Transparent Conductive Oxide with Embedded Film

Abstract

A coated article having low emissivity and low sheet resistance. [Solution] The coated article of the present invention includes a substrate, an underlayer on at least a portion of the substrate, a first transparent conductive oxide layer on at least a portion of the underlayer, an embedding film on at least a portion of the first transparent conductive oxide layer, a second transparent conductive oxide layer on at least a portion of the embedding film, and a protective layer on at least a portion of the second transparent conductive oxide layer.

Description

Technical Field

[0001] The present invention relates to a coated article having a low emissivity and a neutral color.

Background Art

[0002] A transparent conductive oxide (“TCO”) is applied to a substrate to provide a coated article having a low emissivity and a low sheet resistance. Thereby, the TCO is particularly useful for electrodes (e.g., solar cells) or heating layers, activating glazing units or screens. TCOs are typically applied by vacuum deposition techniques such as magnetron sputtering vacuum deposition (“MSVD”). Generally, the thicker the TCO layer, the lower the sheet resistance. However, the thickness of the TCO affects the color of the coated article. Therefore, it is necessary to adjust the coloring effect caused by the TCO layer. Also, it is 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 maintaining the required sheet resistance.

[0003] Coating stacks may corrode over time. To protect against this, a protective overcoat can be applied to the coating. For example, titanium dioxide films disclosed in U.S. Patent No. 4,716,086 and U.S. Patent No. 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. Patent No. 5,425,861, U.S. Patent No. 5,344,718, U.S. Patent No. 5,376,455, U.S. Patent No. 5,584,902 and U.S. Patent No. 5,532,180 and PCT International Patent Publication No. 95 / 29883 pamphlet are also protective films that provide chemical resistance to the coating. This technology may progress with more chemically and / or mechanically durable protective overcoats.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Summary of the Invention

[0005] The coated article includes a substrate and a lower layer on the substrate. The lower layer includes a first layer. The first layer includes a high refractive index material. A second layer is disposed on at least a portion of the first layer. The second layer includes a low refractive index material. A transparent conductive film is disposed on at least a portion of the lower layer. The coated article has a sheet resistance of at least 5 Ω / sq and at most 25 Ω / sq. The coated article has a color having an a* of at least -9 and at most 1, and a b* of at least -9 and at most 1.

[0006] Optionally, the coated article can 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 of the coating stack and includes a mixture of titania and alumina. Optionally, the protective layer can include a third protective film disposed between the first protective film and the second protective film.

[0007] A method of forming a coated substrate includes providing a substrate. A transparent conductive oxide is identified and a thickness of the transparent conductive oxide that provides a sheet resistance of at least 5 Ω / sq and at most 25 Ω / sq is determined. A lower layer having a first lower layer material and a second lower layer material is identified. Thicknesses of the first lower layer and the second lower layer that provide a color having an a* of at least -9 and at most 1 and a b* of at least -9 and at most 1 to the coated substrate are determined. The thicknesses of the two films of the lower layer are 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 the thickness of the transparent conductive oxide film is determined. A first lower layer film including the first lower layer material is applied over at least a portion of the substrate at the first lower layer film thickness. A second lower layer film including the second lower layer material is applied over at least a portion of the first lower layer at the second lower layer thickness. A transparent conductive oxide layer having a transparent conductive oxide is applied over at least a portion of the second lower layer film at the transparent conductive oxide film thickness.

[0008] A coated article having a color with at least -9 and a maximum of 1 for a* and at least -9 and a maximum of 1 for b*, created by the following process. A transparent conductive oxide is identified, and the thickness of the transparent conductive oxide providing a sheet resistance of at least 5 Ω / sq and a maximum of 25 Ω / sq is determined. A lower layer having a first lower layer material and a second lower layer material is identified. The thicknesses of the first lower layer and the second lower layer provided on a substrate coated with a color having at least -9 and a maximum of 1 for a* and at least -9 and a maximum of 1 for b* are determined. The thicknesses of the two films of the lower layer are 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 the thickness of the transparent conductive oxide film is determined. A first lower layer film including the first lower layer material is applied on at least a part of the substrate at the first lower layer film thickness. A second lower layer film including the second lower layer material is applied on at least a part of the first lower layer at the second lower layer thickness. A transparent conductive oxide layer having a transparent conductive oxide is applied on at least a part of the second lower layer film at the transparent conductive oxide film thickness.

[0009] A coated article including a substrate. The lower layer is disposed on at least a part of the substrate. The lower layer includes at least a first lower layer film on at least a part of the substrate and optionally a second lower layer film on at least a part of the first lower layer film. The first lower layer film includes a first high refractive index material. The optional second lower layer film includes a first low refractive index layer. The transparent conductive oxide layer is disposed on at least a part of the first or optional second lower layer film. A second high refractive index material is embedded within the transparent conductive oxide layer. The coated article has a sheet resistance of at least 5 Ω / sq and a maximum of 25 Ω / sq. The sheet resistance is at least 35% higher than when the second high refractive index material is not embedded within the transparent conductive oxide layer.

[0010] Optionally, the coated article can have a protective layer on at least a portion of the transparent conductive oxide layer. The protective layer includes a first protective film on at least a portion of the transparent conductive oxide layer and a second protective film on at least a portion of the first protective film. The second protective film is the outermost film of the coating stack and includes a mixture of titania and alumina. Optionally, the protective layer can include a third protective film disposed between the first protective film and the second protective film.

[0011] A coated article including a substrate. A lower layer is disposed on at least a portion of the substrate. The lower layer includes at least a first lower layer film on at least a portion of the substrate and an optional second lower layer film on at least a portion of the first lower layer film. The first lower layer film includes a first high refractive index material. The optional second lower layer film includes a first low refractive index layer. A first transparent conductive oxide layer is disposed on at least a portion of the first or optional second lower layer film. An embedded film is disposed on at least a portion of the first transparent conductive oxide layer. The embedded film has a second high refractive index material. A second transparent conductive oxide layer is disposed on at least a portion of the second transparent conductive oxide layer. The coated article has a sheet resistance of at least 5 Ω / sq and a maximum of 25 Ω / sq. The sheet resistance is at least 35% higher than without the embedded film.

[0012] Optionally, the coated article can have a protective layer on at least a portion of the transparent conductive oxide layer. The protective layer includes a first protective film on at least a portion of the transparent conductive oxide layer and a second protective film on at least a portion of the first protective film. The second protective film is the outermost film of the coating stack and includes a mixture of titania and alumina. Optionally, the protective layer can include a third protective film disposed between the first protective film and the second protective film.

[0013] A method of forming a coated article, a method of increasing sheet resistance, or a method of increasing the light transmittance of a coated article. A substrate is provided. A lower layer is applied over at least a portion of the substrate. A first lower layer film is applied over at least a portion of the substrate. The first lower layer film has a first high refractive index material. An optional second lower layer film is applied over at least a portion of the first lower layer film. The optional second lower 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 or optional second lower layer film. An embedding film is applied over at least a portion of the first transparent conductive oxide film. The embedding film has a second high refractive index material. A second transparent conductive oxide film is applied over at least a portion of the embedding film. Optionally, a protective layer can 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 of the coating stack and includes a mixture of titania and alumina. Optionally, the protective layer can include a third protective film disposed between the first protective film and the second protective film.

[0014] A coated article made by the following process. A substrate is provided. A lower layer is applied over at least a portion of the substrate. A first lower layer film is applied over at least a portion of the substrate. The first lower layer film has a first high refractive index material. An optional second lower layer film is applied over at least a portion of the first lower layer film. The optional second lower 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 or optional second lower layer film. An embedding film is applied over at least a portion of the first transparent conductive oxide film. The embedding film has a second high refractive index material. A second transparent conductive oxide film is applied over at least a portion of the embedding film. Optionally, a protective layer can 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 of the coating stack and includes a mixture of titania and alumina. Optionally, the protective layer can include a third protective film disposed 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 processed in a post-deposition process. The post-deposition process can include annealing the coated article, heating the coated article by placing the entire coated article 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. Alternatively, the coated article made by the method described in this paragraph has a sheet resistance of less than 25 ohms per square.

[0016] A method for 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 can include annealing the coated article, heating the coated article by placing the entire coated article in a furnace, flash annealing only the surface of the transparent conductive oxide layer, or passing eddy currents 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 contains titania and alumina. Optionally, a third protective film can be disposed between the first protective film and the second protective film, or between the first protective film and the functional coating.

[0018] A method for manufacturing a coated article, including providing a substrate. A functional coating is applied over at least a portion of the substrate. A first protective film is applied over at least a portion of the functional coating. A second protective film containing titania and alumina is applied over at least a portion of the first protective film. Optionally, a third protective film is applied between the first protective film and the second protective film, or between the first protective film and the functional coating.

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

[0021] The patent or application file includes at least one drawing created in color. A copy of this patent or patent application publication that includes the color drawing is provided by the Patent Office upon request and payment of the required fee.

Brief Description of the Drawings

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DETAILED DESCRIPTION OF THE INVENTION

[0023] Spatial or directional terms such as "left", "right", "up", and "down" used herein are related to the present invention as shown in the drawings. It should be understood that the present invention can assume various alternative orientations, and thus such terms should not be regarded as limiting.

[0024] As used herein, spatial or directional terms such as "left", "right", "inner", "outer", "upper", "lower", etc. are relevant to the present invention as shown in the drawings. However, it should be understood that the present invention can assume various alternative orientations, and thus such terms should not be regarded as limiting. Further, as used herein, all numbers representing dimensions, physical properties, processing parameters, amounts of components, reaction conditions, etc. used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims are subject to change depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the claims, each numerical value should be construed at least in light of the reported number of significant digits and by application of ordinary rounding technique. Further, all ranges disclosed herein are to be understood to encompass the starting and ending range values, as well as any and all subranges subsumed therein. For example, a specified range of "1 to 10" encompasses any and all subranges between and including the minimum value of 1 and the maximum value of 10, i.e., all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, such as 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. Further, all documents mentioned herein, such as but not limited to issued patents and patent applications, are to be considered as incorporated by reference in their entirety. Any reference to an amount is, unless otherwise specified, "percent by weight". The term "film" refers to a region of a coating having a desired or selected composition. A "layer" includes one or more "films". A "coating" or "coating stack" is composed of one or more "layers". The terms "metal" and "metal oxide" are to be considered to include silicon and silica, respectively, although silicon is not technically a metal, as well as conventionally recognized metals and metal oxides.

[0025] All numbers used in the specification and claims should be understood to be modified in all cases by the term "about". All ranges disclosed herein should be understood to encompass the starting and ending range values, as well as every sub-range subsumed therein. The ranges described herein represent the average value of the specified range.

[0026] The term "above" means "farther from the substrate". For example, a second layer located "above" a first layer means that the second layer is located farther from the substrate than the first layer. The second layer can be in direct contact with the first layer or one or more other layers can be disposed between the second layer and the first layer.

[0027] All documents referred to herein should be considered to be incorporated by reference in their entirety.

[0028] Any reference to an amount is, unless otherwise specified, "weight percent".

[0029] The term "visible light" means electromagnetic radiation having wavelengths in the range of 380 nm to 780 nm. The term "infrared" means electromagnetic radiation having wavelengths in the range from greater than 780 nm to 100,000 nm. The term "ultraviolet" means electromagnetic energy having wavelengths in the range of 100 nm to less than 380 nm.

[0030] The terms "metal" and "metal oxide" include silicon and silica, respectively, as well as conventionally recognized metals and metal oxides, even when silicon cannot be considered a metal in the conventional sense. "At least" means "more than or equal to". "Not more than" means "less than or equal to".

[0031] All haze and transmittance values in this specification are values determined in accordance with ASTM D 1003-07 using a Haze-Gard Plus haze meter (commercially available from BYK-Gardner USA).

[0032] When % oxygen is referred to in the coater, the % oxygen is the amount of oxygen added to the coater chamber in relation to the other gases. For example, when 2% oxygen is added to the atmosphere of the coater chamber, 2% oxygen and 98% argon are added to the coater chamber. Argon can be used in place of the other gases, but often the gas is an inert gas.

[0033] The discussion of the invention in this specification may describe certain features as "particularly" or "preferably" within certain limitations (e.g., "preferably", "more preferably", or "even more preferably" within certain limitations). It should be understood that the invention is not limited to these specific or preferred limitations but encompasses the entire scope of the present disclosure.

[0034] The present invention includes, consists of, or consists essentially of, in any combination, the following aspects of the invention. The various aspects of the invention are shown in separate figures. However, it should be understood that this is merely for the purpose of simplifying the description and discussion. In the practice of the present invention, one or more aspects of the invention shown in one figure can be combined with one or more aspects of the invention shown in one or more other figures.

[0035] An exemplary article includes a substrate 10, an underlayer 12 on the substrate 10, and a transparent conductive oxide 14 on the underlayer 12, as shown in FIG. 1.

[0036] Article 2 can be a window, a solar 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.

[0037] The substrate 10 can be transparent, translucent, or opaque to visible light. "Transparent" means having a visible light transmittance greater than 0% and up to 100%. Alternatively, the substrate 12 can be translucent or opaque. "Translucent" means allowing electromagnetic energy (e.g., visible light) to pass through but diffusing this energy so that an object on the opposite side from the viewer cannot be clearly seen. "Opaque" means having a visible light transmittance of 0%.

[0038] The substrate 10 can be glass, plastic, or metal. Examples of suitable plastic substrates include acrylic polymers such as polyacrylate; polyalkyl methacrylates such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, etc.; polyurethanes; polycarbonates; polyalkyl terephthalates such as polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, etc.; polysiloxane-containing polymers; or copolymers of any monomers for preparing these, or mixtures thereof); or glass substrates are included. Examples of suitable glass substrates include conventional soda-lime silicate glass, borosilicate glass, or lead glass. The glass can be clear glass. "Clear glass" means non-tinted or non-colored glass. Alternatively, the glass can be tinted or otherwise colored glass. The glass can be annealed glass or heat-treated glass. As used herein, the term "heat-treated" means annealing or at least partial annealing. The glass can be of any type such as conventional float glass and can be of any composition having any value of any optical property, e.g., visible transmittance, ultraviolet transmittance, infrared transmittance, and / or total solar energy transmittance. Examples of suitable metal substrates include aluminum or stainless steel.

[0039] The substrate 10 can have a high visible light transmittance at a reference wavelength of 550 nanometers (nm) and a thickness of 2 millimeters. "High visible light transmittance" means a visible light transmittance at 550 nm of 85% or more, for example 87% or more, for example 90% or more, for example 91% or more, for example 92% or more.

[0040] The lower layer 12 can be a single layer, a homogeneous layer, a gradient layer, a double layer, or can include a plurality of layers. A "homogeneous layer" means a layer in which the material is randomly distributed throughout the coating. A "gradient layer" means a layer having two or more components, and the concentration of the components varies (continuously or stepwise) as the distance from the substrate 12 changes.

[0041] The lower layer 12 can include two films, a first lower layer film 20 and a second lower layer film 22. The first lower layer film 20 is disposed on the substrate 10 and is closer to the substrate 10 than the second lower layer film 22. The first lower layer film 20 can be a material having a refractive index higher than that of the second lower layer film 22 and / or the substrate 10. For example, the first lower layer film 20 can include a metal oxide, nitride, or oxynitride. Examples of metals suitable for the first lower layer film 20 include silicon, titanium, aluminum, zirconium, hafnium, niobium, zinc, bismuth, lead, indium, tin, tantalum, their alloys, or mixtures thereof. For example, the first lower layer film 20 can include oxides of zinc, tin, aluminum, and / or titanium, their alloys, or mixtures thereof. For example, the first lower layer film 20 can include oxides of zinc and / or tin. For example, the first lower layer film 20 can include zinc oxide and tin oxide, or zinc stannate.

[0042] The first lower film 20 can contain zinc oxide. The zinc target for sputtering the zinc oxide film may contain one or more other materials to improve the sputtering characteristics of the zinc target. For example, the zinc target can contain up to 15 wt%, such as up to 10 wt%, such as up to 5 wt% of such materials. The resulting zinc oxide layer contains a small proportion of oxides of the additive material, such as up to 15 wt%, up to 10 wt%, up to 9 wt% of the material oxide. A layer deposited from a zinc target having up to 10 wt%, such as up to 5 wt% of an additional material to improve the sputtering characteristics of the zinc target, is referred to herein as a "zinc oxide layer" even if a small amount of the additive material (or oxide of the additive material) may be present. An example of such a material is tin.

[0043] The first lower film 20 can contain an alloy of zinc oxide and tin oxide. For example, the first lower film 20 can contain a zinc stannate layer or can be a zinc stannate layer. "Zinc stannate" means a composition of formula Zn X Sn 1-X O 2-X (Formula 1), where "x" varies in the range greater than 0 and less than 1. For example, "x" can be greater than 0 and can be any fraction or decimal greater than 0 and less than 1. The zinc stannate layer has one or more forms of formula 1 in a major amount. A zinc stannate layer with x = 2 / 3 has conventionally been called "Zn 2 SnO 4 ". The alloy of zinc oxide and tin oxide can contain 80 wt% to 99 wt% of zinc and 20 wt% to 1 wt% of tin, such as 85 wt% of zinc to 99 wt% of zinc and 15 wt% of tin to 1 wt% of tin, 90 wt% of zinc to 99 wt% of zinc and 10 wt% of tin to 1 wt% of tin, such as about 90 wt% of zinc and 10 wt% of tin.

[0044] The second lower film 22 can be a material with a lower refractive index than the first lower film 20. For example, the second lower film 22 can include metal oxides, nitrides, or oxynitrides. Examples of metals suitable for the second lower film 22 include silicon, titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, tin, tantalum alloys, or mixtures thereof.

[0045] For example, the second lower film 22 can include silica and alumina. According to this example, the second lower film 22 can have at least 50 wt% silica, 50 - 99 wt% silica and 50 - 1 wt% alumina, 60 - 98 wt% silica and 40 - 2 wt% alumina, 70 - 95 wt% silica and 30 - 5 wt% alumina, 80 - 90 wt% silica and 10 - 20 wt% alumina, or 8 wt% silica and 15 wt% alumina.

[0046] The transparent conductive oxide layer 14 is on the lower layer 12. The transparent conductive oxide layer 14 can be a single layer or can have multiple layers or regions. The transparent conductive oxide layer 14 has at least one conductive oxide layer. For example, the transparent conductive oxide layer 14 can include one or more metal oxide materials. For example, the transparent conductive oxide layer 14 can include one or more oxides of Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Bi, Ti, Co, Cr, Si, In or alloys of two or more of these materials. For example, the transparent conductive oxide layer 14 can include tin oxide. In another example, the transparent conductive oxide layer 14 includes zinc oxide.

[0047] The transparent conductive oxide layer 14 can include, but is not limited to, one or more dopant materials such as F, In, Al, P, Cu, Mo, Ta, Ti, Ni, Nb, W, Ga, Mg, and / or Sb. For example, the dopant can be In, Ga, Al, or Mg. The dopant can 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 can 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").

[0048] The transparent conductive oxide layer 14 can have a thickness 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 transparent conductive oxide layer 14 can have a thickness in the range of 125 nm to 450 nm, at least 150 nm, or at least 175 nm. The transparent conductive oxide layer 14 can have a thickness of 600 nm, 500 nm, 400 nm, 350 nm, 300 nm, 275 nm, 250 nm, or 225 nm or less.

[0049] Materials of the different transparent conductive oxide layers 14 have different sheet resistances at the same thickness and similarly have different effects on the optical system of the article. Ideally, the sheet resistance should be less than 25 Ω / □ (ohms per square), or less than 20 Ω / □, or less than 18 Ω / □. For example, when the transparent conductive oxide layer 14 contains GZO, it can have a thickness of at least 300 nm and a maximum of 400 nm. When the transparent conductive oxide layer 14 contains AZO, it should have a thickness of at least 350 nm, or at least 400 nm, and a maximum of 950 nm, or a maximum of 800 nm, or a maximum of 700 nm, or a maximum of 600 nm. When the transparent conductive oxide layer 14 contains ITO, it can have a thickness of 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 a maximum of 350 nm, maximum 300 nm, maximum 275 nm, maximum 250 nm, or maximum 225 nm.

[0050] The transparent conductive oxide layer 14 can have a surface roughness (RMS) in the range of 5 nm to 60 nm, for example 5 nm to 40 nm, for example 5 nm to 30 nm, for example 10 nm to 30 nm, for example 10 nm to 20 nm, for example 10 nm to 15 nm, for example 11 nm to 15 nm.

[0051] For example, when the transparent conductive oxide layer 14 is indium tin oxide, the thickness of the transparent conductive oxide layer 14 can be in the range of 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.

[0052] The transparent conductive oxide layer 14 can have a sheet resistance in the range of 5 Ω / □ to 25 Ω / □, for example 8 Ω / □ to 20 Ω / □. Such as 10 Ω / □ to 18 Ω / □ for example.

[0053] For example, the article can be a glass substrate 10 having a lower layer 12 thereon. The lower layer 12 can have at least two films, a first lower film 20 and a second lower film 22. The first lower film 20 can be an alloy of zinc oxide and tin oxide, and the second lower film 22 can be an alloy of silica and alumina. The transparent conductive oxide layer 14 can be on the second film 22. The transparent conductive oxide layer 14 can be ITO, GZO, or AZO.

[0054] The transparent conductive oxide film provides a specific sheet resistance, for example, less than 25 Ω / sq, to the article. Generally, as the thickness of the transparent conductive oxide increases, the sheet resistance decreases. Once the desired sheet resistance is specified and the thickness of the transparent conductive oxide required to achieve the desired sheet resistance is specified, the thicknesses of the first film and the second film can be determined using optical design software. An example of suitable optical modeling software is FILM STAR. Ideally, the a*, b* color should be -1, -1. Some variation is allowed in this color. For example, a* can be at most 1, 0, or -0.5, and at least -9, -4, -3, or -1.5, and the b* value can be at most 1, 0, or -0.5, and at least -9, -4, -3, or -1.5. To obtain the desired color, the thicknesses of the first film 20 and the second film 22 are varied to obtain the desired color with respect to the specified transparent conductive oxide and the thickness of the transparent conductive oxide. For example, the first film can have a thickness of 10 - 20 nm, or a thickness of 11 - 15 nm, and the second film can have a thickness of 25 - 35 nm, or a thickness of 29 - 34 nm.

[0055] Referring to FIGS. 1c and 1d, the article 2 may optionally include a protective layer 16, such as the protective layer described herein, on 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 titania and silica. For example, the protective layer 16 includes a first protective film 60, a second protective film 62, and a third protective film 64.

[0056] 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, the thickness of the transparent conductive film that provides a sheet resistance of at least 5 Ω / sq and / or 25 Ω / sq or less, specifically 20 Ω / sq or less, more specifically 18 Ω / sq or less, can be determined for the coated substrate. The desired color of the coated substrate is also identified. The first underlayer material and the second underlayer material are identified using optical design software, and the thickness of the first underlayer film and the thickness of the second underlayer film are determined to provide a color for the article having the transparent conductive oxide layer identified above, where the a* value can be from a maximum of 1 to a minimum of -9 and the b* value can be from a maximum of 1 to a minimum of -9. The underlayer 12 is applied onto the substrate by applying the first underlayer material onto the substrate to form the first underlayer film 20 to the identified first film thickness, and then applying the second underlayer material onto the first underlayer film to the identified second underlayer film thickness to form the second underlayer film 22. The transparent conductive oxide material is applied onto the underlayer 12 to the thickness of the identified transparent conductive film to form the transparent conductive oxide layer 14.

[0057] The thickness of the transparent conductive oxide layer 14 affects the sheet resistance and the color of the substrate. The lower layer 12 is used to adjust the color of an article having the transparent conductive oxide layer 14 at a specific thickness. This is done by specifying a first lower layer material and a second lower layer material, and then using a tool such as FILM STAR to specify the thickness of each lower layer material that provides the desired color. Once the first and second lower layer materials are specified, the thickness of each of these materials can be adjusted to achieve any desired color. Usually, the desired color has a*,b* values of -1,-1. Some variation is allowed in this color. For example, the a* value can be from a maximum of 1 to a minimum of -9, and the b* value can be from a maximum of 1 to a minimum of -9.

[0058] For example, it may be desired to create a solar cell having a color with a* = -1 and b* = -1. A glass substrate is provided. The transparent conductive oxide material can be specified as indium-doped tin oxide ("ITO"). It is understood that a sheet resistance of 5 Ω / sq to 25 Ω / sq can be achieved by the invention disclosed herein when the thickness of the ITO transparent conductive oxide film is between 125 nm and 275 nm. To achieve the desired color, the lower layer 12 can be selected to have a first lower layer film 20 containing zinc oxide and tin oxide, and a second lower layer film 22 containing silica and alumina. The thickness of the first lower layer film 20 is between 10 nm and 15 nm, and the thickness of the second lower layer film 22 is between 29 nm and 34 nm. The first lower layer film 20 is applied onto the substrate 10 at a specific thickness, and the second lower layer film 22 is applied onto the first lower layer film 20 at a specific thickness. The transparent conductive oxide layer 14 is applied onto the second lower layer film 22 at a specific thickness, and thus forms an article having a color with a* values of -9 to 1, specifically -4 to 0, more specifically -3 to 1, more specifically -1.5 to -0.5 and b* values of -9 to 1, specifically -4 to 0, more specifically -1.5 to -0.5.

[0059] In another example, a glass substrate 10 is provided. The transparent conductive oxide layer material can be identified as indium-doped tin oxide (“ITO”). It is understood that a sheet resistance of 5 Ω / sq to 25 Ω / sq, specifically 20 Ω / sq or less, more specifically 18 Ω / sq or less can be achieved if the thickness of the ITO transparent conductive oxide film is between 125 nm and 275 nm. To achieve the desired color, a lower layer 12 having a first lower layer film 20 containing zinc oxide and tin oxide, and a second lower layer film 22 containing silica is selected, and the influence of the protective layer 16 on the color of the coated substrate can also be considered. In this example, a protective layer of silica having a thickness of at least 30 nm and 45 nm or less is used. The thickness of the first lower layer film 20 is 10 nm to 15 nm, and the thickness of the second lower layer film 22 is 29 nm to 34 nm. The first lower layer film 20 is applied on the substrate 10 at a specific thickness, and the second lower layer film 22 is applied on the first lower layer film 20 at a specific thickness. The transparent conductive oxide layer 14 is applied on the second lower layer film 22 at a specific thickness that provides the above-described sheet resistance, thus forming a coated substrate having a color between a* -9 to 1, or -4 to 0, or -3 to 1, or -1.5 to -0.5 and b* -9 to 1, or -4 to 0, or -3 to 1, or -1.5 to -0.5.

[0060] In these examples, a lower layer is used to adjust the color of the coated substrate.

[0061] FIG. 2 shows another exemplary article 2 including a substrate 10, a lower layer 12 on the substrate, a transparent conductive oxide layer 14 on the lower layer 12, and an embedded film 24 including a second high refractive index material embedded in the transparent conductive oxide layer 14.

[0062] The substrate 10 can be any of the substrates discussed herein.

[0063] The lower layer 12 can have a first lower film 20 and an optional second lower film 22. The first lower film 20 has a first high refractive index material. The optional second lower film 22 has a first low refractive index material. The first high refractive index material has a higher refractive index than the first low refractive index material.

[0064] The transparent conductive oxide layer 14 can be any of the above-described transparent conductive oxides.

[0065] 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, nitride, or oxynitride. Examples of oxide materials suitable for the embedded film 24 include oxides of silicon, titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, tin, and / or their alloys and / or mixtures. For example, the embedded film 24 can include oxides of silicon and / or aluminum.

[0066] For example, the embedded film 24 can include an oxide of silicon and aluminum. According to this example, the second lower film 22 has at least 50% by volume of silica, 50 - 99% by volume of silica and 50 - 1% by volume of alumina, 60 - 98% by volume of silica and 40 - 2% by volume of alumina, 70 - 95% by volume of silica and 30 - 5% by volume of alumina, 80 - 90% by weight of silica and 10 - 20% by weight of alumina, or 8% by weight of silica and 15% by weight of alumina.

[0067] The embedded film 24 can have a thickness in the range of 5 nm to 50 nm, 10 - 40 nm, or 15 - 30 nm.

[0068] The article may optionally include a protective layer 16 on the transparent conductive oxide layer 14, for example, the protective layer described in this specification. 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 titania and silica. For example, the protective layer 16 includes a first protective film 60, a second protective film 62, and a third protective film 64.

[0069] Figure 3 shows another exemplary article 2 including a substrate 10, an underlying layer 12 on the substrate, a first transparent conductive oxide layer 114 on the underlying layer 12, and an embedded film 124 on the first transparent conductive oxide layer 114. A second transparent conductive oxide layer 115 on the embedded film 124. Optionally, a protective layer 16 can be applied on the second transparent conductive oxide layer 115.

[0070] The embedded film 124 can include a metal oxide, a nitride, or an oxynitride. Examples of materials suitable for the second high refractive index metal include oxides of silicon, titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc, bismuth, lead, indium, tin, and / or their alloys and / or mixtures. For example, the second high refractive index material can include silica and / or alumina.

[0071] For example, the embedded film 124 can include silica and alumina. The second high refractive index material has at least 50% by volume of silica, 50 - 99% by volume of silica and 50 - 1% by volume of alumina, 60 - 98% by volume of silica and 40 - 2% by volume of alumina, or 70 - 95% by volume of silica and 30 - 5% by volume of alumina, 80 - 90% by weight of silica and 10 - 20% by weight of alumina, or 8% by weight of silica and 15% by weight of alumina.

[0072] The embedded film 124 can have a thickness in the range of 5 nm to 50 nm, 10 - 40 nm, or 15 - 30 nm.

[0073] The first transparent conductive oxide layer 114 and the second transparent conductive oxide layer 115 have a total thickness in the range of 75 nm to 950 nm, such as 90 nm to 800 nm, such as 125 nm to 700 nm. For example, the combined thickness can be 950 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 350 nm, 300 nm, 275 nm, 250 nm, or 225 nm or less. The combined thickness can be at least 75 nm, at least 90 nm, at least 100 nm, at least 125 nm, 150 nm or 175 nm. The first transparent conductive oxide layer 114 can have a thickness of at least 10 nm, at least 25 nm, 50 nm, 75 nm or 100 nm and a maximum of 650 nm, 550 nm, 475 nm, 350 nm, 250 nm or 150. The second transparent conductive oxide layer 115 can have a thickness of at least 10 nm, at least 25 nm, 50 nm, 75 nm or 100 nm and a maximum of 650 nm, 550 nm, 475 nm, 350 nm, 250 nm or 150. For example, when the first transparent conductive oxide layer 114 and the second transparent conductive oxide layer 115 contain ITO, the first transparent conductive oxide layer 114 can have a thickness of at least 25 nm, 50 nm, 75 nm or 100 nm, and a maximum of 200 nm, 175 nm, 150 nm or 125 nm, and the second transparent conductive oxide layer 115 can have a thickness of at least 25 nm, 50 nm, 75 nm or 100 nm and a maximum of 200 nm, 175 nm, 150 nm or 125 nm. In another example, when the transparent conductive oxide layer 114 and the second transparent conductive oxide layer 115 contain AZO, the first transparent conductive oxide layer 114 can have a thickness of at least 100 nm, at least 150 nm, at least 200 nm, 250 nm or 300 nm, and a maximum of 650 nm, 550 nm, maximum 450 nm, maximum 325 nm or maximum 200 nm, and the second transparent conductive oxide layer 115 can have a thickness of at least 100 nm, at least 150 nm, at least 200 nm, 250 nm or 300 nm and a maximum of 650 nm, 550 nm, maximum 450 nm, maximum 325 nm or maximum 200 nm.In another example, when the transparent conductive oxide layer 114 and the second transparent conductive oxide layer 115 contain GZO, the first transparent conductive oxide layer 114 can have a thickness of 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 a maximum of 350 nm, a maximum of 300 nm, 275 nm, a maximum of 250 nm, or a maximum of 225 nm, and the second transparent conductive oxide layer 115 can have a thickness of 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 350 nm, a maximum of 300 nm, 275 nm, a maximum of 250 nm, or a maximum of 225 nm.

[0074] By varying the thicknesses of the first and second transparent conductive oxide layers 114, 115, the embedded film 124 is raised or lowered within the transparent conductive oxide layer 14. Surprisingly, the sheet resistance increases significantly (see FIG. 13a) regardless of where the embedded films 24, 124 are located within the coating stack. Also surprisingly, the position of the embedded films 24, 124 within the transparent conductive oxide layer 14 has a different effect on the light transmittance (see FIG. 13b). When the first transparent conductive oxide layer 114 is thinner than the second transparent conductive oxide layer 115, such that the embedded film 124 is at a lower position within the transparent conductive oxide layer 14, the light transmittance increases (see FIG. 13b). This increase is more pronounced when the first transparent conductive oxide layer 114 is thicker than the second transparent conductive oxide layer 115, such that the embedded film 124 is at a higher position within the transparent conductive oxide layer 14 (see FIG. 13b). However, when the thickness of the first transparent conductive oxide layer 114 is approximately equal to the thickness of the second transparent conductive oxide layer 115, such that the embedded film 124 is located approximately in the center of the transparent conductive oxide layer 14, the transmittance decreases (see FIG. 13b). For example, the second transparent conductive oxide film 115 can be at least 25%, at least 50%, at least 75%, at least 100% (i.e., at least 2 times), at least 125% or at least 150% thicker than the first transparent conductive oxide film 114, and up to 250%, up to 200%, up to 150%, up to 125%, up to 100% (i.e., up to 2 times), up to 75%, up to 50%, or up to 25% thicker than the first transparent conductive oxide film 114. Alternatively, the second transparent conductive oxide film 115 can be at least 25%, at least 50%, at least 75%, at least 100% (i.e., at least 2 times), at least 125% or at least 150% thinner than the first transparent conductive oxide film 114, and up to 250%, up to 200%, up to 150%, up to 125%, up to 100% (i.e., up to 2 times), up to 75%, up to 50%, or up to 25% thinner than the first transparent conductive oxide film 114.

[0075] Another example of the present invention is a method for manufacturing a coated article 2. A substrate 10 is provided. A first lower film 20 having a first high refractive index material is coated on at least a part of the substrate 10. A second lower film 22 having a first low refractive index material is coated on at least a part of the first lower film 20, and the first low refractive index material has a refractive index lower than that of the first high refractive index film. A first transparent conductive oxide film 114 is coated on at least a part of the lower layer 12. An embedded film 124 having a second high refractive index material is coated on at least a part of the first transparent conductive oxide film 114, and 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 the refractive index of the first high refractive index, 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 coated on at least a part 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.

[0076] The color of the coated substrate can also be adjusted by the embedded film 124. The color can have an a* of at least -9, -4, -3 or -1.5 and a maximum of 1, 0 or -0.5, and can have a b* of at least -9, -4, -3 or -1.5 and a maximum of 1, 0 or -0.5.

[0077] By changing the thicknesses of the two high refractive index materials and the low refractive index material, the color of the coated substrate can be adjusted. For this purpose, first, the materials used for the transparent conductive oxide films 114 and 115 should be specified. Once the materials are specified, the desired sheet resistance is specified. By knowing the materials and the sheet 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 affects the color of the coated substrate. To offset this color effect, an optical design tool (such as FILM STAR) can be used to specify the thicknesses of the first and second lower layer films 20 and 22, and the thicknesses of the embedded films 24, 124. This is done by inputting the thickness of the transparent conductive oxide layer 14 into the software and specifying the first high refractive index material, the second high refractive index material, and the first low refractive index material. Using these parameters, the thicknesses of the first and second lower layer films 20 and 24, and the embedded films 24, 124 can be determined. Next, these films are coated with these specified thicknesses.

[0078] For example, this method may include specifying a first transparent conductive oxide material used for the first transparent conductive oxide film 114 and a second transparent conductive oxide material used for the second transparent conductive oxide 115. These transparent conductive oxides can be GZO, AZO, IZO, MZO, or ITO.

[0079] The thickness of the transparent conductive oxide layer 14 can be determined by first specifying the desired sheet resistance. Once the sheet resistance is specified, the total thickness of both transparent conductive oxide films 114, 115 can then be determined. The sheet resistance can be at least 8 Ω / sq, at least 10 Ω / sq, or at least 12 Ω / sq, and up to 25 Ω / sq, up to 20 Ω / sq, or up to 18 Ω / sq. To achieve these values, the total thickness of the transparent conductive oxide layer 14 can be at least 75 nm, at least 90 nm, at least 100 nm, at least 175 nm, at least 180 nm, at least 190 nm, at least 200 nm, at least 205 nm, at least 225 nm, or at least 360 nm. Since 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. For this purpose, the combined thickness of the transparent conductive oxide films 114, 115 can be up to 800 nm, up to 700 nm, up to 360 nm, up to 350 nm, up to 300 nm, up to 275 nm, up to 250 nm, up to 225 nm, up to 205 nm, up to 200 nm, up to 190 nm, up to 180 nm, or up to 175 nm.

[0080] The positions of the embedded films 24, 124 within the transparent conductive oxide are also determined. By doing so, consideration is given to whether to increase or decrease the transmittance (see Fig. 13(b)). The first transparent conductive oxide film 114 can be thicker than, thinner than, or approximately the same thickness as the second conductive oxide film 115.

[0081] A first high refractive index material for the first lower film 20, a first low refractive index material for the second lower film 22, and a second high refractive index material for the embedded films 24, 124 are specified. Optionally, the protective layer 16 may be specified with a thickness specified for each of the protective layer films 60, 62 and / or 64. A desired color is specified. These parameters are input into an optical design tool such as FILM STAR, and the thicknesses of the first lower film 20 and the lower film 22 and the embedded film 124 are specified.

[0082] A coating stack having a lower layer 12, a transparent conductive oxide layer 14, embedded films 24, 124 and an optional protective layer 16 is applied onto a substrate with a specified thickness. The thicknesses of the lower films 20, 22 and the embedded films 24, 124 adjust the color of the article 2 to a desired color.

[0083] Figures 4a and 4b show another exemplary article 2 including a substrate 10, a lower layer 12 on the substrate 10, a transparent conductive oxide layer 14 on the lower layer 12, and a protective layer 16 on the transparent conductive oxide layer 14. The substrate 10, the lower layer 12, and the transparent conductive oxide layer 14 can be any of the substrates or lower layers discussed herein. The transparent conductive oxide layer 14 can be divided by the embedded layers 24, 124 described herein.

[0084] The protective layer 16 is on top of the transparent conductive oxide layer 14 or optionally in direct contact with the transparent conductive oxide layer 14. It can include at least two protective films 60, 62 or at least three protective films 60, 62, 64.

[0085] Figure 4a shows an example of an article having a protective layer with two protective films 60, 62. The first protective film 60 is located on 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 of the coating 18 on the coated article.

[0086] The first protective film 60 can include alumina, silica, titania, zirconia, tin oxide, or a mixture thereof. For example, the first protective film can include a mixture of silica and alumina. In another example, the first protective film 60 can include zinc stannate. In another example, the first protective film 60 can include zirconia.

[0087] The second protective film 62 includes a mixture of titania and alumina. The second protective film 62 is the final film of the coating 18 applied on the substrate 10.

[0088] The second protective film 62 includes 40 - 60 weight percent alumina and 60 - 40 weight percent titania, 45 - 55 weight percent alumina and 55 - 45 weight percent titania, 48 - 52 weight percent alumina and 52 - 48 weight percent titania, 49 - 51 weight percent alumina and 51 - 49 weight percent titania, or 50 weight percent alumina and 50 weight percent titania.

[0089] As shown in FIG. 4b, the protective layer 16 may further include a third protective film 64 disposed between the first protective film 60 and the second protective film 62. The third protective film 64 can include alumina, silica, titania, zirconia, tin oxide, or a mixture thereof. For example, the third protective film 64 can include a mixture of silica and alumina. In another example, the third protective film 64 includes zinc stannate. In another example, the third protective film 64 includes zirconia.

[0090] Another exemplary article is shown in FIGS. 5a and 5b and includes a substrate 10, a functional coating 112, and a protective layer 16. The substrate in this method can be glass, plastic, or metal.

[0091] The functional coating 112 can be any functional coating. For example, it can include a plurality of dielectric films or a plurality of metal films. The functional coating can include the underlying layer 12 described herein and / or the transparent conductive oxide layer 14 described herein. The protective layer 16 can be the first protective film 60 and the second protective film 62 as described herein. In this case, the second protective film 62 is the outermost film and includes alumina and titania.

[0092] The protective layer can have a total thickness of at least 20 nm, 40 nm, 60 nm, or 80 nm, 100 nm or 120 nm and a maximum of 275 nm, 255 nm, 240 nm, 170 nm, 150 nm, 125 nm or 100 nm. The first protective film can 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 a maximum of 85 nm, 70 nm, 60 nm, 50 nm, 45 nm, 30 nm. The second protective film can 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 a maximum of 85 nm, 70 nm, 60 nm, 50 nm, 45 nm, 30 nm. The optional third protective film can 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 a maximum of 85 nm, 70 nm, 60 nm, 50 nm, 45 nm, 30 nm. For example, the protective layer can have the thicknesses listed in Table 1 below. In one embodiment, the first protective film has a thickness of at least 20 nm or at least 30 nm and a maximum of 60 nm or maximum 50 nm. The second protective film has a thickness of at least 15 nm, or at least 20 nm and a maximum of 50 nm or maximum 40 nm. The optional third protective layer has a thickness of at least 5 nm, or at least 10 nm and a maximum of 30 nm or maximum 20 nm. The optional third protective layer may be disposed between the first protective film and the functional layer, or between the first protective film and the second protective film.

Table 1

[0093] The functional coating 112 can be a single-film functional coating or a multi-film functional coating including one or more dielectric layers and / or one or more infrared reflective layers.

[0094] The functional coating 112 can be, for example, a solar control coating. The term "solar control coating" refers to a coating composed of one or more layers or films that affect the solar characteristics of the coated article, such as, but not limited to, the amount of solar radiation, such as visible, infrared, or ultraviolet radiation, reflected from, absorbed by, or passing through the coated article, the shading coefficient, the emissivity, etc. A solar control coating can block, absorb, or filter a selected portion of the solar spectrum, such as, but not limited to, the IR, UV, and / or visible spectrum.

[0095] The functional coating 112 can include, for example, one or more dielectric films. The dielectric film can include an anti-reflective material including, but not limited to, metal oxides, oxides of metal alloys, nitrides, oxynitrides, or mixtures thereof. The dielectric film can be transparent to visible light. Examples of metal oxides suitable for the dielectric film include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, and mixtures thereof. These metal oxides can have small amounts of other materials, such as manganese in bismuth oxide, tin in indium oxide, etc. Further, oxides of metal alloys or metal mixtures such as oxides containing zinc and tin (e.g., zinc stannate as defined below), indium-tin alloys, silicon nitride, aluminum silicon nitride, or oxides of aluminum nitride can be used. Further, doped metal oxides such as antimony or indium doped tin oxide or nickel or boron doped silicon oxide can be used. The dielectric film can be a substantially single-phase film, such as a metal alloy oxide film such as zinc stannate, or can be a mixture of phases composed of zinc oxide and tin oxide, or can be composed of multiple films.

[0096] The functional coating 112 can include a radiation-reflective film. The radiation-reflective film can include, but is not limited to, reflective metals such as the metals gold, copper, palladium, aluminum, silver, or mixtures thereof. In one embodiment, the radiation-reflective film includes a silver layer of metal.

[0097] In one embodiment, the functional coating includes a first dielectric layer 120 on the substrate 10, a second dielectric layer 122 on the first dielectric layer 120, and a metal layer 126 between the first dielectric layer and the second dielectric layer 120 (see FIGS. 7a and 7b) or on the second dielectric layer 122 (see FIG. 6a). The protective coating 16 is disposed on the metal layer 126 (see FIG. 6b). Optionally, a primer 128 may be applied between the metal film and the first dielectric layer (see FIG. 6c) or the second dielectric layer (see FIG. 6d).

[0098] The dielectric films 120 and 122 can be transparent to visible light. Examples of metal oxides suitable for the dielectric films 120 and 122 include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, and mixtures thereof. These metal oxides can have small amounts of other materials, such as manganese in bismuth oxide, tin in indium tin oxide, etc. Further, oxides of metal alloys or metal mixtures such as oxides containing zinc and tin (e.g., zinc stannate as defined above), indium-tin alloys, silicon nitride, aluminum silicon nitride, or oxides of aluminum nitride can be used. Further, doped metal oxides such as antimony- or indium-doped tin oxide or nickel- or boron-doped silicon oxide can be used. The dielectric films 120 and 122 can be substantially single-phase films such as metal alloy oxide films such as zinc stannate, or can be mixtures of phases composed of zinc oxide and tin oxide. The dielectric films 120 and 122 can have a total thickness in the range of 100 Å to 600 Å, such as 200 Å to 500 Å, such as 250 Å to 350 Å.

[0099] The metal film 126 may be selected from the group consisting of the metals gold, copper, palladium, aluminum, silver, and alloys thereof. For example, the metal film 126 can be silver.

[0100] The optional primer 128 can be a single film or multiple films. For example, the primer 128 can include an oxygen scavenging material that can be sacrificed during the deposition process to prevent degradation or oxidation of the metal film 126 during a sputtering process or a subsequent heating process. The primer 128 can also absorb at least a portion of electromagnetic radiation such as visible light passing through the coating. Examples of materials useful 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 Stellite (registered trademark)), and mixtures thereof. For example, the primer 148 can be titanium.

[0101] The protective layer 16 can include a first protective film 60 and a second protective film 62, or a first protective film 60 (see FIGS. 5a and 6a - 6d), a second protective film 62, and a third protective film 64 (see FIGS. 5b and 6e - 6h).

[0102] In the method for manufacturing a coated article, an underlayer 12 is applied on a substrate 10, and a transparent conductive oxide layer 14 is applied on the underlayer 12. The undercoating 12 can be applied on the substrate 10, the transparent conductive oxide layer 14 can be applied on at least a part of the underlayer 12, or a substrate 10 having the undercoating 12 and the transparent conductive oxide layer 14 provided thereon can be provided. A protective layer 16 is applied on at least a part of the transparent conductive oxide. The protective layer 16 is applied by first applying a first protective film 60 on the transparent conductive oxide and then applying a second protective film 62 on the first protective film 60. Optionally, a third protective film 64 can be applied on the first protective film 60 and the second protective film 62 can be applied on the third protective film 64.

[0103] In the method for manufacturing a coated article, a functional coating 112 is applied on a substrate 10. The functional coating 112 can be applied on the substrate 10, or a substrate having the functional coating 112 can be provided. A protective layer 16 is applied on the functional coating 112. The protective layer 16 is applied by first applying a first protective film 60 on the transparent conductive oxide and then applying a second protective film 62 on the first protective film 60. Optionally, a third protective film 64 can be applied on the first protective film 60 and the second protective film 62 can be applied on the third protective film 64.

[0104] Another exemplary method of the present invention is a method for 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 on at least a part of the substrate. The coated article is processed in a post-deposition process.

[0105] The post-deposition process can include annealing the coated article, flash annealing only the surface of the transparent conductive oxide layer, or passing an eddy current through the transparent conductive oxide layer.

[0106] The coated article is annealed by heating the entire article such that the surface of the transparent conductive oxide layer reaches 380°F, at least 435°F or at least 635°F for at least 5, 10, 15, 20, 25, or 30 seconds and a maximum of 120, 90, 60, 55, 50, 45, 40, 35, or 30 seconds. The transparent conductive oxide layer should not be heated to above 635°F or above 806°F. After the coated article is heated, it is rapidly cooled to room temperature at a specific rate.

[0107] The coated article can be flash annealed to increase sheet resistance. This is done by using a flash lamp to heat the surface of the coated article. The surface to be heated is the surface where the transparent conductive oxide layer is present. The surface is heated to a temperature above 380°F, at least 435°F or at least 635°F for at least 5, 10, 15, 20, 25, or 30 seconds and a maximum of 120, 90, 60, 50, 55, 45, 40, 35, or 30 seconds. The surface should be heated to 968°F or below, 878°F or below, 806°F or below, or 635°F or below. After the surface is heated, it is cooled to room temperature.

[0108] Eddy currents can be passed through a transparent conductive oxide (「TCO」) by exposing the transparent conductive oxide layer to a changing magnetic field. For example, a magnetic field can be applied to a substrate coated with TCO. The TCO faces the magnetic field. The eddy currents pass through the transparent conductive oxide layer.

[0109] Another exemplary method is a method for reducing the sheet resistance of a coated article. A substrate is provided. The substrate in this method can be glass, plastic or metal. Optionally, the substrate is coated with an underlayer. The underlayer can include one film, two films, or more. The substrate is coated with a transparent conductive oxide by applying the transparent conductive oxide over at least a portion of the substrate or the underlayer. Optionally, an embedded film is applied within the transparent conductive oxide layer. This optional step is performed by applying a first portion of the 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 processed in one of the post-deposition processes described above.

[0110] Optionally, the method may further include applying a protective layer over at least a portion of the transparent conductive oxide layer, as described herein. The protective layer can have two protective films or three protective films.

[0111] By processing the article in a post-deposition process, the sheet resistance of the article is reduced to less than 25 ohms per square, less than 20 ohms per square, less than 18 ohms per square, less than 16 ohms per square, or less than 15 ohms per square. This is particularly useful for reducing the thickness of the TCO. For example, AZO can have a thickness of less than 400 nm or greater than 320 nm and greater than 160 nm. AZO should have a thickness of less than 344 nm and greater than 172 nm. ITO should have a thickness of less than 275 nm or less than 175 nm and greater than 95 nm.

[0112] An exemplary embodiment is a method of manufacturing a coated glass article in which a glass substrate is provided. Preferably, an undercoat is applied onto the glass substrate by a magnetron sputter vacuum deposition or process, or some other process that does not use radiant heat, or the undercoat is applied onto the substrate at room temperature. Preferably, the undercoat includes two films, the first film includes zinc oxide and tin oxide, and the second film includes silica and titania. The transparent conductive oxide is preferably applied onto the undercoat by a magnetron sputter vacuum deposition process, or some other process that does not use radiant heat, or the transparent conductive oxide is applied onto the undercoat at room temperature. Preferably, the transparent conductive oxide is indium tin oxide. The optional protective layer is preferably applied onto the transparent conductive oxide by a magnetron sputter vacuum deposition or process, or some other process that does not use radiant heat, or the optional protective layer is applied onto the transparent conductive oxide at room temperature. The absorption of the transparent conductive oxide is 0.2 or less and / or is at least about 0.05 high.

[0113] In an exemplary embodiment, the article is a refrigerator door. The refrigerator door is processed in a post-deposition process at any point prior to assembly, sufficiently after the metal on the outside of the door has been coated. Typically, the refrigerator door is heated and can be bent into a shape that properly fits the coated article onto the door. This heating process causes the transparent conductive oxide to crystallize and reduces the sheet resistance.

[0114]

Examples

[0115] It will be readily understood by those skilled in the art that modifications may be made to the present invention without departing from the concepts disclosed in the foregoing description. Accordingly, the specific embodiments described in detail herein are illustrative only and not limiting of the scope of the present invention, which should be given the full scope of the appended claims and all equivalents thereof.

[0116] [Example 1](010761)

[0117] A glass substrate was coated with a lower layer and a transparent conductive oxide layer. The lower layer had a first lower layer film and a second lower layer film. The first lower layer film was zinc stannate on the glass substrate, and the second lower layer film was a silica-alumina alloy having about 85 weight percent silica and 15 weight percent alumina on the first lower layer film. The transparent conductive oxide layer on the second lower layer film was tin-doped indium oxide ("ITO").

[0118] To improve the conductivity of the coated article, the whole article was put into a furnace and the temperature of the transparent conductive oxide layer was measured (see FIGS. 7a and 7b).

[0119] The following samples were tested to establish the improvement in conductivity for each thickness of ITO. [Table 2]

[0120] As can be seen from FIGS. 7a and 7b, heating after deposition of ITO reduced the sheet resistance from about 55 - 70 Ω / sq to about 10 - 25 Ω / sq regardless of the thickness. When the thickness of ITO was at least 96.8 nm, the sheet resistance was less than 25 Ω / sq regardless of the heating temperature. When the thickness of ITO was at least 109.2, the sheet resistance when the ITO surface reached 968°F was less than 20 Ω / sq. At about 127.9 nm, the sheet resistance of ITO when heated at any temperature was less than 20 Ω / sq. The improvement in sheet resistance was unexpected. Similar results were obtained with other transparent conductive oxides, and it was shown that regardless of the transparent conductive oxide, the temperature should be above 380°F, at least 435°F, or 806°F or less.

[0121] As shown in FIGS. 8a - c, the crystallinity of the ITO layer increased due to heating after deposition. The samples tested are listed in Table 3 below.

Table 3

[0122] By concentrating on the minimum surface temperature necessary to increase the crystallization of ITO, energy can be saved and significant benefits can be obtained.

[0123] [Example 2]

[0124] A glass substrate was coated with a transparent conductive oxide layer. The transparent conductive oxide was gallium-doped zinc oxide (“GZO”). Several samples with different thicknesses of GZO were prepared, and the sheet resistance of the samples was measured to compare the effect of the post-deposition treatment with the sheet resistance of GZO immediately after deposition. 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. 9. The thickness and sheet resistance of the sample tests are shown in Table 4 below.

Table 4

[0125] As shown in FIG. 9, post-deposition flash annealing of GZO improved the sheet resistance at all thicknesses tested. This improvement was most significant when the thickness of GZO was about 320 - 480 nm. When the thickness of the GZO layer was about 320 nm, the “as-deposited” GZO layer provided a sheet resistance of 35.6 Ω / □, but after heat treatment, the sheet resistance was 12.7 Ω / □. At this thickness, this is important because flash annealing reduced the sheet resistance to an acceptable range, whereas without flash annealing, the sheet resistance was unacceptably high.

[0126] Similar results were observed when the thickness of GZO was 480 nm. The sheet resistance of the “as-deposited” GZO sample was about 21.8 Ω / □, and the heat-treated sample was 7.8 Ω / □.

[0127] The difference in sheet resistance decreases when the thickness of GZO is very thick. For example, at about 950 nm, the sheet resistance of the GZO sample "immediately after deposition" was about 8 Ω / sq, while the sheet resistance of the flash-annealed sample was about 5 Ω / sq. In this case, the sheet resistance of both samples was sufficiently low.

[0128] Therefore, as shown in FIG. 9, for samples using GZO as the transparent conductive oxide, the thicknesses that result in the highest and maximum differences in sheet resistance are such that the GZO layer has a thickness of at least 300 nm and a maximum of 500 nm.

[0129] Heat treatment reduces the thickness of the transparent conductive oxide layer required to reach an acceptable sheet resistance. If no post-deposition treatment is performed, it is necessary to apply GZO to at least 550 nm before the sheet resistance becomes less than 20 Ω / sq. By heating, a thinner GZO layer can be applied. This not only reduces the manufacturing cost of the appropriate coated article but also reduces the impact of GZO on the optics and color of the coated article.

[0130] This is a surprising discovery and provides a cost-effective approach for improving the sheet resistance of thinner transparent conductive oxide layers.

[0131] [Example 3]

[0132] The glass substrate was coated with an aluminum-doped zinc oxide ("AZO") transparent conductive oxide layer. Several samples with different thicknesses of AZO were prepared, and the sheet resistance of the samples was measured to compare the effect of the post-deposition treatment with the sheet resistance of AZO immediately after deposition. The post-deposition process included putting the coated article into a furnace. The sheet resistance of each sample was tested before and after flash annealing, and the results are shown in FIG. 10. The thicknesses and sheet resistances of the sample tests are shown in Table 5 below.

Table 5

[0133] As shown in Figure 10, the sheet resistance of all thicknesses tested was improved by post-deposition heating of AZO. This improvement was most significant when the AZO thickness was approximately 344 - 860 nm. When the AZO layer thickness was 344 nm, the "as-deposited" AZO layer provided a sheet resistance of approximately 78.3 Ω / sq, but after heat treatment, the sheet resistance was 19.5 Ω / sq. This is important because heating at this thickness reduces the sheet resistance within an acceptable range, whereas without heating, the sheet resistance was unacceptably high.

[0134] Similar results were observed when the AZO thickness was 860 nm. The sheet resistance of the "as-deposited" AZO sample was approximately 26.6 Ω / sq, and that of the heat-treated sample was approximately 7.1 Ω / sq.

[0135] The difference in sheet resistance decreases when the AZO thickness is very thick. For example, at approximately 1050 nm, the sheet resistance of the "as-deposited" AZO sample was approximately 17.0 Ω / sq, and that of the heat-treated sample was 3.9 Ω / sq. In this case, the sheet resistance of both samples was sufficiently low.

[0136] Therefore, as shown in Figure 10, for samples using AZO as the transparent conductive oxide, the thicknesses that result in the highest and greatest differences in sheet resistance are when the AZO layer is at least 344 nm and at most 860 nm thick.

[0137] Heating also reduces the thickness of the transparent conductive oxide layer required to reach an acceptable sheet resistance. Without post-deposition treatment, it is necessary to apply AZO to at least 1032 nm before the sheet resistance becomes less than 20 Ω / sq. By heating, a thinner AZO layer can be applied. This not only reduces the manufacturing cost of the appropriate coated article but also reduces the impact of AZO on the optics and color of the coated article.

[0138] This is a surprising discovery and provides a cost-effective approach to improving the sheet resistance of thinner transparent conductive oxide layers.

[0139] [Example 4]

[0140] Using FILM STAR, various thicknesses of the underlying layer were tested to determine which thickness would provide an acceptable color or neutral color. A glass substrate having an underlying layer and a transparent conductive oxide was used. The underlying layer had a first film and a second film. The first underlying film was zinc stannate on the glass substrate, and the second underlying film was a silica-alumina alloy having about 85 weight percent silica and 15 weight percent alumina on the first underlying film. The transparent conductive oxide layer on the second underlying film was a 170 nm thick tin-doped indium oxide ("ITO") layer.

[0141] First, the desired sheet resistance was determined. In this example, the desired sheet resistance was about 10 Ω / sq to 15 Ω / sq. To achieve this sheet resistance, it was determined that the thickness of the transparent conductive oxide layer should be about 170 nm.

[0142] Using FILM STAR, the materials and thicknesses of the glass and the transparent conductive oxide layer were input. Next, the materials of the first underlying film and the second underlying film were determined. In this example, the first underlying film material was zinc stannate, and the second underlying film material was a silica-alumina alloy having 85 weight percent silica and 15 weight percent alumina. The following coatings were analyzed by FILM STAR (see Table 6 and Figure 11). The thickness of the first underlying layer was initially in the range of 8 nm to 17 nm for the samples, and the thickness of the second underlying film was in the range of 27 nm to 35 nm.

Table 6

[0143] As shown in Fig. 11, when the thickness of the first lower layer film was 13 nm and the thickness of the second lower layer film was 31 nm, a neutral color with a* and b* of -1, -1 was obtained. Acceptable colors with a* between -3 and 1 and b* between -3 and 1 were obtained when the first lower layer film had a thickness of 11 nm to 15 nm and the second lower layer film had a thickness of 29 nm to 33.5 nm.

[0144] [Example 5]

[0145] Using FILM STAR, various thicknesses of the transparent conductive oxide layer were tested to determine the appropriate thickness of the lower layer. In this example, the FILM STAR parameters included a glass substrate coated with a lower layer having a first lower layer film and a second lower layer film. The first lower layer film was zinc stannate, and the second lower layer film was silica. The transparent conductive oxide layer on the second lower layer film was indium tin oxide (「ITO」). A silica protective layer was on the ITO layer. Table 7 and Fig. 12 show the tested samples. Table 7 shows the values input into FILM STAR for the ITO layer and the SiO 2 layer. The output provided the thicknesses of the two lower layer films that provided a -1, -1 (a*, b*) color.

Table 7

[0146] These samples show that when the thickness of the transparent conductive oxide layer is 175 nm to 225 nm and the thickness of the protective coating is 30 nm, the thickness of the first lower layer film should be at least 10 nm and at most 15 nm, and the thickness of the second lower layer film should be at least 28 nm and at most 36 nm in order to achieve a color of approximately -1, -1 (a*, b*). The samples also show that when the transparent conductive oxide layer has a thickness of 175 nm to 225 nm and the protective layer has a thickness of 45 nm, the thickness of the first lower layer film should be at least 11 nm and at most 14 nm, and the thickness of the second lower layer film should be at least 32 nm and at most 38 nm in order to achieve an appropriate color.

[0147] Figure 12 shows the ideal thickness for a color of -1, -1. While -1, -1 is desirable, other colors such as the colors enclosed in Figure 11 (i.e., a* ranges from -3 to 1 and b* ranges from -3 to 1) are also acceptable.

[0148] [Example 6]

[0149] The effects of the embedded films were 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 120 nm, 180 nm, or 240 nm. An embedded film was applied on top of the bottom transparent conductive oxide layer. The embedded film was a zinc stannate film with a thickness of 15 nm or 30 nm. An upper transparent conductive oxide film was applied on top of the embedded film. The upper transparent conductive oxide film was ITO and had a thickness of 240 nm, 180 nm, or 120 nm. The total thickness of the bottom and upper transparent conductive oxide films was 360 nm. As a control, ITO oxide was applied on the substrate with a thickness of 360 nm, but no embedded film was included. The sheet resistance and transmittance at 550 nm were measured for the samples. The samples are listed in Table 8 and Figure 13 below.

Table 8

[0150] As shown in Fig. 13a, the experimental samples A - F had at least a 35% improvement in sheet resistance compared to the control sample G. Samples A and B had at least a 40% improvement in sheet resistance compared to sample G. Samples C and D had at least a 35% improvement in sheet resistance compared to sample G. Samples E and F had at least a 37% improvement in sheet resistance compared to sample G.

[0151] Based on this data, the embedded film significantly and surprisingly reduces the sheet resistance of the transparent conductive oxide layer regardless of its position or thickness.

[0152] As shown in Fig. 13b, samples E and F resulted in the largest increase in transmittance. Samples A and B showed a small improvement. Thus, by changing the thickness of the upper and lower transparent conductive oxide layers, the amount of light transmission can be increased. Furthermore, surprisingly, when the upper transparent conductive oxide layer is thinner than the bottom layer, and thereby the embedded layer is closer to the upper surface of the transparent conductive oxide layer rather than the bottom of the transparent conductive oxide layer, a significant increase in transmittance was found. In contrast, when the upper and lower transparent conductive oxide layers are approximately equal, the light transmittance unexpectedly decreases.

[0153] Fig. 13c shows that the embedded film also affects the crystallinity of the transparent conductive oxide. From this XRD data, it can be seen that the degree of crystallinity is unexpectedly improved by having the embedded film.

[0154] [Example 7]

[0155] In this example, various protective layers were examined. The protective layer was disposed on a glass substrate. The coated article included an aluminum-doped zinc oxide transparent conductive oxide between the substrate and the protective layer. It is not expected that the lower layer, the functional layer, or the transparent conductive oxide layer will not affect the observed results.

[0156] The glass substrates were different protective layers. Samples 1 to 3 had a protective layer including a single film. A list of these samples is shown in Table 9.

Table 9

[0157] Samples 5 to 11 had a protective layer including a first protective film and a second protective film on the first protective film. A list of these samples is shown in Table 10. The first film was closer to the substrate than the second film, and the second film was the outermost film.

Table 10

[0158] Samples 12 to 15 had a protective layer including three films. A list of these samples is shown in Table 11. The first film was closer to the substrate than the second or third film. For consistency with the other figures and descriptions above, the second protective film was the outermost film, and the third protective film was disposed between the first film and the third film.

Table 11

[0159] The durability of these samples was tested using the ASTM Cleveland Condensation test. As shown in FIGS. 14 and 15, the protective film having TiAlO in the outermost layer exhibited the highest performance. These figures show the dEcmc of Samples 1 to 15 listed in Tables 9 to 11.

[0160] Specifically, FIG. 14 shows that the durability of the samples with two or three protective films where the outermost film is TiAlO was unexpectedly excellent. Specifically, Sample 6 (SiAlO / TiAlO), Sample 7 (SnZn / TiAlO), and Sample 13 (SnZn / SiAlO / TiAlO). FIG. 15 further shows that the protective layer having titania and alumina as the outermost layer provided unexpectedly greater durability. In FIG. 15, Sample 19 (ZrO 2 / SiAlO / TiAlO) and Sample 20 (SiAlO / ZrO 2 / TiAlO) show unexpectedly excellent durability compared to the other three-film protective layer samples (Samples 16, 17, 18, and 21).

[0161] This data shows the unexpected result that the outermost protective film of titania-alumina significantly improves durability.

[0162] [Example 8]

[0163] Samples containing transparent conductive oxides sputtered in various atmospheres were tested. As shown in FIGS. 16 - 20, the glass substrates were coated with indium-doped tin oxide ("ITO") or aluminum-doped zinc oxide ("AZO") by magnetron sputter vacuum deposition (MSVD). The ITO samples were sputtered in an atmosphere containing 0%, 0.5%, 1%, 1.5%, or 2% oxygen and then heat-treated. The AZO samples were sputtered in an atmosphere containing 0%, 1%, 2%, 3%, 4%, 5%, or 6% oxygen and then heat-treated. The remaining atmosphere was argon. The ITO samples had an ITO thickness of either 225 nm, 175 nm or 150 nm, and the AZO samples had a thickness of AZO from 300 nm to 350 nm coated on the substrate. The samples were tested to determine emissivity, absorbance, and / or sheet resistance. (Emissivity is a measure of conductivity.) These samples were heat-treated by placing the coated article in a furnace for a certain period of time such that the transparent conductive oxide surface of the sample reached at least 435°F for about 30 seconds.

[0164] When coating a transparent article with a transparent conductive oxide, a low absorbance and low sheet resistance (corresponding to emissivity) article is desired. FIG. 16 shows that absorption decreases when oxygen is added to the atmosphere. However, as shown in FIG. 17, when the oxygen in the atmosphere is 0%, the emissivity / sheet resistance of the article is the highest. Using FIGS. 16 and 17, an ideal balance of absorption and emissivity can be obtained when there is 0.75% to 1.25% oxygen in the sputtering atmosphere. As shown in FIG. 17, when the atmosphere has less than 2.0% oxygen, the sheet resistance of the heat-treated article coated with ITO is lower than that of the non-heated article coated with ITO. When the atmosphere is 1.5% oxygen, the sheet resistance increases significantly. Extrapolating from this data, it was concluded that the atmosphere in the coating chamber must have 1.5% or less oxygen, preferably 1.25% or less. To somewhat reduce the absorption of the ITO-coated article, the atmosphere needs to contain at least 0.5% oxygen, preferably at least 0.75% oxygen.

[0165] [Example 9]

[0166] The glass substrate was coated with an aluminum-doped zinc oxide layer by a magnetron sputtering vacuum deposition (「MSVD」) process. The target was a ceramic aluminum-doped zinc oxide containing a certain amount of oxygen. When using the MSVD process to deposit materials such as transparent conductive oxides, the ceramic raw material may dissociate during the process and part of the oxygen may escape. In order to ensure that the deposited material is oxidized, oxygen is often supplied to the coating chamber together with an inert gas. In this example, AZO was deposited by MSVD in a coating chamber with an oxygen content of 0%, 1%, 2%, 3%, 4%, 5%, or 6% supplied to the chamber. The remaining atmosphere supplied to the coating chamber was argon, although any inert gas could be used. The normalized absorption of the coating was determined. As shown in Figure 18, the normalized absorption at 550 nm was optimal when 0% oxygen was supplied to the coating chamber. When 1% oxygen was supplied to the coating chamber, it was acceptable. Based on the data shown in Figure 18, it is estimated that less than 0.5% oxygen in the coating chamber provides significantly better absorption than when using 1% oxygen.

[0167] As shown in Figure 19, the normalized absorption has a sharp decrease from 0% oxygen to 1% oxygen and a minimal decrease from 1% oxygen to 2% oxygen. This data further supports the conclusion, by extrapolation, that less than 1% oxygen, less than 0.5% oxygen, less than 0.25% oxygen, less than 0.1% oxygen, or 0% oxygen supplied to the coating chamber provides the best absorption.

[0168] [Example 10]

[0169] One problem with heating after deposition of a coated article is the amount of energy that is wasted. As described above, post-deposition heating of a transparent conductive oxide (TCO) layer provides improved performance at a smaller thickness. When a coated article is placed in a furnace that heats the entire article, energy is wasted that exceeds the temperature required for crystallization of the TCO layer. To determine the surface temperature required to improve the performance of the transparent conductive oxide layer, indium-doped tin oxide with a thickness of 115 nm or 171 nm was coated on a glass substrate. The surface of the ITO layer of the sample was heated to the temperatures described in Tables 12 and 13. For this experiment, the surface was heated by placing the entire coated article in a furnace, but a flash lamp could also be used instead.

[0170] After post-deposition heating of the surface, the sheet resistance of each sample was measured (see Figure 21, Tables 12 and 13). The results indicate that at about 435°F, the sheet resistance of the layer is the lowest. Furthermore, the sheet resistance did not further decrease even when the surface was heated. 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 exceed 380°F, at least 435°F, 435°F - 806°F, 435°F - 635°F, or 435°F.

Table 12

Table 13

[0171] The present invention is further described in the following numbered paragraphs.

[0172] A coated article comprising a substrate, an underlying layer on the substrate, and a transparent conductive oxide layer on the underlying layer, wherein the underlying layer comprises a first underlying film (the first underlying film comprising a high refractive index material) and a second underlying film on the first layer (the second layer comprising a low refractive index material).

[0173] Item 2. A coated article according to Item 1, wherein the high refractive index material comprises zinc oxide and tin oxide.

[0174] Item 3. A coated article according to Item 1 or 2, wherein the low refractive index material comprises silica and alumina.

[0175] Item 4. A coated article according to any one of Items 1 to 3, wherein the transparent conductive film comprises tin-doped indium oxide.

[0176] Item 5. A coated article according to any one of Items 1 to 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.

[0177] Item 6. A coated article according to any one of Items 1 to 5, wherein the transparent conductive oxide layer has a maximum thickness of 350 nm, particularly a maximum thickness of 300 nm, particularly a maximum thickness of 275 nm, particularly a maximum thickness of 250 nm, more particularly a maximum thickness of 225 nm.

[0178] Item 7. A 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 per square, particularly 5 to 20 ohms per square, more particularly 8 to 18 ohms per square, more particularly 5 to 15 ohms per square.

[0179] Item 8. A coated article according to any one of Items 1 to 7, wherein the first lower film has a first lower thickness, the second lower film has a second lower thickness, and the coated article has a color having an a* of 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, and a b* of 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.

[0180] Item 9. A coated article according to any one of Items 1 to 8, wherein the high refractive index material contains zinc oxide.

[0181] Item 10. A coated article according to any one of Items 1 to 9, further comprising a protective layer on the transparent conductive oxide layer, the protective layer including a first protective film and a second protective film on at least a part of the first protective film, the second protective film being the outermost film, and the second protective film containing titania and alumina.

[0182] Item 11. A coated article according to Item 10, wherein the first protective film contains titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the first protective film does not contain a mixture of titania and alumina.

[0183] Item 12. A coated article according to Item 9 or 10, wherein the second protective film contains 35 to 65 wt% of titania, particularly 45 to 55 wt% of titania, more particularly 50 wt% of titania.

[0184] Item 13. A coated article according to any one of Items 10 to 12, wherein the second protective film contains 65 to 35 wt% of alumina, particularly 55 to 45 wt% of alumina, more particularly 50 wt% of alumina.

[0185] Item 14. A coated article according to any one of Items 10 to 13, further comprising a third protective film that is on at least a part of the first protective film and is located between the first protective film and the second protective film or between the first protective film and the functional coating, the third protective film comprising titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the third protective film does not contain a mixture of titania and alumina.

[0186] Item 15. A method of adjusting the color of a coated substrate, comprising providing a substrate, specifying a transparent conductive oxide of a transparent conductive oxide layer and a thickness of the transparent conductive oxide layer that provides a sheet resistance of at least 5 Ω / sq and at most 25 Ω / sq (especially at most 20 Ω / sq, more specifically at most 18 Ω / sq), specifying a first underlayer material and a first underlayer thickness and a second underlayer material and a second underlayer thickness for a first underlayer film that provides a color having a* of -9 to 1, especially -4 to 0, more specifically -3 to 1, more specifically -1.5 to -0.5 and b* of -9 to 1, especially -4 to 0, more specifically -3 to 1, more specifically -1.5 to -0.5 on the coated substrate having the transparent conductive oxide with the transparent conductive layer thickness, applying the first underlayer film having the first underlayer thickness on at least a part of the substrate, applying a second underlayer film having the second underlayer thickness on at least a part of the first underlayer film, and applying a transparent conductive oxide layer on the transparent conductive oxide with the transparent conductive layer thickness on at least a part of the underlayer.

[0187] Item 16. The method of Item 15, wherein the transparent conductive oxide is indium tin oxide.

[0188] Item 17. The method of Item 15 or 16, wherein the thickness of the transparent conductive layer is at least 125 nm (especially at least 150 nm, more specifically at least 175 nm) and at most 950 nm (especially 500 nm, more specifically 350 nm, more specifically 225 nm).

[0189] Item 18. The method according to any one of Items 15 to 17, wherein the first lower layer material contains zinc oxide and tin oxide.

[0190] Item 19. The method according to any one of Items 15 to 18, wherein the thickness of the first lower layer is at least 11 nm and 15 nm or less.

[0191] Item 20. The method according to any one of Items 15 to 19, wherein the second lower layer material contains silica and alumina.

[0192] Item 21. The method according to any one of Items 15 to 20, wherein the thickness of the second lower layer is at least 29 nm and 34 nm or less.

[0193] Item 22. The method according to any one of Items 15 to 21, further comprising applying a protective layer on a part of the transparent conductive oxide layer, the protective layer including a first protective film and a second protective film on at least a part of the first protective film, the second protective film being the outermost film, and the second protective film containing titania and alumina.

[0194] Item 23. The method according to Item 22, wherein the first protective film contains titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the first protective film does not contain a mixture of titania and alumina.

[0195] Item 24. The method according to Item 22 or 23, wherein the second protective film contains 35 to 65 wt% of titania, particularly 45 to 55 wt% of titania, more particularly 50 wt% of titania.

[0196] Item 25. The method according to any one of Items 22 to 25, wherein the second protective film contains 65 to 35 wt% of alumina, particularly 55 to 45 wt% of alumina, more particularly 50 wt% of alumina.

[0197] Item 26. A method according to any of Items 22 - 25, further comprising a third protective film that is on at least a part of the first protective film and is located between the first and second protective films or between the first protective film and the functional coating, the third protective film comprising titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the third protective film does not contain a mixture of titania and alumina.

[0198] Item 27. A coated article comprising a substrate, a lower layer on at least a part of the substrate, and a transparent conductive oxide layer on at least a part of the lower layer. The lower layer has a first lower layer film and an optional second lower layer film. The first lower layer film comprises a first high refractive index material. The optional second lower 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 therein. 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.

[0199] Item 28. A coated article according to Item 27, wherein the embedded film has a thickness of 5 nm to 50 nm, particularly 10 nm to 40 nm, more particularly 15 nm to 30 nm.

[0200] Item 29. A coated article according to Item 27 or 29, wherein the second high refractive index material comprises tin oxide and zinc oxide.

[0201] Item 30. A coated article according to any of Items 27 - 29, wherein the embedded film is disposed closer to the top of the transparent conductive oxide layer.

[0202] Item 31. A coated article according to any of Items 27 - 29, wherein the embedded film is disposed closer to the bottom of the transparent conductive oxide layer.

[0203] Item 32. A coated article according to any one of Items 27 - 29, wherein the embedded film is disposed substantially at the center of the transparent conductive oxide layer.

[0204] Item 33. A coated article according to any one of Items 27 - 32, wherein the transparent conductive oxide layer is selected from the group consisting of 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"), particularly GZO, AZO, and ITO, and more particularly ITO.

[0205] Item 34. A coated article according to Items 27 - 33, wherein the high refractive index material comprises zinc oxide and tin oxide.

[0206] Item 35. A coated article according to any one of Items 27 - 34, wherein the low refractive index material comprises silica and alumina.

[0207] Item 36. A coated article according to any one of Items 27 - 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.

[0208] Item 37. A coated article according to any one of Items 27 - 34, wherein the transparent conductive oxide layer has a thickness of at most 950 nm, particularly at most 550 nm, more particularly at most 480 nm, more particularly at most 350 nm, more particularly at most 300 nm, more particularly at most 275 nm, more particularly 250 nm, more particularly at most 225 nm.

[0209] Item 38. The coated article according to any one of Items 27 to 37, having a sheet resistance in the range of 5 to 20 ohms per square, particularly 8 to 18 ohms per square, more particularly 5 to 15 ohms per square.

[0210] Item 39. The coated article according to any one of Items 27 to 38, wherein the first underlying film has a first underlying thickness, the second underlying film has a second underlying thickness, and the embedded film has an embedded film thickness such that the coated article has a color having an a* of at least -9 and a maximum of 1, particularly at least -4 and a maximum of 0, more particularly at least -3 and a maximum of 1, more particularly at least -1.5 and a maximum of -0.5, more particularly at least -1, and a b* of at least -9 and a maximum of 1, particularly at least -4 and a maximum of 0, more particularly at least -3 and a maximum of 1, more particularly at least -1.5 and a maximum of -0.5, more particularly -1.

[0211] Item 40. The coated article according to Item 39, wherein the first underlying film thickness is 11 nm to 15 nm and / or the second underlying film thickness is 29 nm to 34 nm.

[0212] Item 41. The coated article according to any one of Items 27 to 40, further comprising a protective layer on the transparent conductive oxide layer, the protective layer including a first protective film and a second protective film on at least a part of the first protective film, the second protective film being the outermost film, and the second protective film including titania and alumina.

[0213] Item 42. The coated article according to Item 41, wherein the first protective film includes titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the first protective film does not include a mixture of titania and alumina.

[0214] Item 43. A coated article according to Item 41 or 42, wherein the second protective film contains 35 to 65 weight percent of titania, particularly 45 to 55 weight percent of titania, and more particularly 50 weight percent of titania.

[0215] Item 44. A coated article according to any one of Items 40 to 43, wherein the second protective film contains 65 to 35 weight percent of alumina, particularly 55 to 45 weight percent of alumina, and more particularly 50 weight percent of alumina.

[0216] Item 45. A coated article according to any one of Items 40 to 44, further comprising a third protective film that is on at least a part of the first protective film, between the first and second protective films, or between the first protective film and the functional coating, and the third protective film contains titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the third protective film does not contain a mixture of titania and alumina.

[0217] Item 46. A method for adjusting the color of a coated article. The method includes applying a first underlayer film on at least a part of a substrate. The first underlayer film contains a first high refractive index material. Optionally, a second underlayer film contains a low refractive index material applied on at least a part of the first underlayer 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 on at least a part of the first underlayer film or the optional second underlayer film. An embedding film is applied on at least a part of the first transparent conductive oxide layer. The embedding film contains 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 on at least a part of the embedding film.

[0218] Item 47. The method according to item 46, wherein the embedded film has a thickness of 5 nm to 50 nm, particularly 10 nm to 40 nm, and more particularly 15 nm to 30 nm.

[0219] Item 48. The method according to item 46 or 47, wherein the second high refractive index material includes tin oxide and zinc oxide.

[0220] Item 49. The method according to any one of items 46 to 47, wherein the embedded film is disposed closer to the upper part of the transparent conductive oxide layer.

[0221] Item 50. The method according to any one of items 46 to 47, wherein the embedded film is disposed closer to the bottom of the transparent conductive oxide layer.

[0222] Item 51. The method according to any one of items 46 to 47, wherein the embedded film is disposed substantially at the center of the transparent conductive oxide layer.

[0223] Item 52. The 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 the group consisting of 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"), particularly GZO, AZO, and ITO, and more particularly ITO.

[0224] Item 53. The method according to any one of items 46 to 52, wherein the high refractive index material includes zinc oxide and tin oxide.

[0225] Item 54. The method according to any one of items 46 to 53, wherein the low refractive index material includes silica and alumina.

[0226] Item 55. The method according to any one of Items 46 to 55, wherein the first transparent conductive oxide layer and / or the second transparent conductive oxide layer has a thickness of at least 80 nm, or in particular at least 120 nm, more particularly at least 180 nm, more particularly at least 240 nm or more particularly at least 360 nm.

[0227] Item 56. The method according to any one of Items 46 to 55, wherein the first transparent conductive oxide layer and / or the second transparent conductive oxide layer has a thickness of at most 400 nm, in particular at most 360 nm, more particularly at most 240 nm, more particularly at most 180 nm, more particularly at most 120 nm or more particularly at most 80 nm.

[0228] 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 per square, in particular 5 to 20 ohms per square, more particularly 5 to 18 ohms per square.

[0229] Item 58. The first lower film has a first lower thickness, the second lower film has a second lower thickness, and the embedding film has an embedding film thickness for providing a coated article having a color with an a* of at least -9 and at most 1, in particular 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 at least -1, and a b* of at least -9 and at most 1, in particular 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. The method according to any one of Items 46 to 57.

[0230] Item 59. The method according to any one of Items 46 to 58, wherein the first lower film thickness is 11 nm to 15 nm and / or the second lower film thickness is 29 nm to 34 nm.

[0231] Item 60. The method according to any one of Items 46 to 59, further comprising applying a protective layer on the transparent conductive oxide layer, the protective layer including a first protective film and a second protective film on at least a part of the first protective film, the second protective film being the outermost film, and the second protective film including titania and alumina.

[0232] Item 61. The method according to Item 60, wherein the first protective film includes titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the first protective film does not include a mixture of titania and alumina.

[0233] Item 62. The method according to Item 60 or 61, wherein the second protective film includes 35 to 65 wt% of titania, particularly 45 to 55 wt% of titania, and more particularly 50 wt% of titania.

[0234] Item 63. The method according to any one of Items 60 to 62, wherein the second protective film includes 65 to 35 wt% of alumina, particularly 55 to 45 wt% of alumina, and more particularly 50 wt% of alumina.

[0235] Item 64. The method according to any one of Items 60 to 63, further comprising a third protective film located on at least a part of the first protective film, between the first protective film and the second protective film, or between the first protective film and the functional coating, the third protective film including titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the third protective film does not include a mixture of titania and alumina.

[0236] Item 65. The method according to any one of Items 47 to 64, wherein the first transparent conductive oxide film and the second transparent conductive oxide film include the same metal oxide.

[0237] Item 66. A coated article comprising a substrate and a lower layer on at least a part of the substrate. The lower layer has a first lower layer film and a second lower layer film. The first lower layer film contains a first high refractive index material. The second lower layer film contains 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 on at least a part of the second lower layer film. An embedded film is on at least a part of the first transparent conductive oxide film. The embedded film contains 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 on at least a part of the embedded film.

[0238] Item 67. A coated article according to Item 66, wherein the embedded film has a thickness of 5 nm to 50 nm, particularly 10 nm to 40 nm, and more particularly 15 nm to 30 nm.

[0239] Item 68. A coated article according to Item 66 or 67, wherein the second high refractive index material contains tin oxide and zinc oxide.

[0240] Item 69. A coated article according to any one of Items 66 to 68, wherein the first transparent conductive oxide film is thicker than the second transparent conductive oxide film.

[0241] Item 70. A coated article according to any one of Items 66 to 68, wherein the first transparent conductive oxide film is thinner than the second transparent conductive oxide film.

[0242] Item 71. A coated article according to any one of Items 66 to 68, wherein the first transparent conductive oxide film has substantially the same thickness as the second transparent conductive oxide film.

[0243] Item 72. A coated article according to any of Items 66 to 71, wherein the first transparent conductive oxide film and / or the second transparent conductive oxide film is selected from the group consisting of 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"), particularly GZO, AZO, and ITO, and more particularly ITO.

[0244] Item 73. A coated article according to any of Items 66 to 72, wherein the high refractive index material includes zinc oxide and tin oxide.

[0245] Item 74. A coated article according to any of Items 66 to 73, wherein the low refractive index material includes silica and alumina.

[0246] Item 75. A coated article according to any of Items 66 to 74, wherein the transparent conductive oxide layer has a thickness of at most 950 nm, particularly at most 550 nm, and more particularly at most 360 nm.

[0247] Item 76. A coated article according to any of Items 66 to 75, wherein the coated article has a sheet resistance in the range of 5 to 20 ohms per square, particularly 8 to 18 ohms per square, and more particularly 5 to 15 ohms per square.

[0248] Item 77. A coated article according to any one of Items 66 - 80, wherein the first underlayer film has a first underlayer thickness, the second underlayer film has a second underlayer thickness, and the embedded film has an embedded film thickness for providing a coated article having a coating with a color having an a* of 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 at least -1, and a b* of 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.

[0249] Item 78. A coated article according to any one of Items 76 - 77, wherein the thickness of the first underlayer film is from 11 nm to 15 nm and / or the thickness of the second underlayer film is from 29 nm to 34 nm.

[0250] Item 79. A coated article according to any one of Items 66 - 78, further comprising a protective layer on the transparent conductive oxide layer, the protective layer including a first protective film and a second protective film on at least a part of the first protective film, the second protective film being the outermost film, and the second protective film including titania and alumina.

[0251] Item 80. A coated article according to Item 79, wherein the first protective film includes titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the first protective film does not include a mixture of titania and alumina.

[0252] Item 81. A coated article according to Item 79 or 80, wherein the second protective film includes 35 - 65 wt% titania, particularly 45 - 55 wt% titania, more particularly 50 wt% titania.

[0253] Item 82. A coated article according to any one of Items 79 - 81, wherein the second protective film contains 65 - 35 wt% alumina, particularly 55 - 45 wt% alumina, more particularly 50 wt% alumina.

[0254] Item 83. A coated article according to any one of Items 79 - 82, further comprising a third protective film located on at least a part of the first protective film, between the first and the second protective films, or between the first protective film and the functional coating, wherein the third protective film contains titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the third protective film does not contain a mixture of titania and alumina.

[0255] Item 84. A coated article according to any one of Items 66 - 83, wherein the first transparent conductive oxide layer and / or the second transparent conductive oxide layer has a thickness of at most 400 nm, particularly at most 360 nm, more particularly at most 240 nm, more particularly at most 180 nm, more particularly at most 120 nm, or more particularly at most 80 nm.

[0256] Item 85. A coated article comprising a substrate, a functional layer on at least a part of the substrate, a first protective film on at least a part of the functional layer, and a second protective film on at least a part of the first protective film. The second protective film contains titania and alumina and is the outermost film.

[0257] Item 86. A coated article according to Item 85, wherein the first protective film contains titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof.

[0258] Item 87. A coated article according to Item 85 or 86, wherein the second protective film contains 35 - 65 wt% titania, particularly 45 - 55 wt% titania, more particularly 50 wt% titania.

[0259] Item 88. A coated article according to any one of Items 85 - 87, wherein the second protective film comprises 65 - 35 wt% silica, particularly 55 - 45 wt% silica, more particularly 50 wt% silica.

[0260] Item 89. A coated article according to any one of Items 85 - 88, wherein the first protective film comprises titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the first protective film does not comprise a mixture of titania and alumina.

[0261] Item 90. A coated article according to any one of Items 85 - 89, wherein the functional layer comprises a transparent conductive oxide layer selected from the group consisting of aluminum-doped zinc oxide, gallium-doped zinc oxide, and tin-doped indium oxide, particularly tin-doped indium oxide.

[0262] Item 91. A coated article according to any one of Items 85 - 90, wherein the functional layer comprises a metal selected from the group consisting of silver, gold, palladium, copper, or a mixture thereof, particularly silver.

[0263] Item 92. A coated article according to any one of Items 85 - 91, further comprising a third protective film that is on at least a portion of the first protective film, between the first protective film and the second protective film, or between the first protective film and the functional coating.

[0264] Item 93. A coated article according to any one of Items 85 - 91, wherein the third protective film comprises titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the third protective film does not comprise a mixture of titania and alumina.

[0265] 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 titania and alumina.

[0266] Item 95. The method of item 94, wherein the first protective film comprises titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof.

[0267] Item 96. The method of item 94 or 95, wherein the second protective film comprises 35 to 65 wt% titania, particularly 45 to 55 wt% titania, more particularly 50 wt% titania.

[0268] Item 97. The method according to any one of items 94 to 99, wherein the second protective film comprises 65 to 35 wt% silica, particularly 55 to 45 wt% silica, more particularly 50 wt% silica.

[0269] Item 98. The method according to any one of items 94 to 97, wherein the first protective film comprises titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the first protective film does not comprise a mixture of titania and alumina.

[0270] 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 the group consisting of aluminum-doped zinc oxide, gallium-doped zinc oxide, and tin-doped indium oxide, particularly tin-doped indium oxide.

[0271] Item 100. The method according to any one of items 94 to 99, wherein the functional layer comprises a metal selected from the group consisting of silver, gold, palladium, copper, or a mixture thereof, particularly silver.

[0272] Item 101. A method according to any one of Items 94 to 100, further comprising a third protective film that is on at least a part of the first protective film and is located between the first protective film and the second protective film or between the first protective film and the functional coating.

[0273] Item 102. A method according to any one of Items 94 to 101, wherein the third protective film contains titania, alumina, zinc oxide, tin oxide, zirconia, silica, or a mixture thereof. Optionally, the third protective film does not contain a mixture of titania and alumina.

[0274] 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 absorbance of a coated article, the method comprising providing a substrate, applying a transparent conductive oxide layer, and heat-treating a coated article including the transparent conductive oxide layer in an atmosphere containing 0% to 1.0% oxygen, particularly 0% to 0.5% oxygen.

[0275] Item 104. A method according to Item 103, wherein the transparent conductive oxide layer contains indium-doped tin oxide (''ITO'') or aluminum-doped zinc oxide (''AZO'').

[0276] Item 105. A method according to Item 103 or 104, wherein the transparent conductive oxide layer has a thickness of at least 125 nm, particularly at least 150 nm, more particularly at least 175 nm, up to 450 nm, up to 400 nm, up to 350 nm, up to 300 nm, up to 250 nm, or up to 250 nm.

[0277] Item 106. A method according to any one of Items 103 to 105, wherein the transparent conductive oxide layer contains indium-doped tin oxide (''ITO'') and the atmosphere contains 0.75% to 1.25% oxygen.

[0278] Item 107. A method according to any one of Items 103 to 106, wherein the transparent conductive oxide layer has a thickness of at least 95 nm and up to 225 nm.

[0279] Item 108. A method according to any one of Items 103 - 107, wherein the transparent conductive oxide layer contains aluminum-doped zinc oxide ("AZO") and the atmosphere contains 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.

[0280] Item 109. A method according to Item 108, wherein the transparent conductive oxide layer has a thickness of at least 225 nm and at most 440 nm.

[0281] Item 110. A method according to any one of Items 103 - 109, further comprising applying a functional coating on at least a part of the substrate, the functional coating being disposed between the substrate and the transparent conductive oxide layer.

[0282] Item 111. A method according to any one of Items 103 - 110, further comprising applying a first protective film (the first protective film contains titania, alumina, zinc oxide, tin oxide, zirconia, silica or a mixture thereof) on at least a part of the transparent conductive oxide layer and a second protective film (the second protective film contains titania and alumina and the second protective film is the outermost film) on at least a part of the first protective film.

[0283] Item 112. A method for reducing the sheet resistance of a coated article, comprising applying a coating containing a transparent conductive oxide layer on a substrate at room temperature and heating the upper 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 120 seconds or less, 90 seconds or less, 60 seconds or less, 55 seconds or less, 50 seconds or less, 45 seconds or less, 40 seconds or less, or 35 seconds or less.

[0284] Item 113. A method according to Item 112, wherein the heating step is flash annealing.

[0285] Item 114. A method according to item 112 or 113, wherein the transparent conductive oxide layer is at least 125 nm and at most 950 nm.

[0286] Item 115. A method according to any one of items 112 to 114, wherein the transparent conductive oxide layer comprises tin-doped indium oxide, is at least 105 nm and at most 171 nm, and the sheet resistance of the coated article after the treatment step is less than 20 Ω / sq.

[0287] Item 116. A method according to any one of items 112 to 115, wherein the transparent conductive oxide layer comprises gallium-doped zinc oxide, has a thickness of at least 320 nm and at most 480 nm, and the sheet resistance of the coated article after the treatment step is less than 20 Ω / sq.

[0288] Item 117. A method according to any one of items 112 to 116, wherein the transparent conductive oxide layer comprises alumina-doped oxide, has a thickness of at least 344 nm and at most 880 nm, and the sheet resistance of the coated article after the treatment step is less than 20 Ω / sq.

[0289] Item 118. A method according to any one of items 112 to 117, wherein the coating application step comprises a magnetron sputtering vacuum deposition process.

[0290] Item 119. A method according to any one of items 112 to 118, wherein the coating application step does not use radiant heat.

[0291] Item 120. A method according to any one of items 112 to 119, further comprising applying a first protective film (the first protective film comprises titania, alumina, zinc oxide, tin oxide, zirconia, silica or a mixture thereof) on at least a part of the transparent conductive oxide layer, and applying a second protective film (the second protective film comprises titania and alumina) on at least a part of the transparent conductive oxide layer, wherein applying the first protective film and applying the second protective film are performed before or after the treatment step.

[0292] Item 121. A method according to any one of Items 112 - 120, wherein the heating step does not raise the upper surface of the transparent conductive oxide above 635°F.

[0293] Item 122. A method according to any one of Items 112 - 121, wherein the substrate is glass and the transparent conductive oxide has an absorption of 0.3 or less.

[0294] Item 123. A method according to any one of Items 112 - 122, wherein the substrate is glass and the transparent conductive oxide has an absorption at least as high as 0.05.

[0295] Item 124. A method according to any one of Items 112 - 123, wherein the coated article is a refrigerator door.

[0296] Item 125. A method according to any one of Items 112 - 124, wherein the coating step is performed in an atmosphere where the oxygen content supplied to the atmosphere is between 0% and 1.5%.

[0297] Item 126. A method according to any one of Items 112 - 125, wherein the substrate is glass and the transparent conductive oxide has an absorption of 0.2 or less and at least as high as 0.05.

[0298] Item 127. A method of manufacturing a coated article, comprising applying a transparent conductive oxide layer onto a substrate, raising the upper surface of the transparent conductive oxide above 380°F or at least to 435°F, and not raising the upper surface of the transparent conductive oxide 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, not more than 90 seconds, not more than 60 seconds, not more than 55 seconds, not more than 50 seconds, not more than 45 seconds, not more than 40 seconds, or not more than 35 seconds.

[0299] Item 128. A method according to Item 127, further comprising not heating the coated article above 635°F.

[0300] Item 129. A method according to any of Items 127 - 128, wherein the transparent conductive oxide layer comprises indium tin oxide having a thickness of at least 96 nm and at most 171 nm and a sheet resistance of less than 25 Ω / □.

[0301] Item 130. A method according to any of Items 1127 - 129, further comprising applying a protective layer over the transparent conductive oxide, the protective layer comprising titania and alumina.

[0302] Item 131. A coated substrate having a* of -9 to 1, particularly -4 to 0, more particularly -3 to 1, more particularly -1.5 to -0.5 and b* of -9 to 1, particularly -4 to 0, more particularly -3 to 1, particularly -1.5 to -0.5, produced by the method according to any of Items 15 - 26.

[0303] Item 132. A coated substrate having a* of -9 to 1, particularly -4 to 0, more particularly -3 to 1, more particularly -1.5 to -0.5 and b* of -9 to 1, particularly -4 to 0, more particularly -3 to 1, more particularly -1.5 to -0.5, produced by the method according to any of Items 46 - 65.

[0304] Item 133. A coated article produced by the method described in any of Items 103 - 111.

[0305] Item 134. A coated article produced by the method described in any of Items 112 - 126.

[0306] Item 135. A coated article produced by the method described in any of Items 127 - 130.

[0307] Item 136. Use of an underlayer according to any of Items 1 - 14 or Items 27 - 45 for providing a* of -9 to 1, particularly -4 to 0, more particularly -3 to 1, more particularly -1.5 to -0.5 and b* of -9 to 1, particularly -4 to 0, more particularly -3 to 1, or particularly -1.5 to -0.5.

[0308] Use of a first underlayer film and a second underlayer film, either of items 15 - 26 or items 46 - 65, to provide an a* of -9 to 1, particularly -4 to 0, more particularly -3 to 1, and more particularly -1.5 to -0.5 and a b* of -9 to 1, particularly -4 to 0, more particularly -3 to 1, or particularly -1.5 to -0.5.

[0309] Use of an embedded film, any of items 27 - 65, to reduce sheet resistance.

[0310] Use of a protective layer, any of items 85 - 93, to improve the durability of a coating on a substrate.

[0311] An item coated according to any of items 85 - 91, having a protective layer thickness of at least 20 nm, 40 nm, 60 nm, or 80 nm, 100 nm, or 120 nm and a maximum thickness of 275 nm, 255 nm, 240 nm, 170 nm, 150 nm, 125 nm, or 100 nm.

[0312] An item coated according to any of items 85 - 91 or 140, wherein the first protective film can have a thickness of 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 a maximum of 85 nm, 70 nm, 60 nm, 50 nm, 45 nm, or 30 nm.

[0313] An item coated according to any of items 85 - 91 or 140 or 141, wherein the second protective film can have a thickness of 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 a maximum of 85 nm, 70 nm, 60 nm, 50 nm, 40 nm, 45 nm, 30 nm.

[0314] Item 143. A coated article according to any of items 85 to 91 or 140 to 142, wherein the optional third protective film can have a thickness of 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 up to 85 nm, 70 nm, 60 nm, 50 nm, 45 nm, 30 nm or up to 30 nm.

Claims

1. A substrate, A lower layer on at least a part of the substrate, The lower layer includes a first lower layer film and a second lower layer film on at least a part of the first lower layer film, the first lower layer film includes a first high refractive index material, the first high refractive index material includes zinc oxide or an oxide of zinc and tin, the second lower layer film includes a first low refractive index material, and the first high refractive index material has a refractive index greater than that of the first low refractive index material; a lower layer, A first transparent conductive oxide layer on at least a part of the lower layer, An embedded film on at least a part of the first transparent conductive oxide layer, the embedded film includes a second high refractive index material, and the second high refractive index material has a refractive index greater than that of the first low refractive index material; an embedded film, A second transparent conductive oxide layer on at least a part of the embedded film, A protective layer on at least a part of the second transparent conductive oxide layer, the protective layer includes a first protective film and a second protective film on at least a part of the first protective film, the first protective film includes a mixture of silica and alumina, zinc stannate, or zirconia, and the second protective film includes a mixture of titania and alumina (TiAlO); a protective layer A coated article comprising.

2. The coated article according to claim 1, wherein the embedded film includes tin oxide and zinc oxide.

3. The coated article according to claim 1, wherein the first transparent conductive oxide layer and the second transparent conductive oxide layer include tin-doped indium oxide ("ITO").

4. The coated article according to claim 1, wherein the embedded film has a thickness of at least 15 nm and at most 30 nm.

5. The coated article according to claim 1, wherein the first transparent conductive oxide layer is thicker than the second transparent conductive oxide layer.

6. The coated article according to claim 1, wherein the first protective film includes titania, alumina, zinc oxide, tin oxide, zirconia, silica or a mixture thereof, and the second protective film includes titania and alumina.

7. (a) applying a first underlayer film on at least a part of a substrate, wherein the first underlayer film contains a first high refractive index material, and the first high refractive index material contains zinc oxide or zinc and tin oxides; (b) applying a second underlayer film on at least a part of the first underlayer film, wherein the second underlayer film contains a first low refractive index material; (c) applying a first transparent conductive oxide layer on at least a part of the second underlayer film; (d) applying an embedded film on at least a part of the first transparent conductive oxide layer, wherein the embedded film contains a second high refractive index material, and the second high refractive index material has a refractive index greater than that of the first low refractive index material; (e) applying a second transparent conductive oxide layer on at least a part of the embedded film; (f) applying a first protective film on at least a part of the second transparent conductive oxide layer and applying a second protective film on at least a part of the first protective film, wherein the first protective film contains a mixture of silica and alumina, zinc stannate, or zirconia, and the second protective film contains a mixture of titania and alumina (TiAlO); A method for reducing the sheet resistance of a coated article, comprising the above steps.

8. The second high refractive index material contains tin oxide and zinc oxide, or The first transparent conductive oxide layer contains tin-doped indium oxide, The method according to claim 7.

9. The method according to claim 7, wherein the embedded film is applied with a thickness of at least 15 nm and at most 30 nm.

10. The method according to claim 7, wherein the first transparent conductive oxide layer is thicker than the second transparent conductive oxide layer.

11. The method according to claim 7, wherein the second protective film contains titania and alumina, and the first protective film contains titania, alumina, zinc oxide, tin oxide, zirconia, silica or a mixture thereof.

Images