Coatings for head-up displays with low visible light reflectance - Patent Application 20070122997

Abstract

The coated article includes a substrate having a first surface and a second surface opposite the first surface, and a functional coating applied to one of the surfaces. The functional coating includes a first dielectric layer, a first metal layer, a second dielectric layer, a second metal layer, a third dielectric layer, a third metal layer, a fourth dielectric layer, an optional fourth metal layer, an optional fifth dielectric layer, and an optional outermost protective coating. The coated article has a total thickness of the metal layers of at least 10 nanometers and no more than 60 nanometers.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and claims priority to U.S. Provisional Patent Application No. 62 / 976,645, filed February 14, 2020, and U.S. Provisional Patent Application No. 62 / 825,326, filed March 28, 2019, the disclosures of which are incorporated by reference.

[0002] FIELD OF THE INVENTION The present invention relates generally to vehicle transparencies, such as vehicle windshields, and in one particular embodiment, to head-up displays. [Background technology]

[0003] Technical considerations Conventional automotive heads-up displays (HUDs) use an electromagnetic radiation source on the dashboard to project light onto the windshield, which is then reflected back to the driver's eyes, creating a virtual image of vehicle data that the driver can view without having to take their eyes off the road. For electromagnetic radiation that reflects off the windshield at angles typically found in conventional vehicles and typical unpolarized light sources such as light-emitting diodes (LEDs), the reflected light is primarily s-polarized, with a much smaller component of light being p-polarized. In the extreme case, when the angle of incidence of electromagnetic radiation on the windshield is the Brewster angle at the air-to-glass interface (approximately 57°), the p-polarized light reflectance is zero percent.

[0004] Light (primarily s-polarized light) from a radiation source reflects off both the innermost surface of the windshield and the outermost surface of the windshield due to the refractive index mismatch between air and glass. This creates two reflected images, one from each surface. The multiple images created by a HUD are a phenomenon known as "ghosting," and eliminating or minimizing the presence of "ghosting" is a goal of HUD technology. A traditional method of solving ghosting is by using a wedge-shaped vinyl layer between the inner and outer glass plies of the windshield and adjusting the geometry of the two glass plies to align the two reflected images. This wedge-shaped vinyl adds cost to the windshield and also increases the complexity of windshield manufacturing.

[0005] It may also be desirable to apply a coating to at least one of the glass plies to provide solar control, heating, and / or antenna functionality to the windshield. This additional coating would result in a third refractive index mismatch within the windshield, which would result in a third reflection and a third reflected image to the HUD system, which would be difficult to correct with a wedge-shaped vinyl layer. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 4,466,562 [Patent Document 2] U.S. Patent No. 4,671,155 [Patent Document 3] U.S. Patent No. 4,746,347 [Patent Document 4] U.S. Patent No. 4,792,536 [Patent Document 5] U.S. Patent No. 5,030,593 [Patent Document 6] U.S. Patent No. 5,030,594 [Patent Document 7] U.S. Patent No. 5,240,886 [Patent Document 8] U.S. Patent No. 5,385,872 [Patent Document 9] U.S. Patent No. 5,393,593 [Patent Document 10] U.S. Patent No. 4,287,107 [Patent Document 11] U.S. Patent No. 3,762,988 [Patent Document 12] U.S. Patent No. 5,796,055 [Patent Document 13] U.S. Patent No. 5,653,903 [Patent Document 14] U.S. Patent No. 5,028,759 [Patent Document 15] U.S. Patent No. 4,898,789 [Patent Document 16] U.S. Patent No. 5,821,001 [Patent Document 17] U.S. Patent No. 4,716,086 [Patent Document 18] U.S. Patent No. 4,610,771 [Patent Document 19] U.S. Patent No. 4,902,580 [Patent Document 20] U.S. Patent No. 4,806,220 [Patent Document 21] U.S. Patent No. 4,898,790 [Patent Document 22] U.S. Patent No. 4,834,857 [Patent Document 23] U.S. Patent No. 4,948,677 [Patent Document 24] U.S. Patent No. 5,059,295 [Patent Document 25] U.S. Patent Application Publication No. 09 / 058440 [Patent Document 26] U.S. Patent No. 4,379,040 [Patent Document 27] U.S. Patent No. 4,861,669 [Patent Document 28] U.S. Patent No. 4,900,633 [Patent Document 29] U.S. Patent No. 4,920,006 [Patent Document 30] U.S. Patent No. 4,938,857 [Patent Document 31] U.S. Patent No. 5,328,768 [Patent Document 32] U.S. Patent No. 5,492,750 [Patent Document 33] U.S. Patent Application No. 10 / 007,382 [Patent Document 34] U.S. Patent Application No. 10 / 133,805 [Patent Document 35] U.S. Patent Application Serial No. 10 / 397,001 [Patent Document 36] U.S. Patent Application No. 10 / 422,095 [Patent Document 37] U.S. Patent Application Serial No. 10 / 422,096 Summary of the Invention [Problem to be solved by the invention]

[0007] Thus, there is a need in the art for systems and / or components to reduce or eliminate one or more of these problems. For example, it would be desirable to provide a HUD system that projects a driver-viewable image that reduces or eliminates ghosting while improving solar performance and reducing energy. [Means for solving the problem]

[0008] The present invention relates to a coated article. The coated article comprises a substrate having a first surface and a second surface opposite the first surface, and a functional coating on the substrate. The coating comprises a first dielectric layer disposed on at least a portion of the surface. A first metal layer is disposed on at least a portion of the first dielectric layer. Optionally, a first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first metal layer or the optional first primer layer. A second metal layer is disposed on at least a portion of the first metal layer or the optional first primer layer. Optionally, a second primer layer is disposed on at least a portion of the second metal layer. A third dielectric layer is disposed on at least a portion of the second metal layer or the optional second primer layer. A third metal layer is disposed on at least a portion of the third dielectric layer. Optionally, a third primer layer is disposed on at least a portion of the third metal layer. A fourth dielectric layer is disposed over at least a portion of the third metal layer or the optional third primer layer. An optional outermost protective coating is formed over at least a portion of the fourth dielectric layer or over the functional coating. The coated article has a total thickness of the metal layers of at least 10 nanometers to 60 nanometers.

[0009] The present invention relates to a coated article. The coated article comprises a substrate having a first surface and a second surface opposite the first surface, and a functional coating on the substrate. The coating comprises a first dielectric layer disposed on at least a portion of the surface. A first metal layer is disposed on at least a portion of the first dielectric layer. Optionally, a first primer layer is disposed on at least a portion of the first metal layer. A second dielectric layer is disposed on at least a portion of the first metal layer or the optional first primer layer. A second metal layer is disposed on at least a portion of the first metal layer or the optional first primer layer. Optionally, a second primer layer is disposed on at least a portion of the second metal layer. A third dielectric layer is disposed on at least a portion of the second metal layer or the optional second primer layer. A third metal layer is disposed on at least a portion of the third dielectric layer. Optionally, a third primer layer is disposed on at least a portion of the third metal layer. A fourth dielectric layer is disposed on at least a portion of the third metal layer or the optional third primer layer. A fourth metal layer is disposed on at least a portion of the fourth dielectric layer. An optional fourth primer layer is disposed on at least a portion of the fourth metal layer. A fifth dielectric layer is disposed on at least a portion of the fourth metal layer or the optional fourth primer layer. An optional outermost protective coating is formed on at least a portion of the fifth dielectric layer or on the functional coating. The coated article has a total thickness of the metal layers of at least 10 nanometers to 60 nanometers.

[0010] The present invention relates to a method for making a coated article. A substrate having a first surface and a second surface opposite the first surface is provided. A functional coating is applied over at least a portion of the surface. A first dielectric layer is formed over at least a portion of the surface. A first metal layer is formed over at least a portion of the first dielectric layer. Optionally, a first primer layer is formed over at least a portion of the first metal layer. A second dielectric layer is formed over at least a portion of the first metal layer. A second metal layer is formed over at least a portion of the second dielectric layer. Optionally, a second primer layer is formed over at least a portion of the second metal layer. A third dielectric layer is formed over at least a portion of the second metal layer. A third metal layer is formed over at least a portion of the third dielectric layer. Optionally, a third primer layer is formed over at least a portion of the third metal layer. A fourth dielectric layer is formed over at least a portion of the third metal layer. An optional outermost protective coating is formed over at least a portion of the fourth dielectric layer or over the functional coating. The coated article has a total thickness of the metal layers of at least 10 nanometers to 60 nanometers.

[0011] The present invention will now be described with reference to the following drawings, in which like reference numerals refer to like parts throughout: [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a non-limiting schematic diagram of a windshield (not to scale). [Figure 2A] FIG. 2A is a diagram of a windshield illustrating the ghosting effect that occurs when using a head-up display. [Figure 2B] FIG. 2B is a diagram of a windshield illustrating the ghosting effect that occurs when using a head-up display. [Figure 3] FIG. 3 shows a windshield having a coating arranged to reduce ghosting when using a head-up display. [Figure 4] FIG. 4 is a cross-sectional view (not to scale) of a non-limiting tri-metal coating according to the present invention. [Figure 5] FIG. 5 is a cross-sectional view (not to scale) of a non-limiting quadruple metal coating in accordance with the present invention. [Figure 6] FIG. 6 is a cross-sectional view (not to scale) of a non-limiting tri-metal coating according to the present invention. [Figure 7] FIG. 7 is a cross-sectional view (not to scale) of a non-limiting quadruple metal coating in accordance with the present invention. [Figure 8] FIG. 8 is a cross-sectional view (not to scale) of a non-limiting tri-metal coating according to the present invention. [Figure 9] FIG. 9 is a cross-sectional view (not to scale) of a non-limiting quadruple metal coating in accordance with the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0013] As used herein, spatial or directional terms, such as "left," "right," "inside," "outside," "top," "bottom," and the like, refer to the present invention as shown in the drawings. However, it is understood that the present invention can assume various alternative orientations, and therefore, such terms are not to be considered limiting. Furthermore, as used herein, all numbers expressing dimensions, physical properties, processing parameters, quantities of ingredients, reaction conditions, and the like, used in the specification and claims, are understood to be 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 may vary depending on the desired properties sought to be obtained by the present invention. At the very least, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should be construed in light of at least the number of reported significant digits and by applying ordinary rounding techniques. Furthermore, all ranges disclosed herein are understood to encompass the beginning and ending values of the range, and any and all subranges subsumed within the range. For example, a stated range of "1 to 10" should be considered to include any and all subranges between (and including) a minimum value of 1 and a maximum value of 10, i.e., all subranges beginning with a minimum value of 1 or greater 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, etc. Furthermore, as used herein, the terms "formed on," "deposited on," or "provided on" mean formed, deposited, or provided on a surface, but not necessarily in contact with the surface. For example, a coating layer "formed on" a substrate does not exclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate. As used herein, the terms "polymer" or "macromolecule" include oligomers, homopolymers, copolymers, and terpolymers, e.g., polymers formed from two or more monomers or polymers. The terms "visible region" or "visible light" refer to electromagnetic radiation having wavelengths ranging from 380 nanometers (nm) to 800 nm.The terms "infrared region" or "infrared" refer to electromagnetic radiation having wavelengths in the range of greater than 800 nm to 100,000 nm. The terms "ultraviolet region" or "ultraviolet" refer to electromagnetic energy having wavelengths in the range of 300 nm to less than 380 nm. Visible (luminous) transmittance (LTA) values (Y, x, y) herein are those determinable using a Lambda 9 spectrophotometer commercially available from Perkin-Elmer or a TCS spectrophotometer commercially available from BYK-Gardner over the wavelength range of 380 nm to 770 nm using CIE (1976) Standard Illuminant "A" with a 2-degree observer (in accordance with U.S. Federal standards). Reflected color values L. * , a * , b * (either R1 or R2) was determined using illuminant "D65" (as conventionally used in the automotive field) with a 10° observer.

[0014] As used herein, the term "film" refers to a coating region of a desired or selected coating composition. A "layer" can include one or more "films," and a "coating" or "coating stack" can include one or more "layers." The terms "metal" and "metal oxide" include silicon and silica, respectively, as well as traditionally recognized metals and metal oxides, although silicon may not traditionally be considered a metal. Unless indicated to the contrary, thickness values are geometric thickness values. Additionally, all documents, including but not limited to issued patents and patent applications, referred to herein are deemed "incorporated by reference" in their entirety.

[0015] The discussion of the present invention may describe certain features as being "particularly" or "preferably" within certain limits (e.g., "preferably," "more preferably," or "most preferably" within certain limits). It is understood that the invention is not limited to these particular or preferred limits, but rather encompasses the full scope of the present disclosure.

[0016] A non-limiting transparency 10 (e.g., an automobile windshield) incorporating features of the present invention is shown in FIG. 1. The transparency 10 can have any desired visible, infrared, or ultraviolet transmission and reflectance properties. For example, the transparency 10 can have any desired amount of visible light transmission, e.g., greater than 70%, from greater than 0% to 100%. For windshield and front sidelight areas in the United States, visible light transmission is typically 70% or greater. For privacy areas such as rear seat sidelights and rear windows, visible light transmission can be lower than that for windshields, e.g., less than 70%.

[0017] As seen in FIG. 1 , the transparency 10 includes a first ply or first substrate 12 having a first major surface, i.e., outer major surface 14 (No. 1 surface), facing the vehicle exterior, and an opposite second or inner major surface 16 (No. 2 surface). The transparency 10 also includes a second ply or second substrate 18 having an outer (first) major surface 22 (No. 4 surface) and an inner (second) major surface 20 (No. 3 surface). This numbering of the ply surfaces reflects practice in the automotive industry. The first and second plies 12, 18 may be bonded together in any suitable manner, such as by a conventional interlayer 24. Although not required, a conventional edge sealant may be applied around the periphery of the laminated transparency 10 during and / or after lamination in any desired manner. A decorative band, such as an opaque, translucent, or colored shade band 26, e.g., a ceramic band, may be provided on at least one surface of the plies 12, 18, for example, around the inner major surface 16 of the first ply 12. A coating 30 may be formed on at least a portion of one of the plies 12, 18, for example, on the No. 2 surface 16 or the No. 3 surface 20.

[0018] 1, the busbar assembly includes a first or lower busbar 96 and a second or upper busbar 98 formed on the inner surface 16 of the outer ply 12 and separated by a busbar distance D. The busbars 96, 98 are in electrical contact with the coating 30. In one non-limiting embodiment of the present invention, the busbars 96, 98 may be at least partially or completely disposed in the decorative band 26, as shown in FIG.

[0019] In the broad practice of the present invention, the plies 12, 18 of the transparency 10 can be of the same or different materials. The plies 12, 18 can comprise any desired material having any desired properties. For example, one or more of the plies 12, 18 can be transparent or translucent to visible light. "Transparent" means having a visible light transmittance of greater than 0% to 100%. Alternatively, one or more of the plies 12, 18 can be translucent. "Translucent" means diffusing electromagnetic energy (e.g., visible light) while allowing this energy to pass through so that objects on the opposite side of 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; polyalkyl methacrylates such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate; polyurethanes; polycarbonates; polyalkyl terephthalates such as polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate; polysiloxane-containing polymers; or copolymers of any monomers therefor, or any mixtures thereof); ceramic substrates; glass substrates; or mixtures or combinations of any of the above. For example, one or more of the plies 12, 18 can comprise conventional soda-lime silicate glass, borosilicate glass, or leaded glass. The glass may be clear glass. "Clear glass" means untinted or uncolored glass. Alternatively, the glass may be tinted or otherwise colored glass. The glass may be annealed glass 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, such as conventional float glass, and may be of any composition having any optical properties, such as any values of visible transmission, ultraviolet transmission, infrared transmission, and / or total solar energy transmission. "Float glass" means glass formed by the conventional float process in which molten glass is deposited onto a molten metal bath and cooled in a controlled manner 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 plies 12, 18 may be, for example, clear float glass, or tinted or colored glass, or one ply 12, 18 may be clear glass and the other ply 12, 18 may be colored glass. While not limiting to the present invention, examples of glasses suitable for the first ply 12 and / or second ply 18 are described in U.S. Patent 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 plies 12, 18 may be of any desired dimensions, such as length, width, shape, or thickness. In one exemplary automotive transparency 10, the first and second plies 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 thick. In one non-limiting example, the first ply 12 and / or the second ply 18 may have a visible light transmittance greater than 90%, e.g., greater than 91%, at a reference wavelength of 550 nm. The glass composition for the first ply 12 and / or the second ply 18 may 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.

[0020] In one non-limiting example, one or both plies 12, 18 can have high visible light transmittance at a reference wavelength of 550 nm. By "high visible light transmittance" is meant a visible light transmittance at 550 nm of 85% or more, such as 87% or more, for example 90% or more, such as 91% or more, for example 92% or more, at 5.5 mm equivalent thickness for glass having a sheet thickness of 2 mm to 25 mm. Glasses particularly useful in the practice of the present invention are disclosed in U.S. Patent Nos. 5,030,593 and 5,030,594.

[0021] The laminated windshield may also include an interlayer 24. The interlayer 24 may be of any desired material and may include one or more layers or plies. The interlayer 24 may be disposed on the No. 2 surface 16 and / or the No. 3 surface 20. The interlayer 24 may be a polymeric or plastic material, such as a multilayer thermoplastic material including polyvinyl butyral (PVB), plasticized polyvinyl chloride, or polyethylene terephthalate. Suitable interlayer materials are disclosed, for example, but not limited to, U.S. Pat. Nos. 4,287,107 and 3,762,988. The interlayer 24 may also be a sound-absorbing or sound-deadening material, for example, as described in U.S. Pat. No. 5,796,055. The interlayer 24 may have a solar control coating disposed thereon or incorporated therein, or may include a tinted material that reduces solar energy transmission. The interlayer 24 may be of any thickness suitable for holding the plies 12, 18 together. In one non-limiting example, the intermediate layer 24 is a 0.76 millimeter (mm) thick PVB layer.

[0022] The coating 30 is deposited on at least a portion of a major surface of one of the glass plies 12, 18, such as the inner surface 16 of the outer glass ply 12 or the outer surface 22 of the inner glass ply 18 (FIGS. 1 and 3). The coating 30 may include three or four metal films disposed between dielectric layers sequentially applied to at least a portion of one of the glass plies 12, 18. The coating 30 may be a heat and / or radiation reflective coating or a solar control coating and may have one or more coating layers or films of the same or different composition and / or functionality. The coating 30 may also be a multilayer coating including three or four metal layers. Examples of electrically conductive coatings used to make heatable windows are disclosed in U.S. Patent Nos. 5,653,903 and 5,028,759. Examples of solar radiation control coatings that can be used in the practice of the present invention are found in U.S. Pat. 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 also in U.S. patent application Ser. No. 09 / 058440.

[0023] Non-limiting examples of suitable coatings include one or more antireflective coatings typically comprising a dielectric or antireflective material transparent to visible light, such as a metal oxide or an oxide of a metal alloy. The coating 30 may also comprise three or four metal layers comprising a reflective metal, e.g., a noble metal such as silver or gold, or a combination of alloys thereof, and may further comprise a primer layer or barrier film, such as titanium or a titanium-aluminum alloy, located above and / or optionally below the metal reflective layer. The coating 30 may have three or four metal layers; or at least three metal layers; or four or fewer metal layers. For example, the coating 30 comprises three metal layers, i.e., a triple-metal coating 32. In another non-limiting example, the coating 30 comprises four metal layers, i.e., a quadruple-metal coating 34. In one non-limiting example, one or more of the metal layers may comprise silver. In another non-limiting example, one or more of the metal layers may be a continuous layer. By "continuous layer," it is meant that the coating forms a continuous film of material and does not form separate coating regions.

[0024] Non-limiting examples of materials suitable 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 take the form of a metal, oxide, suboxide, nitride, and / or subnitride of any of the materials listed above. At least a portion of the primer layer is an oxide or nitride. In certain embodiments, the primer layer is deposited in a 100% argon environment. In certain embodiments, a portion of the primer layer is a nitride formed by sputtering a metal or metal alloy in a nitrogen (N2) atmosphere with a specified flow rate to form an 80% N2 atmosphere, the balance being argon. The flow rate is an approximation of the amount of nitrogen (N2) in the atmosphere, but those skilled in the art will recognize that additional N2 may enter the coating chamber because the coating chamber is not sealed from the outside environment. In certain embodiments, a portion of the primer layer is a suboxide formed by sputtering a metal or metal alloy in an oxygen (O2) atmosphere with a specified flow rate to form an 3-7% O2 atmosphere, the balance being argon. The flow rate is an approximation of the amount of oxygen (O2) in the atmosphere, but those skilled in the art will recognize that additional O2 may enter the coating chamber because the coating chamber is not sealed from the outside environment. The chemical structure of the primer material is indicated by the weight percent (wt%) of component x. For certain compositions, the lower limit of one of the materials in the composition may be greater than zero. If the lower limit is "greater than 0," the weight percent of the material is not equal to zero and can be any wt% to the upper wt% limit greater than 0. The composition can change before or after the layer is heated due to reaction with atmospheric substances.These reactions can change the wt% distribution between the materials of the composition. Non-limiting example compositions of the primer layer can be seen in Table 1, where BH is before heating and AH is after heating. Some materials may only have a BH or AH measurement due to which measurement is more important for the final composition. [Table 1]

[0025] For vision panels (e.g., windshields) in the United States, the transparency should also have a visible light transmittance of 70% or greater, e.g., 71% or greater. As those skilled in the art will recognize, providing a coating with sufficient conductivity, transmittance, and color requires balancing several different competing factors. For example, as the distance D between the busbars 96, 98 increases (i.e., the transparency becomes wider from top to bottom), the busbar 96-to-busbar 98 resistance increases. As the busbar 96-to-busbar 98 resistance increases, the power density decreases. To maintain power density, the resistivity of the coating 30 must decrease as the busbar 96-to-busbar 98 distance D increases. One way to decrease resistivity is by increasing the thickness of one or more of the metal layers of the coating 30 and / or by increasing the number of metal layers of the coating 30.

[0026] Coating 30 can be deposited by any conventional method, including, but not limited to, conventional chemical vapor deposition (CVD) and / or physical vapor deposition (PVD) methods. Examples of CVD methods include spray pyrolysis. Examples of PVD methods include electron beam evaporation and vacuum sputtering (e.g., magnetron sputter vapor deposition (MSVD)). Other coating methods, including, but not limited to, sol-gel deposition, can also be used. In one non-limiting example, coating 30 can be deposited by MSVD. Examples of MSVD coating devices and methods are well understood by those skilled in the art and are described, for example, in U.S. Patent 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 process, a metal or metal alloy oxide can be deposited by sputtering a metal or metal alloy containing cathode in an oxygen-containing atmosphere to deposit a metal oxide or metal alloy oxide film on the surface of a substrate. In one embodiment, the coating 30 is deposited over all or substantially all of the surface, i.e., not to form discrete coating regions. At least one coating 30 can be deposited on a flat substrate, which can then be curved or shaped by any conventional method, such as by heating. Alternatively, at least one coating 30 can be deposited on a curved surface, i.e., a substrate that is already curved or shaped.

[0027] In an exemplary embodiment, the present invention is a coating useful for a windshield HUD, as shown in Figures 1, 2A, 2B, and 3, where the windshield includes first ply 12 and second ply 18 and interlayer 24. Coating 30 may be disposed on No. 2 surface 16 or No. 3 surface 20, preferably No. 2 surface 16.

[0028] 2A , radiation 36 directed toward transparency 10 is directed such that at least a portion of the radiation 36 is reflected from transparency 10 and directed away from transparency 10 toward the driver's eye 38. The portion of radiation 36 that is not reflected from transparency 10 may be refracted, absorbed, or otherwise transmitted through transparency 10. Because PVB interlayer 24 has a refractive index similar to that of glass plies 12, 18, reflections from the radiation coming from No. 1 surface 14 and No. 4 surface 22 create a ghost image in the driver's eye 38 when the glass plies 12, 18 and PVB interlayer 24 within the windshield are parallel to one another.

[0029] 2B, the first ply 12 may not be parallel to the second ply 18. Preferably, the interlayer 24 has a wedge shape, with one side of the interlayer 24 being thicker than the other, to eliminate ghost images when exposed to radiation 36. The wedge shape of the interlayer 24 may be configured so that the two reflected images from the No. 1 surface 14 and the No. 4 surface 22 overlap at the driver's eye 38, eliminating ghosting.

[0030] Because a silver coating reduces energy and improves solar performance, a silver coating may be applied to the No. 2 surface 16 or the No. 3 surface 22, preferably the No. 2 surface 16, as described above. However, it is believed that a silver coating applied to the No. 2 surface 16 would create a strong light reflection from the radiation 36, resulting in a triple ghost image in the driver's eye 38. Referring to FIG. 3, to eliminate reflections from the surface, the specific coating 30, including the metal layer, must be designed so that the total internal reflection to the eye 38 is sufficiently low or the same as that of the transparency 10 of FIG. 2B. The specific coating 30 must also be achromatic in the visible spectral range (400 nm to 700 nm), which can be adjusted using various dielectric layers. When using the specific coating 30, the interlayer 24 does not need to be wedge-shaped to avoid ghosting issues because other aspects of the design counteract ghosting. Therefore, the interlayer 24 can be a uniform thickness layer in other configurations of the transparency 10.

[0031] Coating 30 may be a triple metal coating 33, e.g., three metal layers, or a quadruple metal coating 34 (e.g., four metal layers). Non-limiting exemplary coatings suitable for triple metal coating 33 are shown in Figures 4, 6, and 8. Non-limiting exemplary coatings suitable for quadruple coating 34 are shown in Figures 5, 7, and 9.

[0032] The exemplary coating 30 includes three metal layers (i.e., tri-metal coating 33) disposed between dielectric layers, as shown in FIG. 4 . The tri-metal coating 33 includes a base layer or first dielectric layer 40 disposed on or in direct contact with at least a portion of a major surface of the substrate (e.g., No. 2 surface 16 of first ply 12 or No. 3 surface 20 of second ply 18). A first metal layer 52 is disposed on or in direct contact with at least a portion of first dielectric layer 40. An optional first primer layer 54 may be disposed on or in direct contact with at least a portion of first metal layer 52. A second dielectric layer 60 is disposed on or in direct contact with the optional first primer layer 54 or first metal layer 52. A second metal layer 72 is disposed on or in direct contact with at least a portion of second dielectric layer 60. An optional second primer layer 74 may be disposed on or in direct contact with the second metal layer 72. A third dielectric layer 80 may be disposed on or in direct contact with the optional second primer layer 74 or the second metal layer 72. A third metal layer 92 may be disposed on at least a portion of the third dielectric layer 80. An optional third primer layer 94 may be disposed on at least a portion of the third metal layer 92. A fourth dielectric layer 100 may be disposed on at least a portion of the third metal layer 92 or the optional third primer layer 94. An optional outermost protective layer 200 may be disposed on or in direct contact with the fourth dielectric layer 100.

[0033] The exemplary coating 30 includes four metal layers (i.e., a quadruple metal coating 34) disposed between dielectric layers, as shown in FIG. 5 . The quadruple metal coating 34 includes a base layer or first dielectric layer 40 disposed on or in direct contact with at least a portion of a major surface of the substrate (e.g., the No. 2 surface 16 of the first ply 12 or the No. 3 surface 20 of the second ply 18). A first metal layer 52 is disposed on or in direct contact with at least a portion of the first dielectric layer 40. An optional first primer layer 54 may be disposed on or in direct contact with at least a portion of the first metal layer 52. A second dielectric layer 60 is disposed on or in direct contact with the optional first primer layer 54 or the first metal layer 52. A second metal layer 72 is disposed on or in direct contact with at least a portion of the second dielectric layer 60. An optional second primer layer 74 may be disposed on or in direct contact with the second metal layer 72. A third dielectric layer 80 may be disposed on or in direct contact with the optional second primer layer 74 or the second metal layer 72. A third metal layer 92 may be disposed on at least a portion of the third dielectric layer 80. An optional third primer layer 94 may be disposed on at least a portion of the third metal layer 92. A fourth dielectric layer 100 is disposed on at least a portion of the third metal layer 92 or the optional third primer layer 94. A fourth metal layer 112 is disposed on at least a portion of the fourth dielectric layer 100. An optional primer layer 114 is formed on at least a portion of the fourth metal layer 112. A fifth dielectric layer 120 is formed on at least a portion of the fourth metal layer 112 or the optional fourth primer layer 114. An optional outermost protective layer 200 may be disposed on or in direct contact with the fifth dielectric layer 120 .

[0034] The dielectric layer may include one or more films of an antireflective material and / or a dielectric material, such as, but not limited to, a metal oxide, a metal alloy oxide, a nitride, an oxynitride, or a mixture thereof. The first dielectric layer may be transparent to visible light. Examples of metal oxides suitable for the first dielectric layer include oxides of titanium, niobium, zinc, indium, tin, magnesium, gallium, vanadium, aluminum, silicon, alloys thereof, mixtures thereof, and combinations thereof. These metal oxides may contain small amounts of other materials, such as manganese in bismuth oxide or tin in indium oxide. Alternatively, oxides or metal alloys or metal mixtures, such as oxides containing zinc and tin (e.g., zinc stannate); oxides of indium-tin alloys; silicon nitride; aluminum silicon nitride; or aluminum nitride, may be used. Additionally, metal-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, can be used. In one non-limiting example, the first film 42 of the first dielectric layer can be a zinc / tin alloy oxide formed on at least a portion of the substrate (e.g., the No. 2 surface 16 of the first ply 12 or the No. 3 surface 20 of the second ply 18). The zinc / tin alloy oxide can be obtained from MSVD from a zinc and tin cathode, which can contain zinc and tin in proportions of 10 wt% to 90 wt% zinc and 90 wt% to 10 wt% tin. One suitable metal alloy oxide that can be present in the first film 42 of the first dielectric layer is zinc stannate. "Zinc stannate" refers to a metal alloy oxide containing Zn x Sn 1-x O 2-x (Formula 1) where "x" varies from greater than 0 to less than 1. For example, "x" can be greater than 0 and can be any fraction or decimal number from greater than 0 to less than 1. For example, when x=2 / 3, Formula 1 represents Zn 2 / 3 Sn 1 / 3 O 4 / 3 which is more commonly written as Zn2SnO4. Zinc stannate-containing films have a large amount of one or more of the forms of Formula 1 in the film.

[0035] The first dielectric layer second film 44 is formed on at least a portion of the first dielectric layer first film 42 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, or a combination thereof. In one non-limiting example, the first dielectric layer second film 44 may be a zinc-containing film, such as zinc oxide. The zinc oxide film may be deposited from a zinc cathode that includes other materials to improve the sputtering properties of the cathode. For example, the zinc cathode may include a small amount of tin (e.g., less than 10 wt%, e.g., greater than 0 to 5 wt%) to improve sputtering. In this case, the resulting zinc oxide film would contain a small percentage of tin oxide, e.g., 0 to less than 10 wt% tin oxide, e.g., 0 to 5 wt% tin oxide. An oxide layer sputtered from a zinc / tin cathode containing 95 wt% zinc and 5 wt% tin, or preferably 90 wt% zinc and 10 wt% tin, is referred to as a zinc oxide film. A small amount of tin in the cathode (e.g., less than 10 wt%) is believed to form a small amount of tin oxide in the primarily zinc oxide-containing second film 44 of the first dielectric layer. One non-limiting example is one in which the first film of first dielectric layer 42 is zinc stannate and the second film of first dielectric layer 44 is zinc oxide, over at least a portion of the first film of first dielectric layer 42.

[0036] In a non-limiting exemplary embodiment, the second film 44 is a film comprising 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 sputtering characteristics of the cathode. 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 of tin (e.g., less than 10 wt %, e.g., greater than 0 to 5 wt %) 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 is considered to contain a small percentage of tin oxide, for example, 0 wt% to less than 10 wt% tin oxide, for example, 0 wt% to 5 wt% tin oxide.

[0037] One non-limiting example is where the first dielectric layer first film 42 is zinc stannate and the first dielectric layer second film 44 on at least a portion of the first dielectric layer first film 42 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.

[0038] The first dielectric layer 40 of the triple metal coating 33 may have a total thickness ranging from 10 nm to 50 nm, preferably from 12 nm to 45 nm, more preferably from 15 nm to 42 nm, and most preferably from 18 nm to 40 nm. The first dielectric layer 40 of the quadruple metal coating 34 may have a total thickness ranging from 20 nm to 55 nm, preferably from 25 nm to 50 nm, more preferably from 30 nm to 45 nm, and most preferably from 35 nm to 40 nm.

[0039] In one non-limiting example, the first dielectric layer 40 includes a seed film (not shown) in direct contact with the first metal layer 52. 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, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof. In one example, the seed film may include aluminum zinc, vanadium zinc, zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another example, the seed film may include gallium zinc, indium zinc, indium tin, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. Non-limiting example compositions of seed films can be found in Table 2. In one particular embodiment, a portion of the seed film is formed in an O2 atmosphere with a particular flow rate to form an atmosphere of 1% to 70% O2, with the balance being argon. The flow rate is an approximation of the amount of O2 in the atmosphere, but one skilled in the art will recognize that additional O2 may enter the coating chamber because the coating chamber is not sealed from the outside environment. In one non-limiting example, the second film 44 of the first dielectric layer is the seed film. In another example, the seed film is V x Zn 1-x In another embodiment, the seed film comprises an Al oxide. x Zn 1-x In another embodiment, the seed film comprises a Ga oxide. x Zn 1-x In another embodiment, the seed film comprises an In oxide. x Zn 1-x In another embodiment, the seed film comprises a Sn oxide. x In 1-x In another embodiment, the seed film comprises Ag deposited in an oxygen / argon gas environment. In another embodiment, the seed film comprises Al x Ag 1-xThe seed film may have a total thickness ranging from 0.5 nm to 10 nm, preferably from 0.75 nm to 8 nm, and more preferably from 0.9 nm to 6 nm. In some embodiments, the first dielectric layer 40 includes a first film 42, a second film 44, and a seed film. [Table 2]

[0040] A first metal layer 52 may be deposited on at least a portion of the first dielectric layer 40. The first metal layer 52 may include a reflective metal, such as, but not limited to, metallic gold, silver, alloys thereof, mixtures thereof, or combinations thereof. The first metal layer 52 is a continuous layer. In one example, the first metal layer 52 of the tri-metal coating 33 includes metallic silver. The first metal layer 52 of the tri-metal coating 33 may have a total thickness ranging from 5 nm to 20 nm, preferably from 5 nm to 17.5 nm, more preferably from 7 nm to 15 nm, and most preferably from 8 nm to 10.5 nm.

[0041] In one embodiment, the first metal layer 52 of the quadruple metal coating 34 comprises metallic silver. In another embodiment, the first metal layer 52 of the quadruple metal coating 34 is a continuous layer. The first metal layer 52 of the quadruple metal coating 34 may have a total thickness ranging from 2 nm to 20 nm, preferably from 6 nm to 18 nm, more preferably from 9 nm to 12 nm, and most preferably from 9.5 nm to 10 nm.

[0042] An optional first primer layer 54 may be deposited over at least a portion of the first metal layer 52. The first primer layer 54 may be an oxygen-scavenging material, such as titanium, that may be sacrificed during the deposition process to prevent decomposition or oxidation of the first metal layer during the sputtering process or subsequent heating process. The oxygen-scavenging material may be selected to oxidize before the material of the first metal layer 52. The composition of the first primer layer 54 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, where the primer is deposited as a metal and subsequently oxidized. 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 54, it will preferably oxidize before the oxidation of the underlying metal layer. In one embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 is titanium. In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 includes silver zinc. In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 includes zinc. In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 includes Ag x Zn 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 is Ag x Zn 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 is Al oxide. x Zn 1-xIn another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises In oxide. x Zn 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises a Ga oxide. x Zn 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises V x Zn 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises Al oxide. x Ti 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises Al oxide. x Nb 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises Al oxide. x Nb 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises W. x Nb 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises W. x Ti 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises Ti oxide. x Ta 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises Ti oxide. x Nb 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises Ti oxide. x Nb 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises Nb x Zr 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises Ta oxide. x W1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises W oxide. x Nb 1-x In another embodiment, the first primer layer 54 of the triple and quadruple metal coatings 33, 34 comprises Zn oxide. x Ti 1-x The first primer layer 54 of the triple and quadruple metal coatings 33, 34 has a total thickness in the range of 0.5 nm to 5 nm, preferably 1.0 nm to 2.5 nm, and more preferably 1.5 nm to 2.5 nm.

[0043] The second dielectric layer 60 may be deposited on at least a portion of the first metal layer 52 or the optional first primer layer 54. The second dielectric layer 60 may also include one or more materials discussed above with respect to the first dielectric layer 40. The second dielectric layer 60 may include a second dielectric layer first film 62 deposited on the first metal layer 52 or the optional first primer layer 54. The second dielectric layer first film 62 includes an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys, mixtures, or combinations thereof. The second dielectric layer first film 62 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 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.

[0044] A second film 64 of the second dielectric layer can 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 the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. In one non-limiting example, the second film 64 of the second dielectric layer is zinc stannate.

[0045] An optional third film 66 of the second dielectric layer may be deposited on at least a portion of the second film 64 of the second dielectric layer. The optional third film 66 of the second dielectric layer may comprise an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys, mixtures, or combinations thereof. The optional third film 66 of the second 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 optional third film 66 of the second dielectric layer comprises zinc oxide. In another embodiment, the third film 66 of the second dielectric layer comprises indium-doped zinc oxide. In another embodiment, the third film 66 of the second dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the third film 66 of the second dielectric layer comprises indium-doped tin oxide. In another embodiment, the third film 66 of the second dielectric layer comprises vanadium-doped zinc oxide. In another embodiment, the first dielectric layer 40 or the second dielectric layer 60 comprises a silicon nitride film.

[0046] One non-limiting example 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 on at least a portion of the second film 64 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.

[0047] The second dielectric layer 60 of the triple metal coating 33 may have a total thickness ranging from 40 nm to 110 nm, preferably from 50 nm to 100 nm, more preferably from 55 nm to 80 nm, and most preferably from 67 nm to 76 nm. The second dielectric layer 60 of the quadruple metal coating 34 may have a total thickness ranging from 60 nm to 100 nm, preferably from 65 nm to 95 nm, more preferably from 70 nm to 90 nm, and most preferably from 74 nm to 80 nm.

[0048] In one non-limiting example, the second dielectric layer 60 includes a seed film disposed in direct contact with the second metal layer 72, not shown in the drawings. 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, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof. In one example, the seed film may include aluminum zinc, vanadium zinc, zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another example, the seed film may include gallium zinc, indium zinc, indium tin, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. Non-limiting example compositions of seed films can be found in Table 2. In another example, the seed film may include Al x Zn 1-x In another embodiment, the seed film comprises a Ga oxide. x Zn 1-x In another embodiment, the seed film comprises an In oxide. x Zn 1-x In another embodiment, the seed film comprises a Sn oxide. x In 1-x In another embodiment, the seed film comprises Ag deposited in an oxygen / argon gas environment. In another embodiment, the seed film comprises Al x Ag 1-xThe seed film may have a total thickness ranging from 0.5 nm to 10 nm, preferably from 0.75 nm to 8 nm, and more preferably from 0.9 nm to 6 nm. In some embodiments, the second dielectric layer 60 comprises a first film 62, a second film 64, and a seed film. In some embodiments, the second dielectric layer 60 comprises a first film 62, a second film 64, a third film 66, and a seed film.

[0049] The second metal layer 72 can be deposited over at least a portion of the second dielectric layer 60. The second metal layer 72 is a continuous layer. The second metal layer 72 can include any one or more of the reflective materials described above with respect to the first metal layer 52. In one non-limiting example, the second metal layer 72 includes metallic silver. The second metal layer 72 of the tri-metal coating 33 can have a total thickness ranging from 5 nm to 20 nm, preferably from 5 nm to 15 nm, more preferably from 7.5 nm to 12.5 nm, and most preferably from 8.5 nm to 11.5 nm.

[0050] In one embodiment, the second metal layer 72 of the quadruple metal coating 34 comprises metallic silver. In another embodiment, the second metal layer 72 of the quadruple metal coating 34 is a continuous layer. The second metal layer 72 of the quadruple metal coating 34 may have a total thickness ranging from 2 nm to 20 nm, preferably from 6 nm to 18 nm, more preferably from 8 nm to 15 nm, and most preferably from 9 nm to 12 nm.

[0051] An optional second primer layer 74 may be deposited over at least a portion of the second metal layer 72. The second primer layer 74 may be any of the materials described above with respect to the first primer layer 54. In one non-limiting example, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 includes titanium. In another example, the optional second primer layer 74 includes silver zinc. In another example, the second primer layer 74 includes zinc. In another example, the optional second primer layer 74 of the triple and quadruple metal coatings 33, 34 includes Ag x Zn 1-x In another embodiment, the optional second primer layer 74 of the triple and quadruple metal coatings 33, 34 includes Agx Zn 1-x In another embodiment, the optional second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises Al x Zn 1-x In another embodiment, the optional second primer layer 74 comprises an In oxide. x Zn 1-x In another embodiment, the optional second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises a Ga oxide. x Zn 1-x In another embodiment, the optional second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises a V x Zn 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises Al oxide. x Ti 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises Al oxide. x Nb 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises Al oxide. x Nb 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises W. x Nb 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises W. x Ti 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises Ti oxide. x Ta 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises Ti oxide. x Nb 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises Ti oxide. x Nb 1-xIn another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises Nb x Zr 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises Ta oxide. x W 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises W oxide. x Nb 1-x In another embodiment, the second primer layer 74 of the triple and quadruple metal coatings 33, 34 comprises Zn oxide. x Ti 1-x The optional second primer layer 74 has a total thickness in the range of 0.5 nm to 5 nm, preferably 1.0 nm to 2.5 nm, and more preferably 1.5 nm to 2.5 nm.

[0052] The third dielectric layer 80 may be deposited on at least a portion of the second metal layer 72 or the optional second primer layer 74. The third dielectric layer 80 may also include one or more materials discussed above with respect to the first and second dielectric layers. In one non-limiting example, the third dielectric layer 80 includes a third dielectric layer first film 82. The third dielectric layer first film 82 includes an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys, mixtures, or combinations thereof. The third dielectric layer first film 82 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 example, the third dielectric layer first film 82 includes zinc oxide or 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.

[0053] The third dielectric layer second film 84 can be deposited on at least a portion of the third dielectric layer first film 82. The third dielectric layer second film 84 comprises an oxide, nitride, oxynitride, or mixtures thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. In one embodiment, the third dielectric layer second film 84 comprises zinc stannate. In another embodiment, the third dielectric layer second film 84 comprises zinc oxide.

[0054] The optional third film of the third dielectric layer 86 may be deposited on at least a portion of the second film 84 of the third dielectric layer. The optional third film of the third dielectric layer 86 may include an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys, mixtures, or combinations thereof. The optional third film of the third dielectric layer 86 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 optional third film of the third dielectric layer 86 includes zinc oxide. In another embodiment, the third film of the third dielectric layer 86 includes aluminum-doped zinc oxide. In another embodiment, the third film of the third dielectric layer 86 includes aluminum-doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer comprises indium-doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer comprises indium-doped tin oxide. In another embodiment, the third film 86 of the third dielectric layer comprises vanadium-doped zinc oxide.

[0055] One non-limiting example is where the first film 82 of the third dielectric layer comprises zinc oxide or zinc stannate, the second film 84 of the third dielectric layer comprises zinc oxide or zinc stannate, and the third film 86 of the third dielectric layer on at least a portion of the second film 84 of the third dielectric layer comprises 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.

[0056] The third dielectric layer 80 of the triple metal coating 33 may have a total thickness ranging from 40 nm to 110 nm, preferably from 50 nm to 100 nm, more preferably from 65 nm to 80 nm, and most preferably from 71 nm to 75 nm. The third dielectric layer 80 of the quadruple metal coating 34 may have a total thickness ranging from 55 nm to 90 nm, preferably from 60 nm to 85 nm, more preferably from 68 nm to 80 nm, and most preferably from 70 nm to 75 nm.

[0057] In one non-limiting example, the third dielectric layer 86 includes a seed film disposed in direct contact with the third metal layer 92, not shown in the drawings. 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, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof. In one example, the seed film may include aluminum zinc, vanadium zinc, zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another example, the seed film may include gallium zinc, indium zinc, indium tin, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. Non-limiting example compositions of seed films can be found in Table 2. In another example, the seed film may include V x Zn 1-x In another embodiment, the seed film comprises an Al oxide. x Zn 1-x In another embodiment, the seed film comprises a Ga oxide. x Zn 1-x In another embodiment, the seed film comprises an In oxide. x Zn 1-x In another embodiment, the seed film comprises a Sn oxide. x In 1-x In another embodiment, the seed film comprises Ag deposited in an oxygen / argon gas environment. In another embodiment, the seed film comprises Al x Ag 1-xThe seed film may have a total thickness ranging from 0.5 nm to 10 nm, preferably from 0.75 nm to 8 nm, and more preferably from 0.9 nm to 6 nm. In some embodiments, the third dielectric layer 80 comprises a first film 82, a second film 84, and a seed film. In some embodiments, the third dielectric layer 80 comprises a first film 82, a second film 84, a third film 86, and a seed film. In some embodiments, the third dielectric layer 80 comprises a first film 82, a second film 84, and a third film 86.

[0058] A third metal layer 92 can be deposited over at least a portion of the third dielectric layer 80. The third metal layer 92 is a continuous layer. The third metal layer 92 can include any one or more of the reflective materials described above with respect to the first metal layer 52. In one non-limiting example, the third metal layer 92 includes metallic silver. The third metal layer 92 of the tri-metal coating 33 can have a total thickness ranging from 1 nm to 20 nm, preferably from 5 nm to 20 nm, more preferably from 7.5 nm to 15 nm, and most preferably from 7.5 nm to 10.5 nm.

[0059] In one embodiment, the third metal layer 92 of the quadruple metal coating 34 comprises metallic silver. In another embodiment, the third metal layer 92 of the quadruple metal coating 34 is a continuous layer. The third metal layer 92 of the quadruple metal coating 34 may have a total thickness ranging from 2 nm to 20 nm, preferably from 6 nm to 18 nm, more preferably from 8 nm to 15 nm, and most preferably from 9 nm to 12 nm.

[0060] In one non-limiting example, coating 30 includes only first, second, and third metal layers (FIGS. 4, 6, and 8). No additional metal layers are present in coating 30. Each metal layer has a thickness. In one non-limiting example, the total thickness of metal layers 33 of the tri-metal coating ranges from 10 nm to 60 nm, preferably from 15 nm to 50 nm, most preferably from 20 nm to 40 nm, and most preferably from 25 nm to 31 nm. In cases where the primer layer includes aluminum and zinc, the total thickness of metal layers 33 of the tri-metal coating ranges from 10 nm to 65 nm, preferably from 15 nm to 55 nm, more preferably from 20 nm to 45 nm, and most preferably from 25 nm to 36 nm.

[0061] An optional third primer layer 94 may be deposited over at least a portion of the third metal layer 92. The third primer layer 94 may be any of the materials described above with respect to the first primer layer 54. In one non-limiting example, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 includes titanium. In another example, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 includes silver zinc. In another example, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 includes zinc. In another example, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 includes Ag x Zn 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Ag x Zn 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Al oxide. x Zn 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises In oxide. x Zn 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises a Ga oxide. x Zn 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Vx Zn 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Al oxide. x Ti 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Al oxide. x Nb 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Al oxide. x Nb 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises W. x Nb 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises W. x Ti 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Ti oxide. x Ta 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Ti oxide. x Nb 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Ti oxide. x Nb 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Nb x Zr 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Ta oxide. x W 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises W oxide. x Nb 1-x In another embodiment, the third primer layer 94 of the triple and quadruple metal coatings 33, 34 comprises Zn oxide. x Ti 1-x Contains oxides.

[0062] The third primer layer 94 of the triple and quadruple metal coatings 33, 34 has a total thickness in the range of 0.5 nm to 5 nm, preferably 1.0 nm to 2.5 nm, and more preferably 1.5 nm to 2.5 nm.

[0063] The fourth dielectric layer 100 may be deposited on at least a portion of the third metal layer 92 or the optional third primer layer 94. The fourth dielectric layer 100 may also include one or more materials discussed above with respect to the first, second, and third dielectric layers 40, 60, and 80. In one non-limiting example, the fourth dielectric layer 100 includes a fourth dielectric layer first film 102. The fourth dielectric layer first film 102 includes an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys, mixtures, or combinations thereof. The fourth dielectric layer first film 102 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 first film 102 of the fourth dielectric layer comprises zinc oxide or zinc stannate. In another embodiment, the first film 102 of the fourth dielectric layer comprises aluminum-doped zinc oxide. In another embodiment, the first film 102 of the fourth dielectric layer comprises indium-doped zinc oxide. In another embodiment, the first film 102 of the fourth dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the first film 102 of the fourth dielectric layer comprises indium-doped tin oxide. In another embodiment, the first film 102 of the fourth dielectric layer comprises vanadium-doped zinc oxide.

[0064] The fourth dielectric layer second film 104 can be deposited on at least a portion of the fourth dielectric layer first film 102. The fourth dielectric layer second film 104 comprises an oxide, nitride, oxynitride, or mixtures thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys, mixtures, or combinations thereof. In one embodiment, the fourth dielectric layer second film 104 comprises zinc stannate or zinc oxide. In some embodiments, the first film 102 and the second film 104 are the only films in the fourth dielectric layer 100.

[0065] The optional third film 106 of the fourth dielectric layer may be deposited on at least a portion of the second film 104 of the fourth dielectric layer. The optional third film 106 of the fourth dielectric layer may comprise an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys, mixtures, or combinations thereof. The optional third film 106 of the fourth 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 example, the optional third film 106 of the fourth dielectric layer comprises zinc oxide. In another example, the optional third film 106 of the fourth dielectric layer comprises silicon nitride or silicon oxynitride. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises aluminum-doped zinc oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises indium-doped zinc oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises indium-doped tin oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises vanadium-doped zinc oxide.

[0066] One non-limiting example is where the first film 102 of the fourth dielectric layer comprises zinc oxide or zinc stannate, the second film 104 of the fourth dielectric layer comprises zinc oxide or zinc stannate, and the third film 106 of the fourth dielectric layer on at least a portion of the second film 104 of the third dielectric layer comprises 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.

[0067] The fourth dielectric layer 100 of the triple metal coating 33 may have a total thickness ranging from 10 nm to 50 nm, preferably from 15 nm to 40 nm, more preferably from 20 nm to 35 nm, and most preferably from 27 nm to 31 nm. The fourth dielectric layer 100 of the quadruple metal coating 34 may have a total thickness ranging from 45 nm to 80 nm, preferably from 50 nm to 75 nm, more preferably from 55 nm to 70 nm, and most preferably from 60 nm to 65 nm.

[0068] The quadruple metal coating 34 of Figures 5, 7, and 9 includes additional layers. In one non-limiting example, the fourth dielectric layer 100 of the quadruple metal coating 34 includes a seed film disposed in direct contact with the fourth metal layer 112, not shown in the drawings. The seed film may include aluminum, aluminum silver, aluminum zinc, 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, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof. The seed film may include aluminum zinc, vanadium zinc, zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another example, the seed film may include gallium zinc, indium zinc, indium tin, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. Non-limiting example compositions of the seed film can be found in Table 2. In another example, the seed film may be V x Zn 1-x In another embodiment, the seed film comprises an Al oxide.x Zn 1-x In another embodiment, the seed film comprises a Ga oxide. x Zn 1-x In another embodiment, the seed film comprises an In oxide. x Zn 1-x In another embodiment, the seed film comprises a Sn oxide. x In 1-x In another embodiment, the seed film comprises Ag deposited in an oxygen / argon gas environment. In another embodiment, the seed film comprises Al x Ag 1-x In one non-limiting example, the third film 106 of the fourth dielectric layer of the quadruple metal coating 34 is a seed film. The seed film can have a total thickness ranging from 0.5 nm to 10 nm, preferably from 0.75 nm to 8 nm, and more preferably from 0.9 nm to 6 nm. In some examples, the fourth dielectric layer 100 includes a first film 102, a second film 104, and a seed film. In some examples, the fourth dielectric layer 100 includes a first film 102, a second film 104, a third film 106, and a seed film.

[0069] The fourth metal layer 112 of the quadruple metal coating 34 can be deposited on at least a portion of the fourth dielectric layer 100. The fourth metal layer 112 is a continuous layer. The fourth metal layer 112 can include any one or more of the reflective materials described above with respect to the first metal layer 52. In one non-limiting example, the fourth metal layer 112 of the quadruple metal coating 34 includes metallic silver. The fourth metal layer 112 of the quadruple metal coating 34 can have a total thickness ranging from 2 nm to 20 nm, preferably from 4 nm to 15 nm, more preferably from 6 nm to 11 nm, and most preferably from 7 nm to 10 nm.

[0070] An optional fourth primer layer 114 may be deposited over at least a portion of the fourth metal layer 112 of the quadruple metal coating 34. The fourth primer layer 114 may be any of the materials described above with respect to the first primer layer 54. In one non-limiting example, the fourth primer layer 114 includes titanium. In another example, the fourth primer layer 114 includes silver zinc. In another example, the fourth primer layer 114 includes zinc. In another example, the fourth primer layer 114 includes Ag x Zn 1-x In another embodiment, the fourth primer layer 114 comprises Ag x Zn 1-x In another embodiment, the fourth primer layer 114 comprises an Al oxide. x Zn 1-x In another embodiment, the fourth primer layer 114 comprises an In oxide. x Zn 1-x In another embodiment, the fourth primer layer 114 comprises a Ga oxide. x Zn 1-x In another embodiment, the fourth primer layer 114 comprises a V oxide. x Zn 1-x In another embodiment, the fourth primer layer 114 of the quadruple metal coating 34 comprises an Al oxide. x Ti 1-x In another embodiment, the fourth primer layer 114 of the quadruple metal coating 34 comprises an Al oxide. x Nb 1-x In another embodiment, the fourth primer layer 114 of the quadruple metal coating 34 comprises an Al oxide. x Nb 1-x In another embodiment, the fourth primer layer 114 of the quaternary metal coating 34 comprises W. x Nb 1-x In another embodiment, the fourth primer layer 114 of the quaternary metal coating 34 comprises W. x Ti 1-x In another embodiment, the fourth primer layer 114 of the quaternary metal coating 34 comprises a Ti oxide. x Ta 1-xIn another embodiment, the fourth primer layer 114 of the quaternary metal coating 34 comprises a Ti oxide. x Nb 1-x In another embodiment, the fourth primer layer 114 of the quaternary metal coating 34 comprises a Ti oxide. x Nb 1-x In another embodiment, the fourth primer layer 114 of the quadruple metal coating 34 comprises Nb x Zr 1-x In another embodiment, the fourth primer layer 114 of the tetra-metal coating 34 comprises Ta oxide. x W 1-x In another embodiment, the fourth primer layer 114 of the tetra-metal coating 34 comprises W oxide. x Nb 1-x In another embodiment, the fourth primer layer 114 of the quadruple metal coating 34 comprises Zn oxide. x Ti 1-x Contains oxides.

[0071] The fourth primer layer 114 has a total thickness in the range of 0.5 nm to 5 nm, preferably 1.0 nm to 2.5 nm, and more preferably 1.5 nm to 2.5 nm.

[0072] The fifth dielectric layer 120 can be deposited on at least a portion of the fourth metal layer 112 or the optional fourth primer layer 114. The fifth dielectric layer 120 can also include one or more materials discussed above with respect to the first, second, third, and fourth dielectric layers. In one non-limiting example, the fifth dielectric layer 120 includes a fifth dielectric layer first film 122. The fifth dielectric layer first film 122 includes an oxide, nitride, oxynitride, or mixtures thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys, mixtures, or combinations thereof. In one example, the fifth dielectric layer first film 122 includes zinc oxide or zinc stannate.

[0073] The fifth dielectric layer second film 124 may be deposited on at least a portion of the fifth dielectric layer first film 122. The fifth dielectric layer second film 124 may comprise an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, aluminum, alloys, mixtures, or combinations thereof. The fifth dielectric layer second film 124 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 fifth dielectric layer second film 124 comprises zinc stannate or zinc oxide. In another embodiment, the fifth dielectric layer second film 124 comprises silicon nitride or silicon oxynitride. In another embodiment, the fifth dielectric layer second film 124 comprises aluminum-doped zinc oxide. In another embodiment, the second film 124 of the fifth dielectric layer comprises indium-doped zinc oxide. In another embodiment, the second film 124 of the fifth dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the second film 124 of the fifth dielectric layer comprises indium-doped tin oxide. In another embodiment, the second film 124 of the fifth dielectric layer comprises vanadium-doped zinc oxide.

[0074] An optional third film of the fifth dielectric layer may be deposited on at least a portion of the second film 124 of the fifth dielectric layer. The optional third film of the fifth dielectric layer may comprise an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys, mixtures, or combinations thereof. The optional third film of the fifth 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 non-limiting example, the optional third film of the fifth dielectric layer comprises zinc oxide. In another example, the optional third film of the fifth dielectric layer comprises silicon nitride or silicon oxynitride. In another example, the optional third film of the fifth dielectric layer comprises titanium oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises aluminum doped zinc oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises indium doped zinc oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises gallium doped zinc oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises indium doped tin oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises vanadium doped zinc oxide.

[0075] One non-limiting example of the quaternary metal coating 34 is one in which the first film 122 of the fifth dielectric layer comprises zinc oxide or zinc stannate, and the second film 124 of the fifth dielectric layer on at least a portion of the second film 124 of the fifth 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.

[0076] The fifth dielectric layer 120 of the quadruple metal coating 34 may have a total thickness in the range of 10 nm to 45 nm, preferably 15 nm to 40 nm, more preferably 20 nm to 35 nm, and most preferably 23 nm to 28 nm.

[0077] In one non-limiting example, coating 30 includes first, second, third, and fourth metal layers. The metal layers are continuous metal layers. The metal layers can include only silver or only silver and gold. Each metal layer has a thickness. In one non-limiting example, the total thickness of the metal layers of quadruple metal coating 34 ranges from 10 nm to 60 nm, preferably from 20 nm to 50 nm, most preferably from 30 nm to 45 nm, and most preferably from 35 nm to 40 nm. In cases where the primer layer includes aluminum and zinc, the total thickness of the metal layers of quadruple metal coating 34 ranges from 10 nm to 65 nm, preferably from 20 nm to 60 nm, most preferably from 40 nm to 55 nm, and most preferably from 35 nm to 45 nm.

[0078] The triple and quadruple metal coatings 33, 34 may include an outermost protective layer 200, which, for example, in the non-limiting examples shown in FIGS. 4-7 , is deposited over at least a portion of the fourth or fifth dielectric layer 100, 120 to help protect underlying layers, such as metal layers, from mechanical and chemical attack during processing. The outermost protective layer 200 may be an oxygen barrier coating layer to prevent or reduce the migration of ambient oxygen to layers underlying the coating, such as during heating or bending. The outermost protective layer 200 may be of any desired material or mixture of materials and may be composed of one or more protective films. In one exemplary embodiment, the outermost protective layer 200 may include a single layer comprising one or more metal oxide materials, such as, but not limited to, oxides of aluminum, silicon, or mixtures thereof. For example, the outermost protective coating may comprise alumina in the range of 0 wt% to 100 wt% and / or silica in the range of 100 wt% to 0 wt%, for example 5 wt% to 95 wt% alumina and 95 wt% to 5 wt% silica, for example 10 wt% to 90 wt% alumina and 90 wt% to 10 wt% silica, for example 15 wt% to 90 wt% alumina and 85 wt% to 10 wt% silica, for example 50 wt% to 75 wt% alumina and 50 wt% to 25 wt% silica, for example 50 wt% to 70 wt% alumina and 50 wt% to 30 wt% silica, for example 35 wt% to 50 wt% alumina and 50 wt% to 25 ... The coating layer may comprise a single coating layer containing t% to 100 wt% alumina and 65 wt% to 0 wt% silica, for example, 70 wt% to 90 wt% alumina and 30 wt% to 10 wt% silica, for example, 75 wt% to 85 wt% alumina and 25 wt% to 15 wt% silica, for example, 88 wt% alumina and 12 wt% silica, for example, 65 wt% to 75 wt% alumina and 35 wt% to 25 wt% silica, for example, 70 wt% alumina and 30 wt% silica, for example, 60 wt% to less than 75 wt% alumina and more than 25 wt% to 40 wt% silica. Other materials, for example, aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium, and / or oxides thereof, may also be present, for example, to adjust the refractive index of the outermost protective layer 200.In one non-limiting example, the refractive index of the outermost protective layer 200 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.

[0079] In one non-limiting example, the outermost protective layer 200 is a combination silica and alumina coating. The outermost protective layer 200 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 oxide aluminum outermost protective layer 200 can be 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 200 comprises 15 wt % alumina and 85 wt % silica. In another embodiment, the outermost protective layer 200 comprises SiO2, Al2O3, SiAlO, alloys thereof, and mixtures thereof.

[0080] In one non-limiting example, the outermost protective layer 200 is composed of silicon nitride (Si3N4), silicon oxynitride (SiON), silicon aluminum nitride (SiAlN), silicon aluminum oxynitride (SiAlON), mixtures thereof, and / or alloys thereof, which may increase the durability of the coated article. The outermost protective layer 200 may be formed of silicon nitride deposited on another material with good electrical conductivity to improve silicon sputtering. For example, during deposition, the silicon cathode may contain a small amount of aluminum (e.g., up to 20 wt%, up to 15 wt%, up to 10 wt%, or up to 5 wt%) to improve sputtering. In this case, the resulting silicon nitride layer would contain a small percentage of aluminum, for example, up to 15 wt% aluminum, for example, up to 10 wt% aluminum, or for example, up to 5 wt% aluminum. Coating layers deposited from silicon cathodes having up to 10 wt% aluminum (added to increase the cathode's conductivity) are referred to herein as "silicon nitride" layers, although small amounts of aluminum may be present. Small amounts of aluminum in the cathode (e.g., 15 wt% or less, e.g., 10 wt% or less, e.g., 5 wt% or less) are believed to form aluminum nitride in the primarily silicon nitride outermost protective layer 200. The outermost protective layer 200 may be formed in a nitrogen atmosphere; however, it is understood that other gases, such as oxygen, may be present in the atmosphere during deposition of the outermost protective layer 200.

[0081] In another non-limiting example, the outermost protective layer 200 can be a multi-layer coating including a first protective film 202 and a second protective film 204 formed on at least a portion of the first protective film 202. The first protective film 202 can include alumina, silica, titanium, zirconia, tin oxide, alloys thereof, mixtures thereof, or combinations thereof. In one specific, non-limiting example, the first protective film 202 can include alumina or an alloy including alumina and silica. For example, the first protective film 202 can include a silica / alumina mixture having more than 5 wt% alumina, e.g., more than 10 wt% alumina, e.g., more than 15 wt% alumina, e.g., 50 wt% to 70 wt% alumina, e.g., in the range of 60 wt% to 100 wt% alumina and 40 wt% to 0 wt% silica, e.g., 60 wt% alumina and 40 wt% silica. In another example, the first protective coating 202 can include zinc stannate. In another example, the first protective coating 202 can include zirconia.

[0082] The second protective coating 204 may include, for example, a metal oxide or a metal nitride. The second protective coating 204 may be titania, alumina, silica, zirconia, tin oxide, a mixture thereof, or an alloy thereof. For example, the second protective coating 204 may include a titania / alumina mixture having 40 wt%-60 wt% alumina and 60 wt%-40 wt% titania; 45 wt%-55 wt% alumina and 55 wt%-45 wt% titania; 48 wt%-52 wt% alumina and 52 wt%-48 wt% titania; 49 wt%-51 wt% alumina and 51 wt%-49 wt% titania; or 50 wt% alumina and 50 wt% titania. An example of the second protective coating 204 may include titanium aluminum oxide (TiAlO). Another example of the second protective coating 204 is a silica / alumina mixture having more than 40 wt% silica, such as more than 50 wt% silica, for example more than 60 wt% silica, for example more than 70 wt% silica, for example more than 80 wt% silica, for example in the range of 80 wt% to 90 wt% silica and 10 wt% to 20 wt% alumina, for example 85 wt% silica and 15 wt% alumina.

[0083] In a non-limiting example, the outermost protective layer 200 can include an additional third protective coating formed on at least a portion of the second protective coating 204. The third protective coating can be any of the materials used to form the first and second protective coatings 202, 204. The third protective coating can include, for example, alumina, silica, titania, zirconia, tin oxide, or a mixture thereof. For example, the third protective coating can include a mixture of silica and alumina. In another example, the third protective coating includes alumina and titania. In another example, the third protective coating includes zirconia.

[0084] The outermost protective layer 200 is the outermost layer of the coating. Furthermore, the outermost layer 200 may be of non-uniform thickness. By "non-uniform thickness" it is meant that the thickness of the outermost protective layer 200 may vary over a given unit area; for example, the outermost protective layer may have high and low points or areas. The outermost protective layer 200 may have a total thickness of 20 nm to 120 nm, preferably 25 nm to 110 nm, more preferably 30 nm to 100 nm, and most preferably 35 nm to 90 nm. 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.

[0085] In some non-limiting examples, the coated article 30 further comprises a light absorbing agent selected from the group consisting of tinted glass, PVB, an absorbing layer, or a combination thereof.

[0086] In the above non-limiting examples, the additional optional absorbing layer 140 can be disposed on at least a portion of the fourth dielectric layer 100 of the triple metal coating 33 (FIG. 8) or on at least a portion of the fifth dielectric layer 120 of the quadruple metal coating 34 (FIG. 9), such that the absorbing layer 140 is disposed between the fourth dielectric layer 100 and the optional outermost protective layer 200, or between the fifth dielectric layer 120 and the optional outermost protective layer 200, or is the outermost coating. The absorbing layer 140 can be made of a material such as Ge, GeO x , NbN x, NbN x O y , Si a Al b , Si a Al b O x , Si a Co b , Si a Co b O x , Si a Co b Cu c , Si a Co b Cu c O x , Si a Cr b , Si a Cr b O x , Si a Ni b , SiNiO x , SiO x , SnN x , SnO x , SnO x N y , TiN x , Ti a Nb b N x , Ti a Nb b O x , Ti a Nb b O x N y , TiO x N y , WO x , WO2, ZnO:Co, ZnO:Fe, ZnO:Mn, ZnO:Ni, ZnO:V, ZnO:Cr, Zn a Sn b , Zn a Sn b O x or any combination thereof. In one non-limiting example, the absorbing layer 140 comprises cobalt silicon oxide. The absorbing layer 140 can have a total thickness ranging from 1 nm to 40 nm, preferably from 5 nm to 30 nm, more preferably from 10 nm to 25 nm, and most preferably from 15 nm to 20 nm.

[0087] Alternatively, the absorbing layer 140 can include a subcritical metal film. The term "subcritical thickness" means a thickness below the critical thickness at which the coating material forms interspersed, non-contacting areas of the coating material. The term "interspersed" means that the coating material is deposited so that it forms interspersed areas or islands of material rather than a continuous layer. The metal of the subcritical metal film can include silver, gold, alloys thereof, mixtures thereof, or combinations thereof. In one non-limiting example, the subcritical metal film includes silver. The subcritical metal film can have a total subcritical thickness ranging from 0.5 nm to 20 nm, preferably from 1 nm to 10 nm, and more preferably from 1.5 nm to 3.5 nm.

[0088] In another non-limiting example, the optional additional dielectric layer 160 is formed over at least a portion of the subcritical metal film such that the additional dielectric layer 160 is disposed between the subcritical metal film and the optional outermost protective layer 200. The optional dielectric layer 160 can be a multilayer as described above, including one or more dielectric films. The additional dielectric layer 160 can include one or more materials discussed above with respect to the first, second, third, fourth, and fifth dielectric layers 40, 60, 80, 100, 120. The optional additional dielectric layer 160 includes a total thickness ranging from 25 nm to 33 nm, preferably from 26 nm to 32 nm, more preferably from 27 nm to 31 nm, and most preferably from 28 nm to 30 nm.

[0089] In some non-limiting examples, tinted or clear glass cover plates 12, 18 and / or tinted or untinted PVB interlayers 24 may be utilized in an attempt to match three requirements: a neutral Rf, low Rf and Rg of approximately 8%, and an LTA value of 70% or greater for forward vehicle visibility.

[0090] In one non-limiting implementation of the present invention, the thickness and / or number of silver layers are configured to provide the coating with a total resistivity (sheet resistance) in the range of 0.6 to 1.5 ohms per square (Ω / □), preferably 0.6 to 1.0 Ω / □, and more preferably 0.6 to 0.9 Ω / □. However, as those skilled in the art will recognize, as the number or thickness of silver metal layers increases, visible light transmittance decreases. The thickness and / or number of metal layers should not be increased to the point where visible light transmittance in the field of view drops below about 70%. Furthermore, if the total silver thickness is too high, the color of the glass will appear red, which is undesirable.

[0091] In one non-limiting implementation of the present invention, the coating provides a visible light reflectance of 25% or less, such as 20% or less, such as 10% or less, such as 8% or less.

[0092] In one non-limiting implementation of the present invention, the coating 30 has an external reflectance at an angle of 8 degrees (°) in the range of 1 to −2, for example, 1 to −1, preferably −0.5 to 0.5, more preferably −0.5 to 0, and most preferably 0. * (Rg8a * ) is provided.

[0093] In one non-limiting implementation of the present invention, the coating 30 has an external reflectance b at 8° in the range of 1 to −2, for example, 1 to −1, preferably −0.5 to 0.5, more preferably −0.5 to 0, and most preferably 0. * (Rg8b * ) is provided.

[0094] The invention is further described in the following numbered paragraphs:

[0095] Item 1: A coated article comprising: a substrate having a first surface and a second surface opposite the first surface; and a functional coating applied over the surface, the functional coating comprising: a first dielectric layer over at least a portion of the surface; a first metal layer over at least a portion of the first dielectric layer; a second dielectric layer over at least a portion of the first metal layer; a second metal layer over at least a portion of the second dielectric layer; a third dielectric layer over at least a portion of the second metal layer; a third metal layer over at least a portion of the third dielectric layer; and a fourth dielectric layer over at least a portion of the third metal layer, wherein the total thickness of the metal layers is at least 10 nanometers and no more than 60 nanometers.

[0096] Item 2: The coated article of item 1, wherein the total thickness of the metal layer is at least 20 nm and no more than 40 nanometers.

[0097] Item 3: The coated article of item 1, wherein the total thickness of the metal layer is at least 25 nm and no more than 31 nanometers.

[0098] Item 4: A coated article of any of the preceding items having a visible light reflectance of 8% or less.

[0099] Item 5: The coated article of any of the preceding items having a visible light transmittance of at least 70%.

[0100] Item 6: The coated article of any of the preceding items, wherein at least one of the metal layers comprises at least one of silver, gold, alloys thereof, mixtures thereof, or combinations thereof.

[0101] Item 7: The coated article of item 6, wherein at least one of the metal layers is silver.

[0102] Item 8: The coated article of any of the preceding items, wherein at least one of the metal layers is a continuous layer.

[0103] Item 9: The coated article of any of the preceding items, wherein the first metal layer comprises a total thickness of 5 nm to 20 nm, preferably 5 nm to 17.5 nm, more preferably 7 nm to 15 nm, or most preferably 8 to 10.5 nm.

[0104] Item 10: The coated article of any of the preceding items, wherein the second metal 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, or most preferably 8.5 nm to 11.5 nm.

[0105] Item 11: The coated article of any of the preceding items, wherein the third metal layer comprises a total thickness of 1 nm to 20 nm, preferably 5 nm to 20 nm, more preferably 7.5 nm to 15 nm, or most preferably 7.5 nm to 10.5 nm.

[0106] Item 12: The coated article of any of the preceding items, further comprising at least one primer layer formed over at least one of the metal layers.

[0107] Item 13: The coated article of item 12, wherein the at least one 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 the primer is deposited as a metal and subsequently oxidized.

[0108] Item 14: The coated article of item 12 or 13, wherein when at least one primer layer contains aluminum and zinc, the total thickness of the metal layers is in the range of 10 nm to 65 nm, preferably 15 nm to 55 nm, more preferably 20 nm to 45 nm, or most preferably 25 nm to 36 nm.

[0109] Item 15: The coated article of item 12 or 13, wherein the at least one primer layer has a total thickness of 0.5 nm to 5 nm, preferably 1 nm to 2.5 nm, or more preferably 1.5 nm to 2.5 nm.

[0110] Item 16: The coated article of any of the preceding items, wherein at least one of the dielectric layers 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.

[0111] Item 17: The coated article of any of the preceding items, 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, a mixture thereof, or a combination thereof over at least a portion of the first film.

[0112] Item 18: The coated article of item 17, 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, a mixture thereof, or a combination thereof.

[0113] Item 19: The coated article of item 17 or 18, wherein the first dielectric layer comprises a total thickness of 10 nm to 50 nm, preferably 12 nm to 45 nm, more preferably 15 nm to 42 nm, or most preferably 18 nm to 40 nm.

[0114] Item 20: The coated article of any of the preceding items, wherein the first dielectric layer comprises a seed film in direct contact with the first metal layer, and the seed film can comprise 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, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof.

[0115] Item 21: The coated article of any of the preceding items, wherein the second dielectric layer comprises: a first film comprising zinc oxide on at least a portion of the first primer layer; a second film comprising zinc stannate on 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, a mixture thereof, or a combination thereof on at least a portion of the second film.

[0116] Item 22: The coated article of item 21, wherein the second dielectric layer comprises a total thickness of 40 nm to 110 nm, preferably 50 nm to 100 nm, more preferably 55 nm to 80 nm, or most preferably 67 nm to 76 nm.

[0117] Item 23: The coated article of any of the preceding items, wherein the second dielectric layer comprises a seed film in direct contact with the second metal layer, the seed film comprising 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, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof.

[0118] Item 24: The coated article of any of the preceding items, wherein the third dielectric layer comprises: a first film comprising zinc oxide or zinc stannate on at least a portion of the second primer layer; a second film comprising zinc stannate or zinc oxide on 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, a mixture thereof, or a combination thereof on at least a portion of the second film.

[0119] Item 25: The coated article of item 24, wherein the third dielectric layer comprises a total thickness of 40 nm to 110 nm, preferably 50 nm to 100 nm, more preferably 65 nm to 80 nm, or most preferably 71 nm to 75 nm.

[0120] Item 26: The coated article of any of the preceding items, wherein the third dielectric layer comprises a seed film in direct contact with the third metal layer, and the seed film can comprise 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, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof.

[0121] Item 27: The coated article of any of the preceding items, wherein the fourth dielectric layer comprises a first film comprising zinc oxide or zinc stannate on at least a portion of the third primer layer, and a second film comprising zinc stannate or zinc oxide on 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, or a combination thereof, on at least a portion of the second film.

[0122] Item 28: The coated article of item 27, wherein the fourth dielectric layer comprises a total thickness of 10 nm to 50 nm, preferably 15 nm to 40 nm, more preferably 20 nm to 35 nm, or most preferably 27 nm to 31 nm.

[0123] Item 29: The coated article of any of the preceding items, further comprising an outermost protective coating comprising a protective layer, the protective layer comprising at least one of Si3N4, SiAlN, SiAlON, titania, alumina, silica, zirconia, alloys thereof, mixtures thereof, or combinations thereof.

[0124] Item 30: The coated article of item 29, wherein the outermost protective layer has a total thickness of 15 nm to 120 nm, preferably 25 nm to 110 nm, more preferably 30 nm to 100 nm, or most preferably 20 nm to 90 nm.

[0125] Item 31: The coated article of Item 29 or 30, wherein the outermost protective layer comprises a first protective film and a second protective film formed on the first protective film.

[0126] Item 32: The coated article of Items 29 to 31, wherein the outermost protective layer comprises aluminum silicon oxide, aluminum titanium oxide, a mixture thereof, or a combination thereof.

[0127] Item 33: The coated article of any of the preceding items, further comprising a light absorber selected from the group consisting of tinted glass, polyvinyl butyral ("PVB"), an absorbing layer, or combinations thereof.

[0128] Item 34: The coated article of item 33, wherein an absorbent layer is formed over at least a portion of the fourth dielectric layer.

[0129] Item 35: The absorption layer is Ge or GeO x , NbN x , NbN x O y , Si a Al b , Sia Al b O x , Si a Co b , Si a Co b O x , Si a Co b Cu c , Si a Co b Cu c O x , Si a Cr b , Si a Cr b O x , Si a Ni b , SiNiO x , SiO x , SnN x , SnO x , SnO x N y , TiN x , Ti a Nb b N x , Ti a Nb b O x , Ti a Nb b O x N y , TiO x N y , WO x , WO2, ZnO:Co, ZnO:Fe, ZnO:Mn, ZnO:Ni, ZnO:V, ZnO:Cr, Zn a Sn b , Zn a Sn b O x or any combination thereof.

[0130] Item 36: The coated article of item 35, wherein the absorbing layer comprises cobalt silicon oxide.

[0131] Item 37: The coated article of item 35 or 36, wherein the absorbing layer has a total thickness of 1 nm to 40 nm, preferably 5 nm to 30 nm, more preferably 10 nm to 25 nm, or most preferably 15 nm to 20 nm.

[0132] Item 38: The coated article of item 34, wherein the absorbing layer is a subcritical metal film.

[0133] Item 39: The coated article of item 38, wherein the subcritical metal film comprises silver, gold, an alloy thereof, a mixture thereof, or a combination thereof.

[0134] Item 40: The coated article of Item 38 or 39, wherein the subcritical metal film comprises silver.

[0135] Item 41: The coated article of any of Items 38 to 40, wherein the subcritical metal film has a total thickness of 0.5 nm to 20 nm, preferably 1 nm to 10 nm, or more preferably 1.5 nm to 3.5 nm.

[0136] Item 42: The coated article of item 38, wherein an additional dielectric layer is formed over at least a portion of the subcritical metal film.

[0137] Item 43: The coated article of item 42, wherein the additional dielectric layer formed on at least a portion of the subcritical metal film 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.

[0138] Item 44: The coated article of item 42 or 43, wherein the additional dielectric layer formed on at least a portion of the subcritical metal film comprises a total thickness in the range of 25 nm to 33 nm, preferably 26 nm to 32 nm, more preferably 27 nm to 31 nm, and most preferably 28 nm to 30 nm.

[0139] Item 45: A coated article comprising: a substrate comprising a first surface and a second surface opposite the first surface; and a functional coating applied over the surface, the functional coating comprising: a first dielectric layer over at least a portion of the surface; a first metal layer over at least a portion of the first dielectric layer; a second dielectric layer over at least a portion of the first metal layer; a second metal layer over at least a portion of the second dielectric layer; a third dielectric layer over at least a portion of the second metal layer; a third metal layer over at least a portion of the third dielectric layer; a fourth dielectric layer over at least a portion of the third metal layer; a fourth metal layer over at least a portion of the fourth dielectric layer; and a fifth dielectric layer over at least a portion of the fourth metal layer, wherein the total thickness of the metal layers is at least 10 nanometers and no more than 60 nanometers.

[0140] Item 46: The coated article of item 45, wherein the total thickness of the metal layer is at least 30 nm and no more than 45 nanometers.

[0141] Item 47: The coated article of any of items 45, wherein the total thickness of the metal layer is at least 35 nm and no more than 40 nanometers.

[0142] Item 48: The coated article of any one of Items 45 to 47, having a visible light reflectance of 8% or less.

[0143] Item 49: The coated article of any of Items 45 to 48, having a visible light transmittance of at least 70%.

[0144] Item 50: The coated article of any of Items 45 to 49, wherein at least one of the metal layers contains at least one of silver, gold, an alloy thereof, a mixture thereof, or a combination thereof.

[0145] Item 51: The coated article of any of Items 45 to 50, wherein at least one of the metal layers is silver.

[0146] Item 52: The coated article of any of Items 45 to 51, wherein at least one of the metal layers is a continuous layer.

[0147] Item 53: The coated article of any of Items 45 to 52, wherein the first metal layer comprises a total thickness of 2 nm to 20 nm, preferably 6 nm to 18 nm, more preferably 9 nm to 12 nm, or most preferably 9.5 nm to 10 nm.

[0148] Item 54: The coated article of any of Items 45 to 53, wherein the second metal layer comprises a total thickness of 2 nm to 20 nm, preferably 6 nm to 18 nm, more preferably 8 nm to 15 nm, or most preferably 9 nm to 12 nm.

[0149] Item 55: The coated article of any of items 45 to 54, wherein the third metal layer comprises a total thickness of 2 nm to 20 nm, preferably 6 nm to 18 nm, more preferably 8 nm to 15 nm, or most preferably 9 nm to 12 nm.

[0150] Item 56: The coated article of any of Items 45 to 47, wherein the fourth metal layer has a total thickness of 2 nm to 20 nm, preferably 4 nm to 15 nm, more preferably 6 nm to 11 nm, or most preferably 7 nm to 10 nm.

[0151] Item 57: The coated article of any of items 45 to 56, further comprising at least one primer layer formed on at least one of the metal layers.

[0152] Item 58: The coated article of item 57, wherein one of the at least one primer layers 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 the primer is deposited as a metal and subsequently oxidized.

[0153] Item 59: The coated article of 57 or 58, wherein when at least one primer layer contains aluminum and zinc, the total thickness of the metal layers is in the range of 10 nm to 65 nm, preferably 20 nm to 60 nm, more preferably 40 nm to 55 nm, and most preferably 35 nm to 45 nm.

[0154] Item 60: The coated article of any of items 45 to 59, wherein at least one of the dielectric layers 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.

[0155] Item 61: The coated article of any of Items 45 to 60, wherein the first dielectric layer comprises a total thickness of 20 nm to 55 nm, preferably 25 nm to 50 nm, more preferably 30 nm to 45 nm, or most preferably 35 nm to 40 nm.

[0156] Item 62: The coated article of any of Items 45 to 61, wherein the second dielectric layer has a total thickness of 60 nm to 100 nm, preferably 65 nm to 95 nm, more preferably 70 nm to 90 nm, or more preferably 74 nm to 80 nm.

[0157] Item 63: The coated article of any of Items 45 to 62, wherein the third dielectric layer comprises a total thickness of 55 nm to 90 nm, preferably 60 nm to 85 nm, more preferably 68 nm to 80 nm, or most preferably 70 nm to 75 nm.

[0158] Item 64: The coated article of any of items 45 to 63, wherein the fourth dielectric layer comprises a seed film in direct contact with the fourth metal layer, and the seed film can comprise 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, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof.

[0159] Item 65: The coated article of item 64, wherein the fourth dielectric layer comprises a total thickness of 45 nm to 80 nm, preferably 50 nm to 75 nm, more preferably 55 nm to 70 nm, or most preferably 60 nm to 65 nm.

[0160] Item 66: The coated article of any of items 45 to 65, wherein the fifth dielectric layer comprises a first film comprising zinc oxide or zinc stannate formed on at least a portion of the fourth 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, a mixture thereof, or a combination thereof on at least a portion of the first film.

[0161] Item 67: The coated article of Item 66, wherein the fifth dielectric layer comprises a total thickness of 10 nm to 45 nm, preferably 15 nm to 40 nm, more preferably 20 nm to 35 nm, or most preferably 23 nm to 28 nm.

[0162] Item 68: The coated article of any of Items 45 to 67, further comprising an outermost protective coating including a protective layer, the protective layer comprising at least one of Si3N4, SiAlN, SiAlON, titania, alumina, silica, zirconia, alloys thereof, or mixtures thereof.

[0163] Item 69: The coated article of Item 68, wherein the outermost protective layer includes a first protective film and a second protective film formed on the first protective film.

[0164] Item 70: The coated article of Item 68 or 69, wherein the outermost protective layer comprises a protective film of silicon aluminum oxide or titanium aluminum oxide.

[0165] Item 71: The coated article of any of items 45 to 70, further comprising a light absorber selected from the group consisting of tinted glass, PVB, an absorbing layer, or a combination thereof.

[0166] Item 72: The coated article of item 71, further comprising an absorbent layer formed over at least a portion of the fifth dielectric layer.

[0167] Item 73: Absorbing layer is Ge, GeO x , NbN x , NbN x O y , Si a Al b , Si a Al b O x , Si a Co b , Si a Co b O x , Si a Co b Cu c , Si a Co b Cu c O x , Si a Cr b , Si a Cr b O x , Si a Ni b, SiNiO x , SiO x , SnN x , SnO x , SnO x N y , TiN x , Ti a Nb b N x , Ti a Nb b O x , Ti a Nb b O x N y , TiO x N y , WO x , WO2, ZnO:Co, ZnO:Fe, ZnO:Mn, ZnO:Ni, ZnO:V, ZnO:Cr, Zn a Sn b , Zn a Sn b O x or any combination thereof.

[0168] Item 74: The coated article of item 73, wherein the absorbing layer comprises cobalt silicon oxide.

[0169] Item 75: The coated article of item 72, wherein the absorbing layer is a subcritical metal film.

[0170] Item 76: The coated article of item 75, wherein the subcritical metal film comprises silver, gold, an alloy thereof, a mixture thereof, or a combination thereof.

[0171] Item 77: The coated article of Item 75 or 76, wherein the subcritical metal film comprises silver.

[0172] Item 78: The coated article of any of items 75 to 77, wherein an additional dielectric layer is formed over at least a portion of the subcritical metal film.

[0173] Item 80: A method of making a coated article, comprising the steps of providing a substrate including a first surface and a second surface opposite the first surface; and applying a functional coating over at least a portion of the surface, the steps including forming a first dielectric layer over at least a portion of the surface; forming a first metal layer over at least a portion of the first dielectric layer; forming a second dielectric layer over at least a portion of the first metal layer; forming a second metal layer over at least a portion of the second dielectric layer; forming a third dielectric layer over at least a portion of the second metal layer; forming a third metal layer over at least a portion of the third dielectric layer; and forming a fourth dielectric layer over at least a portion of the third metal layer, wherein the total thickness of the metal layers is at least 10 nanometers and no more than 60 nanometers.

[0174] Item 81: The method of Item 80, wherein the step of applying the functional coating further includes forming a fourth metal layer on at least a portion of the fourth dielectric layer, and forming a fifth dielectric layer on at least a portion of the fourth metal layer, and the overcoat is on at least a portion of the fifth dielectric layer.

[0175] Item 82: The method of Items 80 or 81, further applying an outermost protective coating, wherein the step of applying an outermost protective coating comprises forming an outermost protective layer comprising a protective layer, wherein the protective layer comprises at least one of Si3N4, SiAlN, SiAlON, titania, alumina, silica, or zirconia.

[0176] "Example" The following examples illustrate various embodiments of the present invention, however, it is understood that the invention is not limited to these particular examples.

[0177] "Example 1" Table 3 shows exemplary coating compositions and thicknesses of tri-metal coatings of the present invention. Thicknesses reported are geometric thicknesses in nanometers (nm) unless otherwise stated. The substrate is a clear glass substrate having a thickness of 2.1 mm and a 1.6 mm clear cover disposed on top of the substrate. A 0.7 mm PVB interlayer is utilized. The base layer is the first dielectric layer, the central base layer is the second dielectric layer, the central top layer is the third dielectric layer, and the top layer is the fourth dielectric layer. [Table 3]

[0178] Tables 4 and 5 show the color and optical properties obtained for the samples in Table 3, respectively. [Table 4] [Table 5]

[0179] "Example 2" The solar transmittance (TTs), or total transmitted solar energy, was higher than desired (49-50%) for the triple metal coating of Example 1. The high TTs value indicated that approximately 50% of the solar energy was transmitted through the substrate, leading to undesirable heat generation. Table 6 shows exemplary coating compositions and triple metal coating thicknesses (nm) of the present invention, where tinted coverings were utilized in an attempt to reduce transmitted solar radiation while matching three performance requirements: achromatic Rf, low Rf and Rg (8%), and LTA of 70% or greater. Solex, Atlantica SGN-C4, Caribia, Azuria, and Tintes-PL are greener than clear glass and therefore more absorbing. [Table 6]

[0180] Tables 7 and 8 show the color and optical properties obtained for the samples in Table 6, respectively. [Table 7] [Table 8]

[0181] "Example 3" Table 9 shows exemplary coating compositions and thicknesses (nm) of tri-metal coatings of the present invention, including silicon cobalt oxide (SiCoO x ) or a subcritical metal film absorption layer was added to the coating. x The absorbing layer was disposed between the fourth dielectric layer and the first protective film of the outermost protective layer. The silver-containing subcritical metal film of Sample 8 was disposed between the fourth dielectric layer and the additional dielectric layer already described. The absorbing layer was utilized in combination with a tinted glass cover in an attempt to further reduce transmitted solar radiation while matching three performance requirements: achromatic Rf, low Rf and Rg (8%), and LTA of 70% or greater. [Table 9]

[0182] Tables 10 and 11 show the color and optical properties obtained for the samples in Table 9, respectively. [Table 10] [Table 11]

[0183] "Example 4" Table 12 shows exemplary laminate compositions of tri-metal coatings utilizing a clear or tinted PVB interlayer in combination with a tinted or clear glass cover and glass substrate. The tri-metal coatings utilized are described above in Example 1, Table 3. [Table 12]

[0184] Table 13 shows the color and optical properties of the triple metal coating on a clear glass substrate with tinted or untinted PVB and tinted or untinted glass covering. [Table 13]

[0185] "Example 5" Table 14 shows exemplary coating compositions and thicknesses (nm) of the quadruple metal coating of the present invention, where the base layer is the first dielectric layer, the center base layer is the second dielectric layer, the center layer is the third dielectric layer, the center top layer is the fourth dielectric layer, and the top layer is the fifth dielectric layer. The quadruple metal coating was utilized in an attempt to further reduce transmitted solar radiation while matching three performance requirements: achromatic Rf, low Rf and Rg (8%), and LTA of 70% or greater. [Table 14]

[0186] Tables 15 and 16 show the color and optical properties obtained for the samples in Table 14, respectively. [Table 15] [Table 16]

[0187] The quadruple metal coating on the glass substrate is more conductive (0.86 Ω / □ sheet resistance) than any of the triple metal coating examples 1 to 4 (1.3 to 1.4 Ω / □ sheet resistance). Therefore, the solar radiation performance and low energy characteristics of the quadruple metal coating are superior to those of the triple metal coating. When forming the quadruple metal coating, tinted glass is not required.

[0188] Those skilled in the art will readily recognize that modifications can be made to the present invention without departing from the concepts disclosed in the foregoing description. Accordingly, the specific embodiments detailed herein are illustrative only and do not limit the scope of the invention, which is set forth in the full breadth of the appended claims and any and all equivalents thereof.

Claims

1. a substrate comprising a first surface and a second surface opposite the first surface; and A functional coating applied onto the first surface or the second surface. A coated article comprising the functional coating: a first dielectric layer on at least a portion of the first surface or the second surface, the first dielectric layer including a first film on at least a portion of the first surface or the second surface and a second film on at least a portion of the first film; a continuous first metal layer over at least a portion of the first dielectric layer; a second dielectric layer over at least a portion of the first metal layer, the second dielectric layer including a first film over at least a portion of the first metal layer, a second film over at least a portion of the first film, and a third film over at least a portion of the second film; a continuous second metal layer over at least a portion of said second dielectric layer; a third dielectric layer over at least a portion of the second metal layer, the third dielectric layer including a first film over at least a portion of the second metal layer, a second film over at least a portion of the first film, and a third film over at least a portion of the second film; a continuous third metal layer over at least a portion of said third dielectric layer; a fourth dielectric layer over at least a portion of the third metal layer, the fourth dielectric layer including a first film over at least a portion of the third metal layer and a second film disposed over at least a portion of the first film; and a continuous light absorbing layer disposed on at least a portion of the fourth dielectric layer, the continuous light absorbing layer comprising: Ge, GeO ｘ , NbN ｘ , NbN ｘ O ｙ , Si ａ Co ｂ , Si ａ Co ｂ O ｘ , Si ａ Co ｂ Cu ｃ , Si ａ Co ｂ Cu ｃ O ｘ , Si ａ Cr ｂ , Si ａ Cr ｂ O ｘ , Si ａ Ni ｂ , SiNiO ｘ , SnN ｘ , SnO ｘ , SnO ｘ N ｙ , TiN ｘ , Ti ａ Nb ｂ N ｘ , Ti ａ Nb ｂ O ｘ , Ti ａ Nb ｂ O ｘ N ｙ , T ｉ O ｘ N ｙ , W.O. ｘ or any combination thereof. Including, the light absorbing layer is the outermost layer of the functional coating; and the coated article further comprises an outermost protective coating comprising a protective layer disposed over at least a portion of the functional coating, the continuous light-absorbing layer being disposed between the fourth dielectric layer and the outermost protective coating; the total thickness of the three metal layers is at least 25 nanometers and no more than 31 nanometers; The coated article has a visible light transmittance of at least 70%.

2. 10. The coated article of claim 1 having a visible light reflectance of 8% or less.

3. The coated article of claim 1 or 2, wherein at least one of the metal layers comprises at least one of silver or gold.

4. further comprising at least one primer layer formed on at least one of said metal layers; 4. The coated article of claim 1, wherein the at least one 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 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 the primer is deposited as a metal and subsequently oxidized.

5. 5. The coated article of claim 1, wherein at least one of the dielectric layers comprises zinc stannate, zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, or indium-doped tin oxide.

6. The coated article of claim 1 , wherein the protective layer comprises at least one of titania, alumina, or a combination thereof.

7. 1. A method of making a coated article, comprising: providing a substrate including a first surface and a second surface opposite the first surface; and applying a functional coating onto at least a portion of the first surface or the second surface, forming a first dielectric layer over at least a portion of the first surface or the second surface, the first dielectric layer including a first film over at least a portion of the first surface or the second surface and a second film over at least a portion of the first film; forming a continuous first metal layer over at least a portion of the first dielectric layer; forming a second dielectric layer over at least a portion of the first metal layer, the third dielectric layer including a first film over at least a portion of the second metal layer, a second film over at least a portion of the first film, and a third film over at least a portion of the second film; forming a continuous second metal layer over at least a portion of the second dielectric layer; forming a third dielectric layer over at least a portion of the second metal layer, the third dielectric layer including a first film over at least a portion of the second metal layer, a second film over at least a portion of the first film, and a third film over at least a portion of the second film; forming a continuous third metal layer over at least a portion of the third dielectric layer; forming a fourth dielectric layer over at least a portion of the third metal layer, the fourth dielectric layer including a first film over at least a portion of the third metal layer and a second film over at least a portion of the first film; and forming a continuous light absorbing layer on at least a portion of the fourth dielectric layer, the continuous light absorbing layer comprising: Ge, GeO ｘ , NbN ｘ , NbN ｘ O ｙ , Si ａ Co ｂ , Si ａ Co ｂ O ｘ , Si ａ Co ｂ Cu ｃ , Si ａ Co ｂ Cu ｃ O ｘ , Si ａ Cr ｂ , Si ａ Cr ｂ O ｘ , Si ａ Ni ｂ , SiNiO ｘ , SnN ｘ , SnO ｘ , SnO ｘ N ｙ , TiN ｘ , Ti ａ Nb ｂ N ｘ , Ti ａ Nb ｂ O ｘ , Ti ａ Nb ｂ O ｘ N ｙ , T ｉ O ｘ N ｙ , W.O. ｘ forming a continuous light-absorbing layer selected from the group consisting of: Steps including Including, the light absorbing layer is the outermost layer of the functional coating; The method also includes applying an outermost protective coating comprising a protective layer over at least a portion of the functional coating, the continuous light absorbing layer being disposed between the fourth dielectric layer and the outermost protective coating; the total thickness of the three metal layers is at least 25 nanometers and no more than 31 nanometers; The method wherein the coated article has a visible light transmittance of at least 70%.

8. 8. The method of claim 7, wherein the step of applying the functional coating further comprises forming a fourth metal layer over at least a portion of the fourth dielectric layer, and forming a fifth dielectric layer over at least a portion of the fourth metal layer.

9. The coated article of claim 1 , wherein the light absorbing layer comprises cobalt silicon oxide.

10. 9. The method of claim 7 or 8, wherein the light absorbing layer comprises cobalt silicon oxide.

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