Coatings for head-up displays with low visible reflectance

Abstract

The invention relates to coatings for head-up displays with low visible reflectance. The invention also relates to a coated article comprising a substrate comprising a first surface and a second surface opposite the first surface, and a functional coating applied over one of the surfaces. The functional coating includes: a first dielectric layer; a first metallic layer; a second dielectric layer; a second metallic layer; a third dielectric layer; a third metallic layer; a fourth dielectric layer; optionally, a fourth metallic layer; optionally, a fifth dielectric layer; and optionally, an outermost protective coating. The coated article has a total combined thickness of the metallic layers of at least 10 nanometers and no greater than 60 nanometers.

Description

[0001] This application is a divisional application of Chinese patent application No. 202080031421.4, filed on March 26, 2020, and entitled “Coating for a head-up display with low visible light reflectivity”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

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

[0004] The present invention relates generally to vehicle transparencies, such as vehicle windshields, and in one particular embodiment, to heads-up displays. Background Art

[0005] Conventional automotive head-up displays (HUDs) use an electromagnetic radiation source in the instrument panel that projects light upward onto the windshield, which is then reflected toward the driver's eyes, thereby creating a virtual image of vehicle data, allowing the driver to obtain information about the operation of the vehicle without having to take his eyes off the road. For electromagnetic radiation reflected from the windshield at angles typically found in conventional vehicles and a generally unpolarized light source such as a light emitting diode (LED), the reflected light is primarily s-polarized, while a much smaller light component is p-polarized. In the extreme case, if the angle of incidence of the electromagnetic radiation to the windshield is the Brewster angle of the air-to-glass interface (approximately 57°), the p-polarized reflection is zero percent.

[0006] Light from the radiation source (primarily s-polarized) will reflect from the innermost surface of the windshield and the outermost surface of the windshield due to the refractive index mismatch between air and glass. This results in the formation of two reflected images, one on each surface. The multiple images formed in the HUD is a phenomenon known as "ghosting", and eliminating or minimizing the presence of "ghosting" is a goal of HUD technology. The conventional method to solve ghosting is to adjust the geometry of the two glass sheets to align the two reflected images by using a wedge-shaped vinyl layer between the inner and outer glass sheets of the windshield. This wedge-shaped vinyl plastic increases the cost of the windshield and also increases the complexity of manufacturing the windshield.

[0007] It is also desirable to apply a coating to at least one of the glass sheets to provide solar control, heating and / or antenna functionality to the windshield. This additional coating results in a third refractive index mismatch within the windshield, which results in a third reflection, and a third reflected image on the HUD system, which is difficult to compensate for with a wedge-shaped vinyl layer.

[0008] Therefore, there is a need in the art for systems and / or components that reduce or eliminate one or more of these problems. For example, it would be desirable to provide a HUD system that projects an image visible to the driver that reduces or eliminates ghosting while improving daylight performance and reducing energy. SUMMARY OF THE INVENTION

[0010] The present invention relates to a coated article. The coated article has a substrate having a first surface and a second surface opposite to the first surface, and a functional coating above the substrate. The coating has a first dielectric layer located above at least a portion of the surface. The first metallic layer is located above at least a portion of the first dielectric layer. Optionally, a first primer layer is located above at least a portion of the first metallic layer. The second dielectric layer is located above at least a portion of the first metallic layer or an optional first primer layer. The second metallic layer is located above at least a portion of the first metallic layer or an optional first primer layer. Optionally, a second primer layer is located above at least a portion of the second metallic layer. The third dielectric layer is located above at least a portion of the second metallic layer or an optional second primer layer. The third metallic layer is located above at least a portion of the third dielectric layer. Optionally, the third primer layer is located above at least a portion of the third metallic layer. The fourth dielectric layer is located above at least a portion of the third metallic layer or an optional third primer layer. An optional outermost protective layer is formed above at least a portion of the fourth dielectric layer or above the functional coating. The total combined thickness of the metallic layers that the coated article has is at least 10 nanometers to 60 nanometers.

[0011] The present invention relates to a coated article. The coated article has a substrate having a first surface and a second surface opposite to the first surface, and a functional coating above the substrate. The coating has a first dielectric layer located above at least a portion of the surface. The first metallic layer is located above at least a portion of the first dielectric layer. Optionally, a first primer layer is located above at least a portion of the first metallic layer. The second dielectric layer is located above at least a portion of the first metallic layer or an optional first primer layer. The second metallic layer is located above at least a portion of the first metallic layer or an optional first primer layer. Optionally, the second primer layer is located above at least a portion of the second metallic layer. The third dielectric layer is located above at least a portion of the second metallic layer or an optional second primer layer. The third metallic layer is located above at least a portion of the third dielectric layer. Optionally, the third primer layer is located above at least a portion of the third metallic layer. The fourth dielectric layer is located above at least a portion of the third metallic layer or an optional third primer layer. The fourth metallic layer is located above at least a portion of the fourth dielectric layer. The optional fourth primer layer is located above at least a portion of the fourth metallic layer. The 5th dielectric layer is positioned at least a portion of the 4th metallic layer or above the optional 4th primer layer. Above at least a portion of the 5th dielectric layer or above the functional coating, an optional outermost protective layer is formed. The total combined thickness of the metallic layer that the coated article has is at least 10 nanometers to 60 nanometers.

[0012] The present invention relates to a method for manufacturing a coated article. A substrate having a first surface and a second surface opposite to 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 metallic 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 metallic layer. A second dielectric layer is formed over at least a portion of the first metallic layer. A second metallic 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 metallic layer. A third dielectric layer is formed over at least a portion of the second metallic layer. A third metallic 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 metallic layer. A fourth dielectric layer is formed over at least a portion of the third metallic layer. An optional outermost protective layer is formed over at least a portion of the fourth dielectric layer or over the functional coating. The coated article has a total combined thickness of metallic layers of at least 10 nanometers to 60 nanometers. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The present invention will be described with reference to the following drawings, wherein like reference numerals refer to like parts throughout.

[0015] Figure 1 is a schematic diagram of a non-restrictive windshield (not to scale).

[0016] Figure 2A-2B An explanation of the ghosting effect produced by the windshield display when the head-up display is used.

[0017] Figure 3 is an illustration of a windshield having a coating positioned to reduce ghosting when a heads-up display is used.

[0018] Figure 4 is a cross-sectional view (not to scale) of a non-limiting tri-metallic coating according to the present invention.

[0019] Figure 5 is a cross-sectional view (not to scale) of a non-limiting quad-metal coating according to the present invention.

[0020] Figure 6 is a cross-sectional view (not to scale) of a non-limiting tri-metallic coating according to the present invention.

[0021] Figure 7 is a cross-sectional view (not to scale) of a non-limiting quad-metal coating according to the present invention.

[0022] Figure 8 is a cross-sectional view (not to scale) of a non-limiting tri-metallic coating according to the present invention.

[0023] Fig. 9is a cross-sectional view (not to scale) of a non-limiting quad-metal coating according to the present invention.

[0024] Description of the invention

[0025] As used herein, spatial or directional terms, such as "left", "right", "inside", "outside", "above", "below", etc., refer to the present invention as shown in the accompanying drawings. However, it should be understood that the present invention can take a variety of alternative orientations, and therefore such terms are not considered restrictive. In addition, as used herein, all numerical values ​​used in the specification and claims to represent dimensions, physical properties, processing parameters, amounts of ingredients, reaction conditions, etc. should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical values ​​listed in the following specification and claims may vary depending on the desired properties sought to be obtained by the present invention. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be interpreted in accordance with the number of reported significant figures and by applying ordinary rounding techniques. In addition, all ranges disclosed herein are understood to include starting and ending range values ​​and any and all subranges contained therein. For example, the range of "1 to 10" should be considered to include any and all subranges between a minimum of 1 and a maximum of 10 (and including a minimum of 1 and a maximum of 10); that is, all subranges starting with a minimum of 1 or greater and ending with a maximum of 10 or less, such as 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. In addition, as used herein, the term "formed above...", "deposited above..." or "provided above..." means formed, deposited or provided on a surface but not necessarily in contact with the surface. For example, a coating "formed above a substrate" does not exclude the presence of one or more other coatings or films of the same or different composition located between the formed coating and the substrate. As used herein, the term "polymer" or "polymeric" includes oligomers, homopolymers, copolymers and terpolymers, such as polymers formed from two or more types of monomers or polymers. The term "visible region" or "visible light" refers to electromagnetic radiation with a wavelength in the range of 380 nanometers (nm) to 800 nm. The term "infrared region" or "infrared radiation" refers to electromagnetic radiation with a wavelength in the range of greater than 800nm ​​to 100,000nm. The term "ultraviolet region" or "ultraviolet radiation" means electromagnetic energy with a wavelength in the range of 300nm to less than 380nm. The visible (light) transmittance (LTA) values ​​(Y, x, y) herein are those that can be determined using a λ9 spectrophotometer commercially available from Perkin-Elmer or a TCS spectrophotometer commercially available from BYK-Gardner in the wavelength range of 380nm to 770nm using a CIE (1976) standard illuminant "A" with a 2 degree observation angle (consistent with U.S. Federal Standards). Reflection color values ​​L*, a*, b* (regardless of R1 or R2) are measured using a illuminant "D65" with a 10° observation angle (as conventional in the automotive field).

[0026] As used herein, the term "film" refers to a coating region having a desired or selected coating composition. A "layer" may include one or more "films", and a "coating" or "coating stack" may include one or more "layers". The terms "metal" and "metal oxide" include silicon and silicon oxide, respectively, as well as conventionally recognized metals and metal oxides, even though silicon may not be conventionally considered a metal. Unless otherwise indicated, thickness values ​​are geometric thickness values. In addition, all documents mentioned herein, such as but not limited to issued patents and patent applications, are deemed to be "incorporated by reference" in their entirety.

[0027] The discussion of the present invention may describe some features as "particularly" or "preferably" within some limitations (e.g., "preferably", "more preferably" or "most preferably" within some limitations). It should be understood that the present invention is not limited to these specific or preferred limitations, but includes the entire scope of the disclosure.

[0028] exist Figure 1 A non-limiting transparent article 10 (e.g., an automobile windshield) including features of the present invention is described in detail in the accompanying drawings. The transparent article 10 may have any desired visible light, infrared radiation, or ultraviolet radiation transmission and reflection properties. For example, the transparent article 10 may have any desired amount of visible light transmission, such as greater than 0% to 100%, greater than 70%. For the windshield and front side window areas in the United States, the visible light transmission is typically greater than or equal to 70%. For privacy areas such as rear seat side windows and rear windows, the visible light transmission may be less than the visible light transmission of the windshield, such as less than 70%.

[0029] As in Figure 1 As can be seen in FIG. 1 , the transparent object 10 includes a first sheet or first substrate 12 having a first major surface facing the exterior of the vehicle, namely an outer major surface 14 (surface No. 1) and an opposite second or inner major surface 16 (surface No. 2). The transparent object 10 also includes a second sheet or second substrate 18 having an outer (first) major surface 22 (surface No. 4) and an inner (second) major surface 20 (surface No. 3). This numbering of the sheet surfaces is consistent with conventional practice in the automotive field. The first and second sheets 12, 18 can be combined together in any suitable manner, such as by a conventional intermediate layer 24. Although not required, a conventional edge sealant can be applied to the periphery of the laminated transparent object 10 during and / or after lamination in any desired manner. A decorative strip, such as an opaque, translucent or colored masking strip 26, such as a ceramic strip, can be provided on the surface of at least one of the sheets 12, 18, such as around the periphery of the inner major surface 16 of the first sheet 12. A coating 30 is formed over at least a portion of one of the sheets 12, 18, such as over surface No. 2 16 or surface No. 3 20.

[0030] exist Figure 1In the non-limiting embodiment illustrated in FIG. 1 , the bus bar assembly includes a first or bottom bus bar 96 and a second or top bus bar 98 formed on the inner surface 16 of the outer sheet 12 and separated from the outer sheet 12 by a bus bar distance D. The bus bars 96, 98 are in electrical contact with the coating 30. In one non-limiting embodiment of the present invention, the bus bars 96, 98 may be at least partially located on the decorative strip 26 or completely located on the decorative strip 26, such as Figure 1 Displayed in.

[0031] In the broad practice of the invention, the sheets 12, 18 of the transparent object 10 may be of the same or different materials. The sheets 12, 18 may include any desired material with any desired properties. For example, one or more of the sheets 12, 18 may be transparent or translucent to visible light. "Transparent" means having a visible light transmittance of greater than 0% to 100%. Alternatively, one or more sheets 12, 18 may be translucent. "Translucent" means allowing electromagnetic energy (e.g., visible light) to pass through, but scattering such energy so that objects on the side opposite to the observer are not clearly visible. Examples of suitable materials include, but are not limited to, plastic substrates (e.g., acrylic polymers, such as polyacrylates; polyalkyl methacrylates, such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, etc.; polyurethanes; polycarbonates; polyalkyl terephthalates, such as polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, etc.; polysiloxane-containing polymers; or copolymers of any monomers used to prepare these, or any mixtures thereof); ceramic substrates; glass substrates; or mixtures or combinations of any of the above. For example, one or more of the sheets 12, 18 may include conventional soda-lime silicate glass, borosilicate glass, or leaded glass. The glass may be clear glass. "Clear glass" means untinted or colorless glass. Alternatively, the glass may be tinted or otherwise colored glass. The glass may be annealed or heat-treated glass. As used herein, the term "heat-treated" means tempered or at least partially tempered. The glass may be of any type (e.g., conventional float glass) and may be of any composition with any optical properties (e.g., any value of visible transmittance, ultraviolet transmittance, infrared transmittance, and / or total solar energy transmittance). "Float glass" means glass formed by a conventional float process, in which molten glass is deposited on a molten metal bath and controlled to cool to form a float glass ribbon. The ribbon is then cut and / or shaped and / or heat treated as desired. Examples of float glass processes are disclosed in U.S. Patent Nos. 4,466,562 and 4,671,155. The first and second sheets 12, 18 may be, for example, clear float glass or may be tinted or colored glass, or one sheet 12, 18 may be clear glass and the other sheet 12, 18 may be colored glass. Although not limiting the present invention, examples of glass suitable for the first sheet 12 and / or the second sheet 18 are described in U.S. Pat. Nos. 4,746,347; 4,792,536; 5,030,593; 5,030,594; 5,240,886; 5,385,872 and 5,393,593. The first and second sheets 12, 18 may have any desired dimensions (e.g., length, width, shape, or thickness). In an exemplary automotive transparency 10, the first and second sheets 12, 18 may each be 1 mm to 10 mm thick, e.g., 1 mm to 5 mm thick, or 1.5 mm to 2.5 mm, or 1.8 mm to 2.3 mm.In one non-limiting embodiment, the first sheet 12 and / or the second sheet 18 may have a visible light transmittance greater than 90%, for example greater than 91%, at a reference wavelength of 550 nm. The glass composition of the first sheet 12 and / or the second sheet 18 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.

[0032] In one non-limiting embodiment, one or both of the sheets 12, 18 may have a high visible light transmittance at a reference wavelength of 550 nm. "High visible light transmittance" means that at an equivalent thickness of 5.5 mm for a glass of a sheet thickness of 2 mm to 25 mm, the visible light transmittance at 550 nm is greater than or equal to 85%, such as greater than or equal to 87%, such as greater than or equal to 90%, such as greater than or equal to 91%, such as greater than or equal to 92%. Glasses that are particularly useful for practicing the present invention are disclosed in U.S. Pat. Nos. 5,030,593 and 5,030,594.

[0033] The laminated windshield may also include an intermediate layer 24. The intermediate layer 24 may have any desired material and may include one or more layers or sheets. The intermediate layer 24 may be located above the surface 16 No. 2 and / or the surface 20 No. 3. The intermediate layer 24 may be a polymer material or a plastic material, such as polyvinyl butyral (PVB), plasticized polyvinyl chloride, or a multilayer thermoplastic material, including polyethylene terephthalate, etc. Suitable intermediate layer materials are disclosed in U.S. Patent Nos. 4,287,107 and 3,762,988, for example but not considered to be limiting. The intermediate layer 24 may also be a sound absorbing or attenuating material as described in U.S. Patent No. 5,796,055. The intermediate layer 24 may have a solar control coating provided thereon or incorporated therein, or may include a colored material to reduce solar transmittance. The intermediate layer 24 may have any suitable thickness to combine the sheets 12 and 18 together. In a non-limiting embodiment, the intermediate layer 24 is a 0.76 millimeter (mm) thick PVB layer.

[0034] The coating 30 is deposited over at least a portion of a major surface of one of the glass sheets 12, 18, such as on the inner surface 16 of the outer glass sheet 12 or the outer surface 22 of the inner glass sheet 18. Figure 1 , Figure 3). Coating 30 may include three or four metallic films located between dielectric layers sequentially applied over at least a portion of one of the glass sheets 12, 18. Coating 30 may be a heat and / or radiation reflective coating or a solar control coating and may have one or more coating layers or films having the same or different compositions and / or functions. Coating 30 may be a multilayer coating including three or four metallic layers. Examples of conductive coatings for preparing heatable windows are disclosed in U.S. Pat. Nos. 5,653,903 and 5,028,759. Examples of solar control coatings that may be used in the practice of the present invention are found in U.S. Patent Nos. 4,898,789, 5,821,001, 4,716,086, 4,610,771, 4,902,580, 4,716,086, 4,806,220, 4,898,790, 4,834,857, 4,948,677, 5,059,295 and 5,028,759 and U.S. Patent Application Serial No. 09 / 058440.

[0035] The non-limiting examples of suitable coatings generally include one or more anti-reflective coating films, which include dielectric or anti-reflective materials transparent to visible light, such as oxides of metal oxides or metal alloys. Coating 30 may also include three to four metallic layers, including a combination of reflective metals such as precious metals such as silver or gold or their alloys, and coating 30 may also include a primer layer or a barrier film, such as titanium or titanium aluminum alloy, located above the metal reflective layer and / or optionally under the metal reflective layer. Coating 30 may have three or four metallic layers; or may have at least three metallic layers; or may have no more than four metallic layers. For example, coating 30 is composed of three metallic layers, i.e., tri-metal coating 32. In another non-limiting embodiment, coating 30 includes four metallic layers, i.e., tetra-metal coating 34. In a non-limiting embodiment, one or more of the metallic layers may include silver. In another non-limiting embodiment, one or more of the metallic layers may be continuous layers. "Continuous layer" means a continuous film of coating-forming material rather than a separated coating area.

[0036] Non-limiting examples of suitable materials for the primer layer include zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, germanium, magnesium, molybdenum, silver, silicon carbon, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, aluminum silver, zinc tin, indium zinc, silver zinc, their mixtures, their combinations or any alloys thereof. The primer layer can also be in the form of metal, oxide, suboxide, nitride and / or subnitride of any of the above listed materials. At least a portion of the primer layer is an oxide or nitride. In some embodiments, the primer layer is deposited in a 100% argon environment. In some embodiments, a portion of the primer layer is a nitride formed by sputtering a metal or metal alloy in a nitrogen (N2) atmosphere (which has a specific flow rate to form an atmosphere of 80% N2 with the remainder being argon). Flow is the approximate value of the amount of nitrogen (N2) in the atmosphere, but those of ordinary skill in the art will recognize that additional N2 can leak into the coating chamber because the coating chamber is not hermetically sealed with the external environment. In some embodiments, a part of the primer layer is formed by sputtering metal or metal alloy in oxygen (O2) atmosphere (it has a specific flow to form 3% to 7%O2 and the remainder is an atmosphere of argon). Flow is the approximate value of the amount of oxygen (O2) in the atmosphere, but those of ordinary skill in the art will recognize that additional O2 can leak into the coating chamber because the coating chamber is not hermetically sealed with the external environment. The chemical structure of the primer material is represented by the weight percentage (weight %) of element x. For some compositions, the lower limit of one of the materials in the composition can be "greater than 0". When the lower limit is "greater than zero", the weight percentage of the material is not equal to zero but can be greater than 0 and any weight % up to the upper limit of the weight %. Due to reaction with atmospheric substances, the composition can be changed before or after the heating layer. These reactions can change the weight % distributed between the materials of the composition. The composition of a non-limiting example of a primer layer, where BH before heating and AH after heating, can be found in Table 1. Some materials may only have a unique BH or AH measurement due to the fact that this measurement is more important to the final composition.

[0037] Table 1 Metal composition of metal alloys used as primer layer

[0038]

[0039]

[0040] For sight boards (such as windshields) in the United States, the transparent object should also have a visible light transmittance greater than or equal to 70%, for example, greater than or equal to 71%. As those skilled in the art will appreciate, it is necessary to balance several different competing factors to provide a coating with sufficient conductivity, transmittance and color. For example, as the distance D between busbars 96, 98 increases (i.e., the transparent object widens from top to bottom), the resistance of busbars 96 to busbars 98 increases. As the resistance of busbars 96 to busbars 98 increases, the power density decreases. In order to maintain power density, as busbars 96 are increased to busbars 98 distances D, the resistivity of coating 30 must be reduced. A way to reduce resistivity is by increasing the thickness of one or more of the metallic layers in the coating 30 and / or by increasing the number of metallic layers in the coating 30.

[0041] The coating 30 may be deposited by any conventional method, such as, but not limited to, conventional chemical vapor deposition (CVD) and / or physical vapor deposition (PVD) methods. Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam evaporation and vacuum sputtering (e.g., magnetron sputtering vapor deposition (MSVD)). Other coating methods may also be used, such as, but not limited to, sol-gel deposition. In a non-limiting embodiment, the coating 30 may be deposited by MSVD. Examples of MSVD coating apparatus and methods will be well understood by those of ordinary skill in the art and are described, for example, in U.S. Pat. Nos. 4,379,040; 4,861,669; 4,898,789; 4,898,790; 4,900,633; 4,920,006; 4,938,857; 5,328,768 and 5,492,750. In the MSVD method, the oxide of the metal or metal alloy can be deposited by sputtering a cathode containing the metal or metal alloy in an oxygen-containing atmosphere to deposit a metal oxide or metal alloy oxide film on the surface of the substrate. In one embodiment, the coating 30 is deposited over all or substantially all of the surface, i.e., no discrete coating areas are deposited. At least one coating 30 can be deposited over a flat substrate and then the substrate can be bent into shape in any conventional manner, such as by heating. Alternatively, at least one coating 30 can be deposited over a curved surface, i.e., a substrate that has been bent or shaped.

[0042] In an exemplary embodiment, the present invention is a coating useful for a HUD in a windshield, such as Figure 1 , Figure 2A , Figure 2B and Figure 3 , where the windshield comprises a first sheet 12, a second sheet 18 and an intermediate layer 24. The coating 30 may be located on the second surface 16 or the third surface 20, preferably on the second surface 16.

[0043] refer to Figure 2A, radiation 36 directed toward transparency 10 is deflected from transparency 10 such that at least a portion of radiation 36 is reflected by transparency 10 and directed into 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 sheets 12, 18, reflections from surface No. 1 14 (from the radiation) and surface No. 4 22 produce a ghost image that enters the driver's eye 38 when the glass sheets 12, 18 and PVB interlayer 24 in the windshield are parallel to each other.

[0044] refer to Figure 2B , the first sheet 12 may not be parallel to the second sheet 18. Preferably, in order to eliminate ghost images when exposed to radiation 36, the intermediate layer 24 has a wedge shape, wherein one side of the intermediate layer 24 is thicker than the other side. The wedge shape of the intermediate layer 24 can be configured so that the two reflected images from the surface No. 1 14 and the surface No. 4 22 overlap at the driver's eyes 38 to eliminate ghost images.

[0045] The silver coating may be applied to either surface 2 16 or surface 3 22, preferably surface 2 16 as described above, because the silver coating reduces energy and improves daylight performance. However, a silver coating applied to surface 2 16 will produce strong light reflections from radiation 36 and enhance the triple ghost image in the driver's eye 38. Figure 3 In order to eliminate the reflection from the surface, a specific coating 30 including a metallic layer must be designed so that the total internal reflection into the eye 38 is sufficiently low or equal to Figure 2B The specific coating 30 must also be color neutral in the visible spectrum range (400nm-700nm), which can be adjusted using various dielectric layers. When using the specific coating 30, the intermediate layer 24 can be a layer with uniform thickness in other arrangements of the transparent object 10, because the intermediate layer 24 may not need to be wedge-shaped to avoid ghosting problems, because other aspects of the design offset ghosting.

[0046] Coating 30 may be a tri-metal coating 33, such as three metallic layers, or a quad-metal coating 34, such as four metallic layers. Figure 4 , 6 Exemplary non-limiting coatings suitable for the tri-metal coating 33 are shown in and 8 . Figure 5 , 7 Exemplary non-limiting coatings suitable for the quad coating 34 are shown in and 9 .

[0047] The exemplary coating 30 includes three metallic layers (i.e., a tri-metallic coating 33) disposed between dielectric layers, such as Figure 4. The tri-metal coating 33 includes a base layer or a first dielectric layer 40 located above or in direct contact with at least a portion of the substrate's main surface (e.g., surface No. 2 16 of the first sheet 12 or surface No. 3 20 of the second sheet 18). The first metallic layer 52 is located above or in direct contact with at least a portion of the first dielectric layer 40. The optional first primer layer 54 may be located above or in direct contact with at least a portion of the first metallic layer 52. The second dielectric layer 60 is located above or in direct contact with the optional first primer layer 54 or the first metallic layer 52. The second metallic layer 72 is located above or in direct contact with at least a portion of the second dielectric layer 60. The optional second primer layer 74 may be located above or in direct contact with the second metallic layer 72. The third dielectric layer 80 is located above or in direct contact with the optional second primer layer 74 or the second metallic layer 72. The third metallic layer 92 may be located above at least a portion of the third dielectric layer 80. The optional third primer layer 94 may be located above at least a portion of the third metallic layer 92. The fourth dielectric layer 100 is located above at least a portion of the third metallic layer 92 or the optional third primer layer 94. The optional outermost protective layer 200 may be located above or in direct contact with the fourth dielectric layer 100.

[0048] The exemplary coating 30 includes four metallic layers (i.e., a quad-metal coating 34) disposed between dielectric layers, such as Figure 5. The four-metal coating 34 includes a base layer or a first dielectric layer 40 located above or in direct contact with at least a portion of a substrate major surface (e.g., surface No. 2 16 of the first sheet 12 or surface No. 3 20 of the second sheet 18). A first metallic layer 52 is located above or in direct contact with at least a portion of the first dielectric layer 40. An optional first primer layer 54 may be located above or in direct contact with at least a portion of the first metallic layer 52. A second dielectric layer 60 is located above or in direct contact with an optional first primer layer 54 or first metallic layer 52. A second metallic layer 72 is located above or in direct contact with at least a portion of the second dielectric layer 60. An optional second primer layer 74 may be located above or in direct contact with the second metallic layer 72. The third dielectric layer 80 is located above the optional second primer layer 74 or the second metallic layer 72 or in direct contact with the optional second primer layer 74 or the second metallic layer 72. The third metallic layer 92 may be located above at least a portion of the third dielectric layer 80. The optional third primer layer 94 may be located above at least a portion of the third metallic layer 92. The fourth dielectric layer 100 is located above at least a portion of the third metallic layer 92 or the optional third primer layer 94. The fourth metallic layer 112 is located above at least a portion of the fourth dielectric layer 100. An optional primer layer 114 is formed above at least a portion of the fourth metallic layer 112. A fifth dielectric layer 120 is formed above at least a portion of the fourth metallic layer 112 or the optional fourth primer layer 114. An optional outermost protective layer 200 may be located above the fifth dielectric layer 120 or in direct contact with the fifth dielectric layer 120.

[0049] The dielectric layer may include one or more films of anti-reflective materials and / or dielectric materials such as, but not limited to, metal oxides, oxides of metal alloys, nitrides, oxynitrides, or mixtures thereof. The first dielectric layer may be transparent to visible light. Examples of suitable metal oxides 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 have small amounts of other materials such as manganese in bismuth oxide, tin in indium oxide, and the like. Alternatively, oxides or metal alloys or metal mixtures may be used, such as oxides containing zinc and tin (e.g., zinc stannate); oxides of indium-tin alloys; silicon nitrides; silicon aluminum nitrides; or aluminum nitrides. In addition, 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 may be used. In one non-limiting embodiment, the first film 42 of the first dielectric layer may be a zinc / tin alloy oxide formed over at least a portion of the substrate (e.g., surface No. 2 16 of the first sheet 12 or surface No. 3 20 of the second sheet 18). The zinc / tin alloy oxide may be obtained by MSVD from a zinc and tin cathode, which may include zinc and tin in a ratio of 10 wt % to 90 wt % zinc and 90 wt % to 10 wt % tin. One suitable metal alloy oxide that may be present in the first film 42 of the first dielectric layer is zinc stannate. "Zinc stannate" means Zn x Sn 1-x O 2-x (Formula 1), wherein "x" varies in the range of greater than 0 to less than 1. For example, "x" may be greater than 0 and may be any fraction or decimal between greater than 0 and less than 1. For example, when x=2 / 3, Formula 1 is Zn 2 / 3 Sn 1 / 3 O 4 / 3 , which is more commonly described as Zn2SnO4. The zinc stannate-containing film has one or more forms of Formula 1 present in a major amount in the film.

[0050] The second film 44 of the first dielectric layer is formed over at least a portion of the first film 42 of the first dielectric layer and may include zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, or a mixture thereof. In a non-limiting embodiment, the second film 44 of the first dielectric layer may be a zinc-containing film, such as zinc oxide. The zinc oxide film may be deposited by a zinc cathode that includes other materials to improve the cathode sputtering characteristics. For example, the zinc cathode may include a small amount (e.g., less than 10% by weight, such as greater than 0 to 5% by weight) of tin to improve sputtering. In this case, the resulting zinc oxide film will include a small percentage of tin oxide, such as 0 to less than 10% by weight tin oxide, such as 0 to 5% by weight tin oxide. An oxide layer sputtered from a zinc / tin cathode having 95% by weight zinc and 5% by weight tin, or preferably 90% by weight zinc and 10% by weight tin, is referred to as a zinc oxide film. Small amounts of tin in the cathode (e.g., less than 10% by weight) are believed to form small amounts of tin oxide in the second film 44 of the first dielectric layer that is primarily zinc oxide. A non-limiting embodiment is where the first film 42 of the first dielectric layer is zinc stannate and the second film 44 of the first dielectric layer is zinc oxide and is over at least a portion of the first film 42 of the first dielectric layer.

[0051] In an exemplary non-limiting embodiment, the second film 44 is a film consisting of at least one of aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide. The aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide film is deposited from a zinc cathode that includes other materials to improve the cathode sputtering characteristics. For example, the aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide film may include a small amount (e.g., less than 10 wt %, such as greater than 0 to 5 wt %) of tin to improve sputtering. In this case, the resulting aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide film will include a small percentage of tin oxide, such as 0 wt % to less than 10 wt % tin oxide, such as 0 wt % to 5 wt % tin oxide.

[0052] One non-limiting embodiment is where the first film 42 of the first dielectric layer is zinc stannate, and the second film 44 of the first dielectric layer comprises zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide over at least a portion of the first film 42 of the first dielectric layer.

[0053] The first dielectric layer 40 of the tri-metal coating 33 may have a total thickness in the range of 10 nm to 50 nm, preferably 12 nm to 45 nm, more preferably 15 nm to 42 nm, and most preferably 18 nm to 40 nm. The first dielectric layer 40 of the quad-metal coating 34 may have a total thickness in the range of 20 nm to 55 nm, preferably 25 nm to 50 nm, more preferably 30 nm to 45 nm, and most preferably 35 nm to 40 nm.

[0054] In a non-limiting embodiment, the first dielectric layer 40 comprises a seed crystal (seed) film that directly contacts with the first metallic layer 52, which is not shown in the drawings. The seed crystal film can comprise the silver, silver, silver-zinc, titanium-aluminum, their alloy, their mixture, their oxide, their suboxide, their nitride, their subnitride or their combination of aluminum, aluminum silver, aluminum zinc, zinc, silver-zinc, their metal, their alloy, their oxide or their suboxide. In another embodiment, the seed crystal film can comprise gallium zinc, indium zinc, indium tin, their metal, their alloy, their oxide or their suboxide. The composition of the non-limiting example of seed crystal film can be found in Table 2. In some embodiments, a portion of the seed film is formed in an O2 atmosphere having a specific 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 of ordinary skill in the art will recognize that additional O2 can leak into the coating chamber because the coating chamber is not hermetically sealed from the external environment. In one non-limiting embodiment, the second film 44 of the first dielectric layer is a seed film. In another embodiment, the seed film comprises V x Zn 1-x In another embodiment, the seed film comprises Al x Zn 1-x In another embodiment, the seed film comprises Ga x Zn 1-x In another embodiment, the seed film comprises In x Zn 1-x In another embodiment, the seed film comprises Sn x In 1-x In another embodiment, the seed film comprises Ag deposited in an oxygen / argon environment. In another embodiment, the seed film comprises Al x Ag 1-xThe seed film may have a total thickness in the range of 0.5 nm to 10 nm, preferably 0.75 nm to 8 nm, more preferably 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.

[0055] Table 2 Metal composition of metal alloy used as seed film

[0056]

[0057]

[0058] The first metallic layer 52 can be deposited above at least a portion of the first dielectric layer 40. The first metallic layer 52 can include reflective metals such as but not limited to metallic gold, silver, their alloys, their mixtures or their combinations. The first metallic layer 52 is a continuous layer. In one embodiment, the first metallic layer 52 of the tri-metal coating 33 comprises metallic silver. The total thickness that the first metallic layer 52 of the tri-metal coating 33 has can be in the range of 5nm to 20nm, preferably 5nm to 17.5nm, more preferably 7nm to 15nm, most preferably 8nm to 10.5nm.

[0059] In one embodiment, the first metallic layer 52 of the four-metal coating 34 comprises metallic silver. In another embodiment, the first metallic layer 52 of the four-metal coating 34 is a continuous layer. The first metallic layer 52 of the four-metal coating 34 may have a total thickness in the range of 2 nm to 20 nm, preferably 6 nm to 18 nm, more preferably 9 nm to 12 nm, and most preferably 9.5 nm to 10 nm.

[0060] Optional first primer layer 54 can be deposited above at least a portion of the first metallic layer 52. The first primer layer 54 can be an oxygen capture material, such as titanium, which can sacrifice in the deposition process to prevent degradation or oxidation of the first metallic layer in sputtering process or subsequent heating process. Can select oxygen capture material to oxidize before the material of the first metallic layer 52. The composition of the first primer layer 54 is selected from following: zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, germanium, magnesium, molybdenum, silver, silicon carbon, aluminum-doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum niobium, aluminum titanium, tungsten titanium, tantalum titanium, zinc titanium, aluminum silver, zinc tin, indium zinc, silver zinc, their mixture, their combination or their any alloy, wherein with metal deposition primer and subsequently oxidized. At least a portion of primer layer is 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 prior to oxidation of the underlying metallic layer. In one embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 is titanium. In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises silver zinc. In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises zinc. In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 is Ag. x Zn 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 is Ag. x Zn 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Zn 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises In x Zn 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ga x Zn 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises V x Zn 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Ti 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Nb 1-xIn another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Nb 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises W x Nb 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises W x Ti 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ti x Ta 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ti x Nb 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ti x Nb 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Nb x Zr 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ta x W 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises W x Nb 1-x In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 comprises Zn x Ti 1-x The first primer layer 54 of the tri-metal coating 33 and the quad-metal coating 34 has a total thickness in the range of 0.5 nm to 5 nm, preferably 1.0 nm to 2.5 nm, more preferably 1.5 nm to 2.5 nm.

[0061] The second dielectric layer 60 may be deposited on at least a portion of the first metallic layer 52 or the optional first primer layer 54. The second dielectric layer 60 may also include one or more materials discussed above about the first dielectric layer 40. The second dielectric layer 60 may include a first film 62 of the second dielectric layer deposited on the first metallic layer 52 or the optional first primer layer 54. The first film 62 of the second dielectric layer includes an oxide, nitride, oxynitride, or a mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, their alloys, their mixtures, or their combinations. The first film 62 of the second dielectric layer may include aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, or a mixture thereof. In one embodiment, the first film 62 of the second dielectric layer includes zinc oxide. In another embodiment, the first film 62 of the second dielectric layer includes aluminum-doped zinc oxide. In another embodiment, the first film 62 of the second dielectric layer includes 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.

[0062] The second film 64 of the second dielectric layer may be deposited over at least a portion of the first film 62 of the second dielectric layer. The second film 64 of the second dielectric layer comprises an oxide, nitride, oxynitride, or mixture 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 a non-limiting embodiment, the second film 64 of the second dielectric layer is zinc stannate.

[0063] The optional third film 66 of the second dielectric layer may be deposited over at least a portion of the second film 64 of the second dielectric layer. The optional third film 66 of the second dielectric layer 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 thereof, mixtures thereof, or combinations thereof. The optional third film 66 of the second dielectric layer may include aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, or mixtures thereof. In one embodiment, the optional third film 66 of the second dielectric layer includes zinc oxide. In another embodiment, the third film 66 of the second dielectric layer includes indium-doped zinc oxide. In another embodiment, the third film 66 of the second dielectric layer includes gallium-doped zinc oxide. In another embodiment, the third film 66 of the second dielectric layer includes indium-doped tin oxide. In another embodiment, the third film 66 of the second dielectric layer includes vanadium-doped zinc oxide. In another embodiment, the first dielectric layer 40 or the second dielectric layer 60 includes a silicon nitride film.

[0064] One non-limiting embodiment is where the first film 62 of the second dielectric layer comprises zinc oxide, the second film 64 of the second dielectric layer comprises zinc stannate, and the third film 66 of the second dielectric layer comprises zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide over at least a portion of the second film 64 of the second dielectric layer.

[0065] The second dielectric layer 60 of the tri-metal coating 33 may have a total thickness in the range of 40 nm to 110 nm, preferably 50 nm to 100 nm, more preferably 55 nm to 80 nm, and most preferably 67 nm to 76 nm. The second dielectric layer 60 of the quad-metal coating 34 may have a total thickness in the range of 60 nm to 100 nm, preferably 65 nm to 95 nm, more preferably 70 nm to 90 nm, and most preferably 74 nm to 80 nm.

[0066] In a non-limiting embodiment, the second dielectric layer 60 comprises a seed film located in direct contact with the second metallic layer 72, which is not shown in the figures. The seed film may 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, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides or their combinations. In one embodiment, the seed film may comprise aluminum zinc, vanadium zinc, zinc, silver zinc, their metals, their alloys, their oxides or their suboxides. In another embodiment, the seed film may comprise gallium zinc, indium zinc, indium tin, their metals, their alloys, their oxides or their suboxides. The composition of the non-limiting examples of the seed film can be found in Table 2. In another embodiment, the seed film comprises V x Zn 1-x In another embodiment, the seed film comprises Al x Zn 1-x In another embodiment, the seed film comprises Ga x Zn 1-x In another embodiment, the seed film comprises In x Zn 1-x In another embodiment, the seed film comprises Sn x In 1-x In another embodiment, the seed film comprises Ag deposited in an oxygen / argon environment. In another embodiment, the seed film comprises Al x Ag 1-x The seed film may have a total thickness in the range of 0.5 nm to 10 nm, preferably 0.75 nm to 8 nm, more preferably 0.9 nm to 6 nm. In some embodiments, the second dielectric layer 60 has a first film 62, a second film 64, and a seed film. In some embodiments, the second dielectric layer 60 has a first film 62, a second film 64, a third film 66, and a seed film.

[0067] The second metallic layer 72 can be deposited above at least a portion of the second dielectric layer 60. The second metallic layer 72 is a continuous layer. The second metallic layer 72 can include any one or more of the reflective materials described above about the first metallic layer 52. In a non-limiting embodiment, the second metallic layer 72 comprises metallic silver. The total thickness that the second metallic layer 72 of the tri-metal coating 33 has can be in the range of 5nm to 20nm, preferably 5nm to 15nm, more preferably 7.5nm to 12.5nm, most preferably 8.5nm to 11.5nm.

[0068] In one embodiment, the second metallic layer 72 of the four-metal coating 34 comprises metallic silver. In another embodiment, the second metallic layer 72 of the four-metal coating 34 is a continuous layer. The second metallic layer 72 of the four-coating 34 may have a total thickness in the range of 2nm to 20nm, preferably 6nm to 18nm, more preferably 8nm to 15nm, and most preferably 9nm to 12nm.

[0069] An optional second primer layer 74 may be deposited over at least a portion of the second metallic 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 embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises titanium. In another embodiment, the optional second primer layer 74 comprises silver zinc. In another embodiment, the second primer layer 74 comprises zinc. In another embodiment, the optional second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ag. x Zn 1-x In another embodiment, the optional second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ag. x Zn 1-x In another embodiment, the optional second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Zn 1-x In another embodiment, the optional second primer layer 74 comprises In x Zn 1-x In another embodiment, the optional second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ga x Zn 1-x In another embodiment, the optional second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises V x Zn 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Ti 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Nb 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Nb 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises W x Nb 1-xIn another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises W x Ti 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ti x Ta 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ti x Nb 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ti x Nb 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Nb x Zr 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ta x W 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises W x Nb 1-x In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the quad-metal coating 34 comprises Zn 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, more preferably 1.5 nm to 2.5 nm.

[0070] The third dielectric layer 80 can be deposited on at least a portion of the second metallic layer 72 or the optional second primer layer 74. The third dielectric layer 80 can also include one or more materials discussed above about the first and second dielectric layers. In a non-limiting embodiment, the third dielectric layer 80 comprises the first film 82 of the third dielectric layer. The first film 82 of the third dielectric layer comprises an oxide, nitride, oxynitride or a mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, their alloys, their mixtures or their combinations. The first film 82 of the third dielectric layer can 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 their mixtures. In one embodiment, the first film 82 of the third dielectric layer comprises 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.

[0071] The second film 84 of the third dielectric layer may be deposited over at least a portion of the first film 82 of the third dielectric layer. The second film 84 of the third dielectric layer comprises an oxide, nitride, oxynitride, or mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. In one embodiment, the second film 84 of the third dielectric layer comprises zinc stannate. In another embodiment, the second film 84 of the third dielectric layer comprises zinc oxide.

[0072] The optional third film 86 of the third dielectric layer may be deposited over at least a portion of the second film 84 of the third dielectric layer. The optional third film 86 of the third dielectric layer 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 thereof, mixtures thereof, or combinations thereof. The optional third film 86 of the third dielectric layer may include aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, or mixtures thereof. In one embodiment, the optional third film 86 of the third dielectric layer includes zinc oxide. In another embodiment, the third film 86 of the third dielectric layer includes aluminum-doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer includes indium-doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer includes gallium-doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer includes tin-doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer includes vanadium-doped zinc oxide.

[0073] One non-limiting embodiment is where the first film 82 of the third dielectric layer comprises zinc oxide or zinc stannate, and the second film 84 of the third dielectric layer comprises zinc oxide or zinc stannate, and the third film 86 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 over at least a portion of the second film 84 of the third dielectric layer.

[0074] The third dielectric layer 80 of the tri-metal coating 33 may have a total thickness in the range of 40 nm to 110 nm, preferably 50 nm to 100 nm, more preferably 65 nm to 80 nm, and most preferably 71 nm to 75 nm. The third dielectric layer 80 of the quad-metal coating 34 may have a total thickness in the range of 55 nm to 90 nm, preferably 60 nm to 85 nm, more preferably 68 nm to 80 nm, and most preferably 70 nm to 75 nm.

[0075] In a non-limiting embodiment, the third dielectric layer 86 comprises a seed film located in direct contact with the third metallic layer 92, which is not shown in the drawings. The seed film may 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, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides or their combinations. In one embodiment, the seed film may comprise aluminum zinc, vanadium zinc, zinc, silver zinc, their metals, their alloys, their oxides or their suboxides. In another embodiment, the seed film may comprise gallium zinc, indium zinc, indium tin, their metals, their alloys, their oxides or their suboxides. The composition of the non-limiting examples of the seed film can be found in Table 2. In another embodiment, the seed film comprises V x Zn 1-x In another embodiment, the seed film comprises Al x Zn 1-x In another embodiment, the seed film comprises Ga x Zn 1-x In another embodiment, the seed film comprises In x Zn 1-x In another embodiment, the seed film comprises Sn x In 1-x In another embodiment, the seed film comprises Ag deposited in an oxygen / argon environment. In another embodiment, the seed film comprises Al x Ag 1-x The seed film may have a total thickness in the range of 0.5 nm to 10 nm, preferably 0.75 nm to 8 nm, and more preferably 0.9 nm to 6 nm. In some embodiments, the third dielectric layer 80 has a first film 82, a second film 84, and a seed film. In some embodiments, the third dielectric layer 80 has a first film 82, a second film 84, a third film 86, and a seed film. In some embodiments, the third dielectric layer 80 has a first film 82, a second film 84, and a third film 86.

[0076] The third metallic layer 92 can be deposited above at least a portion of the third dielectric layer 80. The third metallic layer 92 is a continuous layer. The third metallic layer 92 can include any one or more of the reflective materials described above about the first metallic layer 52. In a non-limiting embodiment, the third metallic layer 92 comprises metallic silver. The total thickness that the third metallic layer 92 of the tri-metal coating 33 has can be in the range of 1nm to 20nm, preferably 5nm to 20nm, more preferably 7.5nm to 15nm, most preferably 7.5nm to 10.5nm.

[0077] In one embodiment, the third metallic layer 92 of the four-metal coating 34 comprises metallic silver. In another embodiment, the third metallic layer 92 of the four-metal coating 34 is a continuous layer. The third metallic layer 92 of the four-metal coating 34 has a total thickness that can be in the range of 2nm to 20nm, preferably 6nm to 18nm, more preferably 8nm to 15nm, and most preferably 9nm to 12nm.

[0078] In one non-limiting embodiment, coating 30 comprises only first, second, and third metallic layers ( Figure 4 , 6 In the coating 30, there is no additional metallic layer. Each metallic layer has a thickness. In a non-limiting embodiment, the total thickness of the metallic layer of the tri-metal coating 33 is in the range of 10nm to 60nm, preferably 15nm to 50nm, more preferably 20nm to 40nm, most preferably 25nm to 31nm. In the case where the primer layer comprises aluminum and zinc, the total thickness of the metallic layer of the tri-metal coating 33 is in the range of 10nm to 65nm, preferably 15nm to 55nm, more preferably 20nm to 45nm, most preferably 25nm to 36nm.

[0079] An optional third primer layer 94 may be deposited over at least a portion of the third metallic layer 92. The third primer layer 94 may be any material described above with respect to the first primer layer 54. In one non-limiting embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises titanium. In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises silver zinc. In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises zinc. In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ag. x Zn 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ag. x Zn 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Zn 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises In x Zn 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ga x Zn 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Vx Zn 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Ti 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Nb 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Al x Nb 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises W x Nb 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises W x Ti 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ti x Ta 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ti x Nb 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ti x Nb 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Nb x Zr 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Ta x W 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises W x Nb 1-x In another embodiment, the third primer layer 94 of the tri-metal coating 33 and the quad-metal coating 34 comprises Zn x Ti 1-x Oxide.

[0080] The third primer layer 94 of the tri-metal coating layer 33 and the quad-metal coating layer 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.

[0081] The fourth dielectric layer 100 can be deposited on at least a portion of the third metallic layer 92 or the optional third primer layer 94. The fourth dielectric layer 100 can also include one or more materials discussed above about the first, second and third dielectric layers 40,60,80. In a non-limiting embodiment, the fourth dielectric layer 100 comprises the first film 102 of the fourth dielectric layer. The first film 102 of the fourth dielectric layer comprises an oxide, nitride, oxynitride or a mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, their alloys, their mixtures or their combinations. The first film 102 of the fourth dielectric layer can 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 their mixtures. 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.

[0082] The second film 104 of the fourth dielectric layer may be deposited over at least a portion of the first film 102 of the fourth dielectric layer. The second film 104 of the fourth dielectric layer comprises 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 thereof, mixtures thereof, or combinations thereof. In one embodiment, the second film 104 of the fourth dielectric layer comprises zinc stannate or zinc oxide. In some embodiments, the first film 102 and the second film 104 are the only films of the fourth dielectric layer 100.

[0083] The optional third film 106 of the fourth dielectric layer may be deposited over 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 include an oxide, nitride, oxynitride, or mixture thereof of a metal selected from titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, their alloys, their mixtures, or combinations thereof. The optional third film 106 of the fourth dielectric layer may include aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, or mixtures thereof. In one embodiment, the optional third film 106 of the fourth dielectric layer includes zinc oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer includes silicon nitride or silicon oxynitride. In another embodiment, the optional third film 106 of the fourth dielectric layer includes aluminum-doped zinc oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer includes 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.

[0084] One non-limiting embodiment is where the first film 102 of the fourth dielectric layer comprises zinc oxide or zinc stannate, and 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 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 over at least a portion of the second film 104 of the third dielectric layer.

[0085] The fourth dielectric layer 100 of the tri-metal coating 33 may have a total thickness in the range of 10 nm to 50 nm, preferably 15 nm to 40 nm, more preferably 20 nm to 35 nm, and most preferably 27 nm to 31 nm. The fourth dielectric layer 100 of the quad-metal coating 34 may have a total thickness in the range of 45 nm to 80 nm, preferably 50 nm to 75 nm, more preferably 55 nm to 70 nm, and most preferably 60 nm to 65 nm.

[0086] Figure 5 , 7The four metal coatings 34 of 9 include additional layers. In a non-limiting embodiment, the fourth dielectric layer 100 of the four metal coatings 34 includes a seed film located in direct contact with the fourth metallic layer 112, which is not shown in the figure. The seed film may include aluminum, aluminum silver, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides or their combinations. The seed film may include aluminum zinc, vanadium zinc, zinc, silver zinc, their metals, their alloys, their oxides, or their suboxides. In another example, the seed film may include gallium zinc, indium zinc, indium tin, their metals, their alloys, their oxides, or their suboxides. The composition of the non-limiting examples of the seed film can be found in Table 2. In another embodiment, the seed film includes V x Zn 1-x In another embodiment, the seed film comprises Al x Zn 1-x In another embodiment, the seed film comprises Ga x Zn 1-x In another embodiment, the seed film comprises In x Zn 1-x In another embodiment, the seed film comprises Sn x In 1-x In another embodiment, the seed film comprises Ag deposited in an oxygen / argon environment. In another embodiment, the seed film comprises Al x Ag 1-x In one non-limiting embodiment, the third film 106 of the fourth dielectric layer of the quad metal coating 34 is a seed film. The seed film may have a total thickness in the range of 0.5 nm to 10 nm, preferably 0.75 nm to 8 nm, and more preferably 0.9 nm to 6 nm. In some embodiments, the fourth dielectric layer 100 has a first film 102, a second film 104, and a seed film. In some embodiments, the fourth dielectric layer 100 includes a first film 102, a second film 104, a third film 106, and a seed film.

[0087] The fourth metallic layer 112 of the four metal coatings 34 can be deposited above at least a portion of the fourth dielectric layer 100. The fourth metallic layer 112 is a continuous layer. The fourth metallic layer 112 may include any one or more of the reflective materials described above about the first metallic layer 52. In a non-limiting embodiment, the fourth metallic layer 112 of the four metal coatings 34 includes metallic silver. The total thickness that the fourth metallic layer 112 of the four metal coatings 34 has can be in the range of 2nm to 20nm, preferably 4nm to 15nm, more preferably 6nm to 11nm, most preferably 7nm to 10nm.

[0088] An optional fourth primer layer 114 may be deposited over at least a portion of the fourth metallic layer 112 of the quad-metal coating 34. The fourth primer layer 114 may be any material described above with respect to the first primer layer 54. In one non-limiting embodiment, the fourth primer layer 114 comprises titanium. In another embodiment, the fourth primer layer 114 comprises silver zinc. In another embodiment, the fourth primer layer 114 comprises zinc. In another embodiment, the fourth primer layer 114 comprises 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 Al x Zn 1-x In another embodiment, the fourth primer layer 114 comprises In x Zn 1-x In another embodiment, the fourth primer layer 114 comprises Ga x Zn 1-x In another embodiment, the fourth primer layer 114 comprises V x Zn 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises Al x Ti 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises Al x Nb 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises Al x Nb 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises W x Nb 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises W x Ti 1-xIn another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises Ti x Ta 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises Ti x Nb 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises Ti x Nb 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises Nb x Zr 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises Ta x W 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises W x Nb 1-x In another embodiment, the fourth primer layer 114 of the quad-metal coating 34 comprises Zn x Ti 1-x Oxide.

[0089] 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, more preferably 1.5 nm to 2.5 nm.

[0090] The fifth dielectric layer 120 can be deposited on at least a portion of the fourth metallic layer 112 or above the optional fourth primer layer 114. The fifth dielectric layer 120 can also include one or more materials discussed above about the first, second, third and fourth dielectric layers. In a non-limiting embodiment, the fifth dielectric layer 120 comprises the first film 122 of the fifth dielectric layer. The first film 122 of the fifth dielectric layer comprises an oxide, nitride, oxynitride or the mixture thereof selected from the following metal: titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, their alloy, their mixture or their combination. In one embodiment, the first film 122 of the fifth dielectric layer comprises zinc oxide or zinc stannate.

[0091] The second film 124 of the fifth dielectric layer may be deposited over at least a portion of the first film 122 of the fifth dielectric layer. The second film 124 of the fifth dielectric layer comprises an oxide, a nitride, an oxynitride, or a mixture thereof of a metal selected from the group consisting of titanium, niobium, zinc, indium, tin, silicon, aluminum, an alloy thereof, a mixture thereof, or a combination thereof. The second film 124 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 a mixture thereof. In one embodiment, the second film 124 of the fifth dielectric layer comprises zinc stannate or zinc oxide. In another embodiment, the second film 124 of the fifth dielectric layer comprises silicon nitride or silicon oxynitride. In another embodiment, the second film 124 of the fifth dielectric layer 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 includes indium-doped tin oxide.

[0092] In another embodiment, the first film 124 of the fifth dielectric layer includes vanadium-doped zinc oxide.

[0093] The optional third film of the fifth dielectric layer may be deposited over at least a portion of the second film 124 of the fifth dielectric layer. The optional third film of the fifth dielectric layer may include an oxide, nitride, oxynitride, or mixture thereof of a metal selected from titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, their alloys, their mixtures, or combinations thereof. The optional third film of the fifth dielectric layer may include aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, or mixtures thereof. In a non-limiting embodiment, the optional third film of the fifth dielectric layer includes zinc oxide. In another embodiment, the optional third film of the fifth dielectric layer includes silicon nitride or silicon oxynitride. In another embodiment, the optional third film of the fifth dielectric layer includes titanium oxide. In another embodiment, the optional third film of the fifth dielectric layer includes aluminum-doped zinc oxide. In another embodiment, the optional third film of the fifth dielectric layer includes 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.

[0094] One non-limiting embodiment of the quad-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 comprises zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide over at least a portion of the second film 124 of the fifth dielectric layer.

[0095] The fifth dielectric layer 120 of the quad-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.

[0096] In a non-limiting embodiment, coating 30 comprises first, second, third and fourth metallic layer.Metallic layer is a continuous metallic layer.Metallic layer can comprise only silver or only silver and gold.Each metallic layer has thickness.In a non-limiting embodiment, the total combined thickness of the metallic layer of four metal coatings 34 is in the scope of 10nm to 60nm, preferably 20nm to 50nm, more preferably 30nm to 45nm, most preferably 35nm to 40nm.When the primer layer comprises aluminum and zinc, the total thickness of the metallic layer of four metal coatings 34 is in the scope of 10nm to 65nm, preferably 20nm to 60nm, more preferably 40nm to 55nm, most preferably 35nm to 45nm.

[0097] The three- and four-metal coatings 33, 34 may include an outermost protective layer 200, which is, for example, Figure 4-7In the non-limiting embodiment shown in , it is deposited on at least a portion of the fourth or fifth dielectric layer 100, 120 to help protect the underlying layer, such as the metallic layer, from mechanical and chemical erosion during processing. The outermost protective layer 200 can be an oxygen barrier coating to prevent or reduce ambient oxygen from passing through the underlying layer of the coating (e.g., during heating or blending). The outermost protective layer 200 can have any desired material or mixture of materials and can include one or more protective films. In an exemplary embodiment, the outermost protective layer 200 can include a monolayer, which includes one or more metal oxide materials, such as, but not limited to, the oxide of aluminum, silicon, or a mixture thereof. For example, the outermost protective coating can be a single coating layer, including a range of: 0 wt% to 100 wt% aluminum oxide and / or 100 wt% to 0 wt% silicon oxide, such as 5 wt% to 95 wt% aluminum oxide and 95 wt% to 5 wt% silicon oxide, such as 10 wt% to 90 wt% aluminum oxide and 90 wt% to 10 wt% silicon oxide, such as 15 wt% to 90 wt% aluminum oxide and 85 wt% to 10 wt% silicon oxide, such as 50 wt% to 75 wt% aluminum oxide and 50 wt% to 25 wt% silicon oxide, such as 50 wt% to 70 wt% aluminum oxide and 50 wt% to 30 wt% silicon oxide. Silicon oxide, for example 35 wt % to 100 wt % aluminum oxide and 65 wt % to 0 wt % silicon oxide, for example 70 wt % to 90 wt % aluminum oxide and 30 wt % to 10 wt % silicon oxide, for example 75 wt % to 85 wt % aluminum oxide and 25 wt % to 15 wt % silicon oxide, for example 88 wt % aluminum oxide and 12 wt % silicon oxide, for example 65 wt % to 75 wt % aluminum oxide and 35 wt % to 25 wt % silicon oxide, for example 70 wt % aluminum oxide and 30 wt % silicon oxide, for example 60 wt % to less than 75 wt % aluminum oxide and greater than 25 wt % to 40 wt % silicon oxide. Other materials such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium and / or their oxides may also be present to adjust the refractive index of the outermost protective layer 200. In one non-limiting embodiment, 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.

[0098] In one non-limiting embodiment, the outermost protective layer 200 is a combined silicon oxide and aluminum oxide 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 silicon and aluminum. This silicon aluminum oxide outermost protective layer 200 can be written as Si x Al 1-x O (1.5+x) / 2, where x can vary from greater than 0 to less than 1. In one exemplary embodiment, the outermost protective layer 200 comprises 15 wt % aluminum oxide and 85 wt % silicon oxide. In another embodiment, the outermost protective layer 200 comprises SiO2, Al2O3, SiAlO, alloys thereof, and mixtures thereof.

[0099] In one non-limiting embodiment, the outermost protective layer 200 may be composed of silicon nitride (Si3N4), silicon oxynitride (SiON), silicon aluminum nitride (SiAlN), silicon aluminum oxynitride (SiAlON), mixtures thereof, and / or alloys thereof, and it may provide the coated article with improved durability. The outermost protective layer 200 may be formed of silicon nitride deposited together with other materials having excellent electrical conductivity to improve the sputtering of silicon. For example, during deposition, the silicon cathode may include a small amount (e.g., up to 20 wt%, up to 15 wt%, up to 10 wt%, or up to 5 wt%) of aluminum to improve sputtering. In this case, the resulting silicon nitride layer will include a small percentage of aluminum, such as up to 15 wt% aluminum, such as up to 10 wt% aluminum, such as up to 5 wt% aluminum. The coating layer deposited from a silicon cathode having up to 10 wt% aluminum (added to enhance the conductivity of the cathode) is referred to herein as a "silicon nitride" layer, even though a small amount of aluminum may be present. A small amount of aluminum in the cathode (e.g., less than or equal to 15 wt. %, such as less than or equal to 10 wt. %, such as less than or equal to 5 wt. %) is believed to form aluminum nitride in the outermost protective layer 200, which is primarily silicon nitride. The outermost protective layer 200 can be formed in a nitrogen atmosphere; however, it should be understood that other gases such as oxygen can be present in the atmosphere during deposition of the outermost protective layer 200.

[0100] In another non-limiting embodiment, the outermost protective layer 200 may be a multilayer coating comprising a first protective film 202 and a second protective film 204 formed above at least a portion of the first protective film 202. The first protective film 202 may include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, tin oxide, alloys thereof, mixtures thereof, or combinations thereof. In a specific non-limiting embodiment, the first protective film 202 may include aluminum oxide or an alloy comprising aluminum oxide and silicon oxide. For example, the first protective film 202 may include a silicon oxide / aluminum oxide mixture having greater than 5 wt% aluminum oxide, such as greater than 10 wt% aluminum oxide, such as greater than 15 wt% aluminum oxide, such as 50 wt% to 70 wt% aluminum oxide, such as in the range of 60 wt% to 100 wt% aluminum oxide and 40 wt% to 0 wt% silicon oxide, such as 60 wt% aluminum oxide and 40 wt% silicon oxide. In another example, the first protective film 202 may include zinc stannate. In another example, the first protective film 202 may include zirconium oxide.

[0101] The second protective film 204 may include, for example, a metal oxide or a metal nitride. The second protective film 204 may be titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, tin oxide, a mixture thereof, or an alloy thereof. For example, the second protective film 204 may include a titanium oxide / aluminum oxide mixture having 40 wt % to 60 wt % aluminum oxide and 60 wt % to 40 wt % titanium oxide; 45 wt % to 55 wt % aluminum oxide and 55 wt % to 45 wt % titanium oxide; 48 wt % to 52 wt % aluminum oxide and 52 wt % to 48 wt % titanium oxide; 49 wt % to 51 wt % aluminum oxide and 51 wt % to 49 wt % titanium oxide; or 50 wt % aluminum oxide and 50 wt % titanium oxide. An example of the second protective film 204 may include titanium aluminum oxide (TiAlO). Another example of the second protective film 204 is a silicon oxide / aluminum oxide mixture having greater than 40 wt % silicon oxide, for example greater than 50 wt % silicon oxide, for example greater than 60 wt % silicon oxide, for example greater than 70 wt % silicon oxide, for example greater than 80 wt % silicon oxide, for example in the range of 80 wt % to 90 wt % silicon oxide and 10 wt % to 20 wt % aluminum oxide, for example 85 wt % silicon oxide and 15 wt % aluminum oxide.

[0102] In a non-limiting example, the outermost protective layer 200 may include an additional third protective film formed over at least a portion of the second protective film 204. The third protective film may be any material used to form the first and second protective films 202, 204. The third protective film may, for example, include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, tin oxide, or a mixture thereof. For example, the third protective film may include a mixture of silicon oxide and aluminum oxide. In another example, the third protective film includes aluminum oxide and titanium oxide. In another example, the third protective film includes zirconium oxide.

[0103] The outermost protective layer 200 is the outermost layer of the coating. In addition, the outermost protective layer 200 may have an uneven thickness. "Uneven thickness" means 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 regions. The total thickness that the outermost protective layer 200 has may be in the range of 20nm to 120nm, preferably 25nm to 110nm, more preferably 30nm to 100nm, and most preferably 35nm to 90nm. 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.

[0104] In some non-limiting embodiments, the coated article 30 further comprises a light absorber. The light absorber is selected from the following: tinted glass, PVB, an absorbing layer, or a combination thereof.

[0105] In the non-limiting embodiment described above, an additional optional absorber layer 140 may be located over at least a portion of the fourth dielectric layer 100 of the tri-metal coating 33 ( Figure 8 ) or the fifth dielectric layer 120 of the quad metal coating 34 ( Fig. 9 ), so that the absorption layer 140 will be located 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 will be the outermost coating. The absorption layer 140 is selected from the following: Ge, GeO x 、NbN x 、NbN x O y 、Si a Al b 、Si a Al b O x 、S i a Co b 、Si a Co b O x 、Si a Co b Cu c 、S i a Co b Cu c O x 、S i a Cr b 、Si a Cr b O x 、Si a Ni b 、SiNiO x 、S iO 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 Snb 、Zn a Sn b O x , or any combination thereof. In a non-limiting embodiment, the absorber layer 140 comprises silicon cobalt oxide. The absorber layer 140 may have a total thickness in the range of 1 nm to 40 nm, preferably 5 nm to 30 nm, more preferably 10 nm to 25 nm, and most preferably 15 nm to 20 nm.

[0106] Alternatively, the absorption layer 140 may comprise a subcritical metal film. The term "subcritical thickness" means that the thickness less than the critical thickness causes the coating material to form an island-like unconnected area of ​​the coating material. The term "island-like" means that the coating material is not a continuous layer, but on the contrary, the deposited material forms a separate area or island. The metal in the subcritical metal film may include silver, gold, their alloys, their mixtures, or combinations thereof. In a non-limiting embodiment, the subcritical metal film includes silver. The subcritical metal film may have a total subcritical thickness in the range of 0.5nm to 20nm, preferably 1nm to 10nm, more preferably 1.5nm to 3.5nm.

[0107] In another non-limiting embodiment, an 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 located between the subcritical metal film and the optional outermost protective layer 200. The optional dielectric layer 160 may be a multilayer, as described above, comprising one or more dielectric films. The additional dielectric layer 160 may 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 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.

[0108] In some non-limiting embodiments, a tinted glass cover sheet or a clear glass cover sheet 12, 18 and / or a tinted PVB or untinted PVB interlayer 24 may be used to attempt to match the three requirements, namely, a neutral color of Rf, a low Rf and Rg of approximately 8%, and an LTA value of not less than 70% for the forward viewing area of ​​the vehicle.

[0109] In a non-limiting practice of the present invention, the thickness and / or number of the silver layers are constructed to produce a total resistivity (sheet resistance) in the range of 0.6 to 1.5 ohms / square (Ω / □), preferably 0.6 to 1.0 Ω / □, and more preferably 0.6 to 0.9 Ω / □ for the coating. However, those skilled in the art will also appreciate that as the number or thickness of the silver metallic layers increases, the visible light transmittance decreases. The thickness and / or number of the metallic layers should not be increased to the extent that the visible light transmittance of the sight area drops by less than about 70%. In addition, if the total silver thickness is too thick, the color of the glass will appear undesirable red.

[0110] In one non-limiting practice of the invention, the coating provides a visible light reflectance of no greater than 25%, such as no greater than 20%, such as no greater than 10%, such as no greater than 8%.

[0111] In one non-limiting practice of the present invention, the coating 30 provides an external (ext) reflection a* (Rg8a*) at an 8 degree angle (°) in the range of 1 to -2. For example, in the range of 1 to -1, preferably -0.5 to 0.5, more preferably -0.5 to 0, and most preferably 0.

[0112] In one non-limiting practice of the present invention, coating 30 provides an external reflection b* (Rg8b*) at 8° in the range of 1 to -2. For example, in the range of 1 to -1, preferably -0.5 to 0.5, more preferably -0.5 to 0, and most preferably 0.

[0113] The present invention is further described in the following numbered clauses:

[0114] Item 1: A coated article comprising a substrate comprising a first surface and a second surface opposite the first surface; 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 metallic layer over at least a portion of the first dielectric layer; a second dielectric layer over at least a portion of the first metallic layer; a second metallic layer over at least a portion of the second dielectric layer; a third dielectric layer over at least a portion of the second metallic layer; a third metallic layer over at least a portion of the third dielectric layer; and a fourth dielectric layer over at least a portion of the third metallic layer, wherein the total combined thickness of the metallic layers is at least 10 nanometers and no greater than 60 nanometers.

[0115] Item 2: The coated article of Item 1, wherein the total combined thickness of the metallic layers is at least 20 nm and no greater than 40 nanometers.

[0116] Item 3: The coated article of Item 1, wherein the total combined thickness of the metallic layers is at least 25 nm and no greater than 31 nanometers.

[0117] Clause 4: The coated article of any preceding clause, wherein the coated article has a visible light reflectance of no greater than 8%.

[0118] Clause 5: The coated article of any preceding clause, wherein the coated article has a visible light transmittance of at least 70%.

[0119] Item 6: The coated article of any preceding item, wherein at least one metallic layer comprises at least one of silver, gold, alloys thereof, mixtures thereof, or combinations thereof.

[0120] Item 7: The coated article of Item 6, wherein at least one metallic layer is silver.

[0121] Item 8: The coated article of any preceding item, wherein at least one metallic layer is a continuous layer.

[0122] Item 9: The coated article of any preceding item, wherein the first metallic layer has 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 nm to 10.5 nm.

[0123] Item 10: The coated article of any preceding item, wherein the second metallic layer has 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.

[0124] Item 11: The coated article of any preceding item, wherein the third metallic layer has a total thickness of from 1 nm to 20 nm, preferably from 5 nm to 20 nm, more preferably from 7.5 nm to 15 nm, or most preferably from 7.5 nm to 10.5 nm.

[0125] Item 12: The coated article of any preceding item, further comprising at least one primer layer formed over the at least one metallic layer.

[0126] Item 13: The coated article of Item 12, wherein 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 wherein the primer is deposited as a metal and subsequently oxidized.

[0127] Item 14: The coated article of item 12 or 13, wherein when at least one primer layer comprises aluminum and zinc, the total thickness of the metallic layer 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.

[0128] 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.

[0129] Item 16: The coated article of any preceding item, wherein at least one dielectric layer comprises zinc stannate, zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide.

[0130] Item 17: The coated article of any preceding item, 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, mixtures thereof, or combinations thereof over at least a portion of the first film.

[0131] 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, mixtures thereof, or combinations thereof.

[0132] Item 19: The coated article of items 17 to 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.

[0133] Item 20: The coated article of any preceding item, wherein the first dielectric layer comprises a seed film in direct contact with the first metallic layer, wherein the seed film may 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, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides, or combinations thereof.

[0134] Item 21: The coated article of any preceding item, wherein the second dielectric layer comprises a first film comprising zinc oxide over at least a portion of the first primer layer, and a second film comprising zinc stannate over at least a portion of the first film, and a third film comprising zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, mixtures thereof, or combinations thereof over at least a portion of the second film.

[0135] Item 22: The coated article of Item 21, wherein the second dielectric layer has 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.

[0136] Item 23: The coated article of any preceding item, wherein the second dielectric layer comprises a seed film in direct contact with the second metallic layer, wherein the seed film comprises aluminum, aluminum silver, aluminum zinc, zinc, zinc tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver, silver zinc, titanium aluminum, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides, or combinations thereof.

[0137] Item 24: The coated article of any preceding item, wherein the third dielectric layer comprises a first film comprising zinc oxide or zinc stannate over at least a portion of the second primer layer, and a second film comprising zinc stannate or zinc oxide over at least a portion of the first film, and a third film comprising zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, mixtures thereof, or combinations thereof over at least a portion of the second film.

[0138] 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.

[0139] Item 26: The coated article of any preceding item, wherein the third dielectric comprises a seed film in direct contact with the third metallic layer, wherein the seed film may 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, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides, or combinations thereof.

[0140] Item 27: The coated article of any preceding item, wherein the fourth dielectric layer comprises a first film comprising zinc oxide or zinc stannate over at least a portion of the third primer layer, and a second film comprising zinc stannate or zinc oxide over at least a portion of the first film, and a third film comprising zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide, or a combination thereof, over at least a portion of the second film.

[0141] Item 28: The coated article of Item 27, wherein the fourth dielectric layer has 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.

[0142] Item 29: The coated article of any preceding item, further comprising an outermost protective coating, the outermost protective coating comprising a protective layer, wherein the protective layer comprises at least one of the following: Si3N4, SiAlN, SiAlON, titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, alloys thereof, mixtures thereof, or combinations thereof.

[0143] 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.

[0144] Item 31: The coated article of any one of Items 29 to 30, wherein the outermost protective layer comprises a first protective film and a second protective film formed over the first protective film.

[0145] Item 32: The coated article of Items 29 to 31, wherein the outermost protective layer comprises silicon aluminum oxide, titanium aluminum oxide, mixtures thereof, or combinations thereof.

[0146] Item 33: The coated article of any preceding item, further comprising a light absorber selected from the group consisting of tinted glass, polyvinyl butyral ("PVB"), an absorbing layer, or a combination thereof.

[0147] Item 34: The coated article of Item 33, wherein an absorber layer is formed over at least a portion of the fourth dielectric layer.

[0148] Item 35: The coated article of Item 34, wherein the absorber layer is selected from the group consisting of Ge, GeO x 、NbN x 、NbN x O y 、Si a Al b 、Si a Al b O x 、Si a Co b 、S i a Co b O x 、Si a Co b Cu c 、S i a Co b Cu c O x、S i a Cr b 、S i a Cr b O x 、S i 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.

[0149] Item 36: The coated article of Item 35, wherein the absorber layer comprises silicon cobalt oxide.

[0150] Item 37: The coated article of any one of Items 35 to 36, wherein the absorbing layer has a total thickness of from 1 nm to 40 nm, preferably from 5 nm to 30 nm, more preferably from 10 nm to 25 nm, or most preferably from 15 nm to 20 nm.

[0151] Item 38: The coated article of Item 34, wherein the absorber layer is a subcritical metal film.

[0152] Item 39: The coated article of Item 38, wherein the subcritical metal film comprises silver, gold, alloys thereof, mixtures thereof, or combinations thereof.

[0153] Item 40: The coated article of any of Items 38 to 39, wherein the subcritical metal film comprises silver.

[0154] Item 41: The coated article of any one 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.

[0155] 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.

[0156] Item 43. The coated article of Item 42, wherein the additional dielectric layer formed over 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.

[0157] Item 44: The coated article of any of Items 42 to 43, wherein the additional dielectric layer formed over at least a portion of the subcritical metal film has 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, most preferably 28 nm to 30 nm.

[0158] Item 45: A coated article comprising a substrate comprising a first surface and a second surface opposite the first surface; 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 metallic layer over at least a portion of the first dielectric layer; a second dielectric layer over at least a portion of the first metallic layer; a second metallic layer over at least a portion of the second dielectric layer; a third dielectric layer over at least a portion of the second metallic layer; a third metallic layer over at least a portion of the third dielectric layer; a fourth dielectric layer over at least a portion of the third metallic layer; a fourth metallic layer over at least a portion of the fourth dielectric layer; and a fifth dielectric layer over at least a portion of the fourth metallic layer, wherein the total combined thickness of the metallic layers is at least 10 nanometers and no greater than 60 nanometers.

[0159] Item 46: The coated article of Item 45, wherein the total combined thickness of the metallic layers is at least 30 nm and no greater than 45 nanometers.

[0160] Item 47: The coated article of any Item 45, wherein the total combined thickness of the metallic layers is at least 35 nm and no greater than 40 nanometers.

[0161] Item 48: The coated article of any one of Items 45 to 47, wherein the coated article has a visible light reflectance of no greater than 8%.

[0162] Item 49: The coated article of any of Items 45 to 48, wherein the coated article has a visible light transmittance of at least 70%.

[0163] Item 50: The coated article of any of Items 45 to 49, wherein at least one metallic layer comprises at least one of silver, gold, alloys thereof, mixtures thereof, or combinations thereof.

[0164] Item 51: The coated article of any of Items 45 to 50, wherein at least one metallic layer is silver.

[0165] Item 52: The coated article of any of Items 45 to 51, wherein at least one metallic layer is a continuous layer.

[0166] Item 53: The coated article of any one of Items 45 to 52, wherein the first metallic layer has 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.

[0167] Item 54: The coated article of any one of Items 45 to 53, wherein the second metallic layer has 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.

[0168] Item 55: The coated article of any one of Items 45 to 54, wherein the third metallic layer has 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.

[0169] Item 56: The coated article of any one of Items 45 to 47, wherein the fourth metallic 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.

[0170] Item 57: The coated article of any of Items 45 to 56, further comprising at least one primer layer formed over the at least one metallic layer.

[0171] 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 wherein the primer is deposited as a metal and subsequently oxidized.

[0172] Item 59: The coated article of Item 57 or 58, wherein when at least one primer layer comprises aluminum and zinc, the total thickness of the metallic layers is in the range of 10 nm to 65 nm, preferably 20 nm to 60 nm, most preferably 40 nm to 55 nm, most preferably 35 nm to 45 nm.

[0173] Item 60: The coated article of any of Items 45 to 59, wherein at least one dielectric layer comprises zinc stannate, zinc oxide, silicon nitride, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, vanadium-doped zinc oxide, or indium-doped tin oxide.

[0174] Item 61: The coated article of any one of Items 45 to 60, wherein the first dielectric layer has 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.

[0175] Item 62: The coated article of any one 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.

[0176] Item 63: The coated article of any one of Items 45 to 62, wherein the third dielectric layer has 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.

[0177] 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 metallic layer, wherein the seed film may 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, their alloys, their mixtures, their oxides, their suboxides, their nitrides, their subnitrides, or combinations thereof.

[0178] Item 65: The coated article of Item 64, wherein the fourth dielectric layer has 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.

[0179] Item 66: The coated article of any of Items 45 to 65, wherein the fifth dielectric comprises a first film comprising zinc oxide or zinc stannate formed over 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, mixtures thereof, or combinations thereof, over at least a portion of the first film.

[0180] Item 67: The coated article of Item 66, wherein the fifth dielectric layer has 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.

[0181] Item 68: The coated article of any one of Items 45 to 67, further comprising an outermost protective coating, wherein the outermost protective coating comprises a protective layer, wherein the protective layer comprises at least one of the following: Si3N4, SiAlN, SiAlON, titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, alloys thereof, or mixtures thereof.

[0182] Item 69: The coated article of Item 68, wherein the outermost protective layer comprises a first protective film and a second protective film formed over the first protective film.

[0183] Item 70: The coated article of any one of Items 68 to 69, wherein the outermost protective layer comprises a protective film of silicon aluminum oxide or titanium aluminum oxide.

[0184] 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.

[0185] Item 72: The coated article of Item 71, further comprising an absorber layer formed over at least a portion of the fifth dielectric layer.

[0186] Item 73: The coated article of Item 72, wherein the absorber layer is selected from the group consisting of Ge, GeO x 、NbN x 、NbN x O y 、Si a Al b 、Si a Al b O x 、Si a Co b 、S i a Co b O x 、Si a Co b Cu c 、S i a Co b Cu c O x 、S i a Cr b 、S i a Cr b O x 、S i a Ni b 、SiNiO x 、SiO x 、SnN x SnO x SnO x N y 、TiNx 、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

[0187] Item 74: The coated article of Item 73, wherein the absorber layer comprises silicon cobalt oxide.

[0188] Item 75: The coated article of Item 72, wherein the absorber layer is a subcritical metal film.

[0189] Item 76: The coated article of Item 75, wherein the subcritical metal film comprises silver, gold, alloys thereof, mixtures thereof, or combinations thereof.

[0190] Item 77: The coated article of any of Items 75 to 76, wherein the subcritical metal film comprises silver.

[0191] 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.

[0192] Item 80: A method for preparing a coated article, comprising: providing a substrate comprising 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 step of applying the functional coating comprising: forming a first dielectric layer over at least a portion of the surface; forming a first metallic layer over at least a portion of the first dielectric layer; forming a second dielectric layer over at least a portion of the first metallic layer; forming a second metallic layer over at least a portion of the second dielectric layer; forming a third dielectric layer over at least a portion of the second metallic layer; forming a third metallic 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 metallic layer, wherein the total combined thickness of the metallic layers is at least 10 nanometers and not greater than 60 nanometers.

[0193] Item 81: The method of Item 80, wherein the applying the functional coating step further comprises forming a fourth metallic 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 metallic layer, wherein the overcoat is over at least a portion of the fifth dielectric layer.

[0194] Item 82: The method of items 80-81, further comprising applying an outermost protective coating, wherein the step of applying the 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, titanium oxide, aluminum oxide, silicon oxide, or zirconium oxide. Example

[0195] The following examples illustrate various embodiments of the present invention. However, it should be understood that the present invention is not limited to these specific embodiments.

[0196] Example 1

[0197] Table 3 shows exemplary coating compositions and thicknesses of tri-metal coatings of the present invention. The reported thicknesses are geometric thicknesses in nanometers (nm) unless otherwise noted. The substrate is a transparent glass substrate having a thickness of 2.1 mm and a transparent cover of 1.6 mm located above the substrate. A 0.7 mm PVB interlayer is used. The base layer is the first dielectric layer, the base center layer is the second dielectric layer, the top center layer is the third dielectric layer, and the top layer is the fourth dielectric layer.

[0198] Table 3

[0199]

[0200]

[0201] Tables 4 and 5 show the resulting color and optical properties, respectively, for the samples of Table 3.

[0202] Table 4

[0203]

[0204] Table 5

[0205]

[0206] Example 2

[0207] The daylight factor (TT) or total transmitted energy of solar radiation is higher than expected for the tri-metal coating of Example 1 (49-50%). The high TT value indicates that about 50% of the solar radiation energy is transmitted through the substrate, resulting in undesirable heat generation. Table 6 shows exemplary coating compositions and thicknesses (nm) of tri-metal coatings of the present invention, where a tinted cover is used in an attempt to reduce the transmitted solar radiation while matching the three property requirements (neutral Rf color, low Rf and Rg (8%), and LTA of not less than 70%). Solex, Atlantica SGN-C4, Caribia, Azuria, and Tintes-PL are greener and therefore more absorptive than clear glass.

[0208] Table 6

[0209]

[0210] Tables 7 and 8 show the resulting color and optical properties for the samples of Table 6, respectively.

[0211] Table 7

[0212]

[0213]

[0214] Table 8

[0215]

[0216] Example 3

[0217] Table 9 shows exemplary coating compositions and thicknesses (nm) of tri-metal coatings of the present invention, wherein silicon cobalt oxide (SiCoO x ) or subcritical metal film absorption layer. Sample 7 SiCoO x The absorbing layer is located between the fourth dielectric layer and the first protective film of the outermost protective layer. The subcritical metal film containing silver of Sample 8 is located between the fourth dielectric layer and the additional dielectric layer described previously. The absorbing layer is used in conjunction with the tinted glass covering in an attempt to further reduce the transmitted solar radiation while matching the three property requirements (neutral Rf color, low Rf and Rg (8%) and LTA of not less than 70%).

[0218] Table 9

[0219]

[0220]

[0221] Tables 10 and 11 show the resulting color and optical properties, respectively, for the samples of Table 9.

[0222] Table 10

[0223]

[0224] Table 11

[0225]

[0226] Example 4

[0227] Table 12 shows an exemplary stack composition of a tri-metal coating where a clear or tinted PVB interlayer is used along with a tinted or clear glass cover and glass substrate. The tri-metal coating used is described above in Table 3 Example 1.

[0228] Table 12

[0229]

[0230] Table 13 shows the color and optical properties of tri-metal coatings on clear glass substrates with tinted or untinted PVB and tinted or untinted glass overlays.

[0231] Table 13

[0232]

[0233] Example 5

[0234] Table 14 shows exemplary coating compositions and thicknesses (nm) of the four-metal coating of the present invention. Here, the base layer is the first dielectric layer, the base center layer is the second dielectric layer, the center layer is the third dielectric layer, the top center layer is the fourth dielectric layer, and the top layer is the fifth dielectric layer. The four-metal coating is used in an attempt to further reduce the transmitted solar radiation while matching the three property requirements (neutral Rf color, low Rf and Rg (8%), and LTA of not less than 70%).

[0235] Table 14

[0236] sample 14 Substrate Glass 2.1mm Covering Transparent 1.6mm Middle Layer Transparent PVB 0.7mm Basal layer 37.4 1st metallic layer 9.86 Basal center layer 76.7 Second metallic layer 10.8 Center Layer 72.2 3rd metallic layer 9.68 Top center layer 62.4 4th Metallic Layer 7.91 Top floor 25.5 First protective film 16.0 Second protective film 22.0 Total metallic properties 38.3

[0237] Tables 15 and 16 show the resulting color and optical properties, respectively, for the samples of Table 14.

[0238] Table 15

[0239]

[0240]

[0241] Table 16

[0242]

[0243] The four-metal coating on the glass substrate is more conductive (0.86 Ω / □ sheet resistance) than any of the three-metal coating Examples 1-4 (1.3-1.4 Ω / □ sheet resistance). Therefore, the solar performance and low energy properties of the four-metal coating are greater than the three-metal coating. Tinted glass is not required when forming the four-metal coating.

[0244] Those skilled in the art will readily appreciate that the present invention may be modified without departing from the concepts disclosed in the foregoing description. Therefore, the particular embodiments described in detail herein are merely illustrative and do not limit the scope of the present invention, which is given by the full scope of the appended claims and any and all equivalents thereof.

Claims

1. A coated product comprising: a substrate comprising a first surface and a second surface opposite the first surface; and A functional coating applied over a surface, the functional coating comprising: a first dielectric layer over at least a portion of the surface; a first metallic layer over at least a portion of the first dielectric layer; a second dielectric layer over at least a portion of the first metallic layer; a second metallic layer over at least a portion of the second dielectric layer; a third dielectric layer over at least a portion of the second metallic layer; a third metallic layer over at least a portion of the third dielectric layer; a fourth dielectric layer over at least a portion of the third metallic layer; a fourth metallic layer over at least a portion of the fourth dielectric layer; and a fifth dielectric layer over at least a portion of the fourth metallic layer; The total combined thickness of the metallic layers is at least 10 nanometers and no greater than 60 nanometers.

2. The coated article of claim 1, wherein the total combined thickness of the metallic layers is at least 30 nm and no greater than 45 nanometers.

3. The coated article according to claim 1, wherein the total combined thickness of the metallic layers is at least 35 nm and no greater than 40 nanometers.

4. The coated article according to any one of claims 1 to 3, wherein the coated article has a visible light reflectance of not more than 8%.

5. The coated article according to any one of claims 1 to 3, wherein the coated article has a visible light transmittance of at least 70%.

6. The coated article according to any one of claims 1 to 3, wherein the first metallic layer 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.

7. The coated article of claim 1, wherein the absorber layer comprises silicon cobalt oxide.

8. The coated article of claim 1, wherein the absorber layer is a subcritical metal film.

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