阅读说明：本技术 具有低可见光反射率的平视显示器的涂层 (Head-up display coating with low visible light reflectivity ) 是由 马智训 A·D·波尔西恩 A·瓦格纳 于 2020-03-26 设计创作，主要内容包括：涂覆制品包括基材,所述基材包含第一表面和与第一表面相对的第二表面,和在表面之一上方施加的功能涂层。功能涂层包括：第一介电层；第一金属性层；第二介电层；第二金属性层；第三介电层；第三金属性层；第四介电层；任选的第四金属性层；任选的第五介电层；和任选的最外保护涂层。涂覆制品具有金属性层的总组合厚度为至少10纳米且不大于60纳米。(The coated article includes 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 comprises: 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; an optional fourth metallic layer; an optional 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.)

1. A coated article comprising:

a substrate comprising a first surface and a second surface opposite the first surface; and

a functional coating applied over the surface, the functional coating comprising:

a first dielectric layer over at least a portion of the surface;

a first 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.

2. The coated article of claim 1, wherein the total combined thickness of the metallic layers is at least 20nm and not greater than 40 nanometers.

3. The coated article of claim 2, wherein the total combined thickness of the metallic layers is at least 25nm and no greater than 31 nanometers.

4. The coated article of any of the preceding claims, wherein coated article has a visible light reflectance of no greater than 8%, and

wherein the coated article has a visible light transmission of at least 70%.

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

6. The coated article of any of the preceding claims, further comprising at least one primer layer formed over at least one metallic layer,

wherein the at least one primer layer is selected from the following: zinc, aluminum, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, germanium, magnesium, molybdenum, silver, silicon carbon, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten niobium, aluminum 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 in a metal and subsequently oxidized.

7. The coated article of any of the preceding claims, 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, or indium-doped tin oxide.

8. The coated article of any of the preceding claims, further comprising an outermost protective coating comprising a protective layer, wherein the protective layer comprises at least one of: si₃N₄SiAlN, SiAlON, titanium oxide, aluminum oxide, silicon oxide, or zirconium oxide.

9. A coated article comprising:

a substrate comprising a first surface and a second surface opposite the first surface; and

a functional coating applied over the surface, the functional coating comprising:

a first dielectric layer over at least a portion of the surface;

a first 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.

10. The coated article of claim 9, wherein the total combined thickness of the metallic layers is at least 30nm and not greater than 45 nanometers.

11. The coated article of claim 9, wherein the total combined thickness of the metallic layers is at least 35 and not greater than 40 nanometers.

12. The coated article of claim 9, wherein the total combined thickness of the metallic layers is from 40nm to 55 nm.

13. The coated article of any of the preceding claims 9-12, further comprising at least one primer layer formed over at least one metallic layer.

14. A method of making 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 applying a functional coating step 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 no greater than 60 nanometers.

15. The method of claim 14, wherein the applying a 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.

Technical Field

The present invention relates generally to vehicle transparencies, such as vehicle windshields, and in one particular embodiment, to head-up displays.

Technical considerations

Conventional automotive head-up displays (HUDs) use a source of electromagnetic radiation in the dashboard that projects light up the windshield and then reflects it to the driver's eyes, creating a virtual image of the vehicle data so that the driver obtains information about the vehicle operation without having to look away from the road. For electromagnetic radiation reflected from the windshield at angles typically found in conventional vehicles and light sources that are typically unpolarized, such as Light Emitting Diodes (LEDs), the reflected light is primarily s-polarized, while much less of the light component is p-polarized. In the extreme case, if the angle of incidence of the electromagnetic radiation on the windshield is the Brewster angle (about 57) of the air-glass interface, the p-polarized reflection is zero percent.

Light from the radiation source (primarily s-polarized) will be reflected 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 are a phenomenon called "ghosting", and eliminating or minimizing the presence of "ghosting" is an object of the HUD technique. The conventional approach to addressing ghosting is to align the two reflection images by adjusting the geometry of the two glass sheets using a wedge-shaped vinyl layer between the inner and outer glass sheets of the windshield. This wedge of vinyl increases the cost of the windshield and also increases the complexity of manufacturing the windshield.

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 in the windshield which results in a third reflection, and a third reflection image on the HUD system, which is difficult to compensate by the wedge-shaped vinyl layer.

Accordingly, 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.

Background

Summary of The Invention

The present invention relates to coated articles. The coated article has a substrate having a first surface and a second surface opposite the first surface, and a functional coating over the substrate. The coating has a first dielectric layer over at least a portion of the surface. The first metallic layer is over at least a portion of the first dielectric layer. Optionally, a first primer layer is over at least a portion of the first metallic layer. A second dielectric layer is over at least a portion of the first metallic layer or the optional first primer layer. The second metallic layer is over at least a portion of the first metallic layer or the optional first primer layer. Optionally, a second primer layer is over at least a portion of the second metallic layer. A third dielectric layer is over at least a portion of the second metallic layer or the optional second primer layer. The third metallic layer is over at least a portion of the third dielectric layer. Optionally, a third primer layer is positioned over at least a portion of the third metallic layer. A fourth dielectric layer is over at least a portion of the third metallic layer or the optional third primer 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 the metallic layers of at least 10 nanometers to 60 nanometers.

The present invention relates to coated articles. The coated article has a substrate having a first surface and a second surface opposite the first surface, and a functional coating over the substrate. The coating has a first dielectric layer over at least a portion of the surface. The first metallic layer is over at least a portion of the first dielectric layer. Optionally, a first primer layer is over at least a portion of the first metallic layer. A second dielectric layer is over at least a portion of the first metallic layer or the optional first primer layer. The second metallic layer is over at least a portion of the first metallic layer or the optional first primer layer. Optionally, a second primer layer is over at least a portion of the second metallic layer. A third dielectric layer is over at least a portion of the second metallic layer or the optional second primer layer. The third metallic layer is over at least a portion of the third dielectric layer. Optionally, a third primer layer is positioned over at least a portion of the third metallic layer. A fourth dielectric layer is over at least a portion of the third metallic layer or the optional third primer layer. The fourth metallic layer is over at least a portion of the fourth dielectric layer. An optional fourth primer layer is over at least a portion of the fourth metallic layer. A fifth dielectric layer is over at least a portion of the fourth metallic layer or the optional fourth primer layer. An optional outermost protective layer is formed over at least a portion of the fifth dielectric layer or over the functional coating. The coated article has a total combined thickness of the metallic layers of at least 10 nanometers to 60 nanometers.

The present invention relates to a method of making a coated article. A substrate having a first surface and a second surface opposite the first surface is provided. A functional coating is applied over at least a portion of the surface. A first dielectric layer is formed over at least a portion of the surface. A first 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 the metallic layers of at least 10 nanometers to 60 nanometers.

Brief description of the drawings

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

FIG. 1 is a schematic (not to scale) of a non-limiting windshield.

Fig. 2A-2B are illustrations of the ghosting effect produced by a windshield display when using a head-up display.

FIG. 3 is an illustration of a windshield having a coating positioned to reduce ghosting when using a head-up display.

FIG. 4 is a cross-sectional view (not to scale) of a non-limiting trimetal coating according to the present invention.

FIG. 5 is a cross-sectional view (not to scale) of a non-limiting four-metal coating according to the present invention.

FIG. 6 is a cross-sectional view (not to scale) of a non-limiting trimetal coating according to the present invention.

FIG. 7 is a cross-sectional view (not to scale) of a non-limiting four-metal coating according to the present invention.

FIG. 8 is a cross-sectional view (not to scale) of a non-limiting trimetal coating according to the present invention.

FIG. 9 is a cross-sectional view (not to scale) of a non-limiting four-metal coating according to the present invention.

Description of the invention

As used herein, spatial or directional terms, such as "left", "right", "inner", "outer", "upper", "lower", and the like, relate to the invention as it is shown in the drawings. It is to be understood, however, that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting. Moreover, as used herein, all numbers expressing dimensions, physical characteristics, processing parameters, quantities of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims can vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, all ranges disclosed herein are to be understood to encompass the beginning and ending range values and any and all subranges subsumed therein. For example, a stated range of "1 to 10" should be considered to include any and all subranges between (and including) the minimum value of 1 and the maximum value of 10 (and including both the minimum value of 1 and the maximum value of 10); i.e., all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1 to 3.3, 4.7 to 7.5, 5.5 to 10, and the like. Furthermore, as used herein, the terms "formed over," deposited over, ", or" provided over, ", mean formed, deposited, or provided on a surface, but not necessarily in contact with the surface. For example, a coating "formed over" a substrate does not preclude the presence of one or more other coatings or films of the same or different composition located between the formed coating and the substrate. As used herein, the term "polymer" or "polymeric" includes oligomers, homopolymers, copolymers, and terpolymers, e.g., polymers formed from two or more types of monomers or polymers. The term "visible region" or "visible light" refers to electromagnetic radiation having a wavelength in the range of 380 nanometers (nm) to 800 nm. The term "infrared region" or "infrared radiation" refers to electromagnetic radiation having a wavelength in the range of greater than 800nm to 100,000 nm. The term "ultraviolet region" or "ultraviolet radiation" means electromagnetic energy having a wavelength in the range of 300nm to less than 380 nm. The visible (light) transmittance (LTA) values (Y, x, Y) herein are those that can be determined using a c.i.e. (1976) standard light source "a" with a 2 degree observation angle (consistent with U.S. federal standards) over a wavelength range of 380nm to 770nm using either a λ 9 spectrophotometer commercially available from Perkin-Elmer or a TCS spectrophotometer commercially available from BYK-Gardner. The reflection color values L, a, b (whether R1 or R2) were determined with a 10 ° viewing angle (as is conventional in the automotive field) using a light source "D65".

As used herein, the term "film" refers to a region of a coating having a desired or selected coating composition. A "layer" may comprise one or more "films" and a "coating" or "coating stack" may comprise 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 indicated to the contrary, the thickness values are geometric thickness values. Additionally, 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.

Discussion of the invention may describe certain features as "particularly" or "preferably" within certain limits (e.g., "preferably," "more preferably," or "most preferably" within certain limits). It is to be understood that the invention is not limited to these specific or preferred limitations, but encompasses the full scope of the disclosure.

A non-limiting transparency 10 (e.g., an automotive windshield) incorporating features of the present invention is illustrated in fig. 1. The transparency 10 may have any desired visible, infrared or ultraviolet radiation transmission and reflection properties. For example, the transparency 10 may have a visible light transmission of any desired amount, e.g., greater than 0% to 100%, greater than 70%. For windshield and front side window regions in the united states, visible light transmission is typically greater than or equal to 70%. For privacy zones 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%.

As seen in fig. 1, the transparency 10 includes a first sheet or substrate 12 having a first major surface facing the exterior of the vehicle, namely an outer major surface 14 (surface No. 1) and an opposing second or inner major surface 16 (surface No. 2). The transparency 10 also includes a second sheet or 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 may be joined 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 transparency 10 during and/or after lamination in any desired manner. A decorative band, such as an opaque, translucent or colored masking band 26, such as a ceramic band, may be provided on a surface of at least one of the sheets 12, 18, such as around the perimeter of the inner major surface 16 of the first sheet 12. A coating 30 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.

In 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 bus bar 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 invention, the bus bars 96, 98 may be at least partially located on the fascia 26 or completely located on the fascia 26, as shown in fig. 1.

In the broad practice of the invention, the sheets 12, 18 of the transparency 10 may be of the same or different materials. The sheets 12, 18 may comprise any desired material having any desired characteristics. For example, one or more of the sheets 12, 18 may be transparent or translucent to visible light. By "transparent" is meant having a visible light transmission of greater than 0% to 100%. Alternatively, one or more of the sheets 12, 18 may be translucent. By "translucent" is meant allowing electromagnetic energy (e.g., visible light) to pass through, but diffusing this energy so that objects on the side opposite the viewer are not clearly visible. Examples of suitable materials are, but are not limited to, plastic substrates (e.g., acrylic polymers such as polyacrylates; polyalkylmethacrylates such as polymethyl methacrylate, polyethyl methacrylate, polypropylene methacrylate, and the like; polyurethanes; polycarbonates; polyalkyl terephthalates such as polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, and the like; polysiloxane-containing polymers; or copolymers of any of the monomers used to prepare these, or any mixtures thereof); a ceramic substrate; a glass substrate; or mixtures or combinations of any of the above. For example, one or more of the sheets 12, 18 may comprise conventional soda-lime-silicate glass, borosilicate glass, or leaded glass. The glass may be transparent glass. By "clear glass" is meant uncolored 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 can be of any type (e.g., conventional float glass) and can be of any composition having any optical property (e.g., any value of visible transmittance, ultraviolet transmittance, infrared transmittance, and/or total solar transmittance). By "float glass" is meant glass formed by a conventional float process in which molten glass is deposited on a molten metal bath and controllably cooled to form a float glass ribbon. The strip is then cut and/or shaped and/or heat treated as desired. Examples of float glass processes are disclosed in U.S. Pat. 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 while the other sheet 12, 18 is colored glass. Although not limiting to the invention, examples of glasses suitable for first sheet 12 and/or second sheet 18 are described in U.S. Pat. nos. 4,746,347; 4,792,536; 5,030,593, respectively; 5,030,594, respectively; 5,240,886, respectively; 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 one exemplary automotive transparency 10, the first and second sheets 12, 18 may each be 1mm to 10mm thick, such as 1mm to 5mm thick, or 1.5mm to 2.5mm, or 1.8mm to 2.3 mm. In one non-limiting embodiment, the first sheet 12 and/or the second sheet 18 can have a visible light transmittance of greater than 90%, such as 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 a range of greater than 0 weight percent (wt%) to 0.2 wt% and/or a redox ratio in a range of 0.3 to 0.6.

In one non-limiting embodiment, one or both of the sheets 12, 18 may have a high visible light transmission at a reference wavelength of 550 nm. By "high visible light transmission" is meant a visible light transmission at 550nm of 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%, at 5.5mm equivalent thickness for glass of 2mm to 25mm sheet thickness. Glasses that are particularly useful for practicing the present invention are disclosed in U.S. patent nos. 5,030,593 and 5,030,594.

The laminated windshield may also include an intermediate layer 24. The intermediate layer 24 may be of any desired material and may include one or more layers or sheets. Intermediate layer 24 may be located over surface No. 2 16 and/or surface No. 3 20. The interlayer 24 may be a polymeric or plastic material, such as polyvinyl butyral (PVB), plasticized polyvinyl chloride, or a multilayer thermoplastic material including polyethylene terephthalate, and the like. Suitable interlayer materials are disclosed, for example, but not to be considered limiting, in U.S. Pat. nos. 4,287,107 and 3,762,988. The intermediate layer 24 may also be a sound absorbing or attenuating material as described, for example, in U.S. 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 energy transmission. The intermediate layer 24 may have any suitable thickness to bond the sheets 12, 18 together. In one non-limiting embodiment, interlayer 24 is a 0.76 millimeter (mm) thick layer of PVB.

Coating 30 is deposited over at least a portion of a major surface of one of glass sheets 12, 18, such as on inner surface 16 of outer glass sheet 12 or outer surface 22 of inner glass sheet 18 (fig. 1, 3). The coating 30 may include three or four metallic films between dielectric layers that are sequentially applied over at least a portion of one of the glass sheets 12, 18. The coating 30 may be a heat and/or radiation reflective coating or a solar control coating and may have one or more coating layers or films of the same or different composition and/or functionality. The coating 30 may be a multi-layer coating comprising three or four metallic layers. Examples of conductive coatings for making heatable windows are disclosed in U.S. Pat. nos. 5,653,903 and 5,028,759. Examples of solar control coatings that can 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.

Non-limiting examples of suitable coatings generally include one or more anti-reflective coating films comprising a dielectric or anti-reflective material transparent to visible light, such as a metal oxide or an oxide of a metal alloy. The coating 30 can also include three to four metallic layers comprising a reflective metal, such as a noble metal, e.g., silver or gold, or a combination of alloys thereof, and the coating 30 can further comprise a primer layer or barrier film, e.g., titanium or titanium aluminum alloy, over and/or optionally under the metallic reflective layer. The 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 comprised of three metallic layers, a trimetal coating 32. In another non-limiting embodiment, the coating 30 comprises four metallic layers, namely a four metal coating 34. In one non-limiting embodiment, one or more of the metallic layers may comprise silver. In another non-limiting embodiment, one or more of the metallic layers can be a continuous layer. By "continuous layer" is meant a continuous film of coating-forming material rather than discrete areas of coating.

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 titanium, tungsten titanium, tantalum titanium, zinc titanium, aluminum silver, zinc tin, indium zinc, silver zinc, mixtures thereof, combinations thereof, or any alloys thereof. The primer layer may also take the form of a metal, oxide, suboxide, nitride and/or subnitride of any of the above-listed materials. At least a portion of the primer layer is an oxide or a nitride. In some embodiments, the primer layer is deposited in a 100% argon environment. In some embodiments, a moietyThe primer layer is formed by adding nitrogen (N)₂) Atmosphere (with specific flow rate to form 80% N)₂With the balance being argon) by sputtering a metal or metal alloy. The flux being nitrogen (N) in the atmosphere₂) Approximate of the amount of (b), but one of ordinary skill in the art will recognize additional N₂May leak into the coating chamber because the coating chamber is not hermetically sealed from the external environment. In some embodiments, a portion of the primer layer is formed by oxidizing oxygen (O)₂) Atmosphere (with specific flow rate to form 3% to 7% O₂With the balance being argon) sputtering a metal or metal alloy. The flow rate being oxygen (O) in the atmosphere₂) Approximate of the amount of (b), but one of ordinary skill in the art will recognize additional O₂May leak into the coating chamber because the coating chamber is not hermetically sealed from the external environment. The chemical structure of the primer material is represented by the weight percent (wt%) of the element x. For some compositions, the lower limit of one of the materials in the composition may be "greater than 0". When the lower limit is "greater than zero," the weight percent of the material is not equal to zero but can be any weight percent greater than 0 and up to the weight percent of the upper limit. The composition may change before or after heating the layer due to reaction with atmospheric substances. These reactions may alter the weight% distribution among the constituent materials. A non-limiting example composition of a primer layer can be found in table 1, where BH is before heating and AH is after heating. Some materials may only have a unique BH or AH measurement due to the fact that this measurement is more important for the final composition.

TABLE 1 Metal composition of Metal alloys for use as primer layer

For line-of-sight panels in the united states (e.g., windshields), the transparency should also have a visible light transmission of greater than or equal to 70%, such as greater than or equal to 71%. As will be appreciated by those skilled in the art, several different competing factors need to be balanced to provide a coating with sufficient conductivity, transmittance, and color. For example, as the distance D between the bus bars 96, 98 increases (i.e., the transparency widens from top to bottom), the resistance of the bus bars 96 to 98 increases. As the resistance of bus bar 96 to bus bar 98 increases, the watt density decreases. To maintain power density, the resistivity of the coating 30 must be reduced as the bus bar 96 to bus bar 98 distance D is increased. One way to reduce the 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.

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 one non-limiting embodiment, the coating 30 can 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. patent nos. 4,379,040; 4,861,669, respectively; 4,898,789, respectively; 4,898,790, respectively; 4,900,633, respectively; 4,920,006, respectively; 4,938,857, respectively; 5,328,768 and 5,492,750. In the MSVD method, a metal oxide or metal alloy oxide film may be deposited on the surface of a substrate by depositing an oxide of the metal or metal alloy by sputtering a cathode containing the metal or metal alloy in an oxygen-containing atmosphere. In one embodiment, the coating 30 is deposited over all or substantially all of the surface, i.e., no deposition forms discrete coated areas. The at least one coating 30 may be deposited over a flat substrate and the substrate may then be bent into shape in any conventional manner, such as by heating. Alternatively, the at least one coating 30 may be deposited over a curved surface, i.e., an already curved or shaped substrate.

In an exemplary embodiment, the present invention is a coating useful for HUDs in windshields, as shown in fig. 1, 2A, 2B, and 3, wherein the windshield comprises first and second sheets 12 and 18 and an intermediate layer 24. Coating 30 may be located on surface No. 2 16 or surface No. 3 20, preferably on surface No. 2 16.

Referring to fig. 2A, radiation 36 directed at transparency 10 is deflected away from transparency 10 such that at least a portion of radiation 36 is reflected by transparency 10 and directed into driver's eye 38. Portions of radiation 36 that are not reflected from transparency 10 may be refracted, absorbed, or otherwise transmitted through transparency 10. Because the PVB interlayer 24 has a refractive index similar to that of the glass sheets 12, 18, reflections from surface No. 1 (from radiation) and surface No. 422 produce ghost images into the driver's eyes 38 when the glass sheets 12, 18 and PVB interlayer 24 are parallel to each other in the windshield.

Referring to fig. 2B, the first sheet 12 may not be parallel to the second sheet 18. Preferably, to eliminate ghost images when exposed to radiation 36, the intermediate layer 24 has a wedge shape with one side of the intermediate layer 24 being thicker than the other. The wedge shape of the intermediate layer 24 may be configured so that the two reflected images from surface No. 114 and surface No. 422 overlap at the driver's eye 38 to eliminate ghosting.

A silver coating may be applied to surface No. 2 16 or surface No. 3 22, preferably surface No. 2 16 as described above, because the silver coating reduces energy and improves solar performance. However, a silver coating applied on surface No. 2 16 will produce a strong light reflection from radiation 36 and enhance the triple ghost image in the driver's eye 38. Referring to fig. 3, in order to eliminate reflections from the surface, the particular coating 30 including the metallic layer must be designed such that the total internal reflection into the eye 38 is sufficiently low or the same as the transparency 10 of fig. 2B. The particular coating 30 must also be a neutral color in the visible spectral range (400nm-700nm), which can be tuned using various dielectric layers. When using a particular coating 30, the intermediate layer 24 may be a layer having a uniform thickness in other arrangements of the transparency 10, as the intermediate layer 24 may not necessarily be wedge-shaped to avoid ghost images, as ghosting is counteracted by other aspects of the design.

The coating 30 may be a trimetal coating 33, such as three metallic layers, or a tetrametallic coating 34 (e.g., four metallic layers). Exemplary, non-limiting coatings suitable for trimetal coating 33 are shown in fig. 4,6, and 8. Exemplary, non-limiting coatings suitable for the four-coat layer 34 are shown in fig. 5,7 and 9.

The exemplary coating 30 includes three metallic layers (i.e., a trimetal coating 33) between dielectric layers, as shown in fig. 4. The trimetal coating 33 includes a base (base) layer or first dielectric layer 40 over or in direct contact with at least a portion of a major surface of the substrate, such as 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 over or in direct contact with at least a portion of the first dielectric layer 40. Optional first primer layer 54 may be located over at least a portion of first metallic layer 52 or in direct contact with at least a portion of first metallic layer 52. Second dielectric layer 60 is positioned over or in direct contact with optional first primer layer 54 or first metallic layer 52. The second metallic layer 72 is over or in direct contact with at least a portion of the second dielectric layer 60. Optional second primer layer 74 may be located over second metallic layer 72 or in direct contact with second metallic layer 72. The third dielectric layer 80 is positioned over or in direct contact with the optional second undercoat layer 74 or second metallic layer 72. A third metallic layer 92 may be located over at least a portion of the third dielectric layer 80. An optional third primer layer 94 may be positioned over at least a portion of third metallic layer 92. A fourth dielectric layer 100 is positioned over at least a portion of third metallic layer 92 or optional third primer layer 94. The optional outermost protective layer 200 may be located over the fourth dielectric layer 100 or in direct contact with the fourth dielectric layer 100.

The exemplary coating 30 includes four metallic layers (i.e., four metallic coatings 34) between dielectric layers, as shown in fig. 5. The four-metal coating 34 includes a base layer or first dielectric layer 40 over or in direct contact with at least a portion of a major surface 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 first metallic layer 52 is over or in direct contact with at least a portion of the first dielectric layer 40. Optional first primer layer 54 may be located over at least a portion of first metallic layer 52 or in direct contact with at least a portion of first metallic layer 52. Second dielectric layer 60 is positioned over or in direct contact with optional first primer layer 54 or first metallic layer 52. The second metallic layer 72 is over or in direct contact with at least a portion of the second dielectric layer 60. Optional second primer layer 74 may be located over second metallic layer 72 or in direct contact with second metallic layer 72. The third dielectric layer 80 is positioned over or in direct contact with the optional second undercoat layer 74 or second metallic layer 72. A third metallic layer 92 may be located over at least a portion of the third dielectric layer 80. An optional third primer layer 94 may be positioned over at least a portion of third metallic layer 92. A fourth dielectric layer 100 is positioned over at least a portion of third metallic layer 92 or optional third primer layer 94. Fourth metallic layer 112 is situated over at least a portion of fourth dielectric layer 100. An optional primer layer 114 is formed over at least a portion of fourth metallic layer 112. A fifth dielectric layer 120 is formed over at least a portion of the fourth metallic layer 112 or the optional fourth primer layer 114. The optional outermost protective layer 200 may be located over the fifth dielectric layer 120 or in direct contact with the fifth dielectric layer 120.

The dielectric layer may comprise one or more films of antireflective 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); an oxide of an indium-tin alloy; silicon nitride; siliconAluminum nitride; or aluminum nitride. Furthermore, 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 can 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 can be obtained by MSVD from a cathode of zinc and tin, which can contain zinc and tin in a proportion of 10 to 90 wt.% zinc and 90 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_xSn_1-xO_2-x(formula 1), wherein "x" varies in the range of more than 0 to less than 1. For example, "x" can be greater than 0 and can be any fraction or decimal between greater than 0 to less than 1. For example, when x is 2/3, formula 1 is Zn_2/3Sn_1/3O_4/3More commonly described as Zn₂SnO₄. The zinc stannate-containing film has one or more forms of formula 1 in a predominant amount in the film.

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 can comprise 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 mixtures thereof. In one non-limiting embodiment, the second film 44 of the first dielectric layer can be a zinc-containing film, such as zinc oxide. The zinc oxide film can be deposited from a zinc cathode that includes other materials to improve the sputtering characteristics of the cathode. For example, the zinc cathode can 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 zinc oxide film will comprise a small percentage of tin oxide, for example from 0 to less than 10 wt% tin oxide, for example from 0 to 5 wt% tin oxide. An oxide layer sputtered from a zinc/tin cathode having 95 wt% zinc and 5 wt% tin, or preferably 90 wt% zinc and 10 wt% tin, is referred to as a zinc oxide film. A small amount of tin (e.g., less than 10 wt%) in the cathode is believed to form a small amount of tin oxide in the predominantly zinc oxide-containing second film 44 of the first dielectric layer. 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 is zinc oxide and is over at least a portion of the first film 42 of the first dielectric layer.

In an exemplary non-limiting embodiment, the second film 44 is a film composed 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. 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 films are deposited from zinc cathodes including other materials to improve the sputtering characteristics of the cathode. For example, an 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.%, e.g., 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.

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.

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

In one non-limiting embodiment, the first dielectric layer 40 comprises a seed film, not shown in the figures, in direct contact with the first metallic layer 52. The seed film may comprise aluminum, aluminum silver, aluminum 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 zinc, titanium aluminum, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof. In one embodiment, the seed film may comprise aluminum zinc, vanadium zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another embodiment, the seed film may comprise gallium zinc, indium tin, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. The composition of a non-limiting example of a seed film can be found in table 2. In some embodiments, a portion of the seed film is at O₂Formed in an atmosphere having a specific flow rate to form 1% to 70% O₂With the balance being argon. The flow rate being O in the atmosphere₂Approximate of the amount of (b), but one of ordinary skill in the art will recognize additional O₂May 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_xZn_1-xAn oxide. In another embodiment, the seed film comprises Al_xZn_1-xAn oxide. In another embodiment, the seed film comprises Ga_xZn_1-xAn oxide. In another embodiment, the seed film contains In_xZn_1-xAn oxide. In another embodiment, the seed film comprises Sn_xIn_1-xAn oxide. In another embodiment, the seed film comprises Ag deposited in an oxygen/argon environment. In another embodiment, the seed film comprises Al_xAg_1-x. Seed crystal filmHave a total thickness in the range of 0.5nm to 10nm, preferably 0.75nm to 8nm, more preferably 0.9nm to 6 nm. In some embodiments, the first dielectric layer 40 comprises a first film 42, a second film 44, and a seed film.

TABLE 2 Metal composition of Metal alloys for seed films

A first metallic layer 52 may be deposited over at least a portion of the first dielectric layer 40. The first metallic layer 52 may include a reflective metal such as, but not limited to, metallic gold, silver, alloys thereof, mixtures thereof, or combinations thereof. The first metallic layer 52 is a continuous layer. In one embodiment, the first metallic layer 52 of the trimetal coating 33 comprises metallic silver. The first metallic layer 52 of the trimetal coating 33 may have a total thickness in the range of 5nm to 20nm, preferably 5nm to 17.5nm, more preferably 7nm to 15nm, most preferably 8nm to 10.5 nm.

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 2nm to 20nm, preferably 6nm to 18nm, more preferably 9nm to 12nm, most preferably 9.5nm to 10 nm.

An optional first primer layer 54 may be deposited over at least a portion of the first metallic layer 52. The first primer layer 54 may be an oxygen-trapping material, such as titanium, which may be sacrificial during the deposition process to prevent degradation or oxidation of the first metallic layer during the sputtering process or a subsequent heating process. The oxygen-trapping material may be selected to oxidize prior to the material of the first metallic layer 52. The composition of first primer layer 54 is selected from the following: zinc, aluminium, vanadium, tungsten, tantalum, niobium, zirconium, manganese, chromium, tin, nickel, germanium, magnesium, molybdenum, silverSilicon carbon, aluminum doped silver, aluminum zinc, vanadium zinc, tungsten tantalum, titanium niobium, zirconium niobium, tungsten 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, wherein the primer is deposited with a metal and subsequently oxidized. At least a portion of the primer layer is a nitride or an oxide. If silver 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 be oxidized prior to oxidation of the underlying metallic layer. In one embodiment, the first primer layer 54 of the tri-metal coating 33 and the tetra-metal coating 34 is titanium. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetramal coating 34 comprises silver zinc. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetramal coating 34 comprises zinc. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetrametatal coating 34 is Ag_xZn_1-x. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetrametatal coating 34 is Ag_xZn_1-xAn oxide. In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the tetra-metal coating 34 comprises Al_xZn_1-xAn oxide. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetramal coating 34 comprise In_xZn_1-xAn oxide. In another embodiment, first primer layer 54 of trimetal coating 33 and tetrametatal coating 34 comprises Ga_xZn_1-xAn oxide. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetramal coating 34 comprises V_xZn_1-xAn oxide. In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the tetra-metal coating 34 comprises Al_xTi_1-xAn oxide. In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the tetra-metal coating 34 comprises Al_xNb_1-xAn oxide. In another embodiment, the first primer layer 54 of the tri-metal coating 33 and the tetra-metal coating 34 comprises Al_xNb_1-xAnd (3) nitride. In another embodiment, a trimetal coating 33 and a tetrametallic coating 34First primer layer 54 of (a) comprises W_xNb_1-xAnd (3) nitride. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetrametatal coating 34 comprises W_xTi_1-xAn oxide. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetramal coating 34 comprises Ti_xTa_1-xAn oxide. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetramal coating 34 comprises Ti_xNb_1-xAn oxide. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetramal coating 34 comprises Ti_xNb_1-xAnd (3) nitride. In another embodiment, first primer layer 54 of trimetal coating 33 and tetrametatal coating 34 comprises Nb_xZr_1-xAn oxide. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetrametatal coating 34 comprises Ta_xW_1-xAn oxide. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetrametatal coating 34 comprises W_xNb_1-xAn oxide. In another embodiment, the first primer layer 54 of the trimetal coating 33 and the tetramal coating 34 comprise Zn_xTi_1-xAn oxide. The first primer layer 54 of the trimetal coating 33 and the tetrametatal coating 34 has a total thickness in the range of 0.5nm to 5nm, preferably 1.0nm to 2.5nm, more preferably 1.5nm to 2.5 nm.

A second dielectric layer 60 can be deposited over at least a portion of first metallic layer 52 or optional first primer layer 54. The second dielectric layer 60 may also include one or more of the materials discussed above with respect to the first dielectric layer 40. The second dielectric layer 60 can include a first film 62 of the second dielectric layer deposited over the first metallic layer 52 or the optional first primer layer 54. The first film 62 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. The first film 62 of the second 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 mixtures thereof. In one embodiment, the first film 62 of the second dielectric layer comprises zinc oxide. In another embodiment, the first film 62 of the second dielectric layer comprises aluminum doped zinc oxide. In another embodiment, the first film 62 of the second dielectric layer comprises indium doped zinc oxide. In another embodiment, the first film 62 of the second dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the first film 62 of the second dielectric layer comprises indium-doped tin oxide. In another embodiment, the first film 62 of the second dielectric layer comprises vanadium doped zinc oxide.

A second film 64 of a 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 one non-limiting embodiment, the second film 64 of the second dielectric layer is zinc stannate.

An 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 comprise an oxide, nitride, oxynitride, or mixture thereof, of a metal selected from the group consisting of: titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. The optional third film 66 of the second 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 mixtures thereof. In one embodiment, the optional third film 66 of the second dielectric layer comprises zinc oxide. In another embodiment, the third film 66 of the second dielectric layer comprises indium doped zinc oxide. In another embodiment, the third film 66 of the second dielectric layer comprises gallium doped zinc oxide. In another embodiment, the third film 66 of the second dielectric layer comprises indium doped tin oxide. In another embodiment, the third film 66 of the second dielectric layer comprises vanadium doped zinc oxide. In another embodiment, the first dielectric layer 40 or the second dielectric layer 60 comprises a silicon nitride film.

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.

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

In one non-limiting embodiment, the second dielectric layer 60 comprises a seed film, not shown, that is located in direct contact with the second metallic layer 72. The seed film may comprise aluminum, aluminum silver, aluminum 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 zinc, titanium aluminum, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof. In one embodiment, the seed film may comprise aluminum zinc, vanadium zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another embodiment, the seed film may comprise gallium zinc, indium tin, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. The composition of a non-limiting example of a seed film can be found in table 2. In another embodiment, the seed film comprises V_xZn_1-xAn oxide. In another embodiment, the seed film comprises Al_xZn_1-xAn oxide. In another embodiment, the seed film comprises Ga_xZn_1-xAn oxide. In another embodiment, the seed film contains In_xZn_1-xAn oxide. In another embodiment, the seed film comprises Sn_xIn_1-xAn oxide. In another embodiment, the seed film comprises Ag deposited in an oxygen/argon environment. In another embodiment, the seed film comprises Al_xAg_1-x. The seed film may have a total thickness in the range of 0.5 to 10nm, preferably 0.75 to 8nm, more preferably 0.9 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.

A second metallic layer 72 may be deposited over at least a portion of the second dielectric layer 60. The second metallic layer 72 is a continuous layer. The second metallic layer 72 may include any one or more of the reflective materials described above with respect to the first metallic layer 52. In one non-limiting embodiment, the second metallic layer 72 comprises metallic silver. The second metallic layer 72 of the trimetal coating 33 may have a total thickness in the range of 5nm to 20nm, preferably 5nm to 15nm, more preferably 7.5nm to 12.5nm, most preferably 8.5nm to 11.5 nm.

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-coat layer 34 may have a total thickness in the range of 2nm to 20nm, preferably 6nm to 18nm, more preferably 8nm to 15nm, most preferably 9nm to 12 nm.

An optional second primer layer 74 can be deposited over at least a portion of the second metallic layer 72. Second primer layer 74 may be any of the materials described above with respect to first primer layer 54. In one non-limiting embodiment, the second primer layer 74 of the trimetal coating 33 and the tetrametatal 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 trimetal coating 33 and the tetramal coating 34 comprises Ag_xZn_1-x. In another embodiment, an optional second primer layer of a trimetal coating 33 and a tetrametatal coating 3474 comprises Ag_xZn_1-xAn oxide. In another embodiment, the optional second primer layer 74 of the trimetal coating 33 and the tetrametatal coating 34 comprises Al_xZn_1-xAn oxide. In another embodiment, the optional second primer layer 74 comprises In_xZn_1-xAn oxide. In another embodiment, optional second primer layer 74 of trimetal coating 33 and tetrametatal coating 34 comprises Ga_xZn_1-xAn oxide. In another embodiment, the optional second primer layer 74 of the trimetal coating 33 and the tetramal coating 34 comprises V_xZn_1-xAn oxide. In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the tetra-metal coating 34 comprises Al_xTi_1-xAn oxide. In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the tetra-metal coating 34 comprises Al_xNb_1-xAn oxide. In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the tetra-metal coating 34 comprises Al_xNb_1-xAnd (3) nitride. In another embodiment, the second primer layer 74 of the trimetal coating 33 and the tetrametatal coating 34 comprises W_xNb_1-xAnd (3) nitride. In another embodiment, the second primer layer 74 of the trimetal coating 33 and the tetrametatal coating 34 comprises W_xTi_1-xAn oxide. In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the tetra-metal coating 34 comprises Ti_xTa_1-xAn oxide. In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the tetra-metal coating 34 comprises Ti_xNb_1-xAn oxide. In another embodiment, the second primer layer 74 of the tri-metal coating 33 and the tetra-metal coating 34 comprises Ti_xNb_1-xAnd (3) nitride. In another embodiment, second primer layer 74 of trimetal coating 33 and tetrametatal coating 34 comprises Nb_xZr_1-xAn oxide. In another embodiment, the second primer layer 74 of the trimetal coating 33 and the tetrametatal coating 34 comprises Ta_xW_1-xAn oxide. In another embodiment, the second primer layer 74 of the trimetal coating 33 and the tetrametatal coating 34 comprises W_xNb_1-xAn oxide. In a further embodiment of the process according to the invention,the second primer layer 74 of the trimetal coating 33 and the tetrametallic coating 34 comprises Zn_xTi_1-xAn oxide. Optional second primer layer 74 has a total thickness in the range of 0.5nm to 5nm, preferably 1.0nm to 2.5nm, more preferably 1.5nm to 2.5 nm.

A third dielectric layer 80 can be deposited over at least a portion of the second metallic layer 72 or the optional second primer layer 74. The third dielectric layer 80 may also include one or more of the materials discussed above with respect to the first and second dielectric layers. In one non-limiting embodiment, the third dielectric layer 80 comprises a first film 82 of the third dielectric layer. The first film 82 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. 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 mixtures thereof. 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.

A second film 84 of a 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.

An optional third film 86 of a 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 comprise an oxide, nitride, oxynitride, or mixture thereof, of a metal selected from the group consisting of: titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. The optional third film 86 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 mixtures thereof. In one embodiment, the optional third film 86 of the third dielectric layer comprises zinc oxide. In another embodiment, the third film 86 of the third dielectric layer comprises aluminum doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer comprises indium doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer comprises tin-doped zinc oxide. In another embodiment, the third film 86 of the third dielectric layer comprises vanadium doped zinc oxide.

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.

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

In one 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 figure. The seed film may comprise aluminum, aluminum silver, aluminum 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 zinc, titanium aluminum, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof. In one embodiment, the seed film may comprise aluminum zinc, vanadium zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another embodiment, the seed film may comprise gallium zinc, indium tin, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. The composition of a non-limiting example of a seed film can be found in table 2. In another embodiment, the seed film comprises V_xZn_1-xAn oxide. In another embodiment, the seed film comprises Al_xZn_1-xAn oxide. In another embodiment, the seed film comprises Ga_xZn_1-xAn oxide. In another embodiment, the seed film contains In_xZn_1-xAn oxide. In another embodiment, the seed film comprises Sn_xIn_1-xAn oxide. In another embodiment, the seed film comprises Ag deposited in an oxygen/argon environment. In another embodiment, the seed film comprises Al_xAg_1-x. The seed film may have a total thickness in the range of 0.5 to 10nm, preferably 0.75 to 8nm, more preferably 0.9 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.

A third metallic layer 92 may be deposited over at least a portion of the third dielectric layer 80. The third metallic layer 92 is a continuous layer. The third metallic layer 92 may include any one or more of the reflective materials described above with respect to the first metallic layer 52. In one non-limiting embodiment, the third metallic layer 92 comprises metallic silver. The third metallic layer 92 of the trimetal coating 33 may have a total thickness in the range of 1nm to 20nm, preferably 5nm to 20nm, more preferably 7.5nm to 15nm, most preferably 7.5nm to 10.5 nm.

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 may have a total thickness in the range of 2nm to 20nm, preferably 6nm to 18nm, more preferably 8nm to 15nm, most preferably 9nm to 12 nm.

In one non-limiting embodiment, the coating 30 comprises only the first, second, and third metallic layers (FIGS. 4,6, and 8). There is no additional metallic layer in the coating 30. Each metallic layer has a thickness. In one non-limiting embodiment, the total thickness of the metallic layers of the trimetal coating 33 is in the range of 10nm to 60nm, preferably 15nm to 50nm, more preferably 20nm to 40nm, most preferably 25nm to 31 nm. In case the primer layer comprises aluminium and zinc, the total thickness of the metallic layers of the trimetal coating 33 is in the range of 10nm to 65nm, preferably 15nm to 55nm, more preferably 20nm to 45nm, most preferably 25nm to 36 nm.

An optional third primer layer 94 may be deposited over at least a portion of third metallic layer 92. Third primer layer 94 may be any of the materials described above with respect to first primer layer 54. In one non-limiting embodiment, the third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 comprises titanium. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 comprises silver zinc. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetramal coating 34 comprises zinc. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetramal coating 34 comprises Ag_xZn_1-x. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetramal coating 34 comprises Ag_xZn_1-xAn oxide. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 comprises Al_xZn_1-xAn oxide. In another embodiment, a trimetal coating 33 and a tetrametallic coating 34Third primer layer 94 of (a) contains In_xZn_1-xAn oxide. In another embodiment, third primer layer 94 of trimetal coating 33 and tetrametatal coating 34 comprises Ga_xZn_1-xAn oxide. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetramal coating 34 comprises V_xZn_1-xAn oxide. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 comprises Al_xTi_1-xAn oxide. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 comprises Al_xNb_1-xAn oxide. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 comprises Al_xNb_1-xAnd (3) nitride. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetramal coating 34 comprises W_xNb_1-xAnd (3) nitride. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetramal coating 34 comprises W_xTi_1-xAn oxide. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 comprises Ti_xTa_1-xAn oxide. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 comprises Ti_xNb_1-xAn oxide. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 comprises Ti_xNb_1-xAnd (3) nitride. In another embodiment, third primer layer 94 of trimetal coating 33 and tetrametatal coating 34 comprises Nb_xZr_1-xAn oxide. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 comprises Ta_xW_1-xAn oxide. In another embodiment, the third primer layer 94 of the trimetal coating 33 and the tetramal coating 34 comprises W_xNb_1-xAn oxide. In another embodiment, third primer layer 94 of trimetal coating 33 and tetrametatal coating 34 comprises Zn_xTi_1-xAn oxide.

The third primer layer 94 of the trimetal coating 33 and the tetrametatal coating 34 has a total thickness in the range of 0.5nm to 5nm, preferably 1.0nm to 2.5nm, more preferably 1.5nm to 2.5 nm.

A fourth dielectric layer 100 may be deposited over at least a portion of third metallic layer 92 or optional third primer layer 94. The fourth dielectric layer 100 may also include one or more of the materials discussed above with respect to the first, second, and third dielectric layers 40, 60, 80. In one non-limiting embodiment, the fourth dielectric layer 100 comprises a first film 102 of the fourth dielectric layer. The first film 102 of the fourth 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, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. 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 mixtures thereof. In one embodiment, the first film 102 of the fourth dielectric layer comprises zinc oxide or zinc stannate. In another embodiment, the first film 102 of the fourth dielectric layer comprises aluminum doped zinc oxide. In another embodiment, the first film 102 of the fourth dielectric layer comprises indium doped zinc oxide. In another embodiment, the first film 102 of the fourth dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the first film 102 of the fourth dielectric layer comprises indium-doped tin oxide. In another embodiment, the first film 102 of the fourth dielectric layer comprises vanadium doped zinc oxide.

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.

An optional third film 106 of a 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 comprise an oxide, nitride, oxynitride, or mixture thereof, of a metal selected from the group consisting of: titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. The optional third film 106 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 mixtures thereof. In one embodiment, the optional third film 106 of the fourth dielectric layer comprises zinc oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises silicon nitride or silicon oxynitride. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises aluminum doped zinc oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises indium doped zinc oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises gallium doped zinc oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises indium-doped tin oxide. In another embodiment, the optional third film 106 of the fourth dielectric layer comprises vanadium doped zinc oxide.

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.

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

The four-metal coating 34 of fig. 5,7 and 9 includes additional layers. In a non-limiting mannerIn an embodiment, the fourth dielectric layer 100 of the four-metal coating 34 comprises a seed film, not shown in the figure, located in direct contact with the fourth metallic layer 112. The seed film may comprise aluminum, aluminum silver, aluminum 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 zinc, titanium aluminum, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof. The seed film may comprise aluminum zinc, vanadium zinc, silver zinc, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. In another example, the seed film may comprise gallium zinc, indium tin, metals thereof, alloys thereof, oxides thereof, or suboxides thereof. The composition of a non-limiting example of a seed film can be found in table 2. In another embodiment, the seed film comprises V_xZn_1-xAn oxide. In another embodiment, the seed film comprises Al_xZn_1-xAn oxide. In another embodiment, the seed film comprises Ga_xZn_1-xAn oxide. In another embodiment, the seed film contains In_xZn_1-xAn oxide. In another embodiment, the seed film comprises Sn_xIn_1-xAn oxide. In another embodiment, the seed film comprises Ag deposited in an oxygen/argon environment. In another embodiment, the seed film comprises Al_xAg_1-x. In one non-limiting embodiment, the third film 106 of the fourth dielectric layer of the four metal coating 34 is a seed film. The seed film may have a total thickness in the range of 0.5 to 10nm, preferably 0.75 to 8nm, more preferably 0.9 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 implementations, the fourth dielectric layer 100 includes a first film 102, a second film 104, a third film 106, and a seed film.

A fourth metallic layer 112 of the four metal coating 34 may be deposited over 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 with respect to the first metallic layer 52. In one non-limiting embodiment, the fourth metallic layer 112 of the four metal coating 34 comprises metallic silver. The fourth metallic layer 112 of the four-metal coating 34 may have a total thickness in the range of 2nm to 20nm, preferably 4nm to 15nm, more preferably 6nm to 11nm, most preferably 7nm to 10 nm.

An optional fourth primer layer 114 may be deposited over at least a portion of fourth metallic layer 112 of four metallic coating 34. Fourth primer layer 114 may be any of the materials described above with respect to first primer layer 54. In one non-limiting embodiment, fourth primer layer 114 comprises titanium. In another embodiment, the fourth primer layer 114 includes silver zinc. In another embodiment, the fourth primer layer 114 includes zinc. In another embodiment, the fourth primer layer 114 includes Ag_xZn_1-x. In another embodiment, the fourth primer layer 114 includes Ag_xZn_1-xAn oxide. In another embodiment, fourth primer layer 114 includes Al_xZn_1-xAn oxide. In another embodiment, the fourth primer layer 114 includes In_xZn_1-xAn oxide. In another embodiment, fourth primer layer 114 comprises Ga_xZn_1-xAn oxide. In another embodiment, fourth primer layer 114 comprises V_xZn_1-xAn oxide. In another embodiment, the fourth primer layer 114 of the four-metal coating 34 comprises Al_xTi_1-xAn oxide. In another embodiment, the fourth primer layer 114 of the four-metal coating 34 comprises Al_xNb_1-xAn oxide. In another embodiment, the fourth primer layer 114 of the four-metal coating 34 comprises Al_xNb_1-xAnd (3) nitride. In another embodiment, the fourth primer layer 114 of the four-metal coating 34 comprises W_xNb_1-xAnd (3) nitride. In another embodiment, the fourth primer layer 114 of the four-metal coating 34 comprises W_xTi_1-xAn oxide. In another embodiment, the fourth primer layer 114 of the four-metal coating 34 comprises Ti_xTa_1-xAn oxide. In another embodiment, the fourth primer layer 114 of the four-metal coating 34 comprises Ti_xNb_1-xAn oxide. At another placeIn embodiments, the fourth primer layer 114 of the four-metal coating 34 comprises Ti_xNb_1-xAnd (3) nitride. In another embodiment, fourth primer layer 114 of four metal coating 34 comprises Nb_xZr_1-xAn oxide. In another embodiment, the fourth primer layer 114 of the four-metal coating 34 comprises Ta_xW_1-xAn oxide. In another embodiment, the fourth primer layer 114 of the four-metal coating 34 comprises W_xNb_1-xAn oxide. In another embodiment, the fourth primer layer 114 of the four-metal coating 34 comprises Zn_xTi_1-xAn oxide.

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

A fifth dielectric layer 120 can be deposited over at least a portion of the fourth metallic layer 112 or the optional fourth primer layer 114. The fifth dielectric layer 120 may also include one or more of the materials discussed above with respect to the first, second, third, and fourth dielectric layers. In one non-limiting embodiment, the fifth dielectric layer 120 comprises a first film 122 of a fifth dielectric layer. The first film 122 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, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. In one embodiment, the first film 122 of the fifth dielectric layer comprises zinc oxide or zinc stannate.

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, alloys thereof, mixtures thereof, or combinations 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 comprises indium-doped tin oxide. In another embodiment, the first film 124 of the fifth dielectric layer comprises vanadium doped zinc oxide.

An optional third film of the fifth dielectric layer can 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 comprise an oxide, nitride, oxynitride, or mixture thereof, of a metal selected from the group consisting of: titanium, niobium, zinc, indium, tin, silicon, magnesium, gallium, vanadium, aluminum, alloys thereof, mixtures thereof, or combinations thereof. The optional third film of the fifth 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 mixtures thereof. In one non-limiting embodiment, the optional third film of the fifth dielectric layer comprises zinc oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises silicon nitride or silicon oxynitride. In another embodiment, the optional third film of the fifth dielectric layer comprises titanium oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises aluminum doped zinc oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises indium doped zinc oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises gallium-doped zinc oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises indium-doped tin oxide. In another embodiment, the optional third film of the fifth dielectric layer comprises vanadium doped zinc oxide.

One non-limiting embodiment of the four metal coating 34 is where 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.

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

In one non-limiting embodiment, the coating 30 comprises first, second, third, and fourth metallic layers. The metallic layer is a continuous metallic layer. The metallic layer may comprise only silver or only silver and gold. Each metallic layer has a thickness. In one non-limiting embodiment, the total combined thickness of the metallic layers of the four metal coating 34 is in the range of 10nm to 60nm, preferably 20nm to 50nm, more preferably 30nm to 45nm, most preferably 35nm to 40 nm. In case the primer layer comprises aluminum and zinc, the total thickness of the metallic layers of the four-metal coating 34 is in the range of 10 to 65nm, preferably 20 to 60nm, more preferably 40 to 55nm, most preferably 35 to 45 nm.

The three and four metal coatings 33, 34 may include an outermost protective layer 200, for example deposited over at least a portion of the fourth or fifth dielectric layers 100, 120 in the non-limiting embodiment shown in fig. 4-7, to help protect the underlying layers, e.g., the metallic layers, from mechanical and chemical attack during processing. The outermost protective layer 200 may be an oxygen barrier coating to prevent or reduce the passage of ambient oxygen into the underlying layers of the coating (e.g., during heating or blending). The outermost protective layer 200 may have any desired material or mixture of materials and may include one or more protective films. In one exemplary embodiment, the outermost protective layer 200 may comprise a single layer comprising one or more metal oxide materials, such as, but not limited to, oxides of aluminum, silicon, or mixtures thereof. For example, the outermost protective coating layer may be a single coating layer, including the ranges: 0 to 100 wt% alumina and/or 100 to 0 wt% silica, such as 5 to 95 wt% alumina and 95 to 5 wt% silica, such as 10 to 90 wt% alumina and 90 to 10 wt% silica, such as 15 to 90 wt% alumina and 85 to 10 wt% silica, such as 50 to 75 wt% alumina and 50 to 25 wt% silica, such as 50 to 70 wt% alumina and 50 to 30 wt% silica, such as 35 to 100 wt% alumina and 65 to 0 wt% silica, such as 70 to 90 wt% alumina and 30 to 10 wt% silica, such as 75 to 85 wt% alumina and 25 to 15 wt% silica, such as 88 to 12 wt% alumina and 12 wt% silica, For example, 65 to 75 weight percent alumina and 35 to 25 weight percent silica, for example, 70 to 30 weight percent alumina and 30 weight percent silica, for example, 60 to less than 75 weight percent alumina and greater than 25 to 40 weight percent silica. Other materials such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium, and/or oxides thereof 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 1.8.

In one non-limiting embodiment, the outermost protective layer 200 is a combined silicon oxide and aluminum oxide coating. The outermost protective layer 200 may be sputtered from two cathodes (e.g., one silicon and one aluminum) or from a single cathode containing silicon and aluminum. This outermost protective layer 200 of silicon aluminum oxide can be written as Si_xAl_1-xO_(1.5+x)/2Where x can vary from greater than 0 to less than 1. In one exemplary embodiment, the outermost protective layer 200 comprises 15 wt.% alumina and 85 wt.% silica. In another embodiment, the outermost protective layer 200 comprises SiO₂、Al₂O₃SiAlO, alloys thereof and mixtures thereof.

In one non-limiting embodiment, the outermost protective layer 200 may be made of silicon nitride (Si)₃N₄) Silicon oxynitride (SiON), silicon aluminum nitride (SiAlN), silicon aluminum oxynitride (SiAlON), mixtures thereof, and/or alloys thereof, and which may provide improved durability to the coated article. The outermost protective layer 200 may have excellent electrical characteristicsConductive with other materials that improve sputtering of silicon. For example, during deposition, the silicon cathode may include a small amount (e.g., up to 20 wt.%, up to 15 wt.%, up to 10 wt.%, or up to 5 wt.%) of aluminum to improve sputtering. In this case, the resulting silicon nitride layer will comprise a small percentage of aluminum, for example at most 15 wt.% aluminum, for example at most 10 wt.% aluminum, for example at most 5 wt.% aluminum. A coating layer deposited from a silicon cathode having up to 10 wt.% aluminum (added to enhance the conductivity of the cathode) is referred to herein as a "silicon nitride" layer, even though small amounts of aluminum may be present. A small amount of aluminum (e.g., less than or equal to 15 wt.%, e.g., less than or equal to 10 wt.%, e.g., less than or equal to 5 wt.%) in the cathode is believed to form aluminum nitride in the outermost protective layer 200, which is primarily silicon nitride. The outermost protective layer 200 may be formed in a nitrogen atmosphere; however, it is understood that other gases such as oxygen may be present in the atmosphere during deposition of the outermost protective layer 200.

In another non-limiting embodiment, the outermost protective layer 200 can be a multilayer coating comprising a first protective film 202 and a second protective film 204 formed over at least a portion of the first protective film 202. The first protective film 202 may comprise alumina, silica, titania, zirconia, tin oxide, alloys thereof, mixtures thereof, or combinations thereof. In a specific non-limiting embodiment, the first protective film 202 can comprise alumina or an alloy comprising alumina and silica. For example, the first protective film 202 may comprise 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 can include zinc stannate. In another example, the first protection film 202 may comprise zirconium oxide.

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 film having 40 to 60 wt% of alumina and 60 to 40 wt% of titania; 45 to 55 weight percent alumina and 55 to 45 weight percent titania; 48 to 52 weight percent alumina and 52 to 48 weight percent titania; 49 to 51 weight percent alumina and 51 to 49 weight percent titania; or a titania/alumina mixture of 50 wt.% alumina and 50 wt.% titania. 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, such as greater than 50 wt.% silicon oxide, such as greater than 60 wt.% silicon oxide, such as greater than 70 wt.% silicon oxide, such as greater than 80 wt.% silicon oxide, such as in the range of 80 wt.% to 90 wt.% silicon oxide and 10 wt.% to 20 wt.% aluminum oxide, such as 85 wt.% silicon oxide and 15 wt.% aluminum oxide.

In a non-limiting example, the outermost protective layer 200 can 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 contain, for example, alumina, silica, titania, zirconia, 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 comprises aluminum oxide and titanium oxide. In another example, the third protective film comprises zirconium oxide.

The outermost protective layer 200 is the outermost layer of the coating. In addition, the outermost protective layer 200 may have a non-uniform thickness. By "non-uniform thickness" is meant that the thickness of the outermost protective layer 200 may vary over a given unit area, e.g., the outermost protective layer may have high and low spots or regions. The outermost protective layer 200 may have a total thickness in the range of 20nm to 120nm, preferably 25nm to 110nm, more preferably 30nm to 100nm, and most preferably 35nm to 90 nm. Non-limiting examples of suitable protective layers are described in U.S. patent application nos. 10/007,382; 10/133,805, respectively; 10/397,001, respectively; 10/422,095 and 10/422,096.

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.

In the non-limiting embodiments described above, an additional optional absorber layer 140 can be located over at least a portion of the fourth dielectric layer 100 of the three metal coating 33 (fig. 8) or over the fifth dielectric layer 120 of the four metal coating 34 (fig. 9), such that the absorber 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 absorbing layer 140 is selected from the following: ge. GeO_x、NbN_x、NbN_xO_y、Si_aAl_b、Si_aAl_bO_x、Si_aCo_b、Si_aCo_bO_x、Si_aCo_bCu_c、Si_aCo_bCu_cO_x、Si_aCr_b、Si_aCr_bO_x、Si_aNi_b、SiNiO_x、SiO_x、SnN_x、SnO_x、SnO_xN_y、TiN_x、Ti_aNb_bN_x、Ti_aNb_bO_x、Ti_aNb_bO_xN_y、TiO_xN_y、WO_x、WO₂、ZnO:Co、ZnO:Fe、ZnO:Mn、ZnO:Ni、ZnO:V、ZnO:Cr、Zn_aSn_b、Zn_aSn_bO_xOr any combination thereof. In one non-limiting embodiment, the absorber layer 140 comprises silicon cobalt oxide. The absorption layer 140 may have a total thickness in the range of 1nm to 40nm, preferably 5nm to 30nm, more preferably 10nm to 25nm, and most preferably 15nm to 20 nm.

Alternatively, the absorber layer 140 may comprise a subcritical metal film. The term "subcritical thickness" means a thickness less than the critical thickness such that the coating material forms island-like unconnected regions of the coating material. The term "island-like" means that the coating material is not a continuous layer, but rather, the material is deposited so as to form discrete regions or islands. The metal in the subcritical metal film may comprise silver, gold, alloys thereof, mixtures thereof, or combinations thereof. In one non-limiting embodiment, the subcritical metal film comprises silver. The subcritical metal film may have a total subcritical thickness in a range of 0.5nm to 20nm, preferably 1nm to 10nm, more preferably 1.5nm to 3.5 nm.

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 will be located between the subcritical metal film and the optional outermost protective layer 200. The optional dielectric layer 160 can be a multilayer, as described above, comprising one or more dielectric films. The additional dielectric layer 160 may include one or more of the 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 25nm to 33nm, preferably 26nm to 32nm, more preferably 27nm to 31nm, most preferably 28nm to 30 nm.

In some non-limiting embodiments, colored or clear glass cover sheets 12, 18 and/or colored PVB or uncolored PVB interlayer 24 may be used in an attempt to match the three requirements, i.e., neutral color for Rf, low Rf and Rg of about 8%, and LTA value of not less than 70% for the forward looking area of the vehicle.

In one non-limiting practice of the invention, the thickness and/or number of silver layers is configured to produce a total resistivity (sheet resistance) for the coating in the range of 0.6 to 1.5 ohms/square (Ω/□), preferably 0.6 to 1.0 Ω/□, more preferably 0.6 to 0.9 Ω/□. However, one skilled in the art will also appreciate that as the number or thickness of the metallic layers of silver increases, the visible light transmittance decreases. The thickness and/or amount of the metallic layer should not be increased to the point where the visible light transmission in the line of sight region drops below about 70%. In addition, if the total silver thickness is too thick, the color of the glass will appear undesirably red.

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

In one non-limiting practice of the invention, the coating 30 provides an external (ext) reflection a (Rg8 a) at an angle of 8 degrees (°) 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, most preferably 0.

In one non-limiting practice of the invention, the coating 30 provides an external reflection b (Rg8 b) 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, most preferably 0.

The invention is further described in the following numbered clauses:

clause 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 not greater than 60 nanometers.

Clause 2: the coated article of clause 1, wherein the total combined thickness of the metallic layers is at least 20nm and not greater than 40 nanometers.

Clause 3: the coated article of clause 1, wherein the total combined thickness of the metallic layers is at least 25nm and not greater than 31 nanometers.

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

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

Clause 6: the coated article of any preceding clause, wherein the at least one metallic layer comprises at least one of silver, gold, alloys thereof, mixtures thereof, or combinations thereof.

Clause 7: the coated article of clause 6, wherein the at least one metallic layer is silver.

Clause 8: the coated article of any preceding clause, wherein the at least one metallic layer is a continuous layer.

Clause 9: the coated article of any preceding clause, wherein the first metallic layer has a total thickness from 5nm to 20nm, preferably from 5nm to 17.5nm, more preferably from 7nm to 15nm, or most preferably from 8nm to 10.5 nm.

Clause 10: the coated article of any preceding clause, wherein the second metallic layer has a total thickness from 5nm to 20nm, preferably from 5nm to 15nm, more preferably from 7.5nm to 12.5nm, or most preferably from 8.5nm to 11.5 nm.

Clause 11: the coated article of any preceding clause, wherein the third metallic layer has a total thickness from 1nm to 20nm, preferably from 5nm to 20nm, more preferably from 7.5nm to 15nm, or most preferably from 7.5nm to 10.5 nm.

Clause 12: the coated article of any preceding clause, further comprising at least one primer layer formed over the at least one metallic layer.

Clause 13: the coated article of clause 12, wherein the at least one primer layer is selected from the 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-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 in a metal and subsequently oxidized.

Clause 14: the coated article of clauses 12 or 13, wherein when the at least one primer layer comprises aluminum and zinc, the total thickness of the metallic layer is in the range of 10nm to 65nm, preferably 15nm to 55nm, more preferably 20nm to 45nm, or most preferably 25nm to 36 nm.

Clause 15: the coated article of clauses 12 or 13, wherein the at least one primer layer has a total thickness of from 0.5nm to 5nm, preferably from 1nm to 2.5nm, or more preferably from 1.5nm to 2.5 nm.

Clause 16: the coated article of any preceding clause, wherein the 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.

Clause 17: the coated article of any preceding clause, 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.

Clause 18: the coated article of clause 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.

Clause 19: the coated article of clauses 17-18, wherein the first dielectric layer comprises a total thickness of from 10nm to 50nm, preferably from 12nm to 45nm, more preferably from 15nm to 42nm, or most preferably from 18nm to 40 nm.

Clause 20: the coated article of any preceding clause, wherein the first dielectric layer comprises a seed film in direct contact with the first metallic layer, wherein the seed film can comprise aluminum, aluminum silver, aluminum 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 zinc, titanium aluminum, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof.

Clause 21: the coated article of any preceding clause, wherein the second dielectric layer comprises a first film comprising zinc oxide over at least a portion of the first primer layer, 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.

Clause 22: the coated article of clause 21, wherein the second dielectric layer has a total thickness of from 40nm to 110nm, preferably from 50nm to 100nm, more preferably from 55nm to 80nm, or most preferably from 67nm to 76 nm.

Clause 23: the coated article of any preceding clause, 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 tin, germanium, nickel, magnesium, silicon carbide, aluminum nitride, indium zinc, vanadium zinc, gallium zinc, indium tin, niobium, zirconium, tantalum, molybdenum, aluminum-doped silver, silver zinc, titanium aluminum, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof.

Clause 24: the coated article of any preceding clause, wherein the third dielectric layer comprises a first film comprising zinc oxide or zinc stannate over at least a portion of the second primer layer, and a second film comprising zinc 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.

Clause 25: the coated article of clause 24, wherein the third dielectric layer comprises a total thickness of from 40nm to 110nm, preferably from 50nm to 100nm, more preferably from 65nm to 80nm, or most preferably from 71nm to 75 nm.

Clause 26: the coated article of any preceding clause, wherein the third dielectric comprises a seed film in direct contact with the third metallic layer, wherein the seed film can comprise aluminum, aluminum silver, aluminum 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 zinc, titanium aluminum, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof.

Clause 27: the coated article of any preceding clause, 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.

Clause 28: the coated article of clause 27, wherein the fourth dielectric layer has a total thickness of from 10nm to 50nm, preferably from 15nm to 40nm, more preferably from 20nm to 35nm, or most preferably from 27nm to 31 nm.

Clause 29: the coated article of any preceding clause, further comprising an outermost protective coating layer comprising a protective layer, wherein the protective layer comprises at least one of: si₃N₄SiAlN, SiAlON, titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, alloys thereof, mixtures thereof, or combinations thereof.

Clause 30: the coated article of clause 29, wherein the outermost protective layer has a total thickness of from 15nm to 120nm, preferably from 25m to 110nm, more preferably from 30nm to 100nm, or most preferably from 20nm to 90 nm.

Clause 31: the coated article of any one of clauses 29 to 30, wherein the outermost protective layer comprises a first protective film and a second protective film formed over the first protective film.

Clause 32: the coated article of clauses 29 to 31, wherein the outermost protective layer comprises silicon aluminum oxide, titanium aluminum oxide, mixtures thereof, or combinations thereof.

Clause 33: the coated article of any preceding clause, further comprising a light absorber selected from the group consisting of: colored glass, polyvinyl butyral ("PVB"), an absorbing layer, or combinations thereof.

Clause 34: the coated article of clause 33, wherein an absorbent layer is formed over at least a portion of the fourth dielectric layer.

Clause 35: the coated article of clause 34, wherein the absorbent layerSelected from the following: ge. GeO_x、NbN_x、NbN_xO_y、Si_aAl_b、Si_aAl_bO_x、Si_aCo_b、Si_aCo_bO_x、Si_aCo_bCu_c、Si_aCo_bCu_cO_x、Si_aCr_b、Si_aCr_bO_x、Si_aNi_b、SiNiO_x、SiO_x、SnN_x、SnO_x、SnO_xN_y、TiN_x、Ti_aNb_bN_x、Ti_aNb_bO_x、Ti_aNb_bO_xN_y、TiO_xN_y、WO_x、WO₂、ZnO:Co、ZnO:Fe、ZnO:Mn、ZnO:Ni、ZnO:V、ZnO:Cr、Zn_aSn_b、Zn_aSn_bO_xOr any combination thereof.

Clause 36: the coated article of clause 35, wherein the absorbent layer comprises silicon cobalt oxide.

Clause 37: the coated article of any clause 35 to 36, wherein the absorbing layer has a total thickness from 1nm to 40nm, preferably from 5nm to 30nm, more preferably from 10nm to 25nm, or most preferably from 15nm to 20 nm.

Clause 38: the coated article of clause 34, wherein the absorbent layer is a subcritical metal film.

Clause 39: the coated article of clause 38, wherein the subcritical metal film comprises silver, gold, alloys thereof, mixtures thereof, or combinations thereof.

Clause 40: the coated article of any of clauses 38 to 39, wherein the subcritical metallic film comprises silver.

Clause 41: the coated article of any clause 38-40, wherein the subcritical metal film has a total thickness of 0.5nm to 20nm, preferably 1nm to 10nm, or more preferably 1.5nm to 3.5 nm.

Clause 42: the coated article of clause 38, wherein an additional dielectric layer is formed over at least a portion of the subcritical metal film.

Clause 43: the coated article of clause 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.

Clause 44: the coated article of any clause 42 to 43, wherein the additional dielectric layer formed over at least a portion of the subcritical metal film has a total thickness in a range of 25nm to 33nm, preferably 26nm to 32nm, more preferably 27nm to 31nm, most preferably 28nm to 30 nm.

Clause 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 not greater than 60 nanometers.

Clause 46: the coated article of clause 45, wherein the total combined thickness of the metallic layers is at least 30nm and not greater than 45 nanometers.

Clause 47: the coated article of any clause 45, wherein the total combined thickness of the metallic layers is at least 35nm and not greater than 40 nanometers.

Clause 48: the coated article of any of clauses 45 to 47, wherein the coated article has a visible light reflectance of not greater than 8%.

Clause 49: the coated article of any clause 45 to 48, wherein the coated article has a visible light transmittance of at least 70%.

Clause 50: the coated article of any clause 45 to 49, wherein the at least one metallic layer comprises at least one of silver, gold, alloys thereof, mixtures thereof, or combinations thereof.

Clause 51: the coated article of any clause 45 to 50, wherein at least one metallic layer is silver.

Clause 52: the coated article of any clause 45 to 51, wherein the at least one metallic layer is a continuous layer.

Clause 53: the coated article of any clause 45 to 52, wherein the first metallic layer has a total thickness from 2nm to 20nm, preferably from 6nm to 18nm, more preferably from 9nm to 12nm, or most preferably from 9.5nm to 10 nm.

Clause 54: the coated article of any clause 45 to 53, wherein the second metallic layer has a total thickness from 2nm to 20nm, preferably from 6nm to 18nm, more preferably from 8nm to 15nm, or most preferably from 9nm to 12 nm.

Clause 55: the coated article of any clause 45 to 54, wherein the third metallic layer has a total thickness from 2nm to 20nm, preferably from 6nm to 18nm, more preferably from 8nm to 15nm, or most preferably from 9nm to 12 nm.

Clause 56: the coated article of any clause 45 to 47, wherein the fourth metallic layer has a total thickness from 2nm to 20nm, preferably from 4nm to 15nm, more preferably from 6nm to 11nm, or most preferably from 7nm to 10 nm.

Clause 57: the coated article of any clause 45 to 56, further comprising at least one primer layer formed over the at least one metallic layer.

Clause 58: the coated article of clause 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-titanium, tungsten-titanium, tantalum-titanium, zinc-titanium, aluminum-silver, zinc-tin, indium-zinc, silver-zinc, mixtures thereof, combinations thereof, or any alloy thereof, or alloys thereof, and wherein the primer is deposited in a metal and subsequently oxidized.

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

Clause 60: the coated article of any of clauses 45 to 59, wherein the 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.

Clause 61: the coated article of any clause 45 to 60, wherein the first dielectric layer has a total thickness of 20nm to 55nm, preferably 25nm to 50nm, more preferably 30nm to 45nm, or most preferably 35nm to 40 nm.

Clause 62: the coated article of any clause 45 to 61, wherein the second dielectric layer has a total thickness from 60nm to 100nm, preferably from 65nm to 95nm, more preferably from 70nm to 90nm, or more preferably from 74nm to 80 nm.

Clause 63: the coated article of any clause 45 to 62, wherein the third dielectric layer has a total thickness from 55nm to 90nm, preferably from 60nm to 85nm, more preferably from 68nm to 80nm, or most preferably from 70nm to 75 nm.

Clause 64: the coated article of any of clauses 45 to 63, wherein the fourth dielectric layer comprises a seed film in direct contact with the fourth metallic layer, wherein the seed film can comprise aluminum, aluminum silver, aluminum 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 zinc, titanium aluminum, alloys thereof, mixtures thereof, oxides thereof, suboxides thereof, nitrides thereof, subnitrides thereof, or combinations thereof.

Clause 65: the coated article of clause 64, wherein the fourth dielectric layer has a total thickness of from 45nm to 80nm, preferably from 50nm to 75nm, more preferably from 55nm to 70nm, or most preferably from 60nm to 65 nm.

Clause 66: the coated article of any of clauses 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.

Clause 67: the coated article of clause 66, wherein the fifth dielectric layer has a total thickness of 10nm to 45nm, preferably 15nm to 40nm, more preferably 20nm to 35nm, or most preferably 23nm to 28 nm.

Clause 68: the coated article of any of clauses 45 to 67, further comprising an outermost protective coating layer comprising a protective layer, wherein the protective layer comprises at least one of: si₃N₄SiAlN, SiAlON, titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, alloys thereof, or mixtures thereof.

Clause 69: the coated article of clause 68, wherein the outermost protective layer comprises a first protective film and a second protective film formed over the first protective film.

Clause 70: the coated article of any of clauses 68 to 69, wherein the outermost protective layer comprises a protective film of silicon aluminum oxide or titanium aluminum oxide.

Clause 71: the coated article of any clause 45 to 70, further comprising a light absorber selected from the group consisting of: tinted glass, PVB, an absorbing layer, or a combination thereof.

Clause 72: the coated article of clause 71, further comprising an absorbent layer formed over at least a portion of the fifth dielectric layer.

Clause 73: the coated article of clause 72, wherein the absorbent layer is selected from the group consisting of: ge. GeO_x、NbN_x、NbN_xO_y、Si_aAl_b、Si_aAl_bO_x、Si_aCo_b、Si_aCo_bO_x、Si_aCo_bCu_c、Si_aCo_bCu_cO_x、Si_aCr_b、Si_aCr_bO_x、Si_aNi_b、SiNiO_x、SiO_x、SnN_x、SnO_x、SnO_xN_y、TiN_x、Ti_aNb_bN_x、Ti_aNb_bO_x、Ti_aNb_bO_xN_y、TiO_xN_y、WO_x、WO₂、ZnO:Co、ZnO:Fe、ZnO:Mn、ZnO:Ni、ZnO:V、ZnO:Cr、Zn_aSn_b、Zn_aSn_bO_xOr any combination thereof

Clause 74: the coated article of clause 73, wherein the absorbent layer comprises silicon cobalt oxide.

Clause 75: the coated article of clause 72, wherein the absorbent layer is a subcritical metal film.

Clause 76: the coated article of clause 75, wherein the subcritical metal film comprises silver, gold, alloys thereof, mixtures thereof, or combinations thereof.

Clause 77: the coated article of any of clauses 75 to 76, wherein the subcritical metallic film comprises silver.

Clause 78: the coated article of any of clauses 75 to 77, wherein an additional dielectric layer is formed over at least a portion of the subcritical metal film.

Clause 80: a method of making 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 applying a functional coating step 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.

Clause 81: the method of clause 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 layer is over at least a portion of the fifth dielectric layer.

Clause 82: the method of clauses 80-81, further applying an outermost protective coating layer, the applying the outermost protective coating layer step comprising forming an outermost protective layer comprising a protective layer, wherein the protective layer comprises at least one of: si₃N₄SiAlN, SiAlON, titanium oxide, aluminum oxide, silicon oxide, or zirconium oxide.

Examples

The following examples illustrate various embodiments of the present invention. It should be understood, however, that the intention is not to limit the invention to the particular embodiments described.

Example 1

Table 3 shows exemplary coating compositions and thicknesses of trimetallic coatings of the present invention. The reported thicknesses are geometric thicknesses in nanometers (nm), unless otherwise indicated. The substrate was a transparent glass substrate having a thickness of 2.1mm and a transparent cover of 1.6mm positioned over the substrate. A 0.7mm PVB interlayer was used. The base layer is a first dielectric layer, the base center layer is a second dielectric layer, the top center layer is a third dielectric layer, and the top layer is a fourth dielectric layer.

TABLE 3

Tables 4 and 5 show the resulting color and optical properties, respectively, for the samples of table 3.

TABLE 4

TABLE 5

Example 2

The solar coefficient (TT) or total transmitted energy of solar radiation is higher than expected for the trimetallic coating of example 1 (49-50%). A high TT value indicates that approximately 50% of solar radiation energy is transmitted through the substrate, resulting in undesirable heat generation. Table 6 shows exemplary coating compositions and thicknesses (nm) of the trimetallic coatings of the present invention, wherein a pigmented overlay was used in an attempt to reduce transmitted solar radiation while matching 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-P-L are greener and therefore more absorptive than clear glass.

TABLE 6

Tables 7 and 8 show the resulting color and optical properties, respectively, for the samples of table 6.

TABLE 7

TABLE 8

Example 3

Table 9 shows exemplary coating compositions and thicknesses (nm) of the trimetallic coatings of the present invention, with addition of cobalt silicon oxide (SiCoO) to the coating_x) Or a subcritical metal film absorber layer. SiCoO of sample 7_xThe absorption layer is located between the fourth dielectric layer and the first protection film of the outermost protection layer. The subcritical metallic film comprising silver of sample 8 was located between the fourth dielectric layer and the additional dielectric layer described previously. An absorbing layer is used in conjunction with a tinted glass cover to attempt to further reduce transmitted solar radiation while matching three property requirements (neutral Rf color, low Rf and Rg (8%), and LTA no less than 70%).

TABLE 9

Tables 10 and 11 show the resulting color and optical properties, respectively, for the samples of table 9.

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TABLE 11

Example 4

Table 12 shows an exemplary laminate composition of the trimetal coating, using a clear or tinted PVB interlayer along with a tinted or clear glass cover and a glass substrate. The trimetallic coating used was described above in table 3, example 1.

TABLE 12

Table 13 shows the color and optical properties of the trimetallic coating on a clear glass substrate with tinted or untinted PVB and tinted or untinted glass cover.

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Example 5

Table 14 shows exemplary coating compositions and thicknesses (nm) for the inventive four-metal coating. Here, the base layer is a first dielectric layer, the base center layer is a second dielectric layer, the center layer is a third dielectric layer, the top center layer is a fourth dielectric layer, and the top layer is a fifth dielectric layer. Four metal coatings were used in an attempt to further reduce transmitted solar radiation while matching three property requirements (neutral Rf color, low Rf and Rg (8%), and LTA no less than 70%).

TABLE 14

Sample (I)	14
		Base material	Glass 2.1mm
Covering article	Transparent 1.6mm
		Intermediate layer	Clear PVB 0.7mm
Base layer	37.4
		Metallic layer 1	9.86
Substrate core layer	76.7
		Metallic layer 2	10.8
Center layer	72.2
		Metallic layer No. 3	9.68
Top center layer	62.4
		Metallic layer 4	7.91
Top layer	25.5
		No. 1 protective film	16.0
No. 2 protective film	22.0
		Total metallicity	38.3

Tables 15 and 16 show the resulting color and optical properties, respectively, for the samples of table 14.

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TABLE 16

The four-metal coating on the glass substrate was more conductive (0.86 Ω/□ square resistance) than any of the three-metal coating examples 1-4 (1.3-1.4 Ω/□ square resistance). Thus, the solar and low energy properties of the four-metal coating are greater than the three-metal coating. No colored glass is required when forming the four-metal coating.

Those skilled in the art will readily appreciate that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof.