Transparent conductive oxide with embedded film

Abstract

The present invention relates to a transparent conductive oxide with an embedded film. A substrate is coated with an underlayer having a first underlayer film made of a first high refractive index material. A transparent conductive oxide layer is over at least a portion of the underlayer. An embedded film is embedded in the transparent conductive oxide layer, wherein the embedded film comprises a second high refractive index material.

Description

[0001] This application is a divisional application of Chinese invention patent application No. 201880060703.X (the corresponding international application is PCT / US2018 / 045070), with a priority date of August 4, 2017. Technical Field

[0002] The present invention relates to coated articles having low emissivity and neutral color. Background Art

[0003] Transparent conductive oxides ("TCOs") are applied to substrates to provide lower emissivity and lower sheet resistance to the coated article. This makes TCOs particularly suitable for electrodes (e.g., solar cells) or heating layers, activated glass units or screens. TCOs are typically applied by vacuum deposition techniques, such as magnetron sputtering vacuum deposition ("MSVD"). Typically, thicker TCO layers provide lower sheet resistance. However, the thickness of the TCO affects the color of the coated article. Therefore, there is a need to regulate the coloring effect caused by the TCO layer. It is also necessary to minimize the thickness of the TCO layer in order to minimize the effect of the TCO on the color of the coated article while still maintaining the desired sheet resistance.

[0004] Coating stacks may corrode over time. To prevent this, a protective overcoat may be added to the coating. For example, titanium dioxide films disclosed in U.S. Pat. Nos. 4,716,086 and 4,786,563 are protective films that provide chemical resistance to the coating. Silicon oxide disclosed in Canadian Patent No. 2,156,571, aluminum oxide and silicon nitride disclosed in U.S. Pat. Nos. 5,425,861; 5,344,718; 5,376,455; 5,584,902 and 5,532,180; and PCT International Patent Publication No. 95 / 29883 also provide a chemically resistant "protective film" to the coating. This technology can be improved by a more durable protective overcoat chemically and / or mechanically. Summary of the invention

[0005] The coated article includes a substrate, a bottom layer above the substrate. The bottom layer includes a first layer. The first layer includes a high refractive index material. A second layer is located above at least a portion of the first layer. The second layer includes a low refractive index material. A transparent conductive film is located above at least a portion of the bottom layer. The coated article has a square resistance of at least 5Ω / □ and at most 25Ω / □. The coated article has a * is at least -9 and at most 1 and b * A color that is at least -9 and at most 1.

[0006] Optionally, the coated article may have a protective layer over at least a portion of the transparent conductive oxide layer. The protective layer includes a first protective film over at least a portion of the transparent conductive oxide layer, and a second protective film over at least a portion of the first protective film. The second protective film is the outermost film in the coating stack and includes a mixture of titanium oxide and aluminum oxide. Optionally, the protective layer may include a third protective film located between the first protective film and the second protective film.

[0007] A method of forming a coated substrate includes providing a substrate. Identifying a transparent conductive oxide and determining a thickness of the transparent conductive oxide that will provide a sheet resistance of at least 5 Ω / □ and at most 25 Ω / □. Identifying a bottom layer having a first bottom layer material and a second bottom layer material. Determining the thickness of the first bottom layer and the second bottom layer that will provide a coated substrate with a * is at least -9 and at most 1 and b * The color of the coated substrate is at least -9 and at most 1. The thickness of the two films in the bottom layer is used to adjust the color of the coated substrate. Since the color is affected by the thickness of the transparent conductive oxide film, the color is adjusted after determining the thickness of the transparent conductive oxide film. A first bottom layer film including a first bottom layer material is applied over at least a portion of the substrate with a first bottom layer film thickness. A second bottom layer film including a second bottom layer material is applied over at least a portion of the first bottom layer with a second bottom layer thickness. A transparent conductive oxide layer having a transparent conductive oxide is applied over at least a portion of the second bottom layer film with the thickness of the transparent conductive oxide film.

[0008] The coated article prepared by the following steps has a * is at least -9 and at most 1 and b * A color of at least -9 and at most 1 is determined. A transparent conductive oxide is identified and a thickness of the transparent conductive oxide is determined that will provide a sheet resistance of at least 5 Ω / □ and at most 25 Ω / □. A bottom layer having a first bottom layer material and a second bottom layer material is identified. A thickness of the first bottom layer and the second bottom layer is determined that will provide a coated substrate having a * is at least -9 and at most 1 and b * The color of the coated substrate is at least -9 and at most 1. The thickness of the two films in the bottom layer is used to adjust the color of the coated substrate. Since the color is affected by the thickness of the transparent conductive oxide film, the color is adjusted after determining the thickness of the transparent conductive oxide film. A first bottom layer film including a first bottom layer material is applied over at least a portion of the substrate with a first bottom layer film thickness. A second bottom layer film including a second bottom layer material is applied over at least a portion of the first bottom layer with a second bottom layer thickness. A transparent conductive oxide layer having a transparent conductive oxide is applied over at least a portion of the second bottom layer film with the transparent conductive oxide film thickness.

[0009] A coated article comprising a substrate. The bottom layer is located above at least a portion of the substrate. The bottom layer includes at least a first bottom layer film above at least a portion of the substrate, and an optional second bottom layer film above at least a portion of the first bottom layer film. The first bottom layer film includes a first high refractive index material. The optional second bottom layer film includes a first low refractive index layer. A transparent conductive oxide layer is located above at least a portion of the first bottom layer film or the optional second bottom layer film. The second high refractive index material is embedded in the transparent conductive oxide layer. The coated article has a square resistance of at least 5Ω / □ and at most 25Ω / □. The square resistance is at least 35% higher than when no second high refractive index material is embedded in the transparent conductive oxide layer.

[0010] Optionally, the coated article may have a protective layer over at least a portion of the transparent conductive oxide layer. The protective layer includes a first protective film over at least a portion of the transparent conductive oxide layer, and a second protective film over at least a portion of the first protective film. The second protective film is the outermost film in the coating stack and includes a mixture of titanium oxide and aluminum oxide. Optionally, the protective layer may include a third protective film located between the first protective film and the second protective film.

[0011] A coated article comprising a substrate. The bottom layer is located above at least a portion of the substrate. The bottom layer includes at least a first bottom layer film above at least a portion of the substrate, and an optional second bottom layer film above at least a portion of the first bottom layer film. The first bottom layer film includes a first high refractive index material. The optional second bottom layer film includes a first low refractive index layer. The first transparent conductive oxide layer is located above at least a portion of the first bottom layer film or the optional second bottom layer film. The embedded film is located above at least a portion of the first transparent conductive oxide layer. The embedded film has a second high refractive index material. The second transparent conductive oxide layer is located above at least a portion of the second transparent conductive oxide layer. The coated article has a square resistance of at least 5Ω / □ and at most 25Ω / □. The square resistance is at least 35% higher than that without the embedded film.

[0012] Optionally, the coated article may have a protective layer over at least a portion of the transparent conductive oxide layer. The protective layer includes a first protective film over at least a portion of the transparent conductive oxide layer, and a second protective film over at least a portion of the first protective film. The second protective film is the outermost film in the coating stack and includes a mixture of titanium oxide and aluminum oxide. Optionally, the protective layer may include a third protective film located between the first protective film and the second protective film.

[0013] A method of forming a coated article is provided; a method of increasing sheet resistance; or a method of increasing light transmission through a coated article. A substrate is provided. A base layer is applied over at least a portion of the substrate. A first base layer film is applied over at least a portion of the substrate. The first base layer film has a first high refractive index material. An optional second base layer film is applied over at least a portion of the first base layer film. The optional second base layer film has a first low refractive index layer. A first transparent conductive oxide layer is applied over at least a portion of the first base layer film or the optional second base layer film. An embedded film is applied over at least a portion of the first transparent conductive oxide film. The embedded film has a second high refractive index material. A second transparent conductive oxide film is applied over at least a portion of the embedded film. Optionally, a protective layer may be applied over the second transparent conductive oxide film. The optional protective layer includes a first protective film over at least a portion of the transparent conductive oxide layer, and a second protective film over at least a portion of the first protective film. The second protective film is the outermost film in the coating stack and includes a mixture of titanium oxide and aluminum oxide. Optionally, the protective layer may include a third protective film located between the first protective film and the second protective film.

[0014] A coated article manufactured by the following steps. A substrate is provided. A base layer is applied over at least a portion of the substrate. A first base film is applied over at least a portion of the substrate. The first base film has a first high refractive index material. An optional second base film is applied over at least a portion of the first base film. The optional second base film has a first low refractive index layer. A first transparent conductive oxide layer is applied over at least a portion of the first base film or the optional second base film. An embedded film is applied over at least a portion of the first transparent conductive oxide film. The embedded film has a second high refractive index material. A second transparent conductive oxide film is applied over at least a portion of the embedded film. Optionally, a protective layer may be applied over the second transparent conductive oxide film. The optional protective layer includes a first protective film over at least a portion of the transparent conductive oxide layer, and a second protective film over at least a portion of the first protective film. The second protective film is the outermost film in the coating stack and includes a mixture of titanium oxide and aluminum oxide. Optionally, the protective layer may include a third protective film located between the first protective film and the second protective film.

[0015] A method of increasing the sheet resistance of a coated article. A coated article is provided. The coated article has a substrate and a transparent conductive oxide layer over at least a portion of the substrate. The coated article is treated with a post-deposition process. The post-deposition process can be tempering the coated article, heating the entire coated article by placing it in a furnace, flash annealing only the surface of the transparent conductive oxide layer, or passing eddy currents through the transparent conductive oxide layer. Alternatively, the coated article is provided with a sheet resistance of less than 25 ohms / square by the method described in this paragraph.

[0016] A method of increasing the sheet resistance of a coated article. A substrate is provided. A transparent conductive oxide is applied over at least a portion of the substrate. A post-deposition process is applied to the substrate coated with the transparent conductive oxide. The post-deposition process may be tempering the coated article, heating the entire coated article by placing it in a furnace, flash annealing only the surface of the transparent conductive oxide layer, or passing an eddy current through the transparent conductive oxide layer.

[0017] The coated article is a substrate having a coating stack. At least a portion of the substrate is coated with a functional coating. A protective layer is applied over at least a portion of the functional coating. The protective layer has a first protective film over at least a portion of the functional coating, and a second protective film over at least a portion of the functional coating. The second protective film is the last film in the coating stack and includes titanium oxide and aluminum oxide. Optionally, a third protective film can be located between the first protective film and the second protective film, or between the first protective film and the functional coating.

[0018] A method for preparing a coated article, the method comprising providing a substrate. Applying a functional coating over at least a portion of the substrate. Applying a first protective film over at least a portion of the functional coating. Applying a second protective film comprising titanium oxide and aluminum oxide over at least a portion of the first protective film. Optionally, applying a third protective film between the first protective film and the second protective film or between the first protective film and the functional coating.

[0019] A method of reducing the absorption, resistance or emissivity of a transparent conductive oxide layer. A substrate is provided. A transparent conductive oxide layer is applied over at least a portion of the substrate in an atmosphere containing 0% to 2.0% oxygen.

[0020] A coated article having reduced absorption, resistance or emissivity comprising a transparent conductive oxide layer made by the following steps: providing a substrate and applying a transparent conductive oxide layer over at least a portion of the substrate in an atmosphere comprising 0% to 2.0% oxygen. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The patent or application file contains at least one drawing drawn in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0022] Figure 1a , 1b , 1c and 1d are side views (not to scale) of coatings including features of the present invention;

[0023] Figure 2a , 2b , 2c, 2d, and 2e are side views of other coatings (not to scale) including features of the present invention;

[0024] Figure 3a , 3b , 3c, 3d, 3e are side views of other coatings (not to scale) including inventive features;

[0025] Figure 4a and 4b is a side view of another coating (not to scale) including inventive features;

[0026] Figure 5a and 5b is a side view of another coating (not to scale) including inventive features;

[0027] Figure 6a , 6b , 6c, 6d, 6e, 6f, 6g, and 6h are side views of other coatings (not to scale) that include inventive features;

[0028] Figure 7 This is a graph showing the relationship between the ITO sheet resistance and thickness of a sample in which the surface of the ITO transparent conductive oxide layer is heated to a predetermined temperature.

[0029] Figure 8a -c is an XRD pattern showing the crystallization of the tin-doped indium oxide transparent conductive oxide layer.

[0030] Fig. 9 The sheet resistance of the as-deposited and heated gallium-doped zinc oxide transparent conductive oxide layers is shown.

[0031] Fig.10 The sheet resistance of the aluminum-doped zinc oxide transparent conductive oxide layer is shown as deposited and after being heated.

[0032] Fig.11 is a graph showing the effect of an underlayer on the color of a substrate having a 170 nm thick tin-doped indium oxide transparent conductive oxide layer.

[0033] Fig.12 is a graph showing the effect of an underlayer on the color of a substrate having a 175-225 nm thick tin-doped indium oxide transparent conductive oxide layer and a silicon oxide protective layer.

[0034] Fig.13a is a graph showing the effect of the embedded film on the sheet resistance.

[0035] Fig.13b is a graph showing the effect of the embedded film on the emissivity.

[0036] Fig.13c is the XRD pattern of indium-doped tin oxide with embedded film.

[0037] Fig.14 is a bar graph showing the durability of different protective layers.

[0038] Fig.15 is a bar graph showing the durability of different protective layers.

[0039] 16(a) and 16(b) are line graphs showing the normalized absorption of a transparent conductive oxide layer comprising indium-doped tin oxide in an atmosphere having 0% to 2% oxygen.

[0040] 17(a) and 17(b) are graphs showing the emissivity of a transparent conductive oxide layer including indium-doped tin oxide in an atmosphere having 0% to 2% oxygen.

[0041] Fig.18 The graph shows the normalized absorption rate of a transparent conductive oxide layer including aluminum-doped zinc oxide in an atmosphere with 0% to 6% oxygen.

[0042] Fig.19 The graph shows the normalized absorbance versus the oxygen content supplied to the coater.

[0043] Fig. 20 The graph shows the relationship between the sheet resistance of a transparent conductive oxide layer including indium-doped tin oxide after post-deposition treatment and the surface temperature of the transparent conductive oxide layer.

[0044] Fig.21 The graph shows the relationship between the sheet resistance and the surface temperature of the transparent conductive oxide. Fig. 22 is a graph showing the relationship between the sheet resistance of ITO and the thickness of a sample made of one ITO film or a sample made of two ITO films deposited on each other to obtain the thickness. DETAILED DESCRIPTION

[0045] The spatial or directional terms used herein, such as "left", "right", "upper", "lower", etc., are related to the present invention as shown in the accompanying drawings. It should be understood that the present invention can take various alternative orientations, so these terms should not be considered limiting.

[0046] As used herein, spatial or directional terms, such as "left", "right", "inside", "outside", "above", "below", etc., are related to the present invention, as shown in the accompanying drawings. However, it should be understood that the present invention can take various alternative orientations, and therefore, these terms should not be considered limiting. In addition, as used herein, all numbers used in the specification and claims to represent dimensions, physical properties, processing parameters, ingredient amounts, reaction conditions, etc. should be understood as modified by the term "about" in any case. Therefore, unless otherwise indicated, the numerical values ​​listed in the following specification and claims can vary according to the desired characteristics attempted to be obtained by the present invention. At least, and without intending to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be interpreted according to the number of reported significant figures and by applying ordinary rounding techniques. In addition, it should be understood that all ranges disclosed herein cover range starting values ​​and range ending values ​​and any and all sub-ranges contained therein. For example, the range of "1 to 10" should be considered to include any and all subranges between a minimum of 1 and a maximum of 10 (including the minimum and maximum values); that is, all subranges starting with a minimum of 1 or greater and ending with a maximum of 10 or less, such as 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. In addition, all documents mentioned herein (such as but not limited to issued patents and patent applications) should be considered to be "incorporated by reference" in their entirety. Any reference to quantity is "by weight percentage" unless otherwise stated. The term "film" refers to a coating area having a desired or selected composition. A "layer" includes one or more "films". A "coating" or "coating stack" includes one or more "layers". The terms "metal" and "metal oxide" should be considered to include silicon and silicon oxide, respectively, as well as traditionally recognized metals and metal oxides, although silicon is not technically a metal.

[0047] In all cases, all numbers used in the specification and claims should be understood to be modified by the term "about". All ranges disclosed herein should be understood to cover range starting values ​​and range ending values ​​and any and all subranges contained therein. The ranges described herein represent average values ​​within the specified ranges.

[0048] The term "above" means "further away from the substrate." For example, a second layer located "above" a first layer means that the second layer is located farther away from the substrate than the first layer. The second layer may be in direct contact with the first layer, or one or more other layers may be located between the second layer and the first layer.

[0049] All documents mentioned herein should be considered to be "incorporated by reference" in their entirety.

[0050] Any reference to amounts is "percent by weight" unless otherwise indicated.

[0051] The term "visible light" refers to electromagnetic radiation having a wavelength in the range of 380 nm to 780 nm. The term "infrared radiation" is electromagnetic radiation having a wavelength in the range of greater than 780 nm to 100,000 nm. The term "ultraviolet radiation" refers to electromagnetic energy having a wavelength in the range of 100 nm to less than 380 nm.

[0052] The terms "metal" and "metal oxide" include silicon and silicon oxide, respectively, as well as conventionally recognized metals and metal oxides, although silicon may not be conventionally considered a metal. "At least" means "greater than or equal to." "Not more than" means "less than or equal to."

[0053] All haze and transmittance values ​​herein are those determined using a Haze-Gard Plus haze meter (commercially available from BYK-Gardner USA) and in accordance with ASTM D1003-07.

[0054] Where oxygen percentages are mentioned in a coater, this is the amount of oxygen added to the coater chamber relative to other gases. For example, if 2% oxygen is added to the coater chamber atmosphere, then 2% oxygen and 98% argon are added to the coater chamber. Argon can replace other gases, but typically these gases are inert gases.

[0055] The discussion of the invention herein may describe certain features as "particularly" or "preferably" within certain limits (e.g., "preferably", "more preferably" or "even more preferably" within certain limits). It should be understood that the present invention is not limited to these particular or preferred limits but encompasses the entire scope of the disclosure.

[0056] The present invention includes the following invention aspects in any combination or is basically composed of the following invention aspects. Various aspects of the present invention are described in different drawings. However, it should be understood that this is only for the convenience of description and discussion. In the practice of the present invention, one or more aspects of the present invention shown in a drawing can be combined with one or more aspects of the present invention shown in one or more other drawings.

[0057] An exemplary article includes a substrate 10 , an underlayer 12 over substrate 10 , and a transparent conductive oxide 14 over underlayer 12 , as shown in FIG. 1 .

[0058] The article 2 may be a window, a sun mirror, a solar cell or an organic light emitting diode. The coating applied to the substrate 10 can provide low emissivity, low resistivity, scratch resistance, radio frequency attenuation or a desired color.

[0059] Substrate 10 may be transparent, translucent, or opaque to visible light. "Transparent" means having a visible light transmittance of greater than 0% up to 100%. Alternatively, substrate 12 may be translucent or opaque. "Translucent" means allowing electromagnetic energy (e.g., visible light) to pass through but diffusing the energy so that objects on the side opposite to the observer are not clearly visible. "Opaque" means having a visible light transmittance of 0%.

[0060] The substrate 10 may be glass, plastic or metal. Examples of suitable plastic substrates include acrylic polymers such as polyacrylates; polyalkyl methacrylates such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, etc.; polyurethanes; polycarbonates; polyalkyl terephthalates such as polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, etc.; polymers containing polysiloxanes; or copolymers of any monomers used to prepare these polymers, or any mixture thereof); or glass substrates. Examples of suitable glass substrates include conventional soda-lime silicate glass, borosilicate glass or lead glass. The glass may be clear glass. "Clear glass" refers to colorless or colorless glass. Alternatively, the glass may be tinted glass or other colored glass. The glass may be annealed or heat-treated glass. The term "heat-treated" as used herein refers to tempering or at least partial tempering. The glass may be of any type, such as conventional float glass, and of any composition having any optical properties, such as any value of visible light transmittance, ultraviolet transmittance, infrared transmittance, and / or total solar energy transmittance. Examples of suitable metal substrates include aluminum or stainless steel.

[0061] The substrate 10 may have a high visible light transmittance at a reference wavelength of 550 nanometers (nm) and a thickness of 2 mm. "High visible light transmittance" means that the visible light transmittance at 550 nm is greater than or equal to 85%, such as greater than or equal to 87%, such as greater than or equal to 90%, such as greater than or equal to 91%, such as greater than or equal to 92%.

[0062] The bottom layer 12 can be a single layer, a uniform layer, a gradient layer, a double layer, or can include multiple layers. A "uniform layer" refers to a layer in which the material is randomly distributed throughout the coating. A "gradient layer" refers to a layer having two or more components, wherein the concentration of the component changes as the distance from the substrate 12 changes (continuously or in steps).

[0063] The bottom layer 12 may include two films: a first bottom layer film 20 and a second bottom layer film 22. The first bottom layer film 20 is located above the substrate 10 and is closer to the substrate 10 than the second bottom layer film 22. The first bottom layer film 20 may be a material having a higher refractive index than the second bottom layer film 22 and / or the substrate 10. For example, the first bottom layer film 20 may include metal oxides, nitrides or oxynitrides. Examples of suitable metals for the first bottom layer film 20 include silicon, titanium, aluminum, zirconium, hafnium, niobium, zinc, bismuth, lead, indium, tin, tantalum, their alloys or their mixtures. For example, the first bottom layer film 20 may include oxides of zinc, tin, aluminum and / or titanium, their alloys or their mixtures. For example, the first bottom layer film 20 may include oxides of zinc and / or tin. For example, the first bottom layer film 20 may include zinc oxide and tin oxide, or zinc stannate.

[0064] The first underlying film 20 may include zinc oxide. The zinc target for sputtering the zinc oxide film may include one or more other materials to improve the sputtering characteristics of the zinc target. For example, the zinc target may contain up to 15% by weight of such material, such as up to 10% by weight, such as up to 5% by weight. The resulting zinc oxide layer will include a small percentage of oxides of the added material, for example, up to 15% by weight, up to 10% by weight, up to 9% by weight of the material oxide. The layer deposited by the zinc target (the zinc target having up to 10% by weight, such as up to 5% by weight of additional material to enhance the sputtering characteristics of the zinc target) is referred to herein as a "zinc oxide layer", even though a small amount of the added material (or oxide of the added material) may be present. An example of such a material is tin.

[0065] The first bottom layer film 20 may include an alloy of zinc oxide and tin oxide. For example, the first bottom layer film 20 may include or may be a zinc stannate layer. "Zinc stannate" refers to a composition of the following formula: Zn X Sn 1-X O 2-X (Formula 1), where "x" varies in the range of greater than 0 to less than 1. For example, "x" can be greater than 0 and can be any fraction or decimal greater than 0 to less than 1. The zinc stannate layer has one or more major amounts of the form of Formula 1. A zinc stannate layer with x=2 / 3 is commonly referred to as "Zn2SnO4". An alloy of zinc oxide and tin oxide may include 80 wt% to 99 wt% zinc and 20 wt% to 1 wt% tin; for example, 85 wt% to 99 wt% zinc and 15 wt% to 1 wt% tin; 90 wt% to 99 wt% zinc and 10 wt% to 1 wt% tin; for example, about 90 wt% zinc and 10 wt% tin.

[0066] The second underlying film 22 may be a material having a lower refractive index than the first underlying film 20. For example, the second underlying film 22 may include a metal oxide, a nitride, or an oxynitride. Examples of suitable metals for the second underlying film 22 include silicon, titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, tin, tantalum, alloys thereof, or mixtures thereof.

[0067] For example, the second underlying film 22 may include silicon oxide and aluminum oxide. According to this example, the second underlying film 22 will have at least 50 weight % silicon oxide; 50 to 99 weight % silicon oxide and 50 to 1 weight % aluminum oxide; 60 to 98 weight % silicon oxide and 40 to 2 weight % aluminum oxide; 70 to 95 weight % silicon oxide and 30 to 5 weight % aluminum oxide; 80 to 90 weight % silicon oxide and 10 to 20 weight % aluminum oxide, or 8 weight % silicon oxide and 15 weight % aluminum oxide.

[0068] Transparent conductive oxide layer 14 is above bottom layer 12. Transparent conductive oxide layer 14 may be a single layer or may have multiple layers or regions. Transparent conductive oxide layer 14 has at least one conductive oxide layer. For example, transparent conductive oxide layer 14 may include one or more metal oxide materials. For example, transparent conductive oxide layer 14 may include one or more oxides of one or more of the following: Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Bi, Ti, Co, Cr, Si, In, or an alloy of two or more of these materials. For example, transparent conductive oxide layer 14 may include tin oxide. In another example, transparent conductive oxide layer 14 includes zinc oxide.

[0069] The transparent conductive oxide layer 14 may include one or more dopant materials, such as, but not limited to, F, In, Al, P, Cu, Mo, Ta, Ti, Ni, Nb, W, Ga, Mg and / or Sb. For example, the dopant may be In, Ga, Al or Mg. The dopant may be present in an amount of less than 10 wt%, such as less than 5 wt%, such as less than 4 wt%, such as less than 2 wt%, such as less than 1 wt%. The transparent conductive oxide layer 14 may be a doped metal oxide, such as gallium-doped zinc oxide ("GZO"), aluminum-doped zinc oxide ("AZO"), indium-doped zinc oxide ("IZO"), magnesium-doped zinc oxide ("MZO"), or tin-doped indium oxide ("ITO").

[0070] The thickness of transparent conductive oxide layer 14 can be in the range of 75 nm to 950 nm, such as 90 nm to 800 nm, such as 100 nm to 700 nm. For example, the thickness of transparent conductive oxide layer 14 can be in the range of 125 nm to 450 nm; at least 150 nm; or at least 175 nm. The thickness of transparent conductive oxide layer 14 can be no greater than 600 nm, 500 nm, 400 nm, 350 nm, 300 nm, 275 nm, 250 nm, or 225 nm.

[0071] Different transparent conductive oxide layer 14 materials have different sheet resistances at the same thickness, and also affect the optical properties of the product differently. Ideally, the sheet resistance should be less than 25Ω / □ (ohm / square), or less than 20Ω / □, or less than 18Ω / □. For example, if the transparent conductive oxide layer 14 includes GZO, it can have a thickness of at least 300nm and at most 400nm. If the transparent conductive oxide layer 14 includes AZO, its thickness should be at least 350nm, or at least 400nm, and the thickness is at most 950nm, or at most 800nm, or at most 700nm, or at most 600nm. If transparent conductive oxide layer 14 comprises ITO, its thickness can be at least 75 nm, at least 90 nm, at least 100 nm, at least 125 nm, or at least 150 nm, or at least 175 nm; and at most 350 nm, at most 300 nm, at most 275 nm, or at most 250 nm, or at most 225 nm.

[0072] The surface roughness (RMS) of the transparent conductive oxide layer 14 may be in the range of 5 nm to 60 nm, such as 5 nm to 40 nm, such as 5 nm to 30 nm, such as 10 nm to 30 nm, such as 10 nm to 20 nm, such as 10 nm to 15 nm, such as 11 nm to 15 nm.

[0073] For example, when transparent conductive oxide layer 14 is tin-doped indium oxide, the thickness of transparent conductive oxide layer 14 may be in the following ranges: 75 nm to 350 nm; 100 nm to 300 nm; 125 nm to 275 nm; 150 nm to 250 nm; or 175 nm to 225 nm.

[0074] The sheet resistance of the transparent conductive oxide layer 14 may be in the range of 5Ω / □ to 25Ω / □, such as 8Ω / □ to 20Ω / □, for example 10Ω / □ to 18Ω / □.

[0075] For example, the article may be a glass substrate 10 having a base layer 12 over the glass substrate 10. The base layer 12 may have at least two films: a first base layer film 20 and a second base layer film 22. The first base layer film 20 may be an alloy of zinc oxide and tin oxide, and the second base layer film 22 may be an alloy of silicon oxide and aluminum oxide. A transparent conductive oxide layer 14 may be over the second film 22. The transparent conductive oxide layer 14 may be ITO, GZO, or AZO.

[0076] The transparent conductive oxide film provides a certain square resistance to the article, for example, less than 25Ω / □. Generally, as the thickness of the transparent conductive oxide increases, the square resistance decreases. Once the desired square resistance and the thickness of the transparent conductive oxide necessary to achieve the desired square resistance are determined, optical design software can be used to determine the thickness of the first film and the second film. An example of suitable optical modeling software is FILM STAR. Ideally, efforts should be made to have a * , b * A color with a value of -1, -1. Some variation is acceptable in this color. For example, a * can be as high as 1, 0, or -0.5 and as low as -9, -4, -3, or -1.5, and b * The value can be as high as 1, 0 or -0.5 and as low as -9, -4, -3 or -1.5. To obtain the desired color, the thickness of the first film 20 and the second film 22 can be varied to obtain the desired color for the identified transparent conductive oxide and transparent conductive oxide thickness. For example, the thickness of the first film can be between 10 and 20 nm, or between 11 and 15 nm; and the thickness of the second film can be between 25 and 35 nm, or between 29 and 34 nm.

[0077] Reference Figure 1c and 1d , the article 2 may optionally include a protective layer 16, such as the protective layers described herein, over the transparent conductive oxide layer 14. For example, the protective layer 16 may include a first protective film 60 and a second protective film 62. The second protective film 62 may include a mixture of titanium oxide and silicon oxide. For example, the protective layer 16 includes a first protective film 60, a second protective film 62, and a third protective film 64.

[0078] An exemplary method of the present invention is to form a coated substrate. A substrate 10 is provided. A transparent conductive oxide is identified. Once the transparent conductive oxide is identified, a thickness of a transparent conductive film can be identified that will provide the coated substrate with a sheet resistance of at least 5 Ω / □ and / or no more than 25 Ω / □, particularly no more than 20 Ω / □, and more particularly no more than 18 Ω / □. A desired color of the coated substrate is also identified. Optical design software is used to identify a first bottom layer material and a second bottom layer material, and to determine a first bottom layer film thickness and a second bottom layer film thickness that will provide the following color for an article having a transparent conductive oxide layer identified above, wherein a * can be as high as 1 and as low as -9, and b * The value can be as high as 1 and as low as -9. The base layer 12 is applied over the substrate by applying a first base layer material over the substrate to form a first base layer film 20 having a determined first film thickness, and applying a second base layer material over the first base layer film to a determined second base layer film thickness to form a second base layer film 22. A transparent conductive oxide material is applied over the base layer 12 to a determined transparent conductive film thickness to form a transparent conductive oxide layer 14.

[0079] The thickness of the transparent conductive oxide layer 14 affects the sheet resistance and the color of the substrate. The bottom layer 12 is used to adjust the color of the article having a transparent conductive oxide layer 14 of a specific thickness. This is done by identifying a first bottom layer material and a second bottom layer material, and then using a tool such as FILM STAR, identifying a thickness for each bottom layer material that provides the desired color. Once the first and second bottom layer materials are identified, the thickness of each of these materials can be adjusted to achieve any desired color. Typically, the desired color is a * , b * In this color, some variation is acceptable. For example, a * can be as high as 1 and as low as -9, and b * Values ​​can be as high as 1 and as low as -9.

[0080] For example, you may wish to create a * is -1 and b *A solar cell with a color of -1. A glass substrate will be provided. The transparent conductive oxide material can be confirmed to be indium-doped tin oxide ("ITO"). It will be understood that if the thickness of the ITO transparent conductive oxide film is between 125nm and 275nm, a square resistance of 5Ω / □ to 25Ω / □ can be achieved using the invention disclosed herein. In order to achieve the desired color, a bottom layer 12 having the following films can be selected: a first bottom layer film 20 comprising zinc oxide and tin oxide, and a second bottom layer film 22 comprising silicon oxide and aluminum oxide. The first bottom layer film 20 will have a thickness between 10nm and 15nm, and the second bottom layer film 22 will have a thickness between 29nm and 34nm. The first bottom layer film 20 is applied over the substrate 10 at the confirmed thickness, and the second bottom layer film 22 is applied over the first bottom layer film 20 at the confirmed thickness. A transparent conductive oxide layer 14 is applied over the second bottom layer film 22 at the confirmed thickness, thereby forming an article having the following color, the color of which is a * between -9 and 1, specifically between -4 and 0, more specifically between -3 and 1, more specifically between -1.5 and -0.5; and b * Between -9 and 1, specifically between -4 and 0, more specifically between -1.5 and -0.5.

[0081] In another example, a glass substrate 10 will be provided. The transparent conductive oxide layer material can be confirmed as indium-doped tin oxide ("ITO"). It will be understood that if the thickness of the ITO transparent conductive oxide film is between 125nm and 275nm, a square resistance of 5Ω / □ to 25Ω / □ will be achieved, specifically not more than 20Ω / □, and more specifically not more than 18Ω / □. In order to achieve the desired color, a bottom layer 12 having the following films can be selected: a first bottom layer film 20 containing zinc oxide and tin oxide, and a second bottom layer film 22 containing silicon oxide, and the effect of the color of the protective layer 16 on the coated substrate is also considered. In this example, a silicon oxide protective layer with a thickness of at least 30nm and not more than 45nm is used. The first bottom layer film 20 will have a thickness between 10nm and 15nm, and the second bottom layer film 22 will have a thickness between 29nm and 34nm. The first bottom layer film 20 is applied over the substrate 10 with the confirmed thickness, and the second bottom layer film 22 is applied over the first bottom layer film 20 with the confirmed thickness. A transparent conductive oxide layer 14 is applied over the second base film 22 at a thickness determined to provide the above-mentioned sheet resistance, thereby forming a coated substrate having a color having a * is -9 to 1, or -4 to 0, or -3 to 1, or -1.5 to -0.5; or b * is -9 to 1, or -4 to 0, or -3 to 1, or -1.5 to -0.5.

[0082] In these examples, the primer layer can be used to adjust the color of the coated substrate.

[0083] 2 shows another exemplary article 2 , which includes a substrate 10 , an underlayer 12 over the substrate, a transparent conductive oxide layer 14 over the underlayer 12 , and an embedded film 24 including a second high refractive index material embedded in the transparent conductive oxide layer 14 .

[0084] Substrate 10 may be any substrate discussed herein.

[0085] The bottom layer 12 may have a first bottom layer film 20 and an optional second bottom layer film 22. The first bottom layer film 20 has a first high refractive index material. The optional second bottom layer film 22 has a first low refractive index material. The refractive index of the first high refractive index material is higher than the refractive index of the first low refractive index material.

[0086] Transparent conductive oxide layer 14 can be any transparent conductive oxide discussed above.

[0087] The embedded film 24 has a second high refractive index material embedded in the transparent conductive oxide layer 14. The second high refractive index material can be any material having a higher refractive index than the first low refractive index material. For example, the second high refractive index material forming the embedded film 24 can include a metal oxide, a nitride, or an oxynitride. Examples of suitable oxide materials for the embedded film 24 include oxides of silicon, titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, tin, and / or alloys thereof and / or mixtures thereof. For example, the embedded film 24 can include oxides of silicon and / or aluminum.

[0088] For example, the embedded film 24 may include oxides of silicon and aluminum. According to this example, the second underlying film 22 will have at least 50% by volume silicon oxide; 50 to 99% by volume silicon oxide and 50 to 1% by volume aluminum oxide; 60 to 98% by volume silicon oxide and 40 to 2% by volume aluminum oxide; 70 to 95% by volume silicon oxide and 30 to 5% by volume aluminum oxide; 80 to 90% by weight silicon oxide and 10 to 20% by weight aluminum oxide, or 8% by weight silicon oxide and 15% by weight aluminum oxide.

[0089] The embedded film 24 may have a thickness in the following ranges: 5 nm to 50 nm, 10 to 40 nm, or 15 to 30 nm.

[0090] The article may optionally include a protective layer 16, such as the protective layers described herein, over the transparent conductive oxide layer 14. For example, the protective layer 16 may include a first protective film 60 and a second protective film 62. The second protective film 62 may include a mixture of titanium oxide and silicon oxide. For example, the protective layer 16 includes a first protective film 60, a second protective film 62, and a third protective film 64.

[0091] 3 shows another exemplary article 2, which includes a substrate 10, a bottom layer 12 on the substrate, a first transparent conductive oxide layer 114 on the bottom layer 12, and an embedded film 124 on the first transparent conductive oxide layer 114. A second transparent conductive oxide layer 115 is located on the embedded film 124. Optionally, a protective layer 16 can be applied on the second transparent conductive oxide layer 115.

[0092] The embedded film 124 may include a metal oxide, a nitride, or an oxynitride. Examples of suitable materials for the second high refractive index metal include oxides of silicon, titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, tin, and / or alloys thereof and / or mixtures thereof. For example, the second high refractive index material may include silicon oxide and / or aluminum oxide.

[0093] For example, the embedded film 124 may include silicon oxide and aluminum oxide. The second high refractive index material will have at least 50 volume % silicon oxide; 50 to 99 volume % silicon oxide and 50 to 1 volume % aluminum oxide; 60 to 98 volume % silicon oxide and 40 to 2 volume % aluminum oxide; or 70 to 95 volume % silicon oxide and 30 to 5 volume % aluminum oxide; or 80 to 90 weight % silicon oxide and 10 to 20 weight % aluminum oxide, or 8 weight % silicon oxide and 15 weight % aluminum oxide.

[0094] The embedded film 124 may have a thickness in the following ranges: 5 nm to 50 nm, 10 to 40 nm, or 15 to 30 nm.

[0095] The first transparent conductive oxide layer 114 and the second transparent conductive oxide layer 115 have a total thickness in the following range: 75nm to 950nm, such as 90nm to 800nm, such as 125nm to 700nm. For example, the total thickness may be no greater than 950nm, 800nm, 700nm, 600nm, 500nm, 400nm, 350nm, 300nm, 275nm, 250nm or 225nm. The total thickness may be at least 75nm, at least 90nm, at least 100nm, at least 125nm, 150nm or 175nm. The first transparent conductive oxide layer 114 may have a thickness of at least 10nm, at least 25nm, 50nm, 75nm or 100nm; and at most 650nm, 550nm, 475nm, 350nm, 250nm or 150nm. The thickness of the second transparent conductive oxide layer 115 may be at least 10 nm, at least 25 nm, 50 nm, 75 nm, or 100 nm; and at most 650 nm, 550 nm, 475 nm, 350 nm, 250 nm, or 150 nm. For example, if the first transparent conductive oxide layer 114 and the second transparent conductive oxide layer 115 include ITO, the thickness of the first transparent conductive oxide layer 114 may be at least 25 nm, 50 nm, 75 nm, or 100 nm; and at most 200 nm, 175 nm, 150 nm, or 125 nm; and the thickness of the second transparent conductive oxide layer 115 may be at least 25 nm, 50 nm, 75 nm, or 100 nm; and at most 200 nm, 175 nm, 150 nm, or 125 nm. In another example, if transparent conductive oxide layer 114 and second transparent conductive oxide layer 115 include AZO, the thickness of first transparent conductive oxide layer 114 can be at least 100 nm, at least 150 nm, at least 200 nm, 250 nm, or 300 nm; and at most 650 nm, 550 nm, at most 450 nm, at most 325 nm, or at most 200 nm; and the thickness of second transparent conductive oxide layer 115 can be at least 100 nm, at least 150 nm, at least 200 nm, 250 nm, or 300 nm; and at most 650 nm, 550 nm, at most 450 nm, at most 325 nm, or at most 200 nm.In another example, if transparent conductive oxide layer 114 and second transparent conductive oxide layer 115 include GZO, the thickness of first transparent conductive oxide layer 114 can be at least 30 nm, at least 60 nm, at least 75 nm, at least 90 nm, at least 100 nm, at least 125 nm, at least 150 nm, 200 nm, or 300 nm; and at most 350 nm, at most 300 nm, 275 nm, at most 250 nm, or at most 225 nm; and the thickness of second transparent conductive oxide layer 115 can be at least 30 nm, at least 60 nm, at least 75 nm, at least 90 nm, at least 100 nm, at least 125 nm, at least 150 nm, 200 nm, or 300 nm; and at most 350 nm, at most 300 nm, 275 nm, at most 250 nm, or at most 225 nm.

[0096] By varying the thickness of the first and second transparent conductive oxide layers 114, 115, the embedded film 124 can be moved higher in the transparent conductive oxide layer 14 or lower in the transparent conductive oxide layer 14. Surprisingly, regardless of where the embedded film 24, 124 is positioned in the coating stack, the sheet resistance increases significantly (see Fig.13a ). It is also surprising that the location of the embedded films 24, 124 within the transparent conductive oxide layer 14 has different effects on light transmission (see Fig.13b When the first transparent conductive oxide layer 114 is thinner than the second transparent conductive oxide layer 115, thereby positioning the embedded film 124 at a lower position within the transparent conductive oxide layer 14, light transmission increases (see Fig.13b ). When the first transparent conductive oxide layer 114 is thicker than the second transparent conductive oxide layer 115, the embedded film 124 is positioned at a higher position within the transparent conductive oxide layer 14 (see Fig.13b ), this increase is more significant. However, if the thickness of the first transparent conductive oxide layer 114 is approximately equal to the thickness of the second transparent conductive oxide layer 115, thereby positioning the embedded film 124 approximately in the middle of the transparent conductive oxide layer 14, the transmission is reduced (see Fig.13b). For example, second transparent conductive oxide film 115 may be at least 25%, at least 50%, at least 75%, at least 100% (i.e., at least twice), at least 125%, or at least 150% thicker than first transparent conductive oxide film 114; and may be at most 250% thicker; at most 200% thicker; at most 150% thicker; at most 125% thicker; at most 100% thicker (i.e., at most twice); at most 75% thicker; at most 50% thicker; or at most 25% thicker than first transparent conductive oxide film 114. Alternatively, second transparent conductive oxide film 115 may be at least 25%, at least 50%, at least 75%, at least 100% (i.e., at least twice), at least 125%, or at least 150% thinner than first transparent conductive oxide film 114; and may be up to 250% thinner; up to 200% thinner; up to 150% thinner; up to 125% thinner; up to 100% (i.e., up to twice); up to 75% thinner; up to 50% thinner; or up to 25% thinner than first transparent conductive oxide film 114.

[0097] Another example of the present invention is a method of making a coated article 2. A substrate 10 is provided. A first base film 20 having a first high refractive index material is applied over at least a portion of the substrate 10. A second base film 22 having a first low refractive index material is applied over at least a portion of the first base film 20, wherein the first low refractive index material has a lower refractive index than the first high refractive index film. A first transparent conductive oxide film 114 is applied over at least a portion of the base film 12. An embedded film 124 having a second high refractive index material is applied over at least a portion of the first transparent conductive oxide film 114, wherein the second high refractive index material has a refractive index greater than that of the first low refractive index material, or has a refractive index within 10% or 5% of that of the first high refractive index material, or is the same material as the first high refractive index material, or has the same refractive index as the first high refractive index material. A second transparent conductive oxide film 115 is applied over at least a portion of the embedded film 124. The second high refractive index film divides the transparent conductive oxide film into two parts, the first transparent conductive oxide film and the second transparent conductive oxide film.

[0098] The embedded film 124 also allows one to adjust the color of the coated substrate. * can be at least -9, -4, -3 or -1.5, and at most 1, 0 or -0.5, and the b of the color * is at least -9, -4, -3 or -1.5, and at most 1, 0 or -0.5.

[0099] By changing the thickness of the two high refractive index materials and the low refractive index material, the color of the coated substrate can be adjusted. To do this, the materials to be used for the transparent conductive oxide films 114 and 115 should first be confirmed. Once the material is confirmed, the desired square resistance is confirmed. By knowing the material and the square resistance, the thickness of the transparent conductive oxide layer 14, or the total thickness of the first and second transparent conductive oxide films 114 and 115, can be determined. The transparent conductive oxide layer 14 will affect the color of the coated substrate. In order to offset this color effect, an optical design tool (such as FILM STAR) can be used to confirm the thickness of the first and second underlying films 20 and 22, as well as the thickness of the embedded films 24, 124. This is done as follows: the thickness of the transparent conductive oxide layer 14 is entered into the software, and the first high refractive index material, the second high refractive index material, and the first lower refractive index material are confirmed. Using these parameters, the thickness of the first and second underlying films 20 and 24 and the embedded films 24, 124 can be determined. These films are then applied with those confirmed thicknesses.

[0100] For example, the method may include identifying a first transparent conductive oxide material to be used in first transparent conductive oxide film 114 and a second transparent conductive oxide material to be used in second transparent conductive oxide 115. These transparent conductive oxides may be GZO, AZO, IZO, MZO, or ITO.

[0101] The thickness of the transparent conductive oxide layer 14 can be determined by first determining the desired sheet resistance. Once the sheet resistance is determined, the total thickness of the two transparent conductive oxide films 114, 115 can then be determined. The sheet resistance can be at least 8Ω / □, at least 10Ω / □, or at least 12Ω / □; and can be at most 25Ω / □, at most 20Ω / □, or at most 18Ω / □. To achieve these values, the total thickness of the transparent conductive oxide layer 14 can be at least 75nm, at least 90nm, at least 100nm; at least 175nm; at least 180nm; at least 190nm; at least 200nm; at least 205nm; at least 225nm; or at least 360nm. Because the transparent conductive oxide layer 14 affects the color of the coated substrate, it is important to minimize the total thickness of the transparent conductive oxide films 114, 115. To this end, the total thickness of transparent conductive oxide films 114, 115 can be at most 800nm; at most 700nm; at most 360nm; at least 350nm, at most 300nm, at most 275bnm, at most 250nm, at most 225nm; at most 205nm; at most 200nm; at most 190nm; at most 180nm or at most 175nm.

[0102] The location of the embedded film 24, 124 within the transparent conductive oxide is also determined. In doing so, consider whether it is desired to have increased or decreased transmission (see FIG. 13(b)). The first transparent conductive oxide film 114 can be thicker, thinner, or have approximately the same thickness as the second conductive oxide film 115.

[0103] Confirm the first high refractive index material for the first base film 20, the first low refractive index material for the second base film 22, and the second high refractive index material for the embedded film 24, 124. Optionally, the protective layer 16 can be confirmed with the confirmed thickness of each protective layer film 60, 62 and / or 64. Confirm the desired color. Input these parameters into an optical design tool (such as FILM STAR) and confirm the thickness of the first base film 20 and the base film 22 and the embedded film 124.

[0104] A coating stack having the following layers is applied over the substrate at identified thicknesses: base layer 12, transparent conductive oxide layer 14, embedded films 24, 124 and optional protective layer 16. The thickness of base films 20, 22 and embedded films 24, 124 adjusts the color of article 2 to the desired color.

[0105] Figure 4a and 4b Another exemplary article 2 is shown, which includes: a substrate 10, a bottom layer 12 on the substrate 10, a transparent conductive oxide layer 14 on the bottom layer 12, and a protective layer 16 on the transparent conductive oxide layer 14. The substrate 10, the bottom layer 12 and the transparent conductive oxide layer 14 can be any substrate or bottom layer discussed herein. The transparent conductive oxide layer 14 can be divided by the embedded layers 24, 124 discussed herein.

[0106] The protective layer 16 is above the transparent conductive oxide layer 14, or optionally in direct contact with the transparent conductive oxide layer 14. It may include at least two protective films 60, 62 or at least three protective films 60, 62, 64.

[0107] Figure 4a An example of an article with a protective layer is shown, which has two protective films 60, 62. The first protective film 60 is located above the transparent conductive oxide layer 14 and closer to the transparent conductive oxide layer 14 than the second protective film 62. The second protective film 62 is the outermost film in the coating 18 on the coated article.

[0108] The first protective film 60 may include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, tin oxide, or a mixture thereof. For example, the first protective film may include a mixture of silicon oxide and aluminum oxide. In another example, the first protective film 60 may include zinc stannate. In another example, the first protective film 60 may include zirconium oxide.

[0109] The second protective film 62 includes a mixture of titanium oxide and aluminum oxide. The second protective film 62 is the last film in the coating layer 18 applied over the substrate 10.

[0110] The second protective film 62 contains 40-60 wt% aluminum oxide and 60-40 wt% titanium oxide; 45-55 wt% aluminum oxide and 55-45 wt% titanium oxide; 48-52 wt% aluminum oxide and 52-48 wt% titanium oxide; 49-51 wt% aluminum oxide and 51-49 wt% titanium oxide; or 50 wt% aluminum oxide and 50 wt% titanium oxide.

[0111] like Figure 4b As shown, the protective layer 16 may further include a third protective film 64 located between the first protective film 60 and the second protective film 62. The third protective film 64 may include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, tin oxide, or a mixture thereof. For example, the third protective film 64 may include a mixture of silicon oxide and aluminum oxide. In another example, the third protective film 64 includes zinc stannate. In another example, the third protective film 64 includes zirconium oxide.

[0112] Another exemplary article is shown in Figure 5a and 5b , which includes a substrate 10, a functional coating 112 and a protective layer 16. The substrate in the method can be glass, plastic or metal.

[0113] Functional coating 112 can be any functional coating. For example, it can include multiple dielectric films or multiple metal films. The functional coating can include the bottom layer 12 described herein, and / or the transparent conductive oxide layer 14 described herein. As described herein, protective layer 16 can be a first protective film 60 and a second protective film 62. In this case, second protective film 62 is the outermost film and includes aluminum oxide and titanium oxide.

[0114] The protective layer may have a total thickness of at least 20 nm, 40 nm, 60 nm or 80 nm, 100 nm or 120 nm; and at most 275 nm, 255 nm, 240 nm, 170 nm, 150 nm, 125 nm or 100 nm. The first protective film may have a thickness of at least 10 nm, at least 15 nm, at least 27 nm, at least 35 nm, at least 40 nm, at least 54 nm, at least 72 nm; and at most 85 nm, 70 nm, 60 nm, 50 nm, 45 nm, 30 nm. The second protective film may have a thickness of at least 10 nm, at least 15 nm, at least 27 nm, at least 35 nm, at least 40 nm, at least 54 nm, at least 72 nm; and at most 85 nm, 70 nm, 60 nm, 50 nm, 45 nm, 30 nm. The optional third protective film may have a thickness of at least 10 nm, at least 15 nm, at least 27 nm, at least 35 nm, at least 40 nm, at least 54 nm, at least 72 nm; and at most 85 nm, 70 nm, 60 nm, 50 nm, 45 nm, 30 nm. For example, the protective layer may have a thickness as listed in Table 1 below. In one embodiment, the thickness of the first protective film is at least 20 nm or at least 30 nm; and at most 60 nm or at most 50 nm. The thickness of the second protective film is at least 15 nm or at least 20 nm; and at most 50 nm or at most 40 nm. The optional third protective layer has a thickness of at least 5 nm or at least 10 nm; and at most 30 nm or at most 20 nm. The optional third protective layer may be located between the first protective film and the functional layer, or between the first protective film and the second protective film.

[0115] Table 1: Exemplary thickness of protective layer

[0116]

[0117]

[0118] The functional coating 112 may be a single film functional coating, or may be a multi-film functional coating including one or more dielectric layers and / or one or more infrared reflective layers.

[0119] Functional coating 112 may be, for example, a solar control coating. The term "solar control coating" refers to a coating comprising one or more layers or films that affect the solar properties of a coated article, such as, but not limited to: the amount of solar radiation (e.g., visible, infrared, or ultraviolet radiation) reflected from, absorbed by, or passing through the coated article; shielding factor; emissivity, etc. Solar control coatings are capable of blocking, absorbing, or filtering selected portions of the solar spectrum, such as, but not limited to, the infrared, ultraviolet, and / or visible spectrum.

[0120] Functional coating 112 may, for example, include one or more dielectric films. The dielectric film may contain antireflective materials, including but not limited to metal oxides, oxides of metal alloys, nitrides, oxynitrides, or mixtures thereof. The dielectric film may be transparent to visible light. Examples of suitable metal oxides for dielectric films include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, and mixtures thereof. These metal oxides may have small amounts of other materials, such as manganese in bismuth oxide, tin in indium oxide, and the like. In addition, oxides of metal alloys or metal mixtures may be used, such as oxides containing zinc and tin (e.g., zinc stannate, as defined below), oxides of indium-tin alloys, silicon nitride, silicon aluminum nitride, or aluminum nitride. In addition, doped metal oxides may be used, such as tin oxide doped with antimony or indium, or silicon oxide doped with nickel or boron. The dielectric film may be a substantially single-phase film, such as a metal alloy oxide film, such as zinc stannate, or may be a mixture of phases consisting of zinc and tin oxides, or may be composed of multiple films.

[0121] Functional coating 112 may include a radiation reflective film. The radiation reflective film may include a reflective metal, such as but not limited to metallic gold, copper, palladium, aluminum, silver, or mixtures thereof. In one embodiment, the radiation reflective film comprises a metallic silver layer.

[0122] In one embodiment, the functional coating comprises: a first dielectric layer 120 on the substrate 10, a second dielectric layer 122 on the first dielectric layer 120, and a dielectric layer 122 between the first dielectric layer and the second dielectric layer 120 (see Figure 7 ) or above the second dielectric layer 122 (see Figure 6a ) of the metal layer 126. The protective coating 16 is located above the metal layer 126 (see Figure 6b ). Optionally, a layer of dielectric material may be formed between the metal film and the first dielectric layer (see Figure 6c ) or a second dielectric layer (see Figure 6d ) is applied between the two surfaces.

[0123] Dielectric films 120 and 122 may be transparent to visible light. Examples of suitable metal oxides for dielectric films 120 and 122 include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, and mixtures thereof. These metal oxides may have small amounts of other materials, such as manganese in bismuth oxide, tin in indium oxide, and the like. In addition, oxides of metal alloys or metal mixtures may be used, such as oxides containing zinc and tin (e.g., zinc stannate, as defined above), oxides of indium-tin alloys, silicon nitride, silicon aluminum nitride, or aluminum nitride. In addition, doped metal oxides may be used, such as tin oxide doped with antimony or indium, or silicon oxide doped with nickel or boron. Dielectric films 120 and 122 may be substantially single-phase films, such as metal alloy oxide films, such as zinc stannate, or may be a mixture of phases consisting of oxides of zinc and tin. Dielectric films 120 and 122 may have a total thickness in a range of 100 angstroms to 600 angstroms, such as 200 angstroms to 500 angstroms, such as 250 angstroms to 350 angstroms.

[0124] The metal film 126 may be selected from metals such as gold, copper, palladium, aluminum, silver, and alloys thereof. For example, the metal film 126 may be silver.

[0125] The optional primer 128 can be a single film or multiple films. For example, the primer 128 can include an oxygen trapping material that can be sacrificial during the deposition process to prevent degradation or oxidation of the metal film 126 during the sputtering process or subsequent heating process. The primer 128 can also absorb at least a portion of the electromagnetic radiation that passes through the coating, such as visible light. Examples of materials suitable for the primer 128 include: titanium, silicon, silicon dioxide, silicon nitride, silicon oxynitride, nickel-chromium alloys (such as Inconel), zirconium, aluminum, alloys of silicon and aluminum, alloys containing cobalt and chromium (such as, ), and mixtures thereof. For example, the primer 148 may be titanium.

[0126] The protective layer 16 may include a first protective film 60 and a second protective film 62; or the first protective film 60 (see Figure 5a and 6a -d), the second protective film 62 and the third protective film 64 (see Figure 5b and 6e -h).

[0127] In the method for making a coated article, a base coat 12 is applied over a substrate 10, and a transparent conductive oxide layer 14 is applied over the base coat 12. The base coat 12 may be applied over the substrate 10, and the transparent conductive oxide layer 14 may be applied over at least a portion of the base coat 12; or the substrate 10 may be provided with the base coat 12 and the transparent conductive oxide layer 14 thereon. A protective layer 16 is applied over at least a portion of the transparent conductive oxide. The protective layer 16 is applied by first applying a first protective film 60 over the transparent conductive oxide, and then applying a second protective film 62 over the first protective film 60. Optionally, a third protective film 64 may be applied over the first protective film, and a second protective film 62 may be applied over the third protective film 64.

[0128] In the method for making a coated article, a functional coating 112 is applied over a substrate 10. The functional coating 112 may be applied over the substrate 10, or a substrate having the functional coating 112 may be provided. A protective layer 16 is applied over the functional coating 112. The protective layer 16 is applied by first applying a first protective film 60 over the transparent conductive oxide, and then applying a second protective film 62 over the first protective film 60. Optionally, a third protective film 64 may be applied over the first protective film 60, and a second protective film 62 may be applied over the third protective film 64.

[0129] Another exemplary method of the present invention is a method of increasing the sheet resistance of a coated article. A coated article is provided. The coated article has a substrate and a transparent conductive oxide layer over at least a portion of the substrate. The coated article is treated with a post-deposition process.

[0130] Post-deposition processing may be tempering the coated article, flash annealing of only the surface of the transparent conductive oxide layer, or passing an eddy current through the transparent conductive oxide layer.

[0131] The coated article is tempered by heating the entire article so that the surface of the transparent conductive oxide layer reaches more than 380°F, at least 435°F, or at least 635°F for at least 5, 10, 15, 20, 25, or 30 seconds, and at most 120, 90, 60, 55, 50, 45, 40, 35, or 30 seconds. The transparent conductive oxide layer should not be heated to more than 635°F or 806°F. After heating the coated article, it is quickly cooled to room temperature at a specific rate.

[0132] The coated article can be flash annealed to increase the sheet resistance. This is done by heating the surface of the coated article using a flash lamp. The heated surface is the surface where the transparent conductive oxide layer is located. The surface is heated to a temperature exceeding 380°F, at least 435°F, or at least 635°F for at least 5, 10, 15, 20, 25, or 30 seconds, and at most 120, 90, 60, 50, 55, 45, 40, 35, or 30 seconds. The surface should be heated to no more than 968°F, no more than 878°F, no more than 806°F, or no more than 635°F. After heating the surface, it is cooled to room temperature.

[0133] Eddy currents can be caused to pass through a transparent conductive oxide ("TCO") by exposing the transparent conductive oxide layer to a varying magnetic field. For example, a magnetic field can be applied above a substrate coated with a TCO. The TCO faces the magnetic field. Eddy currents pass through the transparent conductive oxide layer.

[0134] Another exemplary method is a method of reducing the square resistance of a coated article. A substrate is provided. The substrate in the method can be glass, plastic or metal. Optionally, the substrate is coated with a base layer. The base layer can include one film, two films or more. The substrate is coated with a transparent conductive oxide by applying a transparent conductive oxide over at least a portion of the substrate or the base layer. Optionally, an embedded film is applied within the transparent conductive oxide layer. This optional step is performed by applying a first portion of a transparent conductive oxide layer, applying an embedded layer over at least a portion of the first portion of the transparent conductive oxide layer, and applying a second portion of the transparent conductive oxide layer over at least a portion of the embedded layer. The coated article is treated with one of the above-described post-deposition processes.

[0135] Optionally, the method may further include applying a protective layer as described herein over at least a portion of the transparent conductive oxide layer. The protective layer may have two protective films or three protective films.

[0136] By treating the article with a post-deposition process, the sheet resistance of the article is reduced to less than 25 ohms / square, less than 20 ohms / square; less than 18 ohms / square, less than 16 ohms / square, or less than 15 ohms / square. This is particularly useful for reducing the thickness of TCO. For example, AZO can have a thickness of less than 400nm or 320nm and greater than 160nm. AZO should have a thickness of less than 344nm and greater than 172nm. The thickness of ITO should be less than 275nm or 175nm; and greater than 95nm.

[0137] One exemplary embodiment is a method of making a coated glass article, wherein a glass substrate is provided. A primer layer is applied over the glass substrate, preferably by vacuum deposition by magnetron sputtering or some other process without using radiant heat, or the primer layer is applied over the substrate at room temperature. Preferably, the primer layer comprises two films, wherein the first film comprises zinc oxide and tin oxide, and the second film comprises silicon oxide and titanium oxide. A transparent conductive oxide is applied over the primer layer, preferably by vacuum deposition by magnetron sputtering or some other process without using radiant heat, or the transparent conductive oxide is applied over the primer layer at room temperature. Preferably, the transparent conductive oxide is tin-doped indium oxide. An optional protective layer is applied over the transparent conductive oxide, preferably by vacuum deposition by magnetron sputtering or some other process without using radiant heat, or the optional protective layer is applied over the transparent conductive oxide at room temperature. The absorptivity of the transparent conductive oxide is no greater than 0.2, and / or at least up to 0.05.

[0138] In one exemplary embodiment, the article is a refrigerator door. Sometime before assembly, but long after the exterior metal of the door is coated, the refrigerator door is treated with a post-deposition process. Typically, the refrigerator door is heated to allow the coated article to be bent into a shape that will properly fit the door. This heating process will crystallize the transparent conductive oxide and reduce the sheet resistance.

[0139] Example

[0140] Those skilled in the art will readily appreciate that the present invention may be modified without departing from the concepts disclosed in the foregoing description. Therefore, the particular embodiments described in detail herein are merely illustrative and do not limit the scope of the present invention, which will be given by the full scope of the appended claims and any and all equivalent forms thereof.

[0141] Example 1 (010761)

[0142] The glass substrate is coated with a primer layer and a transparent conductive oxide layer. The primer layer has a first primer film and a second primer film. The first primer film is zinc stannate on the glass substrate, and the second primer film is a silicon oxide-aluminum oxide alloy having about 85 weight percent silicon oxide and 15 weight percent aluminum oxide on the first primer film. The transparent conductive oxide layer on the second primer film is tin-doped indium oxide ("ITO").

[0143] To improve the conductivity of the coated article, the entire article was placed in an oven and the temperature of the transparent conductive oxide layer was measured (see Figure 7 ).

[0144] The following samples were tested to establish the improved conductivity for various ITO thicknesses.

[0145]

[0146]

[0147]

[0148] from Figure 7 It can be seen that post-deposition heating of ITO reduces the sheet resistance from about 55-70Ω / □ to about 10-25Ω / □, regardless of thickness. When the ITO thickness is at least 96.8nm thick, the sheet resistance is less than 25Ω / □, regardless of the heating temperature. When the ITO thickness is at least 109.2, the sheet resistance is less than 20Ω / □ if the ITO surface reaches 968℉. At about 127.9nm, the sheet resistance of ITO is less than 20Ω / □ when heated to any temperature. This improvement in sheet resistance is unexpected. Similar results were obtained using other transparent conductive oxides, indicating that regardless of the transparent conductive oxide, the temperature should be above 380℉, at least 435℉, or no higher than 806℉.

[0149] like Figure 8a -c, heating after deposition increases the crystallinity of the ITO layer. The samples tested are listed in Table 2 below.

[0150] sample Sample name illustrate A Uncoated transparent Uncoated clear glass B PC-4042 Transparent glass coated with 168.7nm ITO C PC-4042-40AH PC-4042 after heating D PC-4045 Transparent glass coated with 141.7nm ITO E PC-4045-30AH PC-4045 after heating F PC-4046 Transparent glass coated with 129.4nm ITO G PC-4046-30AH PC-4046 after heating

[0151] Focusing on increasing the minimum surface temperature required for crystal formation of ITO has yielded significant benefits through energy savings.

[0152] Example 2

[0153] The glass substrate was coated with a transparent conductive oxide layer. The transparent conductive oxide was gallium-doped zinc oxide ("GZO"). Several samples with different GZO thicknesses were prepared and the sheet resistance of the samples was measured in order to compare the effect of post-deposition treatment on the sheet resistance of the as-deposited GZO. The post-deposition process was to place the coated article in a furnace. The sheet resistance of each sample was measured before and after flash annealing and the results are shown in Fig. 9 The thickness and sheet resistance used for the sample testing are listed in Table 3 below.

[0154] Table 3: Samples from Example 2

[0155]

[0156] like Fig. 9As shown, post-deposition flash annealing of the GZO improves the sheet resistance for all thicknesses tested. This improvement is most pronounced when the GZO is about 320-480nm thick. When the GZO layer is about 320nm thick, the "as deposited" GZO layer provides a sheet resistance of 35.6Ω / □, while after thermal treatment, the sheet resistance is 12.7Ω / □. This is significant because at this thickness, flash annealing reduces the sheet resistance to an acceptable range, while without flash annealing, the sheet resistance is too high.

[0157] Similar results were observed when the GZO was 480 nm thick. The sheet resistance of the "as deposited" GZO sample was about 21.8 Ω / □, while the heat treated sample was 7.8 Ω / □.

[0158] At very high GZO thicknesses, the difference in sheet resistance decreases. For example, at about 950nm, the "as deposited" GZO sample has a sheet resistance of about 8Ω / □, while the flash-annealed sample has a sheet resistance of about 5Ω / □. In this case, both samples have sufficiently low sheet resistance.

[0159] Therefore, if Fig. 9 As shown, for samples having GZO as the transparent conductive oxide, the thickness that provides the largest and most significant difference in sheet resistance is when the GZO layer is at least 300 nm thick and at most 500 nm thick.

[0160] Thermal treatment reduces the thickness of the transparent conductive oxide layer required to achieve an acceptable sheet resistance. Without any post-deposition treatment, GZO must be applied to at least 550nm before the sheet resistance is less than 20Ω / □. Heating allows thinner GZO layers to be applied. This not only reduces the cost of making a suitable coated article, but also reduces the impact of GZO on the optics and color of the coated article.

[0161] This is surprising, as a cost effective method to improve the sheet resistance of thinner transparent conductive oxide layers has been discovered and provided.

[0162] Example 3

[0163] The glass substrate was coated with an aluminum-doped zinc oxide ("AZO") transparent conductive oxide layer. Several samples with different AZO thicknesses were prepared and the sheet resistance of the samples was measured in order to compare the effect of post-deposition treatment on the sheet resistance of the as-deposited AZO. The post-deposition process involved placing the coated article in a furnace. The sheet resistance of each sample was tested before and after flash annealing and the results are shown in Fig.10 The thickness and sheet resistance of the samples tested are listed in Table 4 below.

[0164] Table 4: Samples from Example 3

[0165]

[0166] like Fig.10 As shown, post-deposition heating of AZO improves the sheet resistance for all tested thicknesses. This improvement is most pronounced when the AZO is about 344 to 860 nm thick. When the AZO layer is 344 nm thick, the "as deposited" AZO layer provides a sheet resistance of about 78.3 Ω / □, while after heat treatment, the sheet resistance is 19.5 Ω / □. This is important because at this thickness, heating reduces the sheet resistance to an acceptable range, while without heating, the sheet resistance is too high.

[0167] Similar results were observed when the AZO was 860 nm thick. The sheet resistance of the "as deposited" AZO sample was about 26.6 Ω / □, while the heat treated sample was about 7.1 Ω / □.

[0168] At very high AZO thicknesses, the difference in sheet resistance decreases. For example, at about 1050 nm, the "as deposited" AZO sample has a sheet resistance of about 17.0 Ω / □, while the heat-treated sample has a sheet resistance of 3.9 Ω / □. In this case, both samples have sufficiently low sheet resistance.

[0169] Therefore, if Fig.10 As shown, for samples having AZO as the transparent conductive oxide, the thickness that provides the largest and most significant difference in sheet resistance is when the AZO layer is at least 344 nm thick and at most 860 nm thick.

[0170] Heating also reduces the thickness of the transparent conductive oxide layer required to achieve an acceptable sheet resistance. Without any post-deposition treatment, AZO must be applied to at least 1032 nm before the sheet resistance is less than 20 Ω / □. Heating allows thinner AZO layers to be applied. This not only reduces the cost of making a suitable coated article, but also reduces the impact of AZO on the optics and color of the coated article.

[0171] This is surprising, as a cost effective method to improve the sheet resistance of thinner transparent conductive oxide layers has been discovered and provided.

[0172] Example 4

[0173] Using FILM STAR, various bottom layer thicknesses were tested to determine which thicknesses provided acceptable or neutral colors. A glass substrate with a bottom layer and a transparent conductive oxide was used. The bottom layer had a first film and a second film. The first bottom layer film was zinc stannate over the glass substrate, and the second bottom layer film was a silicon oxide-aluminum oxide alloy having about 85 weight percent silicon oxide and 15 weight percent aluminum oxide over the first bottom layer film. The transparent conductive oxide layer over the second bottom layer film was a 170 nm thick tin-doped indium oxide ("ITO") layer.

[0174] First, the desired sheet resistance is determined. For this embodiment, the desired sheet resistance is about 10Ω / □ to 15Ω / □. To achieve this sheet resistance, it is determined that the transparent conductive oxide layer should be about 170nm thick.

[0175] Using FILM STAR, input the materials and thickness of the glass and transparent conductive oxide layers. Next, determine the materials for the first and second base films. For this example, the first base film material is zinc stannate and the second base film material is a silicon oxide-aluminum oxide alloy having 85 wt% silicon oxide and 15 wt% aluminum oxide. The following coatings (see Tables 5 and Fig.11 ). In the sample, the thickness of the first underlying film is in the range of 8 nm to 17 nm, and the thickness of the second underlying film is in the range of 27 nm to 35 nm.

[0176] Table 5: Samples from Example 4

[0177]

[0178] like Fig.11 As shown, when the first bottom film is 13 nm thick and the second bottom film is 31 nm thick, a * , b * When the first bottom layer film is 11nm to 15nm thick and the second bottom layer film is 29nm to 33.5nm thick, an acceptable color is obtained, where a * Between -3 and 1, and b * Between -3 and 1.

[0179] Example 5

[0180] Using FILM STAR, different thicknesses of the transparent conductive oxide layer were tested to determine the appropriate thickness for the base layer. In this example, the FILM STAR parameters included a glass substrate coated with a base layer having a first base film and a second base film. The first base film was zinc stannate and the second base film was silicon oxide. The transparent conductive oxide layer over the second base film was tin-doped indium oxide ("ITO"). A protective layer of silicon oxide was over the ITO layer. Table 6 and Fig.12 The samples tested are shown in Table 6. Table 6 shows the values ​​for the ITO layer and the SiO2 layer entered into FILM STAR. The output provides the thickness of the two underlying films, which will provide -1, -1 (a * , b * )color.

[0181] sample ITO <![CDATA[SiO2]]> 1 225nm 30nm 2 205nm 30nm 3 200nm 30nm 4 190nm 30nm 5 180nm 30nm 6 175nm 30nm 7 175nm 45nm 8 180nm 45nm 9 190nm 45nm 10 200nm 45nm 11 205nm 45nm 12 225nm 45nm

[0182] These samples show that when the transparent conductive oxide layer is 175nm to 225nm thick and the protective coating is 30nm thick, the first underlying film should be at least 10nm thick and at most 15nm thick and the second underlying film should be at least 28nm thick and at most 36nm thick in order to achieve about -1, -1 (a * , b * The samples also show that when the transparent conductive oxide layer is 175nm to 225nm thick and the protective layer is 45nm thick, the first underlying film should be at least 11nm thick and at most 14nm thick, and the second underlying film should be at least 32nm thick and at most 38nm thick in order to achieve appropriate color.

[0183] Fig.12 The ideal thickness that will result in a -1, -1 color is shown. Although -1, -1 is preferred, other colors are also acceptable, such as Fig.11 The circled color (i.e. a * Between -3 and 1, and b * between -3 and 1).

[0184] Example 6

[0185] The effect of the embedded film was tested at various depths and thicknesses and compared with a transparent conductive oxide layer without an embedded layer. A glass substrate was coated with a bottom transparent conductive oxide film. The bottom transparent conductive oxide film was made of tin-doped indium oxide ("ITO") and had a thickness of 120nm, 180nm, or 240nm. An embedded film was applied over the bottom transparent conductive oxide layer. The embedded film had a thickness of 15nm or 30nm and was a zinc stannate film. A top transparent conductive oxide film was applied over the embedded film. The top transparent conductive oxide film was ITO and had a thickness of 240nm, 180nm, or 120nm. The total thickness of the bottom and top transparent conductive oxide films was 360nm. As a control, ITO oxide was applied over the substrate at a thickness of 360nm and did not contain an embedded film. The square resistance of the samples was measured at 550nm. The samples are listed in Table 7 and Figure 13 below.

[0186] sample Bottom ITO <![CDATA[Zn2SnO4]]> Top ITO A 120nm 15nm 240nm B 120nm 30nm 240nm C 180nm 15nm 180nm D 180nm 30nm 180nm E 240nm 15nm 240nm F 240nm 30nm 240nm G 360nm N / A N / A

[0187] like Fig.13a As shown, experimental samples AF have at least 35% improvement in sheet resistance compared to control sample G. Samples A and B have at least 40% improvement in sheet resistance compared to sample G. Samples C and D have at least 35% improvement in sheet resistance compared to sample G. Samples E and F have at least 37% improvement in sheet resistance compared to sample G.

[0188] Based on this data, the embedded films surprisingly and significantly reduce the sheet resistance of the transparent conductive oxide layer regardless of their location or thickness.

[0189] like Fig.13b As shown, samples E and F provide the greatest increase in transmittance. Smaller improvements are seen in samples A and B. Thus, by having a thickness difference between the top and bottom transparent conductive oxide layers, the amount of light transmission can be increased. Furthermore, it was surprisingly found that if the top transparent conductive oxide layer is thinner than the bottom transparent conductive oxide layer, and the embedded layer is positioned closer to the surface of the top of the transparent conductive oxide layer than the bottom of the transparent conductive oxide, the transmittance increases more. Conversely, if the top and bottom transparent conductive oxide layers are approximately equal, the light transmittance unexpectedly decreases.

[0190] Fig.13c It is shown that the embedded film also affects the crystallinity of the transparent conductive oxide. By having an embedded film, the crystallinity can be unexpectedly improved as can be seen from the XRD data.

[0191] Example 7

[0192] In this example, various protective layers were examined. A protective layer was placed over a glass substrate. The coated article did include an aluminum-doped zinc oxide transparent conductive oxide between the substrate and the protective layer. Unexpectedly, the underlying layer, the functional layer, or the transparent conductive oxide layer did not affect the observed results.

[0193] The glass substrates are different protective layers. Samples 1-3 have protective layers comprising a single film. A list of these samples is provided in Table 8.

[0194] sample Protective layer 1 none 2 SiAlO 3 TiAlO 4 <![CDATA[ZrO2]]>

[0195] Samples 5-11 have a protective layer comprising a first protective film and a second protective film over the first protective film. A list of these samples is provided in Table 9. The first film is closer to the substrate than the second film, and the second film is the outermost film.

[0196] sample Film 1 No. 2 film 5 TiAlO SiAlO 6 SiAlO TiAlO 7 SnZnO TiAlO 8 SnZnO SiAlO 9 TiAlO <![CDATA[ZrO2]]> 10 SiAlO <![CDATA[ZrO2]]> 11 SnZnO <![CDATA[ZrO2]]>

[0197] Samples 12-15 have a protective layer including three films. A list of these samples is provided in Table 10. The first film is closer to the substrate than the second film or the third film. In order to be consistent with other drawings and descriptions above, the second protective film is the outermost film, and the third protective film is located between the first film and the third film.

[0198] sample Film 1 No. 3 film No. 2 film 12 SnZnO TiAlO SiAlO 13 SnZnO SiAlO TiAlO 14 SnZnO TiAlO <![CDATA[ZrO2]]> 15 SnZnO SiAlO <![CDATA[ZrO2]]> 16 TiAlO SiAlO <![CDATA[ZrO2]]> 17 SiAlO TiAlO <![CDATA[ZrO2]]> 18 <![CDATA[ZrO2]]> TiAlO SiAlO 19 <![CDATA[ZrO2]]> SiAlO TiAlO 20 SiAlO <![CDATA[ZrO2]]> TiAlO 21 TiAlO <![CDATA[ZrO2]]> SiAlO

[0199] The durability of these samples was tested using the ASTM Cleveland condensation test. Fig.14 and 15 As shown, the protective film having TiAlO as the outermost layer performs best. These figures show the dEcmc of samples 1-15 listed in Tables 8-10.

[0200] Specifically, Fig.14 It is shown that samples having two or three protective films (where the outermost film is TiAlO) have unexpectedly better durability, specifically, sample 6 (SiAlO / TiAlO), sample 7 (SnZn / TiAlO), and sample 13 (SnZn / SiAlO / TiAlO). Fig.15 It was further confirmed that a protective layer having titanium oxide and aluminum oxide as the outermost layer provided unexpectedly greater durability. Fig.15 It is shown that Sample 19 (ZrO2 / SiAlO / TiAlO) and Sample 20 (SiAlO / ZrO2 / TiAlO) exhibit unexpectedly better durability compared to the other three-film protective layer samples (Samples 16, 17, 18, and 21).

[0201] The data show the unexpected result that the outermost protective film of titanium oxide-aluminum oxide provides greatly improved durability.

[0202] Example 8

[0203] Samples with transparent conductive oxides sputtered in various atmospheres were tested. As shown in Figures 16-20, glass substrates were coated with indium-doped tin oxide ("ITO") or aluminum-doped zinc oxide ("AZO") by magnetron sputtering vacuum deposition ("MSVD") method. The ITO samples were sputtered in an atmosphere containing 0%, 0.5%, 1%, 1.5%, or 2% oxygen and then heat treated; and the AZO samples were sputtered in an atmosphere containing 0%, 1%, 2%, 3%, 4%, 5%, or 6% oxygen and then heat treated. The balance of the atmosphere was argon. The ITO samples had an ITO thickness of 225nm, 175nm, or 150nm, and the AZO samples had an AZO thickness of 300nm to 350nm applied to the substrate. The samples were tested to determine their emissivity, absorptivity, and / or sheet resistance. (Emissivity is a measure of conductivity). These samples were heat treated by placing the coated articles in an oven for a period of time such that the transparent conductive oxide surface of the samples reached at least 435° F. for at least 30 seconds.

[0204] When coating a transparent article with a transparent conductive oxide, what is desired is an article with low absorptivity and low sheet resistance (which corresponds to emissivity). Figure 16 shows that when oxygen is added to the atmosphere, the absorption decreases. However, as shown in Figure 17, the emissivity / sheet resistance of the article is highest when there is 0% oxygen in the atmosphere. Using Figures 16 and 17, the ideal balance between absorptivity and emissivity is obtained when the sputtering atmosphere has 0.75% to 1.25% oxygen. As shown in Figure 17, if the atmosphere has less than 2.0% oxygen, the sheet resistance of the heat-treated ITO-coated article is lower than that of the non-heat-treated ITO-coated article. When the atmosphere is 1.5% oxygen, the sheet resistance increases significantly. Extrapolating from this data, it is concluded that the atmosphere in the coating chamber should not exceed 1.5% oxygen, preferably not more than 1.25%. In order to obtain some reduced absorption for ITO-coated articles, the atmosphere should contain at least 0.5% oxygen, preferably at least 0.75% oxygen.

[0205] Example 9

[0206] A glass substrate is coated with an aluminum doped zinc oxide layer by a magnetron sputtering vacuum deposition ("MSVD") process. The target material is a ceramic aluminum doped zinc oxide which contains a certain amount of oxygen. When a material such as a transparent conductive oxide is deposited using an MSVD process, the process causes the ceramic raw material to separate, which may cause some oxygen to escape. In order to ensure that the deposited material is oxidized, oxygen is typically supplied to the coating chamber along with an inert gas. In this embodiment, AZO is deposited by MSVD in a coating chamber having an oxygen content supplied to the chamber of 0%, 1%, 2%, 3%, 4%, 5%, or 6%. The balance of the atmosphere supplied to the coating chamber is argon, however any inert gas may be used. The normalized absorbance of the coating is determined. As Fig.18 As shown in Figure 18, the normalized absorption at 550 nm is optimal when 0% oxygen is supplied to the coating chamber. It is acceptable when 1% oxygen is supplied to the coating chamber. Based on the data shown in Figure 18, it can be inferred that less than 0.5% oxygen in the coating chamber provides significantly better absorption than when 1% oxygen is used.

[0207] like Fig.19 As shown, the normalized absorption has a sharp drop from 0% oxygen to 1% oxygen, and a minimal drop from 1% oxygen to 2% oxygen. This data further supports the conclusion that less than 1% oxygen, less than 0.5% oxygen, or less than 0.25% oxygen, or less than 0.1% oxygen, or 0% oxygen supplied to the coating chamber provides the best absorption.

[0208] Example 10

[0209] A problem associated with post-deposition heating of coated articles is energy waste. As described above, post-deposition heating of transparent conductive oxide ("TCO") layers provides improved performance at lower thicknesses. Placing the coated article in an oven that heats the entire article wastes energy beyond the temperature required to crystallize the TCO layer. To determine the surface temperature required to improve the performance of a transparent conductive oxide layer, glass substrates were coated with either 115 nm or 171 nm thick indium-doped tin oxide. The ITO layer surfaces of the samples were heated to the temperatures listed in Tables 11 and 12. For the purposes of this experiment, the surface was heated by placing the entire coated article in an oven, however, a flash lamp could be used as an alternative.

[0210] After post-deposition heating of the surface, the sheet resistance of each sample was measured (see Fig.21and Tables 11 and 12). The results indicate that at about 435°F, the layer reaches its lowest sheet resistance. Additional heating of the surface does not provide any additional reduction in sheet resistance. Therefore, to reduce the sheet resistance of the transparent conductive oxide layer, post-deposition heating should heat the surface of the transparent conductive oxide layer to above 380°F, at least 435°F, between 435°F and 806°F, between 435°F and 635°F, or to 435°F.

[0211] Maximum surface temperature (℉) Sheet resistance (Ω / □) 72 200 69.7 300 67 317 68.9 350 65.3 380 62.6 435 21.2 635 22.4 806 18.9 878 18.9 968 17.9

[0212] Maximum surface temperature (℉) Sheet resistance (Ω / □) Room temperature 200 52.3 300 52.3 317 43.9 350 49 380 43.5 435 15.3 635 16.5 806 14.1 878 14.1 968 12

[0213] The invention is further described in the following numbered clauses.

[0214] Item 1: A coated article comprising: a substrate, an underlayer over the substrate, and a transparent conductive oxide layer over the underlayer, the underlayer comprising a first underlayer film and a second underlayer film over the first layer, wherein the first underlayer film comprises a high refractive index material, and wherein the second layer comprises a low refractive index material.

[0215] Clause 2: The coated article of claim 1, wherein the high refractive index material comprises zinc oxide and tin oxide.

[0216] Clause 3: A coated article according to clause 1 or 2, wherein the low refractive index material comprises silicon oxide and aluminum oxide.

[0217] Item 4: The coated article of any one of Items 1 to 3, wherein the transparent conductive film comprises tin-doped indium oxide.

[0218] Item 5: The coated article according to any of Items 1-4, wherein the transparent conductive oxide layer has a thickness of at least 75 nm, particularly at least 90 nm, more particularly at least 100 nm, more particularly at least 125 nm, more particularly at least 150 nm, or more particularly at least 175 nm.

[0219] Item 6: The coated article according to any one of items 1 to 5, wherein the transparent conductive oxide layer has a thickness of at most 350 nm, in particular at most 300 nm, in particular at most 275 nm, in particular at most 250 nm, more in particular at most 225 nm.

[0220] Item 7: The coated article according to any one of items 1 to 6, wherein the coated article has a sheet resistance in the range of 5 to 25 ohms / square, specifically 5 to 20 ohms / square, more specifically 8 to 18 ohms / square, more specifically 5 to 15 ohms / square.

[0221] Clause 8: A coated article according to any one of clauses 1 to 7, wherein the first base film has a first base thickness and the second base film has a second base thickness to provide the coated article with a color having the following values: a * is at least -9 and at most 1, in particular at least -4 and at most 0, more in particular at least -3 and at most 1, more in particular at least -1.5 and at most -0.5, more in particular -1; and b * It is at least -9 and at most 1, particularly at least -4 and at most 0, more particularly at least -3 and at most 1, more particularly at least -1.5 and at most -0.5, more particularly -1.

[0222] Clause 9: A coated article according to any one of clauses 1 to 8, wherein the high refractive index material comprises zinc oxide.

[0223] Item 10: The coated article according to any one of items 1 to 9, further comprising a protective layer over the transparent conductive oxide layer, wherein the protective layer comprises a first protective film and a second protective film over at least a portion of the first protective film, wherein the second protective film is the outermost film, and the second protective film comprises titanium oxide and aluminum oxide.

[0224] Clause 11: The coated article according to Clause 10, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the first protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0225] Item 12: A coated article according to Item 9 or 10, wherein the second protective film comprises 35 to 65 wt % titanium oxide; in particular 45-55 wt % titanium oxide; more particularly 50 wt % titanium oxide.

[0226] Item 13: The coated article according to any one of items 10 to 12, wherein the second protective film comprises 65 to 35 wt% aluminum oxide, in particular 55 to 45 wt% aluminum oxide, more in particular 50 wt% aluminum oxide.

[0227] Clause 14: A coated article according to any one of clauses 10 to 13, further comprising a third protective film, the third protective film being over at least a portion of the first protective film and being located between the first protective film and the second protective film, or between the first protective film and the functional coating, wherein the third protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the third protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0228] Item 15: A method of adjusting the color of a coated substrate, comprising: providing a substrate; identifying a transparent conductive oxide and a thickness of a transparent conductive oxide layer to achieve a transparent conductive oxide layer that will provide a sheet resistance of at least 5 Ω / □ and not more than 25 Ω / □ (particularly not more than 20 Ω / □, more particularly not more than 18 Ω / □), identifying a first primer material and a first primer thickness for the first primer film, and a second primer material and a second primer thickness that will provide a color having the following values ​​for the coated substrate of the transparent conductive oxide having the transparent conductive layer thickness: a * between -9 and 1, in particular between -4 and 0, more in particular between -3 and 1, more in particular between -1.5 and -0.5; and b. * Between -9 and 1, particularly between -4 and 0, more particularly between -3 and 1, and more particularly between -1.5 and -0.5, a first underlying film having the first underlying thickness is applied over at least a portion of the substrate; a second underlying film having the second underlying thickness is applied over at least a portion of the first underlying film; and a transparent conductive oxide layer is applied over the transparent conductive oxide with the transparent conductive layer thickness over at least a portion of the underlying layer.

[0229] Item 16: The method of Item 15, wherein the transparent conductive oxide is tin-doped indium oxide.

[0230] Item 17: The method according to item 15 or 16, wherein the transparent conductive layer has a thickness of at least 125 nm (particularly at least 150 nm, more particularly at least 175 nm) and not more than 950 nm (particularly 500 nm, more particularly 350 nm, more particularly 225 nm).

[0231] Clause 18: The method of any one of Clauses 15 to 17, wherein the first primer material comprises zinc oxide and tin oxide.

[0232] Clause 19: The method of any one of clauses 15 to 18, wherein the first bottom layer has a thickness of at least 11 nm and no greater than 15 nm.

[0233] Item 20: The method of any one of items 15 to 19, wherein the second underlying material comprises silicon oxide and aluminum oxide.

[0234] Item 21: The method of any one of items 15 to 20, wherein the second bottom layer has a thickness of at least 29 nm and no greater than 34 nm.

[0235] Clause 22: The method according to any one of clauses 15 to 21, further comprising: applying a protective layer over a portion of the transparent conductive oxide layer, wherein the protective layer comprises a first protective film and a second protective film over at least a portion of the first protective film, wherein the second protective film is an outermost film and the second protective film comprises titanium oxide and aluminum oxide.

[0236] Item 23: The method of Item 22, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the first protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0237] Item 24: The method according to Item 22 or 23, wherein the second protective film comprises 35 to 65 wt % titanium oxide; in particular 45 to 55 wt % titanium oxide; more particularly 50 wt % titanium oxide.

[0238] Item 25: The method according to any one of items 22 to 25, wherein the second protective film comprises 65 to 35 wt% aluminum oxide, in particular 55 to 45 wt% aluminum oxide, more in particular 50 wt% aluminum oxide.

[0239] Clause 26: The method according to any one of clauses 22 to 25, further comprising a third protective film, the third protective film being over at least a portion of the first protective film and being located between the first protective film and the second protective film, or between the first protective film and the functional coating, wherein the third protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the third protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0240] Item 27: A coated article comprising: a substrate, a bottom layer over at least a portion of the substrate, and a transparent conductive oxide layer over at least a portion of the bottom layer. The bottom layer has a first bottom layer film and an optional second bottom layer film. The first bottom layer film comprises a first high refractive index material. The optional second bottom layer film comprises a low refractive index material. The first high refractive index material has a higher refractive index than the low refractive index material. The transparent conductive oxide layer has an embedded film embedded in the transparent conductive oxide layer. The embedded film comprises a second high refractive index material. The second high refractive index material has a higher refractive index than the low refractive index material.

[0241] Item 28: The coated article according to Item 27, wherein the embedded film has a thickness of 5 nm to 50 nm, in particular 10 nm to 40 nm, more in particular 15 nm to 30 nm.

[0242] Item 29: A coated article according to Item 27 or 29, wherein the second high refractive index material comprises tin oxide and zinc oxide.

[0243] Item 30: The coated article of any one of Items 27 to 29, wherein the embedded film is positioned closer to the top of the transparent conductive oxide layer.

[0244] Item 31: The coated article of any one of Items 27 to 29, wherein the embedded film is positioned closer to the bottom of the transparent conductive oxide layer.

[0245] Item 32: The coated article of any one of Items 27 to 29, wherein the embedded film is located approximately in the middle of the transparent conductive oxide layer.

[0246] Item 33: A coated article according to any one of items 27 to 32, wherein the transparent conductive oxide layer is selected from: gallium-doped zinc oxide ("GZO"), aluminum-doped zinc oxide ("AZO"), indium-doped zinc oxide ("IZO"), magnesium-doped zinc oxide ("MZO"), or tin-doped indium oxide ("ITO"), in particular GZO, AZO and ITO, more in particular ITO.

[0247] Clause 34: A coated article according to any one of clauses 27 to 33, wherein the high refractive index material comprises zinc oxide and tin oxide.

[0248] Clause 35: A coated article according to any one of clauses 27 to 34, wherein the low refractive index material comprises silicon oxide and aluminum oxide.

[0249] Item 36: A coated article according to any one of Items 27 to 35, wherein the transparent conductive oxide layer has a thickness of at least 75 nm, more particularly at least 90 nm, more particularly at least 100 nm, more particularly at least 125 nm, more particularly at least 150 nm, more particularly at least 175 nm, or more particularly at least 320 nm.

[0250] Item 37: A coated article according to any one of items 27 to 34, wherein the transparent conductive oxide layer has a thickness of at most 950 nm, in particular at most 550 nm, more in particular at most 480 nm, more in particular at most 350 nm, more in particular at most 300 nm, more in particular at most 275 nm, more in particular at most 250 nm, more in particular at most 225 nm.

[0251] Item 38: The coated article according to any one of items 27 to 37, wherein the coated article has a sheet resistance in the range of 5 to 20 ohms / square, specifically 8 to 18 ohms / square, more specifically 5 to 15 ohms / square.

[0252] Clause 39: A coated article according to any one of clauses 27 to 38, wherein the first base film has a first base thickness, the second base film has a second base thickness, and the embedded film has an embedded film thickness so as to provide the coated article with a color having the following values: a * is at least -9 and at most 1, in particular at least -4 and at most 0, more in particular at least -3 and at most 1, more in particular at least -1.5 and at most -0.5, more in particular -1; and b * It is at least -9 and at most 1, particularly at least -4 and at most 0, more particularly at least -3 and at most 1, more particularly at least -1.5 and at most -0.5, more particularly -1.

[0253] Item 40: A coated article according to Item 39, wherein the first primer film thickness is between 11 nm and 15 nm, and / or the second primer film thickness is between 29 nm and 34 nm.

[0254] Item 41: A coated article according to any one of items 27 to 40, further comprising a protective layer over the transparent conductive oxide layer, wherein the protective layer comprises a first protective film and a second protective film over at least a portion of the first protective film, wherein the second protective film is an outermost film, and the second protective film comprises titanium oxide and aluminum oxide.

[0255] Item 42: The coated article according to Item 41, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the first protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0256] Item 43: A coated article according to Item 41 or 42, wherein the second protective film comprises 35 to 65 wt % titanium oxide; in particular 45 to 55 wt % titanium oxide; more in particular 50 wt % titanium oxide.

[0257] Item 44: The coated article according to any one of items 40 to 43, wherein the second protective film comprises 65 to 35 wt% aluminum oxide, in particular 55 to 45 wt% aluminum oxide, more in particular 50 wt% aluminum oxide.

[0258] Clause 45: A coated article according to any one of clauses 40 to 44, further comprising a third protective film, the third protective film being over at least a portion of the first protective film and being located between the first protective film and the second protective film, or between the first protective film and the functional coating, wherein the third protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the third protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0259] Item 46: A method of adjusting the color of a coated article. The method includes applying a first base film over at least a portion of a substrate. The first base film comprises a first high refractive index material. Optionally, the second base film comprises a low refractive index material applied over at least a portion of the first base film. The first high refractive index material has a higher refractive index than the low refractive index material. A first transparent conductive oxide film is applied over at least a portion of the first base film or the optional second base film. An embedded film is applied over at least a portion of the first transparent conductive oxide layer. The embedded film comprises a second high refractive index material. The second high refractive index material has a higher refractive index than the low refractive index material. A second transparent conductive oxide film is applied over at least a portion of the embedded film.

[0260] Item 47: The method according to Item 46, wherein the thickness of the embedded film is 5 nm to 50 nm, in particular 10 nm to 40 nm, more particularly 15 nm to 30 nm.

[0261] Clause 48: The method of clause 46 or 47, wherein the second high refractive index material comprises tin oxide and zinc oxide.

[0262] Clause 49: The method of any one of clauses 46 to 47, wherein the embedded film is positioned closer to the top of the transparent conductive oxide layer.

[0263] Clause 50: The method of any one of clauses 46 to 47, wherein the embedded film is positioned closer to a bottom of the transparent conductive oxide layer.

[0264] Item 51: The method of any one of Items 46 to 47, wherein the embedded film is located approximately in the middle of the transparent conductive oxide layer.

[0265] Item 52: A method according to any one of items 46 to 51, wherein the first transparent conductive oxide film and / or the second transparent conductive oxide film is selected from: gallium-doped zinc oxide ("GZO"), aluminum-doped zinc oxide ("AZO"), indium-doped zinc oxide ("IZO"), magnesium-doped zinc oxide ("MZO"), or tin-doped indium oxide ("ITO"), in particular GZO, AZO and ITO, more in particular ITO.

[0266] Clause 53: The method of any one of clauses 46 to 52, wherein the high refractive index material comprises zinc oxide and tin oxide.

[0267] Clause 54: The method of any one of clauses 46 to 53, wherein the low refractive index material comprises silicon oxide and aluminum oxide.

[0268] Item 55: The method according to any one of items 46 to 55, wherein the thickness of the first transparent conductive oxide layer and / or the second transparent conductive oxide layer is at least 80 nm, or in particular at least 120 nm, more in particular at least 180 nm, more in particular at least 240 nm, or more in particular at least 360 nm.

[0269] Item 56: The method according to any one of items 46 to 55, wherein the thickness of the first transparent conductive oxide layer and / or the second transparent conductive oxide layer is at most 400 nm, specifically at most 360 nm, more specifically at most 240 nm, more specifically at most 180 nm, more specifically at most 120 nm or more specifically at most 80 nm.

[0270] Item 57: The method according to any one of Items 46 to 56, wherein the coated article has a sheet resistance in the range of 5 to 25 ohms / square, specifically 5 to 20 ohms / square, more specifically 5 to 18 ohms / square.

[0271] Clause 58: A method according to any one of clauses 46 to 57, wherein the first base film has a first base thickness, the second base film has a second base thickness, and the embedded film has an embedded film thickness, so as to provide the coated article with a color having the following values: a * is at least -9 and at most 1, in particular at least -4 and at most 0, more in particular at least -3 and at most 1, more in particular at least -1.5 and at most -0.5, more in particular -1; and b * It is at least -9 and at most 1, particularly at least -4 and at most 0, more particularly at least -3 and at most 1, more particularly at least -1.5 and at most -0.5, more particularly -1.

[0272] Item 59: The method of any one of items 46 to 58, wherein the first underlying film thickness is between 11 nm and 15 nm, and / or the second underlying film thickness is between 29 nm and 34 nm.

[0273] Item 60: The method of any one of Items 46 to 59, further comprising applying a protective layer over the transparent conductive oxide layer, wherein the protective layer comprises a first protective film and a second protective film over at least a portion of the first protective film, wherein the second protective film is an outermost film, and the second protective film comprises titanium oxide and aluminum oxide.

[0274] Item 61: The method of Item 60, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the first protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0275] Item 62: The method according to Item 60 or 61, wherein the second protective film comprises 35 to 65 wt % titanium oxide; in particular 45 to 55 wt % titanium oxide; more particularly 50 wt % titanium oxide.

[0276] Item 63: The method according to any one of items 60 to 62, wherein the second protective film comprises 65 to 35 wt% aluminum oxide, in particular 55 to 45 wt% aluminum oxide, more in particular 50 wt% aluminum oxide.

[0277] Clause 64: The method according to any one of clauses 60 to 63, further comprising a third protective film, the third protective film being over at least a portion of the first protective film and being located between the first protective film and the second protective film, or being located between the first protective film and the functional coating, wherein the third protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the third protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0278] Item 65: The method of any one of Items 47 to 64, wherein the first transparent conductive oxide film and the second transparent conductive oxide film comprise the same metal oxide.

[0279] Item 66: A coated article comprising a substrate, a bottom layer over at least a portion of the substrate. The bottom layer has a first bottom layer film and a second bottom layer film. The first bottom layer film comprises a first high refractive index material. The second bottom layer film comprises a low refractive index material. The first high refractive index material has a higher refractive index than the low refractive index material. A first transparent conductive oxide film is over at least a portion of the second bottom layer film. An embedded film is over at least a portion of the first transparent conductive oxide film. The embedded film comprises a second high refractive index material. The second high refractive index material has a higher refractive index than the low refractive index material. The second transparent conductive oxide film is over at least a portion of the embedded film.

[0280] Item 67: A coated article according to Item 66, wherein the embedded film has a thickness of 5 nm to 50 nm, in particular 10 nm to 40 nm, more in particular 15 nm to 30 nm.

[0281] Item 68: A coated article according to Item 66 or 67, wherein the second high refractive index material comprises tin oxide and zinc oxide.

[0282] Item 69: The coated article of any one of Items 66 to 68, wherein the first transparent conductive oxide film is thicker than the second transparent conductive oxide film.

[0283] Item 70: The coated article of any one of Items 66 to 68, wherein the first transparent conductive oxide film is thinner than the second transparent conductive oxide film.

[0284] Item 71: The coated article of any of Items 66 to 68, wherein the thickness of the first transparent conductive oxide film is approximately the same as the thickness of the second transparent conductive oxide film.

[0285] Item 72: A coated article according to any one of items 66 to 71, wherein the first transparent conductive oxide film and / or the second transparent conductive oxide film is selected from: gallium-doped zinc oxide ("GZO"), aluminum-doped zinc oxide ("AZO"), indium-doped zinc oxide ("IZO"), magnesium-doped zinc oxide ("MZO"), or tin-doped indium oxide ("ITO"), in particular GZO, AZO and ITO, more in particular ITO.

[0286] Clause 73: A coated article according to any one of clauses 66 to 72, wherein the high refractive index material comprises zinc oxide and tin oxide.

[0287] Clause 74: A coated article according to any one of clauses 66 to 73, wherein the low refractive index material comprises silicon oxide and aluminum oxide.

[0288] Item 75: A coated article according to any one of Items 66 to 74, wherein the transparent conductive oxide layer has a thickness of at most 950 nm, in particular at most 550 nm, more in particular at most 360 nm.

[0289] Item 76: The coated article according to any one of items 66 to 75, wherein the coated article has a sheet resistance in the range of 5 to 20 ohms / square, specifically 8 to 18 ohms / square, more specifically 5 to 15 ohms / square.

[0290] Clause 77: A coated article according to any one of clauses 66 to 80, wherein the first base film has a first base thickness, the second base film has a second base thickness, and the embedded film has an embedded film thickness, so as to provide the coated article with a color having the following values: a * is at least -9 and at most 1, in particular at least -4 and at most 0, more in particular at least -3 and at most 1, more in particular at least -1.5 and at most -0.5, more in particular -1; and b * It is at least -9 and at most 1, particularly at least -4 and at most 0, more particularly at least -3 and at most 1, more particularly at least -1.5 and at most -0.5, more particularly -1.

[0291] Item 78: A coated article according to any one of items 76 to 77, wherein the first primer film thickness is between 11 nm and 15 nm, and / or the second primer film thickness is between 29 nm and 34 nm.

[0292] Item 79: A coated article according to any one of items 66 to 78, further comprising a protective layer over the transparent conductive oxide layer, wherein the protective layer comprises a first protective film and a second protective film over at least a portion of the first protective film, wherein the second protective film is the outermost film, and the second protective film comprises titanium oxide and aluminum oxide.

[0293] Item 80: The coated article of Item 79, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the first protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0294] Item 81: A coated article according to Item 79 or 80, wherein the second protective film comprises 35 to 65 wt% titanium oxide; in particular 45-55 wt% titanium oxide; more in particular 50 wt% titanium oxide.

[0295] Item 82: The coated article according to any one of items 79 to 81, wherein the second protective film comprises 65 to 35 wt% aluminum oxide, in particular 55 to 45 wt% aluminum oxide, more in particular 50 wt% aluminum oxide.

[0296] Clause 83: A coated article according to any one of clauses 79 to 82, further comprising a third protective film, the third protective film being over at least a portion of the first protective film and being located between the first protective film and the second protective film, or between the first protective film and the functional coating, wherein the third protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the third protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0297] Item 84: A coated article according to any one of items 66 to 83, wherein the thickness of the first transparent conductive oxide layer and / or the second transparent conductive oxide layer is at most 400 nm, in particular at most 360 nm, more in particular at most 240 nm, more in particular at most 180 nm, more in particular at most 120 nm or more in particular at most 80 nm.

[0298] Item 85: A coated article comprising a substrate, a functional layer over at least a portion of the substrate, a first protective film over at least a portion of the functional layer, and a second protective film over at least a portion of the first protective film. The second protective film comprises titanium oxide and aluminum oxide and is the outermost film.

[0299] Item 86: The coated article of Item 85, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof.

[0300] Item 87: A coated article according to Item 85 or 86, wherein the second protective film comprises 35 to 65 wt % titanium oxide, in particular 45 to 55 wt % titanium oxide, more in particular 50 wt % titanium oxide.

[0301] Item 88: The coated article according to any one of items 85 to 87, wherein the second protective film comprises 65 to 35 wt% silicon oxide, in particular 55 to 45 wt% silicon oxide, more in particular 50 wt% silicon oxide.

[0302] Clause 89: A coated article according to any one of clauses 85 to 88, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the first protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0303] Item 90: A coated article according to any one of Items 85 to 89, wherein the functional layer comprises a transparent conductive oxide layer selected from aluminum-doped zinc oxide, gallium-doped zinc oxide, and tin-doped indium oxide, in particular tin-doped indium oxide.

[0304] Item 91: A coated article according to any one of items 85 to 90, wherein the functional layer comprises a metal selected from silver, gold, palladium, copper or mixtures thereof, in particular silver.

[0305] Item 92: The coated article of any one of items 85 to 91, further comprising a third protective film over at least a portion of the first protective film and between the first and second protective films, or between the first protective film and the functional coating.

[0306] Clause 93: A coated article according to any one of clauses 85 to 91, wherein the third protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the third protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0307] Item 94: A method of protecting a functional layer, comprising providing an article coated with a functional layer, applying a first protective film over at least a portion of the functional coating; and applying a second protective film over at least a portion of the first protective film, wherein the second protective film comprises titanium oxide and aluminum oxide.

[0308] Item 95: The method of Item 94, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof.

[0309] Item 96: The method according to Item 94 or 95, wherein the second protective film comprises 35 to 65 wt % titanium oxide, in particular 45 to 55 wt % titanium oxide, more in particular 50 wt % titanium oxide.

[0310] Item 97: The method according to any one of items 94 to 99, wherein the second protective film comprises 65 to 35 wt % silicon oxide, in particular 55 to 45 wt % silicon oxide, more in particular 50 wt % silicon oxide.

[0311] Clause 98: The method of any one of clauses 94 to 97, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the first protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0312] Item 99: The method according to any one of items 94 to 98, wherein the functional layer comprises a transparent conductive oxide layer selected from aluminum-doped zinc oxide, gallium-doped zinc oxide, and tin-doped indium oxide, in particular tin-doped indium oxide.

[0313] Item 100: The method according to any one of items 94 to 99, wherein the functional layer comprises a metal selected from silver, gold, palladium, copper or mixtures thereof, in particular silver.

[0314] Clause 101: The method of any of clauses 94 to 100, further comprising a third protective film over at least a portion of the first protective film and between the first protective film and the second protective film, or between the first protective film and the functional coating.

[0315] Clause 102: The method of any one of clauses 94 to 101, wherein the third protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof. Optionally, the third protective film does not comprise a mixture of titanium oxide and aluminum oxide.

[0316] Item 103: A method for reducing the absorption of a transparent conductive oxide layer, reducing the emissivity of a coated article and / or reducing the absorptivity of a coated article, the method comprising: providing a substrate; applying a transparent conductive oxide layer, and heat treating the coated article comprising the transparent conductive oxide layer in an atmosphere comprising 0% to 1.0% oxygen, in particular 0% to 0.5% oxygen.

[0317] Item 104: The method of Item 103, wherein the transparent conductive oxide layer comprises indium-doped tin oxide ("ITO") or aluminum-doped zinc oxide ("AZO").

[0318] Item 105: A method according to item 103 or 104, wherein the transparent conductive oxide layer has a thickness of at least 125 nm, in particular at least 150 nm, more in particular at least 175 nm, and at most 450 nm, at most 400 nm, at most 350 nm, at most 300 nm, at most 250 nm or at most 250 nm.

[0319] Item 106: The method of any of items 103 to 105, wherein the transparent conductive oxide layer comprises indium-doped tin oxide ("ITO"), and wherein the atmosphere comprises 0.75% to 1.25% oxygen.

[0320] Item 107: The method of any of Items 103 to 106, wherein the transparent conductive oxide layer comprises a thickness of at least 95 nm and at most 225 nm.

[0321] Item 108: A method according to any of items 103 to 107, wherein the transparent conductive oxide layer comprises aluminum-doped zinc oxide ("AZO"), and wherein the atmosphere comprises 0% to 0.5% oxygen, particularly 0% to 0.5% oxygen, particularly 0% to 0.25% oxygen, more particularly 0% to 0.1% oxygen by volume, or more particularly 0% oxygen by volume.

[0322] Item 109: The method of Item 108, wherein the transparent conductive oxide layer has a thickness of at least 225 nm and at most 440 nm.

[0323] Clause 110: The method of any of clauses 103 to 109, further comprising applying a functional coating over at least a portion of the substrate, wherein the functional coating is located between the substrate and the transparent conductive oxide layer.

[0324] Item 111: A method according to any one of items 103 to 110, the method also includes applying a first protective film over at least a portion of the transparent conductive oxide layer, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof, and a second protective film over at least a portion of the first protective film, wherein the second protective film comprises titanium oxide and aluminum oxide, wherein the second protective film is the outermost film.

[0325] Item 112: A method of reducing the sheet resistance of a coated article, the method comprising applying a coating to a substrate at room temperature, wherein the coating comprises a transparent conductive oxide layer; and heating a top surface of the transparent conductive oxide layer to above 380°F or at least 435°F for at least 5 seconds, at least 10 seconds, at least 30 seconds, and no more than 120 seconds, 90 seconds, 60 seconds, 55 seconds, 50 seconds, 45 seconds, 40 seconds, or 35 seconds.

[0326] Clause 113: The method of clause 112, wherein the heating step is flash annealing.

[0327] Item 114: The method of Item 112 or 113, wherein the transparent conductive oxide layer is at least 125 nm and at most nm to 950 nm.

[0328] Item 115: The method of any of items 112 to 114, wherein the transparent conductive oxide layer comprises tin-doped indium oxide and is at least 105 nm and at most 171 nm, and wherein the sheet resistance of the coated article after the treating step is less than 20 Ω / □.

[0329] Item 116: The method of any of items 112 to 115, wherein the transparent conductive oxide layer comprises gallium-doped zinc oxide having a thickness of at least 320 nm and at most 480 nm, and wherein the coated article has a sheet resistance of less than 20Ω / □ after the treating step.

[0330] Item 117: The method of any of items 112 to 116, wherein the transparent conductive oxide layer comprises an aluminum oxide doped oxide having a thickness of at least 344 nm and at most 880 nm, and wherein the coated article has a sheet resistance of less than 20 Ω / □ after the treating step.

[0331] Clause 118: The method of any of clauses 112 to 117, wherein the step of applying a coating comprises a magnetron sputtering vacuum deposition process.

[0332] Clause 119: The method of any of clauses 112 to 118, wherein the step of applying the coating does not use radiant heat.

[0333] Item 120: A method according to any one of items 112 to 119, the method also includes applying a first protective film over at least a portion of the transparent conductive oxide layer, wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof, and applying a second protective film over at least a portion of the transparent conductive oxide layer, wherein the second protective film comprises titanium oxide and aluminum oxide, and wherein the steps of applying the first protective film and applying the second protective film are performed before or after the processing step.

[0334] Clause 121: The method of any of clauses 112 to 120, wherein the heating step does not raise the top surface of the transparent conductive oxide above 635°F.

[0335] Clause 122: The method of any of clauses 112 to 121, wherein the substrate is glass and the transparent conductive oxide has an absorptivity of no greater than 0.3.

[0336] Clause 123: The method of any of clauses 112 to 122, wherein the substrate is glass and the transparent conductive oxide has an absorptivity at least as high as 0.05.

[0337] Clause 124: The method of any one of clauses 112 to 123, wherein the coated article is a refrigerator door.

[0338] Clause 125: The method of any one of clauses 112 to 124, wherein the applying step is performed in an atmosphere having an oxygen content supplied to the atmosphere of 0% to 1.5%.

[0339] Clause 126: The method of any of clauses 112 to 125, wherein the substrate is glass and the transparent conductive oxide has an absorptivity no greater than 0.2 and at least up to 0.05.

[0340] Item 127: A method of making a coated article, the method comprising applying a transparent conductive oxide layer over a substrate, raising the top surface of the transparent conductive oxide to above 380°F or at least 435°F and not raising the top surface of the transparent conductive oxide to above 806°F (or particularly 635°F) for at least 5 seconds, at least 10 seconds, at least 15 seconds, at least 20 seconds, at least 25 seconds, at least 30 seconds, and not more than 120 seconds, 90 seconds, 60 seconds, 55 seconds, 50 seconds, 45 seconds, 40 seconds or 35 seconds.

[0341] Clause 128: The method of clause 127, further comprising not heating the coated article to a temperature exceeding 635°F.

[0342] Item 129: The method of any of items 127 to 128, wherein the transparent conductive oxide layer comprises tin-doped indium oxide having a thickness of at least 96 nm and at most 171 nm and a sheet resistance of less than 25 Ω / □.

[0343] Item 130: The method of any of items 1127 to 129, further comprising applying a protective layer over the transparent conductive oxide, wherein the protective layer comprises titanium oxide and aluminum oxide.

[0344] Clause 131: A coated article produced by the method of any one of clauses 15 to 26, wherein a * between -9 and 1, in particular between -4 and 0, more in particular between -3 and 1, more in particular between -1.5 and -0.5; and its b* Between -9 and 1, in particular between -4 and 0, more in particular between -3 and 1, more in particular between -1.5 and -0.5.

[0345] Clause 132: A coated article produced by the method of any one of clauses 46 to 65, wherein a * between -9 and 1, in particular between -4 and 0, more in particular between -3 and 1, more in particular between -1.5 and -0.5; and its b * Between -9 and 1, in particular between -4 and 0, more in particular between -3 and 1, more in particular between -1.5 and -0.5.

[0346] Item 133: A coated article made by the method of any one of items 103 to 111.

[0347] Item 134: A coated article produced by the method of any one of items 112 to 126.

[0348] Item 135: A coated article produced by the method of any one of items 127 to 130.

[0349] Clause 136: Use of a substrate according to any of clauses 1 to 14 or 27 to 45 to provide: a * between -9 and 1, in particular between -4 and 0, more in particular between -3 and 1, more in particular between -1.5 and -0.5; and b * Between -9 and 1, particularly between -4 and 0, more particularly between -3 and 1, or more particularly between -1.5 and -0.5.

[0350] Clause 137: Use of a first base film and a second base film according to any one of clauses 15 to 26 or 46 to 65 to provide the following values: a * between -9 and 1, in particular between -4 and 0, more in particular between -3 and 1, more in particular between -1.5 and -0.5; and b * Between -9 and 1, particularly between -4 and 0, more particularly between -3 and 1, or more particularly between -1.5 and -0.5.

[0351] Item 138: Use of the embedded film according to any one of items 27 to 65 for reducing sheet resistance.

[0352] Clause 139: Use of a protective layer according to any one of clauses 85 to 93 for increasing the durability of a coating on a substrate.

[0353] Item 140: A coated article according to any one of items 85 to 91, wherein the protective layer has a thickness of at least 20 nm, 40 nm, 60 nm, or 80 nm, 100 nm or 120 nm; and at most 275 nm, 255 nm, 240 nm, 170 nm, 150 nm, 125 nm or 100 nm.

[0354] Item 141: A coated article according to any one of items 85 to 91 or item 140, wherein the thickness of the first protective film can be at least 10 nm, at least 15 nm, at least 20 nm, at least 27 nm, at least 30 nm, at least 35 nm, at least 40 nm, at least 54 nm, at least 72 nm; and at most 85 nm, 70 nm, 60 nm, 50 nm, 45 nm or 30 nm.

[0355] Item 142: A coated article according to any one of items 85 to 91, 140 or 141, wherein the thickness of the second protective film may be at least 10 nm, at least 15 nm, at least 20 nm, at least 27 nm, at least 35 nm, at least 40 nm, at least 54 nm, at least 72 nm; and at most 85 nm, 70 nm, 60 nm, 50 nm, 40 nm, 45 nm, 30 nm.

[0356] Item 143: A coated article according to any one of items 85 to 91 or 140 to 142, wherein the thickness of the optional third protective film can be at least 5 nm, at least 10 nm, at least 15 nm, at least 27 nm, at least 35 nm, at least 40 nm, at least 54 nm, at least 72 nm; and at most 85 nm, 70 nm, 60 nm, 50 nm, 45 nm, 30 nm or at most 30 nm.

Claims

1. A coated article comprising: Base, a bottom layer over at least a portion of the substrate, the bottom layer comprising a first refractive index material and a second refractive index material, wherein the bottom layer is in direct contact with the substrate; a transparent conductive oxide layer over at least a portion of the base layer; and an embedded film embedded in the transparent conductive oxide layer, wherein the embedded film has a thickness in a range of 15 nm to 30 nm, and wherein the embedded film comprises a third refractive index material having a refractive index within 10% of the refractive index of the first refractive index material, wherein the refractive index of the first refractive index material is greater than the refractive index of the second refractive index material, and The bottom layer comprises: a first underlying film formed of a metal oxide, metal nitride or metal oxynitride selected from titanium, aluminum, zirconium, hafnium, niobium, zinc, bismuth, lead, indium, tin, tantalum, or alloys thereof or mixtures thereof, wherein the first underlying film comprises a first refractive index material, and A second underlying film formed of a metal oxide, metal nitride or metal oxynitride selected from titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, tin, tantalum, or alloys thereof or mixtures thereof, wherein the second underlying film is formed over at least a portion of the first underlying film, and wherein the second underlying film comprises a second refractive index material.

2. The coated article of claim 1, wherein the third refractive index material has a refractive index greater than the refractive index of the second refractive index material.

3. The coated article of claim 1, wherein the embedded film comprises an alloy, mixture, oxide, nitride, or oxynitride of at least one of silicon, titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, or tin.

4. The coated article of claim 1, wherein the transparent conductive oxide layer comprises tin-doped indium oxide. 5 . The coated article according to claim 1 , wherein the embedded film is positioned closer to a bottom of the transparent conductive oxide layer. 6 . The coated article of claim 1 , wherein the embedded film is positioned closer to the top of the transparent conductive oxide layer.

7. The coated article of claim 1, wherein the embedded film is located approximately in the middle of the transparent conductive oxide layer.

8. The coated article according to claim 1, further comprising a protective layer over at least a portion of the transparent conductive oxide layer, wherein the protective layer comprises: a first protective film, the first protective film comprising titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, alloys thereof, or mixtures thereof; and a second protective film over at least a portion of the first protective film, wherein the second protective film comprises titanium oxide and aluminum oxide.

9. A coated article comprising: substrate; a bottom layer over at least a portion of the substrate, the bottom layer comprising a first refractive index material and a second refractive index material, wherein the bottom layer is in direct contact with the substrate; a transparent conductive oxide layer over at least a portion of the base layer, the transparent conductive oxide layer having a top surface and a bottom surface opposite the top surface; and an embedded film, wherein the embedded film is embedded in the transparent conductive oxide layer, wherein the embedded film is either closer to the top surface of the transparent conductive oxide layer or closer to the bottom surface of the transparent conductive oxide layer, and wherein the embedded film comprises a third refractive index material having a refractive index within 10% of the refractive index of the first refractive index material, wherein the refractive index of the first refractive index material is greater than the refractive index of the second refractive index material, and The bottom layer comprises: a first underlying film formed of a metal oxide, metal nitride or metal oxynitride selected from titanium, aluminum, zirconium, hafnium, niobium, zinc, bismuth, lead, indium, tin, tantalum, or alloys thereof or mixtures thereof, wherein the first underlying film comprises a first refractive index material, and A second underlying film formed of a metal oxide, metal nitride or metal oxynitride selected from titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, tin, tantalum, or alloys thereof or mixtures thereof, wherein the second underlying film is formed over at least a portion of the first underlying film, and wherein the second underlying film comprises a second refractive index material.

10. The coated article of claim 9, wherein the embedded film comprises a third refractive index material, and wherein the third refractive index material has a refractive index greater than the refractive index of the second refractive index material.

11. The coated article according to claim 9, wherein the thickness of the embedded film is at least 15 nm and at most 30 nm.

12. The coated article of claim 9, wherein the embedded film comprises an alloy, mixture, oxide, nitride, or oxynitride of at least one of silicon, titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, or tin.

13. The coated article according to claim 9, further comprising a protective layer over at least a portion of the transparent conductive oxide layer, wherein the protective layer comprises: a first protective film, the first protective film comprising titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof; and a second protective film over at least a portion of the first protective film, wherein the second protective film comprises titanium oxide and aluminum oxide.

14. A method of reducing the sheet resistance of a coated article, comprising: (a) applying a first base film over at least a portion of a substrate, wherein the first base film comprises a first refractive index material, and wherein the first base film is in direct contact with the substrate; (b) applying a second base film over at least a portion of the first base film, wherein the second base film comprises a second refractive index material, and wherein the first refractive index material has a greater refractive index than the second refractive index material; (c) applying a first transparent conductive oxide layer over at least a portion of the second base film; (d) applying an embedded film over at least a portion of the first transparent conductive oxide layer, wherein the embedded film has a thickness in a range of 15 nm to 30 nm, wherein the embedded film comprises a third refractive index material, wherein the refractive index of the third refractive index material is within 10% of the refractive index of the first refractive index material, and wherein the refractive index of the third refractive index material is greater than the refractive index of the second refractive index material; and (e) applying a second transparent conductive oxide layer over at least a portion of the embedded film, The first bottom layer film and the second bottom layer film constitute a bottom layer, and the bottom layer comprises: a first underlying film formed of a metal oxide, metal nitride or metal oxynitride selected from titanium, aluminum, zirconium, hafnium, niobium, zinc, bismuth, lead, indium, tin, tantalum, or alloys thereof or mixtures thereof, and A second underlying film formed of a metal oxide, metal nitride or metal oxynitride selected from titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, tin, tantalum, or alloys thereof or mixtures thereof, wherein the second underlying film is formed over at least a portion of the first underlying film.

15. The method of claim 14, wherein the embedded film comprises an alloy, mixture, oxide, nitride, or oxynitride of at least one of silicon, titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, or tin.

16. The method of claim 14, wherein the first transparent conductive oxide layer comprises tin-doped indium oxide. 17 . The method of claim 14 , wherein the first transparent conductive oxide layer is thinner or thicker than the second transparent conductive oxide layer.

18. The method of claim 14, wherein the coated article further comprises: applying a first protective film over at least a portion of the second transparent conductive oxide layer, and applying a second protective film over at least a portion of the first protective film, wherein the second protective film comprises titanium oxide and aluminum oxide, and wherein the first protective film comprises titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, or a mixture thereof.

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