available from Perkin-Elmer or a TCS spectrophotometer commercially available from BYK-Gardner in the wavelength range of 380nm to 770nm using a CIE (1976) standard illuminant "A" with a 2 degree observation angle (consistent with U.S. Federal Standards). Reflection color values ​​L*, a*, b* (whether R1 or R2) are measured using a illuminant "D65" with a 10° observation angle (as conventional in the automotive field).

[0022] As used herein, the term "film" refers to a coating region having a desired or selected coating composition. A "layer" may include one or more "films", and a "coating" or "coating stack" may include one or more "layers". The terms "metal" and "metal oxide" include silicon and silicon dioxide, respectively, as well as traditionally recognized metals and metal oxides, even though silicon may not be conventionally considered a metal. Unless otherwise indicated, thickness values ​​are geometric thickness values. In addition, all documents mentioned herein, such as but not limited to issued patents and patent applications, are deemed to be "incorporated by reference" in their entirety.

[0023] The discussion of the present invention may describe some features as "particularly" or "preferably" within some limitations (e.g., "preferably", "more preferably" or "most preferably" within some limitations). It should be understood that the present invention is not limited to these specific or preferred limitations, but includes the entire scope of the disclosure.

[0024] exist Figure 1 A non-limiting transparent article 10 (e.g., an automobile windshield) including features of the present invention is described in detail. The transparent article 10 can have any desired transmittance and reflectance of visible light, infrared radiation, or ultraviolet radiation. For example, the transparent article 10 can have any desired amount of visible light transmittance, such as greater than 0% to 100%, greater than 70%. For the windshield and front side window areas in the United States, the visible light transmittance is typically greater than or equal to 70%. For privacy areas such as rear seat side windows and rear windows, the visible light transmittance can be less than the visible light transmittance of the windshield, such as less than 70%.

[0025] As in Figure 1 As can be seen in FIG. 1 , the transparent object 10 includes a first sheet or first substrate 12 having a first major surface facing the exterior of the vehicle, namely an outer major surface 14 (surface No. 1) and an opposite second or inner major surface 16 (surface No. 2). The transparent object 10 also includes a second sheet or second substrate 18 having an outer (first) major surface 22 (surface No. 4) and an inner (second) major surface 20 (surface No. 3). This numbering of the sheet surfaces is consistent with conventional practice in the automotive field. The first and second sheets 12, 18 can be combined together in any suitable manner, such as by a conventional intermediate layer 24. Although not required, a conventional edge sealant can be applied to the perimeter of the laminated transparent object 10 during and / or after lamination in any desired manner. A decorative strip, such as an opaque, translucent or colored masking strip 26, such as a ceramic strip, can be provided on the surface of at least one of the sheets 12, 18, such as around the perimeter of the inner major surface 16 of the first sheet 12. A coating 30 can be formed over at least a portion of one of the sheets 12, 18, such as over surface No. 2 16 or surface No. 3 20.

[0026] exist Figure 1In the non-limiting embodiment illustrated in FIG. 1 , the bus bar assembly includes a first or bottom bus bar 96 and a second or top bus bar 98 formed on the inner surface 16 of the outer sheet 12 and separated by a bus bar to bus bar distance. The bus bars 96, 98 are in electrical contact with the coating. In a non-limiting embodiment of the present invention, the bus bars 96, 98 may be at least partially located on the decorative strip 26 or completely located on the decorative strip 26, such as Figure 1 Displayed in.

[0027] In the broad practice of the invention, the sheets 12, 18 of the transparent object 10 may be of the same or different materials. The sheets 12, 18 may include any desired material with any desired properties. For example, one or more of the sheets 12, 18 may be transparent or translucent to visible light. "Transparent" means having a visible light transmittance of greater than 0% to 100%. Alternatively, one or more sheets 12, 18 may be translucent. "Translucent" means allowing electromagnetic energy (e.g., visible light) to pass through, but scattering such energy so that objects on the side opposite to the observer are not clearly visible. Examples of suitable materials include, but are not limited to, plastic substrates (e.g., acrylic polymers, such as polyacrylates; polyalkyl methacrylates, such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, etc.; polyurethanes; polycarbonates; polyalkyl terephthalates, such as polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, etc.; polysiloxane-containing polymers; or copolymers of any monomers used to prepare these, or any mixtures thereof); ceramic substrates; glass substrates; or mixtures or combinations of any of the above. For example, one or more of the sheets 12, 18 may include conventional soda-lime silicate glass, borosilicate glass, or leaded glass. The glass may be clear glass. "Clear glass" means untinted or colorless glass. 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-treated" means tempered or at least partially tempered. The glass may be of any type (e.g., conventional float glass) and may be of any composition with any optical properties (e.g., any value of visible transmittance, ultraviolet transmittance, infrared transmittance, and / or total solar energy transmittance). "Float glass" means glass formed by a conventional float process, in which molten glass is deposited on a molten metal bath and controlled to cool to form a float glass ribbon. The ribbon is then cut and / or shaped and / or heat treated as desired. Examples of float glass processes are disclosed in U.S. Patent Nos. 4,466,562 and 4,671,155. The first and second sheets 12, 18 may be, for example, clear float glass or may be tinted or colored glass, or one sheet 12, 18 may be clear glass and the other sheet 12, 18 may be colored glass. Although not limiting the present invention, examples of glass suitable for the first sheet 12 and / or the second sheet 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 first and second sheets 12, 18 may have any desired dimensions (e.g., length, width, shape, or thickness). In an exemplary automotive transparency 10, the first and second sheets 12, 18 may each be 1 mm to 10 mm thick, e.g., 1 mm to 5 mm thick, or 1.5 mm to 2.5 mm, or 1.8 mm to 2.3 mm.In one non-limiting embodiment, the first sheet 12 and / or the second sheet 18 can each have a visible light transmittance greater than 90%, for example greater than 91%, at a reference wavelength of 550 nm. The glass composition of the first sheet 12 and / or the second sheet 18 can have a total iron content in the range of greater than 0 weight percent (wt%) to 0.2 wt% and / or a redox ratio in the range of 0.3 to 0.6.

[0028] In one non-limiting embodiment, one or both of the sheets 12, 18 may have a high visible light transmittance at a reference wavelength of 550 nm. "High visible light transmittance" means a visible light transmittance at 550 nm greater than or equal to 85%, such as greater than or equal to 87%, such as greater than or equal to 90%, such as greater than or equal to 91%, such as greater than or equal to 92%, with a 5.5 mm equivalent thickness for glass of 2 mm-25 mm sheet thickness. Glasses particularly useful for practicing the present invention are disclosed in U.S. Pat. Nos. 5,030,593 and 5,030,594.

[0029] The intermediate layer 24 may have any desired material and may include one or more layers or sheets. The intermediate layer 24 may be a polymeric or plastic material, such as polyvinyl butyral (PVB), plasticized polyvinyl chloride, or a multilayer thermoplastic material, including polyethylene terephthalate, etc. Suitable intermediate layer materials are disclosed, for example but not limited to, in U.S. Pat. Nos. 4,287,107 and 3,762,988. The intermediate layer 24 may also be a sound absorbing or attenuating material as described, for example, in U.S. Pat. No. 5,796,055. The intermediate layer 24 may have a solar control coating provided thereon or incorporated therein, or may include a colored material to reduce solar transmittance.

[0030] The coating 30 is deposited over at least a portion of a major surface of one of the glass sheets 12, 18, such as the inner surface 16 of the outer glass sheet 12 or the inner surface 20 of the inner glass sheet 18. Figure 1). Coating 30 may include two metallic films located between dielectric layers sequentially applied over at least a portion of one of the glass sheets 12, 18. Coating 30 may be a heat and / or radiation reflective coating or a solar control coating and may have one or more coatings or films having the same or different composition and / or function. Coating 30 may be a multilayer coating including two metallic layers. Examples of conductive coatings for preparing heatable windows are disclosed in U.S. Pat. Nos. 5,653,903 and 5,028,759. Examples of solar control coatings that may be used in the practice of the present invention are found in U.S. Patent Nos. 4,898,789, 5,821,001, 4,716,086, 4,610,771, 4,902,580, 4,716,086, 4,806,220, 4,898,790, 4,834,857, 4,948,677, 5,059,295 and 5,028,759 and in U.S. Patent Application Publication No. 09 / 058440.

[0031] The non-limiting examples of suitable coating 30 generally include one or more anti-reflection coating films, which include dielectric or anti-reflection materials transparent to visible light, such as oxides of metal oxides or metal alloys. Coating 30 may also include two metallic layers, including reflective materials such as precious metals such as silver or gold, or alloys, mixtures or their compositions, and coating 30 may also include a primer layer or a barrier film, such as titanium or titanium-aluminum alloys, as known in the art, located above the metal reflective layer and / or optionally under the metal reflective layer. Coating 30 may have a metallic layer; or may have at least two metallic layers. For example, coating 30 is composed of two metallic layers. In a non-limiting embodiment, one or more of the metallic layers may include silver.

[0032] Non-limiting examples of suitable materials for the primer layer include zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, germanium, magnesium, molybdenum, silver, silicon carbon, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, aluminum silver, zinc tin, indium zinc, silver zinc, mixtures thereof, combinations thereof, or any alloys thereof. The primer layer may also be in the form of any of the metals, oxides, suboxides, nitrides, and / or subnitrides of the above listed materials. At least a portion of the primer layer is an oxide or nitride. In some embodiments, the primer layer is deposited in a 100% argon environment. In some embodiments, a portion of the primer layer is deposited by depositing the primer layer in a 100% argon environment with a specific flow rate to form 80% N 2 The balance of the atmosphere is argon and the nitrogen (N 2 ) atmosphere by sputtering metal or metal alloy. The flow rate is a function of the N 2 The amount of N is approximate, but one of ordinary skill in the art will recognize that the additional 2The coating chamber may leak into the coating chamber because the coating chamber is not hermetically sealed from the external environment. In some embodiments, a portion of the primer layer is formed by coating with a specific flow rate to form 3% to 7% O 2 The balance of the atmosphere is argon. 2 ) atmosphere. The flow rate is a measure of the oxygen (O 2 ), but one of ordinary skill in the art will recognize that the additional O 2 The chemical structure of primer material is represented by the weight percentage (weight %) of element x. For some compositions, the lower limit of one of material in the composition can be "greater than 0". When the lower limit is greater than zero (> 0), the weight % of material is not equal to zero but can be any weight % of the weight % greater than 0 until the upper limit. Due to reacting with atmospheric substances, the composition can be changed before or after the heating layer. These reactions can change the weight % distributed between the material of the composition. The composition of the non-limiting examples of primer layer can be found in Table 1, wherein before heating, it is BH and after heating, it is AH. Some materials can only have unique BH or AH measurement results, which are more important for the final composition due to this measurement.

[0033] Table 1 Composition of metals used as metal alloys for primer layer

[0034]

[0035]

[0036] The coating 30 may be deposited by any conventional 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, such as magnetron sputtering vapor deposition (MSVD). Other coating methods may also be used, such as, but not limited to, sol-gel deposition. In a non-limiting embodiment, the coating 30 may be 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. Pat. Nos. 4,379,040; 4,861,669; 4,898,789; 4,898,790; 4,900,633; 4,920,006; 4,938,857; 5,328,768 and 5,492,750. In the MSVD method, the oxide of the metal or metal alloy can be deposited by sputtering a cathode containing the metal or metal alloy in an atmosphere containing oxygen to deposit a metal oxide or metal alloy oxide film on the surface of the substrate. In one embodiment, the coating 30 is deposited over all or substantially all of the surface, i.e., no discrete coating areas are deposited. At least one coating 30 can be deposited over a flat substrate and then the substrate can be bent into shape in any conventional manner, such as by heating. Alternatively, at least one coating 30 can be deposited over a curved surface, i.e., a substrate that has been bent or shaped.

[0037] The present invention relates to a coating stack having a total silver thick enough to provide a visible light reflectance in the range of 8% to 50%, preferably 8% to 30%, more preferably 8% to 20%, most preferably 9% to 18% and an RgL* of 35 to 55, preferably 42 to 54, more preferably 46 to 53, or most preferably 50 to 52 to produce a neutral color.

[0038] In a non-limiting practice of the present invention, the coating provides a visible light reflectance of no more than 50%. For example, no more than 30%, such as no more than 20%, such as no more than 18%. As will be appreciated by those skilled in the art, for laminated articles, reflectance is typically defined relative to the external reflectance of the laminated article. "External reflectance" means the reflectance of the outer surface (surface No. 1 14), wherein a coating 30 is provided on an inner surface such as surface No. 2 16 or surface No. 3 20.

[0039] In one non-limiting practice of the present invention, coating 30 provides an external reflectance L at 8 degrees. * (R8L * ) has a range of 35 to 55, preferably 40 to 54, more preferably 46 to 53, or most preferably 50 to 52. In one non-limiting practice of the present invention, the coating 30 provides an external reflection color of a in the color space at 8 degrees. * (Rg8a* ) is in the range of 0 to -10. For example, in the range of -1 to -8, preferably -1.2 to -7.0, more preferably -1.5 to -6.8, or most preferably -1.7 to -5.0. In one non-limiting practice of the present invention, the coating 30 provides an external reflectance b at 8 degrees. * (Rg8b * ) is in the range of 1 to -20. For example, in the range of 0 to -19, preferably -2.0 to -10, more preferably -10 to -20, or most preferably -15 to -19.

[0040] As will be appreciated by those skilled in the art, the color of an object, and in particular glass, is highly subjective. The observed color will depend on the lighting conditions and the observer's preference. In order to evaluate color on a quantitative basis, several color order systems have been developed. One such method for specifying a color adopted by the International Commission on Illumination (CIE) uses dominant wavelength (DW) and excitation purity (Pe). The values ​​of these two specifications for a given color can be determined by calculating the color coordinates x and y from the so-called tristimulus values ​​X, Y, Z of the color. The color coordinates are then plotted on the 1931 CIE chromaticity diagram and compared to the coordinate values ​​of the CIE standard illuminant C, as determined in CIE Publication No. 15.2. This comparison provides a color space position on the diagram to determine the excitation purity and dominant wavelength of the glass color.

[0041] In another color order system, colors are specified in terms of hue and lightness. This system is often referred to as the CIELAB color system. Hue distinguishes colors such as red, yellow, green, and blue. Lightness or value distinguishes how bright or dim it is. The numerical values ​​of these properties (which are determined as L) are calculated from the tristimulus values ​​(X, Y, Z). * 、a * and b * ). * Indicates the brightness or dullness of a color and represents the brightness plane on which the color resides. * Indicates that the color is red (+a * )Green(-a * ) axis. b * Indicates that in yellow (+b * )Blue(-b * ) axis. When the rectangular coordinates of the CIELAB system are converted into cylindrical polar coordinates, the resulting color system is called the CIELCH color system, which has * ) and hue angle (H°) and chromaticity (C * ) specifies the color. *Indicates the brightness or dullness of a color as in the CIELAB system. Chroma, or saturation or intensity, distinguishes between color intensity or transparency (i.e., vividness versus dullness) and is the vector distance from the center of the color space to the measured color. The lower the chroma of a color, i.e., the less intense it is, the closer the color is to a so-called neutral color. * =(a *2 +b *2 ) 1 / 2 The hue angle distinguishes colors such as red, yellow, green and blue and is the value from red (+a * ) axis measured counterclockwise from a * ,b * The angular measure of a vector whose coordinates extend through the center of the CIELCH color space.

[0042] It will be appreciated that color may be characterized in any of these color systems and one skilled in the art may calculate equivalent DW and Pe values ​​from the transmittance curve of an observed glass or composite transparency, L * 、a * , b * Value and L * , C * , H° values. A detailed discussion of color calculations is given in U.S. Pat. No. 5,792,559. In this document, the CIELAB system (L * a * b * ) characterizes the color. However, it should be understood that this is merely to simplify the discussion and the disclosed colors may be defined by any conventional system such as those discussed above.

[0043] Figure 2 and 3An exemplary non-limiting coating 30 suitable for the present invention is shown in FIG. This exemplary coating 30 includes two metallic layers located between dielectric layers. It includes a base layer or first dielectric layer 40 located above or in direct contact with at least a portion of a substrate major surface (e.g., surface No. 2 16 of the first sheet 12 or surface No. 3 20 of the second sheet 18). A first metallic layer 48 is located above or in direct contact with at least a portion of the first dielectric layer 40. A first primer layer 50 is located above or in direct contact with at least a portion of the first metallic layer 48. A second dielectric layer 60 is located above or in direct contact with the first primer layer 50. A second metallic layer 70 is located above or in direct contact with at least a portion of the second dielectric layer 60. A second primer layer 72 may be located above or in direct contact with the second metallic layer 70. The third dielectric layer 80 is located over the second primer layer 72 or in direct contact with the second primer layer 72. The outermost protective layer 100 may be located over the third dielectric layer 80 or in direct contact with the third dielectric layer 80.

[0044] The dielectric layer may include one or more films of anti-reflective materials and / or dielectric materials such as, but not limited to, metal oxides, oxides of metal alloys, nitrides, oxynitrides, or mixtures thereof. The first dielectric layer 40 may be transparent to visible light. Examples of suitable metal oxides for the first dielectric layer 40 include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, magnesium, gallium, vanadium, aluminum, silicon, alloys thereof, mixtures thereof, or combinations thereof. These metal oxides may have small amounts of other materials such as manganese in bismuth oxide, tin in indium oxide, etc. Alternatively, oxides or metal alloys or metal mixtures may be used, such as oxides containing zinc and tin (e.g., zinc stannate), oxides of indium-tin alloys, silicon nitrides, silicon aluminum nitrides, or aluminum nitrides. In addition, doped metal oxides such as aluminum-doped zinc oxide, antimony-doped tin oxide, nickel or boron-doped silicon oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, indium-doped tin oxide, or mixtures thereof may be used. In one non-limiting embodiment, the first film 42 of the first dielectric layer may be a zinc / tin alloy oxide formed over at least a portion of the substrate (e.g., surface No. 2 16 of the first sheet 12 or surface No. 3 20 of the second sheet 18). The zinc / tin alloy oxide may be obtained by MSVD from a cathode of zinc and tin that may include zinc and tin in a ratio of 10 wt % to 90 wt % zinc and 90 wt % to 10 wt % tin. One suitable metal alloy oxide that may be present in the first film 42 of the first dielectric layer is zinc stannate. "Zinc stannate" means Zn x Sn 1-x O 2-x(Formula 1), wherein "x" varies in the range of greater than 0 to less than 1. For example, "x" may be greater than 0 and may be any fraction or decimal between greater than 0 and less than 1. For example, when x=2 / 3, Formula 1 is Zn 2 / 3 Sn 1 / 3 O 4 / 3 , which is more commonly described as Zn 2 SnO 4 The zinc stannate-containing film has one or more forms of Formula 1 present in a major amount in the film.

[0045] The second film 44 of the first dielectric layer is formed over at least a portion of the first film 42 of the first dielectric layer and may include zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide or indium-doped tin oxide, mixtures or combinations thereof. In a non-limiting embodiment, the second film 44 of the first dielectric layer may be a zinc-containing film, such as zinc oxide. The zinc oxide film may be deposited by a zinc cathode that includes other materials to improve the cathode sputtering characteristics. For example, the zinc cathode may include a small amount (e.g., less than 10% by weight, such as greater than 0 to 5% by weight) of tin to improve sputtering. In this case, the resulting zinc oxide film will include a small percentage of tin oxide, such as 0 to less than 10% by weight tin oxide, such as 0 to 5% by weight tin oxide. An oxide layer sputtered from a zinc / tin cathode having 95% by weight zinc and 5% by weight tin, or preferably 90% by weight zinc and 10% by weight tin, is referred to as a zinc oxide film. Small amounts of tin in the cathode (eg, less than 10 weight percent) are believed to form small amounts of tin oxide in the second film 44 of the first dielectric layer comprising primarily zinc oxide.

[0046] In an exemplary non-limiting embodiment, the second film 44 is a film consisting of at least one of aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide. The aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide film is deposited from a zinc cathode that includes other materials to improve the cathode sputtering characteristics. For example, the aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide film may include a small amount (e.g., less than 10 wt %, such as greater than 0 to 5 wt %) of tin to improve sputtering. In this case, the resulting aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide film will include a small percentage of tin oxide, such as 0 wt % to less than 10 wt % tin oxide, such as 0 wt % to 5 wt % tin oxide.

[0047] One non-limiting embodiment is where the first film 42 of the first dielectric layer is zinc stannate and the second film 44 of the first dielectric layer comprises zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide over at least a portion of the first film 42 of the first dielectric layer.

[0048] The first dielectric layer 40 may have a total thickness in the range of 10 nm to 55 nm, preferably 20 nm to 53 nm, more preferably 25 nm to 50 nm, and most preferably 29 nm to 48 nm.

[0049] In a non-limiting embodiment, the first dielectric layer 40 includes a first seed film in direct contact with the first metallic layer 48, which is not described in the figure. The seed film may include aluminum, aluminum silver, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides or their combinations. In a non-limiting embodiment, the seed film may include aluminum zinc, vanadium zinc, zinc, silver zinc, their metals, their alloys, their oxides, or their suboxides. In another embodiment, the seed film may include gallium zinc, indium zinc, indium tin, their metals, their alloys, their oxides, or their suboxides. The composition of the non-limiting examples of the seed film can be found in Table 2. In some embodiments, a portion of the seed film is formed at a specific flow rate to form 1% to 70% O 2 The balance is argon atmosphere of O 2 The flow rate is the O 2 The amount is an approximation of , but one of ordinary skill in the art will recognize that the additional O 2 can leak into the coating chamber because the coating chamber is not hermetically sealed from the external environment. In one embodiment, the seed film comprises V x Zn 1-x In another embodiment, the seed film comprises Al x Zn 1-x In another embodiment, the seed film comprises Ga x Zn 1-x In another embodiment, the seed film comprises In x Zn 1-x In another embodiment, the seed film comprises Sn x In 1-x In another embodiment, the seed film comprises Ag deposited in an oxygen / argon environment. In another embodiment, the seed film comprises Al xAg 1-x In one non-limiting embodiment, the second film 44 of the first dielectric layer is a seed film. In some embodiments, the first dielectric layer 40 comprises a first film 42, a second film 44, and a seed film. The seed film may have a total thickness in the range of 0.5 nm to 10 nm, preferably 0.75 nm to 8 nm, and more preferably 0.9 nm to 6 nm.

[0050] Table 2 Composition of metals of metal alloys used as seed films

[0051]

[0052] The first metallic layer 48 can be deposited above at least a portion of the first dielectric layer 40. The first metallic layer 48 can include a reflective metal such as but not limited to metallic gold, silver, their mixture, their alloy or their combination. In one embodiment, the first metallic layer 48 comprises a metallic silver layer. The first metallic layer 48 can have a total thickness in the range of 5nm to 20nm, preferably 7.5nm to 15nm, more preferably 9nm to 14nm, most preferably 9.7 to 13.3nm.

[0053] The first primer layer 50 can be deposited on at least a portion of the first metallic layer 48. The first primer layer 50 can be an oxygen capture material, such as titanium, which can sacrifice in the deposition process to prevent the degradation or oxidation of the first metallic layer 48 in sputtering process or subsequent heating process. The oxygen capture material can be selected to be oxidized before the material of the first metallic layer 48. The example of suitable material for the primer layer comprises zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, germanium, magnesium, molybdenum, silver, silicon carbon, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, aluminum silver, zinc tin, indium zinc, silver zinc, their mixture, their combination or their any alloy, wherein the primer is deposited as metal and oxidized subsequently. The example of suitable material for the first primer layer 50 can be found in Table 1. At least a portion of the primer layer is a nitride or oxide. If silver zinc, zinc, silver zinc oxide, titanium, aluminum zinc oxide, indium zinc oxide, gallium zinc oxide, or vanadium zinc oxide is used as the first primer layer 50, it will preferably oxidize prior to oxidation of the underlying metallic layer. In one embodiment, the first primer layer 50 is titanium. In another embodiment, the first primer layer 50 comprises silver zinc. In another embodiment, the first primer layer 50 comprises zinc. In another embodiment, the first primer layer 50 comprises Ag. x Zn 1-x In another embodiment, the first primer layer 50 comprises Ag x Zn 1-x In another embodiment, the first primer layer 50 comprises Al x Zn 1-xIn another embodiment, the first primer layer 50 comprises In x Zn 1-x In another embodiment, the first primer layer 50 comprises Ga x Zn 1-x In another embodiment, the first primer layer 50 comprises V x Zn 1-x In another embodiment, the first primer layer 50 comprises Al x Ti 1-x In another embodiment, the first primer layer 50 comprises Al x Nb 1-x In another embodiment, the first primer layer 50 comprises Al x Nb 1-x In another embodiment, the first primer layer 50 comprises W x Nb 1-x In another embodiment, the first primer layer 50 comprises W x Ti 1-x In another embodiment, the first primer layer 50 comprises Ti x Ta 1-x In another embodiment, the first primer layer 50 comprises Ti x Nb 1-x In another embodiment, the first primer layer 50 comprises Ti x Nb 1-x In another embodiment, the first primer layer 50 comprises Nb x Zr 1-x In another embodiment, the first primer layer 50 comprises Ta x W 1-x In another embodiment, the first primer layer 50 comprises W x Nb 1-x In another embodiment, the first primer layer 50 comprises Zn x Ti 1-x The first primer layer 50 has a total thickness in the range of 0.5 nm to 10 nm, preferably 1.0 nm to 5.0 nm, more preferably 1.0 to 2.5 nm.

[0054] The second dielectric layer 60 may be deposited over at least a portion of the first metallic layer 48 or the optional first primer layer 50. The second dielectric layer 60 may include one or more of the materials discussed above with respect to the first dielectric layer. Figure 2In the non-limiting example of the description, the second dielectric layer 60 includes a first film 62 of the second dielectric layer deposited on the first metallic layer 48 or the optional first primer layer 50. The first film 62 of the second dielectric layer comprises an oxide, nitride, oxynitride, or mixture of a metal selected from the following: titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, their alloys, their mixtures, or combinations thereof. In one embodiment, the first film 62 of the second dielectric layer comprises zinc oxide. In another embodiment, the first film 62 of the second dielectric layer comprises aluminum-doped zinc oxide. In another embodiment, the first film 62 of the second dielectric layer comprises indium-doped zinc oxide. In another embodiment, the first film 62 of the second dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the first film 62 of the second dielectric layer comprises indium-doped tin oxide. In another embodiment, the first film 62 of the second dielectric layer comprises vanadium-doped zinc oxide.

[0055] The second film 64 of the second dielectric layer may be deposited over at least a portion of the first film 62 of the second dielectric layer. The second film 64 of the second dielectric layer comprises an oxide, nitride, oxynitride, or mixtures thereof of a metal selected from titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. In a non-limiting embodiment, the second film 64 of the second dielectric layer is zinc stannate.

[0056] The third film 66 of the second dielectric layer may be deposited over at least a portion of the second film 64 of the second dielectric layer. The third film 66 of the second dielectric layer may include an oxide, nitride, oxynitride, or mixtures thereof of a metal selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. The third film 66 of the second dielectric layer may include aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, or mixtures thereof. In one embodiment, the third film 66 of the second dielectric layer includes zinc oxide. In another embodiment, the third film 66 of the second dielectric layer includes indium-doped zinc oxide. In another embodiment, the third film 66 of the second dielectric layer includes gallium-doped zinc oxide. In another embodiment, the third film 66 of the second dielectric layer includes indium-doped tin oxide. In another embodiment, the third film 66 of the second dielectric layer includes vanadium-doped zinc oxide. In another embodiment, the first dielectric layer 40 or the second dielectric layer 60 includes a silicon nitride film.

[0057] One non-limiting embodiment is where the first film 62 of the second dielectric layer comprises zinc oxide, the second film 64 of the second dielectric layer comprises zinc stannate, and the third film 66 of the second dielectric layer comprises zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide over at least a portion of the second film 44 of the second dielectric layer.

[0058] The second dielectric layer 60 may have a total thickness in the range of 50 nm to 150 nm, preferably 75 nm to 125 nm, more preferably 90 nm to 110 nm, and most preferably 93 nm to 100 nm.

[0059] In a non-limiting embodiment, the second dielectric layer 60 includes a seed film located in direct contact with the second metallic layer 70. The seed film may include one or more materials discussed above about the seed film of the first dielectric layer and Table 2. The seed film may include aluminum, aluminum silver, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides or their combinations. In a non-limiting embodiment, the seed film may include aluminum zinc, vanadium zinc, zinc, silver zinc, their metals, their alloys, their oxides, or their suboxides. In another embodiment, the seed film may include gallium zinc, indium zinc, indium tin, their metals, their alloys, their oxides, or their suboxides. In one embodiment, the seed film includes V x Zn 1-x In another embodiment, the seed film comprises Al x Zn 1-x In another embodiment, the seed film comprises Ga x Zn 1-x In another embodiment, the seed film comprises In x Zn 1-x In another embodiment, the seed film comprises Sn x In 1-x In another embodiment, the seed film comprises Ag deposited in an oxygen / argon environment. In another embodiment, the seed film comprises Al x Ag 1-x In some embodiments, the second dielectric layer 60 has a first film 62, a second film 64, and a seed film. In some embodiments, the second dielectric layer 60 has a first film 62, a second film 64, a third film 66, and a seed film. The seed film may have a total thickness in the range of 0.5 nm to 10 nm, preferably 0.75 nm to 8 nm, and more preferably 0.9 nm to 6 nm.

[0060] The second metallic layer 70 may be deposited above at least a portion of the second dielectric layer 60. The second metallic layer 70 may include any one or more of the reflective materials described above with respect to the first metallic layer 48. In a non-limiting embodiment, the second metallic layer 70 comprises silver. The second metallic layer 70 may have a total thickness in the range of 5nm to 20nm, preferably 5nm to 15nm, more preferably 7.5nm to 12.5nm, most preferably 7.5nm to 10.3nm.

[0061] A second primer layer 72 may be deposited over at least a portion of the second metallic layer 70. The second primer layer 72 may be any of the materials described above with respect to the first primer layer 50 and Table 1. In one non-limiting embodiment, the second primer layer 72 comprises titanium. In another embodiment, the second primer layer 72 comprises silver zinc. In another embodiment, the second primer layer 72 comprises zinc. In another embodiment, the second primer layer 72 comprises Ag. x Zn 1-x In another embodiment, the second primer layer 72 comprises Ag x Zn 1-x In another embodiment, the second primer layer 72 comprises Al x Zn 1-x In another embodiment, the second primer layer 72 comprises In x Zn 1-x In another embodiment, the second primer layer 72 comprises Ga x Zn 1-x In another embodiment, the second primer layer 72 comprises V x Zn 1-x In another embodiment, the second primer layer 72 comprises Al x Ti 1-x In another embodiment, the second primer layer 72 comprises Al x Nb 1-x In another embodiment, the second primer layer 72 comprises Al x Nb 1-x In another embodiment, the second primer layer 72 comprises W x Nb 1-x In another embodiment, the second primer layer 72 comprises W x Ti 1-x In another embodiment, the second primer layer 72 comprises Ti x Ta 1-x In another embodiment, the second primer layer 72 comprises Ti x Nb 1-xIn another embodiment, the second primer layer 72 comprises Ti x Nb 1-x In another embodiment, the second primer layer 72 comprises Nb x Zr 1-x In another embodiment, the second primer layer 72 comprises Ta x W 1-x In another embodiment, the second primer layer 72 comprises W x Nb 1-x In another embodiment, the second primer layer 72 comprises Zn x Ti 1-x The second primer layer 72 has a total thickness in the range of 0.5 nm to 10 nm, preferably 1.0 nm to 5 nm, more preferably 1.0 nm to 2.5 nm.

[0062] The third dielectric layer 80 can be deposited on at least a portion of the second metallic layer 70 or the second primer layer 72. The third dielectric layer 80 can also include one or more materials discussed above about the first and second dielectric layers. In a non-limiting embodiment, the third dielectric layer 80 comprises the first film 82 of the third dielectric layer. The first film 82 of the third dielectric layer comprises an oxide, nitride, oxynitride or their mixture of a metal selected from the following: titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, their alloy, their mixture or their combination. In one embodiment, the first film 82 of the third dielectric layer comprises zinc oxide. In another non-limiting embodiment, the first film 82 of the third dielectric layer comprises zinc stannate. In another embodiment, the first film 82 of the third dielectric layer comprises aluminum-doped zinc oxide. In another embodiment, the first film 82 of the third dielectric layer comprises indium-doped zinc oxide. In another embodiment, the first film 82 of the third dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the first film 82 of the third dielectric layer comprises indium-doped tin oxide. In another embodiment, the first film 82 of the third dielectric layer comprises vanadium-doped zinc oxide.

[0063] The second film 84 of the third dielectric layer may be deposited over at least a portion of the first film 82 of the third dielectric layer. The second film 84 of the third dielectric layer comprises an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. The second film 84 of the third dielectric layer may comprise aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, or mixtures thereof. In one embodiment, the second film 84 of the third dielectric layer comprises zinc oxide. In one embodiment, the second film 84 of the third dielectric layer comprises zinc stannate. In another embodiment, the second film 84 of the third dielectric layer comprises silicon nitride or silicon oxynitride. In another embodiment, the second film 84 of the third dielectric layer comprises indium-doped zinc oxide. In another embodiment, the second film 84 of the third dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the second film 84 of the third dielectric layer comprises indium-doped tin oxide. In another embodiment, the second film 84 of the third dielectric layer comprises vanadium-doped zinc oxide.

[0064] The optional third film of the third dielectric layer may be deposited over at least a portion of the second film 84 of the third dielectric layer. The optional third film of the third dielectric layer comprises an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. The third film of the third dielectric layer may comprise aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, or mixtures thereof. In a non-limiting embodiment, the optional third film of the third dielectric layer comprises zinc oxide. In another embodiment, the third film of the third dielectric layer comprises indium-doped zinc oxide. In another embodiment, the third film of the third dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the third film of the third dielectric layer comprises indium-doped tin oxide. In another embodiment, the third film of the third dielectric layer comprises vanadium-doped zinc oxide. In another embodiment, the optional third film of the third dielectric layer comprises silicon nitride or silicon oxynitride. In another embodiment, the optional third film of the third dielectric layer comprises titanium oxide.

[0065] One non-limiting embodiment is where the first film 82 of the third dielectric layer comprises zinc oxide or zinc stannate and the second film 84 of the third dielectric layer comprises zinc oxide, zinc stannate, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide over at least a portion of the first film 82 of the third dielectric layer.

[0066] The third dielectric layer 80 may have a total thickness in the range of 20 nm to 75 nm, preferably 25 nm to 50 nm, more preferably 30 nm to 45 nm, most preferably 36 nm to 41 nm.

[0067] In one non-limiting embodiment, the coated article comprises first and second metallic layers 48, 70. No additional metallic layers are present in the coated article. The metallic layers may include only silver or only silver and gold.

[0068] Each metallic layer has a thickness. In a non-limiting embodiment, the total combined thickness of the metallic layers is in the range of 10 nm to 30 nm, preferably 12 nm to 25 nm, most preferably 15 nm to 22 nm, most preferably 16 nm to 18 nm.

[0069] The coating may include an outermost protective layer 100, which is for example Figure 2In the non-limiting embodiment shown in , the outermost protective layer 100 is deposited on at least a portion of the third dielectric layer 80 to help protect the underlying layer, such as the metallic layer, from mechanical and chemical erosion during processing. The outermost protective layer 100 can be an oxygen barrier coating to prevent or reduce ambient oxygen from passing through the underlying layer of the coating 30, such as during heating or blending. The outermost protective layer 100 can have any desired material or mixture of materials and can be composed of one or more protective films. In an exemplary embodiment, the outermost protective layer 100 can include a monolayer comprising one or more metal oxide materials, such as, but not limited to, the oxide of aluminum, silicon or a mixture thereof. For example, the outermost protective coating 100 may be a single coating comprising 0 wt % to 100 wt % aluminum oxide and / or 100 wt % to 0 wt % silicon oxide, such as 5 wt % to 95 wt % aluminum oxide and 95 wt % to 5 wt % silicon oxide, such as 10 wt % to 90 wt % aluminum oxide and 90 wt % to 10 wt % silicon oxide, such as 15 wt % to 90 wt % aluminum oxide and 85 wt % to 10 wt % silicon oxide, such as 50 wt % to 75 wt % aluminum oxide and 50 wt % to 25 wt % silicon oxide, such as 50 wt % to 70 wt % aluminum oxide and 50 wt % to 30 wt % silicon oxide. % to 0 wt % silicon, such as 35 wt % to 100 wt % aluminum oxide and 65 wt % to 0 wt % silicon oxide, such as 70 wt % to 90 wt % aluminum oxide and 30 wt % to 10 wt % silicon oxide, such as 75 wt % to 85 wt % aluminum oxide and 25 wt % to 15 wt % silicon oxide, such as 88 wt % aluminum oxide and 12 wt % silicon oxide, such as 65 wt % to 75 wt % aluminum oxide and 35 wt % to 25 wt % silicon oxide, such as 70 wt % aluminum oxide and 30 wt % silicon oxide, such as 60 wt % to less than 75 wt % aluminum oxide and greater than 25 wt % to 40 wt % silicon oxide. Other materials such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium and / or their oxides may also be present to adjust the refractive index of the outermost protective layer 100. In one non-limiting embodiment, the refractive index of the outermost protective layer 100 may be in the range of 1 to 3, such as 1 to 2, such as 1.4 to 2, such as 1.4 to 1.8.

[0070] In one non-limiting embodiment, the protective layer 100 is a combined silicon oxide and aluminum oxide coating. The outermost protective layer 100 can be sputtered from two cathodes (e.g., one silicon and one aluminum) or from a single cathode containing both silicon and aluminum. This silicon aluminum oxide outermost protective layer 100 can be written as Si x Al 1-x O (1.5+x) / 2 , where x can vary from greater than 0 to less than 1. In one exemplary embodiment, the outermost protective layer 100 comprises 15 wt % aluminum oxide and 85 wt % silicon oxide. In another embodiment, the outermost protective coating 100 comprises SiO 2、Al 2 O 3 , SiAlO, their alloys and their mixtures.

[0071] In one non-limiting embodiment, the outermost protective layer 100 may be made of silicon nitride (Si 3 N 4 ), silicon oxynitride (SiON), silicon aluminum nitride (SiAlN), silicon aluminum oxynitride (SiAlON), mixtures thereof and / or alloys thereof, and which can provide improved durability to the coated article. The outermost protective layer 100 can be formed of silicon nitride deposited together with other materials having excellent electrical conductivity to improve the sputtering of silicon. For example, during deposition, the silicon cathode may include a small amount (e.g., up to 20 weight %, up to 15 weight %, up to 10 weight %, or up to 5 weight %) of aluminum to improve sputtering. In this case, the resulting silicon nitride layer will include a small percentage of aluminum, such as up to 15 weight % aluminum, such as up to 10 weight % aluminum, such as up to 5 weight % aluminum. The coating deposited from a silicon cathode having up to 10 weight % aluminum (added to enhance the conductivity of the cathode) is referred to herein as a "silicon nitride" layer, even though a small amount of aluminum may be present. A small amount of aluminum in the cathode (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. %) is believed to form aluminum nitride in the outermost protective layer 100, which is primarily silicon nitride. The outermost protective layer 100 can 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 the outermost protective layer 100.

[0072] In another non-limiting embodiment, the outermost protective layer 100 may be a multilayer coating comprising a first protective film and a second protective film formed above at least a portion of the first protective film. The first protective film may include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, tin oxide, mixtures thereof, or alloys thereof. In a specific non-limiting embodiment, the first protective film may include aluminum oxide or an alloy comprising aluminum oxide and silicon oxide. For example, the first protective film may include a silicon oxide / aluminum oxide mixture having greater than 5 wt % aluminum oxide, such as greater than 10 wt % aluminum oxide, such as greater than 15 wt % aluminum oxide, such as 50 wt % to 70 wt % aluminum oxide, such as in the range of 60 wt % to 100 wt % aluminum oxide and 40 wt % to 0 wt % silicon oxide, such as 60 wt % aluminum oxide and 40 wt % silicon oxide. In another example, the first protective film may include zinc stannate. In another example, the first protective film may include zirconium oxide.

[0073] The second protective film may include, for example, a metal oxide or a metal nitride. The second protective film 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 may include a titanium oxide / aluminum oxide mixture having 40-60 wt % aluminum oxide and 60-40 wt % titanium oxide, 45-55 wt % aluminum oxide and 55-45 wt % titanium oxide, 48-52 wt % aluminum oxide and 52-48 wt % titanium oxide, 49-51 wt % aluminum oxide and 51-49 wt % titanium oxide, or 50 wt % aluminum oxide and 50 wt % titanium oxide. An example of the second protective film may include titanium aluminum oxide (TiAlO). Another example of a second protective film is a silicon oxide / aluminum oxide mixture having greater than 40 wt % silicon oxide, for example greater than 50 wt % silicon oxide, for example greater than 60 wt % silicon oxide, for example greater than 70 wt % silicon oxide, for example greater than 80 wt % silicon oxide, for example in the range of 80 to 90 wt % silicon oxide and 10 to 20 wt % aluminum oxide, for example 85 wt % silicon oxide and 15 wt % aluminum oxide.

[0074] In a non-limiting example, the outermost protective layer 100 may include an additional third protective film formed over at least a portion of the second protective film. The third protective film may be any material used to form the first and second protective films. The third protective film may, for example, include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, tin oxide, or a mixture thereof. For example, the third protective film may include a mixture of silicon oxide and aluminum oxide. In another example, the third protective film includes aluminum oxide and titanium oxide. In another example, the third protective film includes zirconium oxide.

[0075] The outermost protective layer 100 is the outermost layer of the coated article. In addition, the outermost protective layer 100 may have a non-uniform thickness. "Non-uniform thickness" means that the thickness of the outermost protective layer 100 may vary over a given unit area, for example, the outermost protective layer 100 may have high and low points or areas. Non-limiting examples of suitable protective layers are described in U.S. Patent Application Nos. 10 / 007,382, 10 / 133,805, 10 / 397,001, 10 / 422,095 and 10 / 422,096.

[0076] The outermost protective layer 100 may have a total thickness in the range of 20 nm to 120 nm, preferably 25 nm to 110 nm, more preferably 30 nm to 100 nm, most preferably 35 nm to 90 nm.

[0077] The present invention is further described in the following numbered clauses:

[0078] Clause 1. A coated article comprising a substrate; a functional coating applied over at least a portion of the substrate, the functional coating comprising a first dielectric layer over at least a portion of the substrate; a first metallic layer over at least a portion of the first dielectric layer; a first primer layer over at least a portion of the first metallic layer; a second dielectric layer over at least a portion of the first primer layer; a second metallic layer over at least a portion of the second dielectric layer; a second primer layer over at least a portion of the second metallic layer; and a third dielectric layer over at least a portion of the second primer layer; wherein the coated article has an RgL * The value must be at least 35 and no greater than 55.

[0079] Item 2. The coated article of Item 1, wherein RgL * The value must be at least 42.

[0080] Item 3. The coated article of Item 1, wherein RgL * The value cannot be greater than 52.

[0081] Clause 4. The coated article of any preceding clause, wherein at least one metallic layer comprises at least one of silver, gold, mixtures thereof, or alloys thereof.

[0082] Clause 5. The coated article of any preceding clause, wherein at least one metallic layer comprises metallic silver.

[0083] Clause 6. The coated article of any preceding clause, wherein the first metallic layer comprises a total thickness of 5 nm to 20 nm, preferably 7.5 nm to 15 nm, more preferably 9 nm to 14 nm, most preferably 9.7 nm to 13.3 nm.

[0084] Clause 7. The coated article of any preceding clause, wherein the second metallic layer comprises a total thickness of 5 nm to 20 nm, preferably 5 nm to 15 nm, more preferably 7.5 nm to 12.5 nm, most preferably 7.5 nm to 10.3 nm.

[0085] Item 8. The coated article of Item 1, wherein at least one dielectric layer comprises zinc stannate, zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof.

[0086] Item 9. The coated article of Item 1, wherein the first dielectric layer comprises a first film comprising zinc stannate over at least a portion of the substrate, and a second film comprising zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof over at least a portion of the first film.

[0087] Item 10. The coated article of Item 9, wherein the second film comprises aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof.

[0088] Item 11. The coated article of Items 8 to 10, wherein the first dielectric layer comprises a total thickness of 10 nm to 55 nm, preferably 20 to 53 nm, more preferably 25 to 50 nm, most preferably 29 to 48 nm.

[0089] Item 12. The coated article of any preceding item, wherein the first dielectric layer comprises a seed film in direct contact with the first metallic layer, wherein the seed film comprises aluminum, aluminum silver, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides, or combinations thereof.

[0090] Clause 13. The coated article of any preceding clause, wherein the second dielectric layer comprises a first film comprising zinc oxide over at least a portion of the first primer layer, a second film comprising zinc stannate over at least a portion of the first film, and a third film comprising zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof over at least a portion of the second film.

[0091] Item 14. The coated article of Item 13, wherein the second dielectric layer comprises a total thickness of 50 nm to 150 nm, preferably 75 nm to 125 nm, more preferably 90 nm to 110 nm, most preferably 93 nm to 100 nm.

[0092] Item 15. The coated article of any preceding item, wherein the second dielectric layer comprises a seed film in direct contact with the second metallic layer, wherein the seed film comprises aluminum, aluminum silver, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides, or combinations thereof.

[0093] Clause 16. The coated article of any preceding clause, wherein the third dielectric layer comprises a first film comprising zinc oxide or zinc stannate over at least a portion of the second primer layer, and a second film comprising zinc oxide, zinc stannate, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof over at least a portion of the first film.

[0094] Item 17. The coated article of Item 16, wherein the third dielectric layer comprises a total thickness of 20 nm to 75 nm, preferably 25 nm to 50 nm, more preferably 30 nm to 45 nm, most preferably 36 nm to 41 nm.

[0095] Clause 18. The coated article of any preceding clause, further comprising an outermost protective coating, the outermost protective coating comprising a protective layer, wherein the protective layer comprises at least one of the following: Si 3 N 4 , SiAlN, SiAlON, titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, alloys thereof, mixtures thereof, or combinations thereof.

[0096] Item 19. The coated article of Item 18, wherein the protective layer comprises a total thickness of 20 nm to 120 nm, preferably 25 nm to 110 nm, more preferably 30 nm to 100 nm, most preferably 35 nm to 90 nm.

[0097] Clause 20. The coated article of any one of Clauses 18 to 19, wherein the protective layer comprises a first protective film and a second protective film formed over at least a portion of the first protective film.

[0098] Item 21. The coated article of any one of Items 18 to 20, wherein the protective layer comprises silicon aluminum oxide, titanium aluminum oxide, mixtures thereof, or combinations thereof.

[0099] Clause 22. The coated article of any preceding clause, wherein at least one of the first primer layer or the second primer layer is selected from the group consisting of zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, germanium, magnesium, molybdenum, silver, silicon carbon, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, aluminum silver, zinc tin, indium zinc, silver zinc, mixtures thereof, combinations thereof, or any alloys thereof, and wherein the primer is deposited as a metal and subsequently oxidized.

[0100] Item 23. The coated article of Item 22, wherein the first primer layer comprises a total thickness of 0.5 nm to 10 nm, preferably 1.0 nm to 5 nm, more preferably 1.0 nm to 2.5 nm.

[0101] Item 24. The coated article of Item 22, wherein the second primer layer comprises a total thickness of 0.5 nm to 5 nm, preferably 1 nm to 2.5 nm, more preferably 1.5 nm to 2.5 nm.

[0102] Item 25. A coated article comprising a substrate; a functional coating applied over at least a portion of the substrate, the functional coating comprising a first dielectric layer over at least a portion of the substrate; a first metallic layer over at least a portion of the first dielectric layer; a first primer layer over at least a portion of the first metallic layer; a second dielectric layer over at least a portion of the first primer layer; a second metallic layer over at least a portion of the second dielectric layer; a second primer layer over at least a portion of the second metallic layer; and a third dielectric layer over at least a portion of the second primer layer, wherein the total combined thickness of the metallic layers is at least 10 nanometers and no greater than 30 nanometers.

[0103] Item 26. The coated article of Item 25, wherein the total combined thickness of the metallic layers is no greater than 22 nanometers.

[0104] Item 27. The coated article of Item 26, wherein the total combined thickness of the metallic layers is no greater than 18 nanometers.

[0105] Clause 28. The coated article of any of Clauses 25 to 27, wherein the at least one metallic layer comprises at least one of silver, gold, alloys thereof, mixtures thereof, or combinations thereof.

[0106] Item 29. The coated article of any one of Items 25 to 28, wherein at least one metallic layer comprises metallic silver.

[0107] Item 30. The coated article of Item 25, wherein at least one dielectric layer comprises zinc stannate, zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof.

[0108] Item 31. The coated article of any of Items 25 to 30, wherein the first dielectric layer comprises a first film comprising zinc stannate, zinc oxide, silicon nitride, or a mixture thereof over at least a portion of the substrate, and a second film comprising zinc oxide, zinc stannate, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof over at least a portion of the first film.

[0109] Item 32. The coated article of any of Items 25 to 31, wherein the first dielectric layer comprises a seed film in direct contact with the first metallic layer, wherein the seed film comprises aluminum, aluminum silver, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides, or combinations thereof.

[0110] Clause 33. The coated article of any of Clauses 25 to 31, wherein the second dielectric layer comprises a first film comprising zinc oxide over at least a portion of the first primer layer, a second film comprising zinc stannate over at least a portion of the first film, and a third film comprising zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof over at least a portion of the second film.

[0111] Item 34. The coated article of items 25 to 33, wherein the second dielectric layer comprises a seed film in direct contact with the second metallic layer, wherein the seed film comprises aluminum, aluminum silver, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides, or combinations thereof.

[0112] Item 35. The coated article of items 25 to 34, wherein the third dielectric layer comprises a first film comprising zinc oxide or zinc stannate over at least a portion of the second primer layer, and a second film comprising zinc oxide, zinc stannate, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof over at least a portion of the first film.

[0113] Clause 36. The coated article of any of clauses 25 to 35, further comprising an outermost protective coating, the outermost protective coating comprising a protective layer, wherein the protective layer comprises at least one of the following: Si 3 N 4 , SiAlN, SiAlON, titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, alloys thereof, mixtures thereof, or combinations thereof.

[0114] Item 37. The coated article of Item 36, wherein the protective layer comprises a first protective film and a second protective film formed over the first protective film.

[0115] Item 38. The coated article of any one of Items 36 to 37, wherein the protective layer comprises silicon aluminum oxide, titanium aluminum oxide, alloys thereof, mixtures thereof, or combinations thereof.

[0116] Clause 39. The coated article of any of clauses 25 to 38, wherein at least one of the first primer layer or the second primer layer is selected from the group consisting of zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, germanium, magnesium, molybdenum, silver, silicon carbon, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, aluminum silver, zinc tin, indium zinc, silver zinc, mixtures thereof, combinations thereof, or any alloys thereof, or alloys thereof, and wherein the primer is deposited as a metal and subsequently oxidized.

[0117] Clause 40. A method of making a coated article, comprising: providing a substrate; and applying a functional coating over at least a portion of the substrate, wherein the step of applying the functional coating comprises: forming a first dielectric layer over at least a portion of the substrate; forming a first metallic layer over at least a portion of the first dielectric layer; forming a first primer layer over at least a portion of the first metallic layer; forming a second dielectric layer over at least a portion of the first primer layer; forming a second metallic layer over at least a portion of the second dielectric layer; forming a second primer layer over at least a portion of the second metallic layer; and forming a third dielectric layer over at least a portion of the second primer layer, wherein the total combined thickness of the metallic layers is at least 10 nanometers and no greater than 30 nanometers, and wherein RgL * The value must be at least 35 and no greater than 55.

[0118] Clause 41. The method of clause 40, wherein applying the outermost protective coating comprises forming a protective layer, wherein the protective layer comprises at least one of: Si 3 N 4 , SiAlN, SiAlON, titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, alloys thereof, mixtures thereof, or combinations thereof.

[0119] The following examples illustrate various embodiments of the present invention. However, it should be understood that the present invention is not limited to these specific embodiments. Example

[0120] Table 3 shows exemplary coating compositions of the present invention. The reported thickness is the geometric thickness in nanometers (nm) unless otherwise indicated. The substrate is a transparent glass substrate with a thickness of 2.1 mm, with a transparent cover of 2.1 mm. The base layer is the first dielectric layer, the center layer is the second dielectric layer, and the top layer is the third dielectric layer.

[0121] Table 3

[0122] sample 1 2 3 4 Glass substrate 2.1mm 2.1mm 2.1mm 2.1mm Glass Covering 2.1mm 2.1mm 2.1mm 2.1mm Base 37 29.7 32.6 47.2 1st metallic layer 13.3 10.6 9.7 9.9 center 99.6 94.9 93.1 94.8 Second metallic layer 7.9 7.6 7.5 10.3 top 39.6 40.2 39.0 36.8 Protective layer 51 51 51 51 Total metallic properties 21.2 18.1 17.2 20.2

[0123] Table 4 shows the resulting color and optical properties for the samples of Table 3. For articles containing a substrate and a cover (laminate), R1 refers to the reflectance from the outer surface closest to the coating and R2 refers to the reflectance from the outer surface farthest from the coating.

[0124] Table 4

[0125]

[0126] Those skilled in the art will readily appreciate that the present invention may be modified without departing from the concepts disclosed in the foregoing description. Therefore, the particular embodiments described in detail herein are merely illustrative and do not limit the scope of the present invention, which is given by the full scope of the appended claims and any and all equivalents thereof.

Claims

1. A coated article comprising: a substrate; a functional coating applied over at least a portion of the substrate, the functional coating comprising: a first dielectric layer over at least a portion of the substrate; a first metallic layer over at least a portion of the first dielectric layer; a first primer layer over at least a portion of the first metallic layer; a second dielectric layer over at least a portion of the first primer layer; a second metallic layer over at least a portion of the second dielectric layer; a second primer layer over at least a portion of the second metallic layer; and a third dielectric layer over at least a portion of the second primer layer, wherein the coated article has an RgL of at least 42 and no greater than 55 * value, wherein the first metallic layer comprises a total thickness of 5 nm to 20 nm, and wherein the second metallic layer comprises a total thickness of 5 nm to 20 nm.

2. The coated article according to claim 1, wherein RgL * The value is no greater than 52.

3. The coated article of any one of the preceding claims, wherein at least one metallic layer comprises at least one of silver, gold, mixtures thereof, or alloys thereof.

4. The coated article according to any one of the preceding claims, wherein at least one metallic layer comprises metallic silver.

5. The coated article of claim 1, wherein at least one dielectric layer comprises zinc stannate, zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof.

6. The coated article of any one of the preceding claims, wherein the first dielectric layer comprises a total thickness of 10 nm to 55 nm.

7. A coated article according to any one of the preceding claims, wherein the first dielectric layer comprises a seed film in direct contact with the first metallic layer, wherein the seed film comprises aluminum, aluminum silver, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides or their combinations.

8. The coated article of any of the preceding claims, wherein the second dielectric layer comprises a first film comprising zinc oxide over at least a portion of the first primer layer, a second film comprising zinc stannate over at least a portion of the first film, and a third film comprising zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof over at least a portion of the second film.

9. The coated article of claim 8, wherein the second dielectric layer comprises a total thickness of 50 nm to 150 nm.

10. A coated article according to any one of the preceding claims, wherein the second dielectric layer comprises a seed film in direct contact with the second metallic layer, wherein the seed film comprises aluminum, aluminum silver, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides or their combinations.

11. The coated article of any of the preceding claims, wherein the third dielectric layer comprises a first film comprising zinc oxide or zinc stannate over at least a portion of the second primer layer, and a second film comprising zinc oxide, zinc stannate, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, alloys thereof, mixtures thereof, or combinations thereof over at least a portion of the first film. 12 . The coated article of claim 11 , wherein the third dielectric layer comprises a total thickness of 20 nm to 75 nm.

13. The coated article according to any one of the preceding claims, further comprising an outermost protective coating, the outermost protective coating comprising a protective layer, wherein the protective layer comprises at least one of the following: Si3N4, SiAlN, SiAlON, titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, alloys thereof, mixtures thereof, or combinations thereof. 14 . The coated article according to claim 14 , wherein the protective layer comprises a first protective film and a second protective film formed over at least a portion of the first protective film.

15. The coated article of any of the preceding claims, wherein at least one of the first primer layer or the second primer layer is selected from the group consisting of zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, germanium, magnesium, molybdenum, silver, silicon carbon, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, aluminum silver, zinc tin, indium zinc, silver zinc, mixtures thereof, combinations thereof, or any alloys thereof, and wherein the primer is deposited as a metal and subsequently oxidized.

Images