CN116119938A

CN116119938A - Coated article and method of manufacture

Info

Publication number: CN116119938A
Application number: CN202111345695.3A
Authority: CN
Inventors: 陈海星; 欧阳煦; 孙亚伟
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2021-11-15
Filing date: 2021-11-15
Publication date: 2023-05-16
Also published as: WO2023086238A1; TW202330863A

Abstract

The coated article includes a coating disposed on a substrate. The coating includes a surface having a contact angle with deionized water of 90 ° or more. The refractive index of the coating is less than the refractive index of the substrate. The coating comprises an interpenetrating network of hydrogenated amorphous carbon and amorphous silica. Methods of forming coated articles may include providing a coating on a substrate using plasma enhanced chemical vapor deposition or physical vapor deposition on a precursor. The precursor includes one or more of hydrogen, carbon, and silicon, and oxygen or nitrogen. The coating includes a surface having a contact angle with deionized water of 90 ° or more. The refractive index of the coating is less than the refractive index of the substrate. The coating includes an interpenetrating network of hydrogenated amorphous carbon and at least one of amorphous silicon oxide or amorphous silicon nitride.

Description

Coated article and method of manufacture

Technical Field

The present disclosure relates generally to coated articles and methods of manufacture, and more particularly, to coated articles having a contact angle with deionized water of 90 ° or greater, and methods of manufacture thereof.

Background

Glass-based substrates are commonly used, for example, in display devices (e.g., liquid Crystal Displays (LCDs), electrophoretic displays (EPDs), organic light emitting diode displays (OLEDs), plasma Display Panels (PDPs), etc.).

It is known to provide fluorinated easy-to-clean coatings on glass-based substrates. However, such coatings may exhibit poor durability after repeated use, with reduced contact angles and/or increased coefficients of friction, which may negate the function of such coatings. Thus, there is a need to develop coatings that are durable and that can provide functions such as easy-to-clean functions that can be used in coated articles.

Disclosure of Invention

Described herein are coated articles having a contact angle with deionized water of 90 ° or more. The coated article may include a substrate including a glass-based material and/or a ceramic-based material, which may provide good dimensional stability, good impact resistance, and/or good puncture resistance. The substrate comprising glass-based material and/or ceramic-based material may comprise one or more compressive stress regions, which may further provide increased impact resistance and/or increased puncture resistance.

The coatings of the coated articles described herein may be porous and hydrophobic to reduce transfer of material (e.g., fingerprint oil, water) onto the surface of the coating. Providing a porous coating can reduce the refractive index of the coating and advantageously reduce the available surface area to which material is transferred. Providing a porous coating can reduce the water contact angle, thereby making the surface more hydrophobic. The coating may include a skewness Rsk greater than 0 and a kurtosis Rku less than 3, which reduces the surface area to which the material is transferred. For example, the coating may be used as an easy-to-clean coating and/or an anti-fingerprint coating. Furthermore, the coating may be, for example, durable so that its properties are maintained after repeated wear. Providing the coating may increase the transmittance and/or decrease the reflectance of the coated article compared to a substrate without the coating. Providing a coating with a low refractive index may enable the coating to be disposed on top of the anti-reflective stack or included as an outermost layer in the anti-reflective stack.

The methods of the present disclosure may be used to manufacture coated articles using Plasma Enhanced Chemical Vapor Deposition (PECVD) and/or Physical Vapor Deposition (PVD), which may produce the coating in a single step process. The method is capable of forming interpenetrating networks of hydrogenated amorphous carbon with amorphous silicon oxide and/or amorphous silicon nitride, which may provide the benefits described above.

Some example aspects of the disclosure are described below, with the understanding that any of the features of the various aspects may be used alone or in combination with one another.

Aspect 1. A coated article comprising a substrate, the substrate comprising a first major surface. The coated article includes a coating disposed on the substrate. The coating includes a surface having a contact angle with deionized water of 90 ° or more. The refractive index of the coating is less than the refractive index of the substrate. The coating comprises an interpenetrating network of hydrogenated amorphous carbon and amorphous silica.

Aspect 2 the coated article of aspect 1, wherein the refractive index of the coating is in the range of about 1.3 to about 1.4.

Aspect 3 the coated article of any one of aspects 1-2, wherein the refractive index of the coating is less than 1.37.

Aspect 4 the coated article of any one of aspects 1-3, wherein the coating has a thickness in the range of about 0.1 nanometers to about 200 nanometers.

Aspect 5 the coated article of aspect 4, wherein the thickness of the coating is in the range of about 1 nanometer to about 50 nanometers.

Aspect 6 the coated article of any one of aspects 1-5, wherein the contact angle is in the range of about 100 ° to about 140 °.

Aspect 7 the coated article of any one of aspects 1-6, wherein the surface of the coating comprises a surface roughness Ra in the range of about 10 nanometers to about 20 nanometers.

Aspect 8 the coated article of any one of aspects 1-7, wherein the surface of the coating comprises a surface roughness Rz in the range of about 100 nanometers to about 300 nanometers.

Aspect 9 the coated article of any one of aspects 1-8, wherein the surface of the coating comprises a skewness Rsk in the range of about 0 to about 0.3.

Aspect 10 the coated article of any one of aspects 1-9, wherein the surface of the coating comprises a kurtosis Rku of less than 3.

Aspect 11 the coated article of any one of aspects 1-10, wherein the coated article comprises a transmittance of 91% or more at 500 nm.

Aspect 12 the coated article of aspect 1, wherein the transmittance of the coated article at 500nm is greater than the transmittance of a substrate without the coating at 500 nm.

Aspect 13 the coated article of any one of aspects 1-12, wherein the coated article has an average transmittance of about 91% or more over an optical wavelength of 400 nm to 700 nm.

Aspect 14 the coated article of aspect 13, wherein the average transmittance of the coated article is in the range of about 92% to about 95%.

Aspect 15 the coated article of any one of aspects 1-14, wherein the average reflectivity of the surface of the coating averages about 2.0% or less over an optical wavelength of 400 nm to 700 nm.

Aspect 16 the coated article of aspect 15, wherein the average reflectivity of the surface of the coating is in the range of about 0.5% to about 1.5%.

Aspect 17 the coated article of any one of aspects 1-16, wherein the coating comprises a coating of about 0.01cm at about 500 nanometers ^-1 Or less.

Aspect 18 the coated article of any one of aspects 1-17, wherein the average extinction coefficient averages about 0.00 over an optical wavelength ranging from 400 nanometers to about 700 nanometers1cm ^-1 To about 0.004cm ^-1 Within a range of (2).

Aspect 19 the coated article of any one of aspects 1-18, wherein the coating has a porosity in the range of about 5% to about 50%.

Aspect 20 the coated article of any one of aspects 1-19, wherein the surface of the coating is an outer surface of the coated article.

Aspect 21 the coated article of any one of aspects 1-20, wherein the coating contacts the first major surface of the substrate.

Aspect 22 the coated article of any of aspects 1-20, further comprising a layer disposed between the coating and the substrate, the layer comprising one or more of silicon oxide, silicon nitride, titanium oxide, or niobium oxide.

Aspect 23 the coated article of aspect 22, wherein the layer comprises a plurality of layers that function as an antireflective stack.

Aspect 24 the coated article of aspect 23, wherein the refractive index of the coating is about 0.05 or more less than the outermost layer of the plurality of layers.

Aspect 25 the coated article of aspect 23, wherein the refractive index of the coating is about 0.1 or more less than the outermost layer of the plurality of layers.

Aspect 26 the coated article of any one of aspects 1-25, wherein the contact angle of the coating is about 70 ° or more after the surface of the coating is abraded with cheesecloth for 10,000 cycles according to ISO 9211-4:2012.

Aspect 27 the coated article of any one of aspects 1-26, wherein the coated article comprises a CIE b x value in the range of about 0 to about-6.

Aspect 28 the coated article of aspect 27, wherein the coated article comprises a CIE a x value in the range of about 0 to about-6.

Aspect 29 the coated article of any one of aspects 1-28, wherein the coating is fluorine-free.

Aspect 30 the coated article of any one of aspects 1-29, wherein the coating is nitrogen-free.

Aspect 31 the coated article of any one of aspects 1-29, wherein the coating comprises amorphous silicon nitride.

Aspect 32 the coated article of any one of aspects 1-31, wherein the coating comprises a silicon to carbon atomic ratio of about 0.7 to about 2.

Aspect 33 the coated article of any one of aspects 1-32, wherein the coating comprises an oxygen to carbon atomic ratio of about 2 to about 5.

Aspect 34 the coated article of any one of aspects 1-33, wherein the coating comprises a dynamic coefficient of friction of about 0.3 or less.

Aspect 35 the coated article of any one of aspects 1-34, wherein the substrate comprises a glass-based material or a ceramic-based material.

Aspect 36 the coated article of aspect 35, wherein the substrate is a cover lens of a display and the coating is used as an easy-to-clean coating.

Aspect 37 the coated article of aspect 35, wherein the display is a component of a vehicle interior system.

Aspect 38. A method of forming a coated article includes disposing a coating on a substrate using plasma enhanced chemical vapor deposition of a precursor. The precursors include hydrogen, carbon, and silicon. The precursor also includes at least one of oxygen or nitrogen. The contact angle of the surface of the coating with deionized water is 90 DEG or more. The refractive index of the coating is less than the refractive index of the substrate. The coating includes an interpenetrating network of the coating, the coating including an interpenetrating network of hydrogenated amorphous carbon and at least one of amorphous silicon oxide or amorphous silicon nitride.

Aspect 39. A method of forming a coated article includes disposing a coating on a substrate using physical vapor deposition of a precursor. The precursors include hydrogen, carbon, and silicon. The precursor also includes at least one of oxygen or nitrogen. The contact angle of the surface of the coating with deionized water is 90 DEG or more. The refractive index of the coating is less than the refractive index of the substrate. The coating includes an interpenetrating network of the coating, the coating including an interpenetrating network of hydrogenated amorphous carbon and at least one of amorphous silicon oxide or amorphous silicon nitride.

Aspect 40 the method of any one of aspects 38-39, wherein the precursor comprises methane, hydrogen, and orthosilicate.

Aspect 41 the method of any one of aspects 38-40, wherein the refractive index of the coating is in the range of about 1.3 to about 1.4.

Aspect 42 the method of any one of aspects 38-40, wherein the refractive index of the coating is less than 1.37.

Aspect 43 the method of any one of aspects 38-42, wherein the coating has a thickness in a range of about 0.1 nanometers to about 200 nanometers.

Aspect 44 the method of aspect 43, wherein the thickness of the coating is in the range of about 1 nanometer to about 50 nanometers.

Aspect 45 the method of any one of aspects 38-44, wherein the contact angle is in the range of about 100 ° to about 140 °.

Aspect 46 the method of any one of aspects 38-45, wherein the surface of the coating comprises a surface roughness Ra in a range of about 10 nanometers to about 20 nanometers.

Aspect 47 the method of any one of aspects 38-46, wherein the surface of the coating comprises a surface roughness Rz in the range of about 100 nanometers to about 300 nanometers.

Aspect 48 the method of any one of aspects 38-47, wherein the surface of the coating includes a skewness Rsk in the range of 0 to about 0.3.

Aspect 49 the method of any one of aspects 38-48, wherein the surface of the coating comprises a kurtosis Rku of less than 3.

Aspect 50 the method of any one of aspects 38-49, wherein the coating comprises a silicon to carbon atomic ratio of about 0.7 to about 2.

Aspect 51 the method of any one of aspects 38-50, wherein the coating comprises an oxygen to carbon atomic ratio of about 2 to about 5.

Aspect 52 the method of any of aspects 38-51, wherein the coating comprises a dynamic coefficient of friction of about 0.3 or less.

Aspect 53 the method of any one of aspects 38-52, wherein the substrate comprises a glass-based material or a ceramic-based material.

Aspect 54 the method of any one of aspects 38-53, wherein the coated article comprises a transmittance of 92% or more at 500 nm.

Aspect 55 the method of aspect 54, wherein the transmittance of the coated article at 500nm is greater than the transmittance of a substrate without the coating at 500 nm.

Aspect 56 the method of any one of aspects 35-55, wherein the coated article has an average transmittance of about 91% or more over an optical wavelength of 400 nm to 700 nm.

Aspect 57 the method of aspect 56, wherein the average transmittance of the coated article is in the range of about 92 percent to about 95 percent.

Aspect 58 the method of any one of aspects 38-57, wherein the average reflectivity of the surface of the coating averages about 0.2% or less over an optical wavelength of 400 nm to 700 nm.

Aspect 59 the method of aspect 58, wherein the average reflectivity of the surface of the coating is in the range of about 0.05% to about 0.15%.

Aspect 60 the method of any one of aspects 38-59, wherein the coating comprises about 0.01cm at about 500 nanometers ^-1 Or less.

Aspect 61 the method of any one of aspects 38-60, wherein the average extinction coefficient averages about 0.001cm over an optical wavelength ranging from 400 nanometers to about 700 nanometers ^-1 To about 0.004cm ^-1 Within a range of (2).

Aspect 62 the method of any one of aspects 38-61, wherein the coating has a porosity in the range of about 5% to about 50%.

Aspect 63 the method of any one of aspects 38-62, wherein the coating comprises the contact angle of about 70 ° or greater after the surface is abraded with cheesecloth for 10,000 cycles according to ISO 9211-4:2012.

Aspect 64 the method of any one of aspects 38-63, wherein the coated article comprises a CIE b x value in the range of about 0 to about-6.

Aspect 65 the method of aspect 64, wherein the coated article comprises a CIE a x value in the range of about 0 to about-6.

Aspect 66 the method of any one of aspects 38-65, wherein the coating contacts the substrate.

Aspect 67 the method of any one of aspects 38-65, further comprising disposing one or more layers prior to disposing the coating, wherein the one or more layers comprise one or more of silicon oxide, silicon nitride, or niobium oxide.

Aspect 68 the method of aspect 67, wherein the layer comprises a plurality of layers that function as an antireflective stack.

Aspect 69 the method of aspect 67, wherein the refractive index of the coating is about 0.05 or more less than an outermost layer of the plurality of layers.

Aspect 70 the method of aspect 67, wherein the refractive index of the coating is about 0.1 or more less than an outermost layer of the plurality of layers.

Aspect 71 the method of any one of aspects 38-70, wherein the coating is fluorine-free.

Aspect 72 the method of any one of aspects 38-71, wherein the coating is nitrogen-free.

Drawings

The foregoing and other features and advantages of aspects of the disclosure will be better understood upon reading the following detailed description with reference to the drawings in which:

FIG. 1 is a schematic illustration of an exemplary coated article;

FIG. 2 is a schematic illustration of an exemplary coated article;

FIG. 3 is a schematic illustration of an exemplary coated article;

FIG. 4 is a perspective view of a vehicle interior having a vehicle interior system according to aspects;

FIG. 5 is a schematic plan view of an exemplary consumer electronic device in accordance with aspects;

FIG. 6 is a schematic perspective view of the exemplary consumer electronic device of FIG. 5;

FIG. 7 schematically illustrates a Scanning Electron Microscope (SEM) image of a surface of a coating according to aspects;

FIG. 8 illustrates the transmittance of a coated article according to aspects;

FIG. 9 illustrates reflectivity of a surface of a coating of a coated article according to aspects;

FIG. 10 illustrates absorption and extinction coefficients of a coated article according to aspects;

FIG. 11 illustrates the refractive index of a coating of a coated article according to aspects;

FIG. 12 illustrates reflectivity of a surface of a coating of a coated article according to aspects;

FIG. 13 is a flow chart illustrating an exemplary method of manufacturing a coated article according to aspects of the present disclosure;

FIG. 14 schematically illustrates steps in a method of making a coated article;

FIG. 15 schematically illustrates steps in a method of manufacturing a coated article; and is also provided with

Fig. 16 schematically illustrates steps in a method of manufacturing a coated article.

Throughout this disclosure, the drawings serve to emphasize certain aspects. As such, it should not be assumed that the relative sizes of the different regions, portions and substrates shown in the drawings are proportional to their actual relative sizes unless explicitly stated otherwise.

Detailed Description

Aspects will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplary aspects are shown. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.

Fig. 1-3 illustrate

coated articles

101, 201, and 301 including a coating 113 disposed on a substrate 103 according to aspects of the present disclosure. Unless otherwise indicated, discussion of features of aspects of one coated article may apply equally to corresponding features of any aspect of the present disclosure. For example, like partial designations may indicate that, in some aspects, identified features are identical to one another, and that discussion of identified features of one aspect may be equally applicable to identified features of any other aspect of the disclosure, unless otherwise indicated.

As shown in fig. 1-3, the substrate 103 coating each of the

articles

101, 201, and 301 includes a first major surface 105 and a second major surface 107 opposite the first major surface 105. In some aspects, as shown, the first major surface 105 may extend along the first plane 104 and/or the second major surface 107 may extend along the second plane 106. In a further aspect, as shown, the first plane 104 and the first major surface 105 may be parallel to the second plane 106 and the second major surface 107. As shown in fig. 1-3, the substrate 103 may include a substrate thickness 109 defined as an average distance between the first and second

major surfaces

105, 107. In some aspects, the substrate thickness 109 can be about 25 micrometers (μm) or more, about 80 μm or more, about 100 μm or more, about 125 μm or more, about 150 μm or more, about 200 μm or more, about 500 μm or more, about 700 μm or more, about 3 millimeters (mm) or less, about 2mm or less, about 1mm or less, about 800 μm or less, about 500 μm or less, about 300 μm or less, about 200 μm or less, about 180 μm or less, or about 160 μm or less. In some aspects, the substrate thickness 109 may be less, within the following ranges: about 25 μm to about 3mm, about 25 μm to about 2mm, about 80 μm to about 1mm, about 80 μm to about 800 μm, about 100 μm to about 500 μm, about 100 μm to about 300 μm, about 125 μm to about 200 μm, about 150 μm to about 160 μm, or any range or subrange therebetween. In some aspects, the substrate thickness 109 can be about 500 μm or more, for example, about 500 μm to about 3mm, about 700 μm to about 2mm, about 700 μm to about 1mm, or any range or subrange therebetween.

The substrate 103 may comprise a glass-based material and/or a ceramic-based material. For example, the substrate 103 may include a glass-based material and/or a ceramic-based material having a pencil hardness of 8H or more, such as 9H or more. As used herein, pencil hardness is measured using ASTM D3363-20 with a standard lead grade pencil. Throughout this disclosure, the modulus of elasticity (e.g., young's modulus) is measured using ISO 527-1:2019. In some aspects, the substrate 103 may include an elastic modulus of about 1 gigapascal (GPa) or more, about 10GPa or more, about 30GPa or more, about 100GPa or less, about 80GPa or less, about 75GPa or less. In some aspects, the substrate 103 can include an elastic modulus in the following range: about 1GPa to about 100GPa, about 10GPa to about 80GPa, about 30GPa to about 80GPa, about 50GPa to about 75GPa, or any range or subrange therebetween.

As used herein, "glass-based" includes both glass and glass-ceramics, wherein the glass-ceramic has one or more crystalline phases and an amorphous residual glass phase. The glass-based material may include an amorphous material (e.g., glass) and optionally one or more crystalline materials (e.g., ceramic). Amorphous materials and glass-based materials may be strengthened. As used herein, the term "strengthen" may refer to a material that has been chemically strengthened, for example, by ion exchange of larger ions with smaller ions in the surface of the substrate. As used herein, the term "strengthened" may also refer to materials strengthened by other techniques (e.g., thermal tempering), or utilizing a mismatch in coefficients of thermal expansion between substrate portions to form regions of compressive stress and central tension, which may be used to form a strengthened substrate. Exemplary glass-based materials that may be free of lithium oxide include soda lime glass, alkali aluminosilicate glass, alkali borosilicate glass, alkali aluminoborosilicate glass, alkali phosphosilicate glass, and alkali aluminophosphosilicate glass. In some aspects, the glass-based material may include alkali-containing glass or alkali-free glass, either of which may be free of lithium. In some aspects, the glass material may be alkali-free and/or include a low level of alkali metal (e.g., about 10mol% or less of R ₂ O, where R is ₂ O includes Li ₂ O、Na ₂ O、K ₂ O). "glass-ceramic" includes materials produced by controlled crystallization of glass. In some aspects, the glass-ceramic has a crystallinity of about 1% to about 99%. Examples of suitable glass ceramics may include Li ₂ O-Al ₂ O ₃ -SiO ₂ System (i.e., LAS system) glass ceramic, mgO-Al ₂ O ₃ -SiO ₂ System (i.e., MAS system) glass ceramic, znO×Al ₂ O ₃ ×nSiO ₂ (i.e., ZAS systems) and/or glass ceramics comprising a predominant crystalline phase comprising a beta-quartz solid solution, beta-spodumene, cordierite, petalite and/or lithium disilicate. The glass-ceramic substrate may be strengthened using a chemical strengthening process. In one or more aspects, the MAS-system glass-ceramic substrate can be a glass-ceramic substrate of the type described in Li ₂ SO ₄ Strengthening in molten salts, in which 2Li can occur ⁺ With Mg ²⁺ Is a function of the exchange of (a).

In some aspects, the substrate 103 may comprise a ceramic-based material. As used herein, "ceramic-based" includes both ceramics and glass-ceramics, wherein the glass-ceramic has one or more crystalline phases and an amorphous residual glass phase. The ceramic-based material may be strengthened (e.g., chemically strengthened). In some aspects, the ceramic-based material may be formed by heating a glass-based material to form a ceramic (e.g., crystalline) portion. In a further aspect, the ceramic-based material may include one or more nucleating agents that may promote the formation of one or more crystalline phases. In some aspects, the ceramic-based material may include one or more oxides, nitrides, oxynitrides, carbides, expanded boulders, and/or silicides. Exemplary aspects of the ceramic oxide include zirconia (ZrO ₂ ) Zircon (ZrSiO) ₄ ) Alkali metal oxides (e.g., sodium oxide (Na) ₂ O)), alkaline earth metal oxides (e.g., magnesium oxide (MgO)), titanium dioxide (TiO) ₂ ) Hafnium oxide (Hf) ₂ O), yttrium oxide (Y) ₂ O ₃ ) Iron oxide, beryllium oxide, vanadium oxide (VO ₂ ) Fused silica, mullite (a mineral composed of alumina and silica) and spinel (MgAl) ₂ O ₄ ). Exemplary aspects of ceramic nitrides include silicon nitride (Si ₃ N ₄ ) Aluminum nitride (AlN), gallium nitride (GaN), beryllium nitride (Be) ₃ N ₂ ) Boron Nitride (BN), tungsten nitride (WN), vanadium nitride, alkaline earth metal nitride (e.g. magnesium nitride (Mg) ₃ N ₂ ) Nickel nitride and tantalum nitride). Exemplary aspects of oxynitride ceramics include silicon oxynitride, aluminum oxynitride, and silicon aluminum oxynitride. Exemplary aspects of carbides and carbon-containing ceramics include silicon carbide (SiC), tungsten carbide (WC), carbonIron carbide and boron carbide (B) ₄ C) Alkali metal carbides (e.g., lithium carbide (Li) ₄ C ₃ ) Alkaline earth metal carbides (e.g., magnesium carbide (Mg) ₂ C ₃ ) And graphite. Exemplary aspects of the boride include chromium boride (CrB ₂ ) Molybdenum boride (Mo) ₂ B ₅ ) Tungsten boride (W) ₂ B ₅ ) Iron boride, titanium boride, zirconium boride (ZrB) ₂ ) Hafnium boride (HfB) ₂ ) Vanadium Boride (VB) ₂ ) Niobium boride (NbB) ₂ ) And lanthanum boride (LaB) ₆ ). Exemplary aspects of the silicide include molybdenum disilicide (MoSi ₂ ) Tungsten disilicide (WSi) ₂ ) Titanium disilicide (TiSi) ₂ ) Nickel silicide (NiSi), alkaline earth silicide (e.g., sodium silicide (NaSi)), alkali silicide (e.g., magnesium silicide (Mg) ₂ Si)), hafnium disilicide (HfSi) ₂ ) And platinum silicide (PtSi).

In some aspects, the substrate 103 may be optically transparent. As used herein, "optically transparent" or "optically clear" means an average transmittance of 70% or more over a wavelength range of 400nm to 700nm through a 1.0mm thick sheet of material. Throughout this disclosure, transmittance (and average transmittance) is measured according to ASTM C1649-14 (2021). In some aspects, an "optically transparent material" or "optically clear material" may have an average transmittance of 75% or more, 80% or more, 85% or more, or 90% or more, 92% or more, 94% or more, 96% or more through a 1.0mm thick sheet of material in the wavelength range of 400nm to 700 nm. The average transmittance in the wavelength range of 400nm to 700nm is calculated by measuring transmittance at an integer wavelength of about 400nm to about 700nm and averaging the measured values. For example, the substrate 103 may include a transmittance of between about 80% to about 92%, between about 85% to about 91%, 88% to about 91%, or any range or subrange therebetween.

As shown in fig. 1-3, the coating 113 may include a first surface region 115 and a second surface region 117 opposite the first surface region 115. In some aspects, as shown in fig. 1-3, the first surface region 115 may comprise a planar surface and/or the second surface region 117 may comprise a planar surface. The coating thickness 119 of the coating 113 can be defined as the average distance between the first surface region 115 and the second surface region 117 along a direction perpendicular to the first major surface 105. In some aspects, the coating thickness 119 can be about 0.1 nanometers (nm) or more, about 1nm or more, about 5nm or more, about 10nm or more, about 200nm or less, about 100nm or less, about 50nm or less, or about 30nm or less. In some aspects, the substrate thickness 119 can be within the following range: about 0.1nm to about 200nm, about 1nm to about 100nm, about 1nm to about 50nm, about 5nm to about 30nm, about 10nm to about 30nm, or any range or subrange therebetween.

As used herein, if a first layer and/or component is described as being "disposed on" a second layer and/or component, then other layers may or may not be present between the first layer and/or component and the second layer and/or component. Furthermore, as used herein, "disposed on … …" does not refer to a relative position with respect to gravity. For example, a first layer and/or component may be considered to be "disposed on" a second layer and/or component where, for example, the first layer and/or component is positioned below, above, or to one side of the second layer and/or component. As used herein, a first layer and/or component being described as being "bonded to" a second layer and/or component means that the layers and/or components are bonded to each other by direct contact and/or bonding between the two layers and/or components or by an adhesive layer. As used herein, a first layer and/or component described as "contacting" or "contacting" a second layer and/or component refers to direct contact and includes the case where the layers and/or components are bonded to one another.

In some aspects, as in fig. 1-3, the first surface region 115 of the coating 113 can be an outer surface of the

coated article

101, 201, and/or 301. In some aspects, as in fig. 1-3, the coating 113 (e.g., the second surface region 117) can be disposed on the substrate 103 (e.g., the first major surface 105). In a further aspect, as shown in fig. 1, the coating 113 (e.g., the second surface region 117) can contact and/or be bonded to the substrate 103 (e.g., the first major surface 105). In a further aspect, as shown in fig. 2-3, one or more layers 223 can be positioned between the second surface region 117 of the coating 113 and the first major surface 105 of the substrate 103, as will be discussed in more detail below.

The coating 113 comprises an interpenetrating network of hydrogenated amorphous carbon and amorphous silica. As used herein, amorphous means amorphous. As used herein, amorphous carbon includes sp ² Hybridization and sp ³ Hybrid mixing, which places it at full sp of diamond ³ Full sp of hybrid network and graphite or graphene ² And hybridized networks. As used herein, "interpenetrating" and "interpenetrating" means that there is at least one bond between networks. For a network of hydrogenated amorphous carbon and amorphous silicon oxide, there is at least one carbon-silicon bond where the network interpenetrates. In some aspects, the coating 113 may also include amorphous silicon nitride. In a further aspect, the amorphous silicon nitride can interpenetrate hydrogenated amorphous carbon. In other aspects, amorphous silicon nitride may be substituted in at least a portion of the amorphous silicon oxide network. In some aspects, the coating 113 may be fluorine-free. In some aspects, the coating 113 may be nitrogen-free.

Throughout this disclosure, contact angle is measured by measuring the angle formed by a drop of deionized water on a surface according to ASTM D7334-08 (2013). In some aspects, the coating 113 can be hydrophobic, e.g., include a contact angle of the first surface region 115 of greater than about 90 °. In some aspects, the first surface region 115 of the coating 113 can include a contact angle of about 90 ° or more, about 100 ° or more, about 110 ° or more, about 120 ° or more, about 150 ° or less, about 140 ° or less, or about 130 ° or less. In some aspects, the first surface region 115 of the coating 113 can include a contact angle in the range of: about 90 ° to about 150 °, about 100 ° to about 140 °, about 110 ° to about 140 °, about 120 ° to about 130 °, or any range or subrange therebetween. Throughout this disclosure, the coefficient of dynamic friction is measured according to ASTM D1894-14. In some aspects, the first surface region 115 of the coating 113 can include a dynamic coefficient of friction (i.e., dynamic coefficient of friction) of about 0.3 or less, about 0.25 or less, about 0.2 or less, or about 0.1 or less. In some aspects, the first surface region 115 of the coating 113 can include a coefficient of dynamic friction within the range: about 0.01 to about 0.3, about 0.05 to about 0.25, about 0.1 to about 0.2, or any range or subrange therebetween.

In some aspects, the coating 113 may be used as an easy-to-clean coating and/or an anti-fingerprint coating. For example, the coating 113 may be hydrophobic and/or include a dynamic coefficient of friction of about 0.3 or less. The anti-fingerprint coating may reduce transfer of material (e.g., fingerprint oil, water) onto the coating surface. The easy-to-clean coating may allow for easy removal (e.g., with microfibers) of any material transferred to the surface of the coating. In a further aspect, the coating may be used as an easy-to-clean coating and/or an anti-fingerprint coating.

Throughout the present disclosure, the surface profile of the first surface region of the coating was measured on a 10 μm x 10 μm test region as measured using an Atomic Force Microscope (AFM) for characterizing the first surface region using the parameters defined in ISO 4287:1997. As used herein, the surface roughness Ra is calculated as the arithmetic mean of the absolute deviation of the surface profile from the mean position. As used herein, the surface roughness Rz is calculated as the average of five maximum height differences between peaks and adjacent valleys of the surface profile. As used herein, the surface roughness Rq is calculated as the Root Mean Square (RMS) of the deviation of the surface profile from the average position in the surface normal direction. As used herein, the skewness Rsk is the average of the third power of the deviation of the surface profile from the average position divided by the third power of the surface roughness Rq. As used herein, kurtosis Rku is the average of the fourth power of the deviation of the surface profile from the average position divided by the fourth power of the surface roughness Rq. In some aspects, the first surface region 115 of the coating 113 can include a surface roughness Ra of about 5nm or more, about 10nm or more, about 12nm or more, about 25nm or less, about 20nm or less, or about 17nm or less. In some aspects, the first surface region 115 of the coating 113 can include a surface roughness Ra within the following range: about 5nm to about 25nm, about 10nm to about 20nm, about 12nm to about 17nm, or any range or subrange therebetween. In some aspects, the first surface region 115 of the coating 113 can include a surface roughness Rz of about 100nm or more, about 200nm or more, about 230nm or more, about 350nm or less, about 300nm or less, or about 280nm or less. In some aspects, the first surface region 115 of the coating 113 can include a surface roughness Rz within the following range: about 100nm to about 350nm, about 100nm to about 300nm, about 200nm to about 300nm, about 230nm to about 280nm, or any range or subrange therebetween. The first surface region 115 of the coating 113 can include a surface roughness Rq of about 5nm or more, about 10nm or more, about 12nm or more, about 25nm or less, about 20nm or less, or about 17nm or less. In some aspects, the first surface region 115 of the coating 113 can include a surface roughness Rq within the following range: about 5nm to about 25nm, about 10nm to about 20nm, about 12nm to about 17nm, or any range or subrange therebetween. In some aspects, the first surface region 115 of the coating 113 can include a skewness Rsk of about 0 or more, about 0.1 or more, about 0.3 or less, or about 0.2nm or less. In some aspects, the first surface region 115 of the coating 113 can include a surface roughness Rq within the following range: about 0 to about 0.3, about 0.1 to about 0.2, or any range or subrange therebetween. Without wishing to be bound by theory, a skewness Rsk of greater than 0 means that the surface profile is biased toward a lower height, while a skewness Rsk of less than 0 means that the surface profile is biased toward a higher height. In some aspects, the first surface region 115 of the coating 113 can include a kurtosis Rku of less than 3. Without wishing to be bound by theory, kurtosis Rku less than 3 may be characterized as relatively flat, while kurtosis greater than 3 may be characterized as relatively sharp. In a further aspect, skewness Rsk greater than 0 and kurtosis Rku less than 3 may form a porous structure, which reduces the available surface area on the micrometer scale. Without wishing to be bound by theory, reducing the available surface area on the micrometer scale may create a hydrophobic surface. The surface roughness Ra, rz or Rq provided within one or more of the above ranges may enable the coating to be hydrophobic.

As used herein, the porosity of a coating may be defined as the percentage of the volume of the coating occupied by voids (e.g., air, lack of coating material). The porosity of the coating was calculated from images taken using Scanning Electron Microscopy (SEM), where SEM images were fractions of images corresponding to heights below a threshold determined using automated thresholding analysis using ImageJ. Without wishing to be bound by theory, the effect of increasing porosity is that the portion of the coating accessible to the probe (e.g., water) is reduced because more of the coating surface is recessed from the surface peaks of the coating. In some aspects, the coating 113 can include a porosity of about 5% or more, about 10% or more, about 20% or more, about 30% or more, about 70% or less, about 50% or less, about 40% or less, or about 35% or less. In some aspects, the coating 113 can include a porosity within the following ranges: about 5% to about 70%, about 5% to about 50%, about 10% to about 40%, about 20% to about 35%, about 30% to about 35%, or any range or subrange therebetween. Providing a porous coating can reduce the refractive index of the coating because more air (refractive index 1) is present in the coating. Providing a porous coating may increase the contact angle of deionized water, for example, by reducing the water-accessible surface area.

Throughout this disclosure, the composition of the coating of the coated article is measured using energy dispersive X-ray analysis (EDX). Without wishing to be bound by theory, EDX does not provide information about the presence of hydrogen in the coating. Thus, the experimentally measured coating composition is based on the absence of hydrogen, which means that the contribution of hydrogen is ignored in determining the composition. As used herein, atomic% refers to the fraction of all atoms that comprise the formulated atomic element. In some aspects, the coating 113 can include a silicon (Si) to carbon (C) ratio (i.e., atomic percent) of about 0.3 or more, about 0.5 or more, about 0.7 or more, about 1 or more, about 8 or less, about 4 or less, about 2 or less, or about 1.5 or less. In some aspects, the coating 113 can include Si C atomic ratios within the following ranges: about 0.3 to about 8, about 0.5 to about 4, about 0.7 to about 2, about 1 to about 1.5, or any range or subrange therebetween. In some aspects, the coating 113 can include an oxygen (O) carbon (C) atomic ratio of about 1.5 or more, about 2 or more, about 2.5 or more, about 3 or more, about 10 or less, about 6 or less, about 5 or less, or about 4.5 or less. In some aspects, the coating 113 can include O C atomic ratios within the following ranges: about 1.5 to about 10, about 1.5 to about 6, about 2 to about 5, about 2.5 to about 4.5, about 3 to about 4.5, or any range or subrange therebetween. In some aspects, the coating 113 may include a scaled composition of C, O and atomic% of Si (i.e., based on no hydrogen and not including other elements not mentioned). In further aspects, the scaled composition may include C in an amount of about 5 atomic% or more, about 10 atomic% or more, about 50 atomic% or less, or about 20 atomic% or less. In a further aspect, the scalable composition may include about 5 atomic% to about 50 atomic%, about 10 atomic% to about 20 atomic%, or any range or subrange therebetween. In further aspects, the scalable composition may include O in an amount of about 10 atomic% or more, about 30 atomic% or more, 50 atomic% or more, about 80 atomic% or less, or 70 atomic% or less. In a further aspect, the scalable composition may comprise between about 10 atomic% to about 80 atomic%, about 30 atomic% to about 70 atomic%, about 50 atomic% to about 70 atomic%, or any range or subrange therebetween. In further aspects, the scaled composition may include Si in an amount of about 10 atomic% or more, about 15 atomic% or more, about 30 atomic% or less, or about 25 atomic% or less. In a further aspect, the scalable composition may include about 10 atomic% to about 30 atomic%, about 15 atomic% to about 25 atomic%, or any range or subrange therebetween, of Si.

In some aspects, the coating 113 may be optically transparent. In further aspects, the coating 113 and/or the

coated article

101, 201, and/or 301 may include a transmittance of about 91% or more, about 92% or more, or about 93% or more at a wavelength of 500 nm. In a further aspect, the coating 113 and/or the

coated article

101, 201, and/or 301 may include a transmittance at a wavelength of 500nm in the following range: about 91% to about 95%, about 92% to about 95%, about 93% to about 94%, or any range or subrange therebetween. In a further aspect, the transmittance of the

coated article

101, 201, and/or 301 (i.e., including the coating 113) can be greater than the transmittance without the coating 113 (i.e., bare substrate), wherein the transmittance is measured at an optical wavelength of 500 nm. In further aspects, the coating 113 and/or the

coated article

101, 201, and/or 301 can include an average transmittance of about 91% or more, about 92% or more, or about 93% or more, on average, over an optical wavelength of 400nm to 700 nm. In a further aspect, the coating 113 and/or the

coated article

101, 201, and/or 301 may include an average transmittance over an optical wavelength of 400nm to 700nm that averages in the following range: about 91% to about 95%, about 92% to about 95%, about 93% to about 94%, or any range or subrange therebetween. In a further aspect, the average transmittance of the

coated articles

101, 201, and/or 301 (i.e., including the coating 113) can be greater than the average transmittance of the substrate 103 without the coating 113 (i.e., bare substrate), wherein the average transmittance is averaged over an optical wavelength of 400nm to 700 nm.

As used herein, reflectance (and average reflectance) is measured at an angle of 8 ° with respect to the normal direction of the surface according to ASTM F1252-21. Just as the average transmittance, the average reflectance is calculated by measuring reflectance at all wavelengths from about 400nm to about 700nm and then averaging the measurements. In some aspects, the

coated article

101, 201, and/or 301 and/or the coating 113 can include an average reflectivity of about 2.0% or less, about 1.8% or less, about 1.5% or less, about 1.2% or less, or 1.0% or less of the first surface region 115 of the coating 113 at 500 nm. In a further aspect, the

coated article

101, 201, and/or 301 and/or the coating 113 can include an average reflectance of the first surface region 115 of the coating 113 at 500nm within the following range: about 0.1% to about 0.2%, about 0.5% to about 1.5%, about 0.8% to about 1.2%, about 0.8% to about 1.0%, or any range or subrange therebetween. In some aspects, the

coated article

101, 201, and/or 301 and/or the coating 113 can include an average reflectivity of the first surface region 115 of the coating 113 of about 2.0% or less, about 1.8% or less, about 1.5% or less, about 1.2% or less, or 1.0% or less, on average, over an optical wavelength of 400nm to 700 nm. In some aspects, the

coated article

101, 201, and/or 301 and/or the coating 113 can include a first surface region 115 of the coating 113 having an average reflectance over an optical wavelength of 400nm to 700nm that is in the range of: about 0.1% to about 2.0%, about 0.5% to about 1.5%, about 0.8% to about 1.2%, about 0.8 to about 1.0%, or any range or subrange therebetween.

Throughout this disclosure, the extinction coefficient is calculated based on absorbance, which is equal to 100% minus reflectance and transmittance. In some aspects, the coating 113 may comprise about 0.01cm at 500nm ^-1 Or less, about 0.007cm ^-1 Or less, about 0.004cm ^-1 Or less or about 0.002cm ^-1 Or less. At the position ofIn some aspects, the coating 113 may include an extinction coefficient at 500nm in the following range: about 0.0005cm ^-1 To about 0.01cm ^-1 About 0.001cm ^-1 To about 0.007cm ^-1 About 0.001cm ^-1 To about 0.004cm ^-1 About 0.002cm ^-1 To about 0.004cm ^-1 Or any range or subrange therebetween.

Coating 113 may include a first refractive index. The first refractive index may be a function of the wavelength of light passing through the coating 113. For light of a first wavelength, the refractive index of the material is defined as the ratio between the speed of light in vacuum and the speed of light in the corresponding material. Without wishing to be bound by theory, the refractive index of the coating 113 may be determined using a ratio of a sine of a first angle at which light of a first wavelength is refracted from air, such as provided on a surface of the coating 113, and at the surface of the coating 113 to propagate light within the coating 113 at a second angle. Both the first angle and the second angle are measured relative to a direction normal to the surface of the coating 113. As used herein, refractive index is measured according to ASTM E1967-19, wherein the first wavelength comprises 500nm unless indicated otherwise. In some aspects, the first refractive index of the coating 113 can be about 1.2 or more, about 1.3 or more, about 1.35 or more, about 1.5 or less, about 1.45 or less, about 1.4 or less, or about 1.37 or less. In some aspects, the first refractive index of the coating 113 can be in the following range: about 1.2 to about 1.5, about 1.3 to about 1.45, about 1.3 to about 1.4, about 1.35 to about 1.37, or any range or subrange therebetween. Just as the average transmittance, average reflectance, the average refractive index is calculated by measuring at all wavelengths from about 400nm to about 700nm and then averaging the measurements. In some aspects, the average refractive index may be within one or more of the ranges discussed above in this paragraph with reference to refractive index.

In some aspects, the substrate 103 can include a second refractive index. In some aspects, the second refractive index of the substrate 103 can be about 1.45 or more, about 1.49 or more, about 1.7 or less, about 1.6 or less, about 1.55 or less, or about 1.52 or less. In some aspects, the second refractive index of the substrate 103 can be in the following range: about 1.45 to about 1.7, about 1.45 to about 1.6, about 1.45 to about 1.55, about 1.49 to about 1.52, or any range or subrange therebetween. In some aspects, the first refractive index of the coating 113 may be less than the second refractive index of the substrate 103. In further aspects, the first refractive index of the coating may be about 0.05 or more, about 0.1 or more, about 0.15 or more, or about 0.2 or more less than the second refractive index. In a further aspect, the first refractive index of the coating 113 may be less than the second refractive index by an amount within the following range: about 0.05 to about 0.3, about 0.1 to about 0.2, about 0.15 to about 0.2, or any range or subrange therebetween.

In some aspects, as shown in fig. 2-3, one or more layers 223 can be positioned between the second surface region 117 of the coating 113 and the first major surface 105 of the substrate 103. In a further aspect, one or more layers 223 disposed on the substrate 103 may be combined with the coating 113 or function as an anti-reflective stack by itself. As used herein, an antireflective stack may reduce reflectivity when disposed on a substrate relative to the reflectivity of a substrate without the antireflective stack. Without wishing to be bound by theory, if the coating thickness 119 is less than 10nm or less than 5nm, the coating 113 may have minimal impact on the optical properties of the antireflective stack. In some aspects, the one or more layers 223 may include silicon oxide (e.g., silicon dioxide), silicon nitride, titanium oxide (e.g., titanium dioxide), or niobium oxide. In a further aspect, the one or more layers may also include one or more of the following: aluminum oxide (e.g., aluminum oxide), zirconium oxide (e.g., zirconium dioxide), tin oxide, titanium nitride, alkaline earth metal fluorides (e.g., magnesium fluoride, calcium fluoride, barium fluoride), magnesium oxide, or oxynitride (e.g., aluminum oxynitride or silicon oxynitride). In some aspects, as in fig. 2-3, the one or more layers 223 may include a stack thickness 229 of about 50nm or more, about 100nm or more, about 200nm or more, about 1 μm or less, about 500nm or less, or about 300nm or less. In some aspects, the stack thickness 229 may be within the following range: about 50nm to about 1 μm, about 100nm to about 500nm, about 200nm to about 300nm, or any range or subrange therebetween.

As used herein, the outermost layer of the one or more layers 223 refers to the layer that contacts the second surface area 117 of the coating 113. In a further aspect, the third refractive index of the outermost layer of the one or more layers 223 can be greater than the first refractive index of the coating 113. In still further aspects, the first refractive index of the coating 113 may be about 0.05 or more, about 0.1 or more, about 0.15 or more, or about 0.2 or more less than the third refractive index of the outermost layer of the one or more layers 223. In a still further aspect, the amount by which the first refractive index of the coating 113 is less than the third refractive index of the outermost layer of the one or more layers 223 may be within the following range: about 0.05 to about 0.5, about 0.1 to about 0.4, about 0.15 to about 0.35, about 0.2 to about 0.3, or any range or subrange therebetween.

In still further aspects, as shown in fig. 3, one or more layers 223 may include five layers, although in further aspects other numbers of layers may be provided. In a still further aspect, as shown in fig. 3, from the substrate 103 to the coating 113, one or more layers may include a first layer 303, a second layer 313, a third layer 323, a fourth layer 333, and a fifth layer 343. As used herein, a "high RI" layer has a refractive index greater than about 1.6, and a "low RI" layer has a refractive index less than about 1.5. In a still further aspect, the first layer 303, the third layer 323, and the fifth layer 343 may be low RI layers, and the second layer 313 and the fourth layer 333 may be high RI layers. Exemplary aspects of the high RI layer may include niobium oxide, silicon nitride, and/or titanium oxide. Exemplary aspects of the low RI layer may include, but are not limited to, silicon oxide, silicon oxynitride, aluminum oxynitride, and/or alkaline earth metal fluorides. In a still further aspect, the first layer 303 can contact the first major surface 105 of the substrate 103, and the fifth layer 343 can contact the second surface region 117 of the coating 113. In a further aspect, but not shown, the one or more layers 223 may include four layers, wherein an outermost layer of the one or more layers 223 includes a high RI layer that contacts the coating 113, and the coating 113 functions as a low RI layer.

Throughout this disclosure, coating the

articles

101, 201, and/or 301 can include CIE (L, a, b) color coordinates measured using a colorimeter (e.g., a trichromatic colorimeter) and/or a spectrophotometer (e.g., a CR-400 colorimeter (Konica Minolta) or a TR 520 spectrophotometer (Lazar Scientific)) at an observation angle of 10 ° using D65 illuminators. In some aspects, the CIE b x values of the

coated articles

101, 201, and/or 301 can be 0 or less, about-0.5 or less, about-1 or less, about-6 or more, about-4 or more, or about-2 or more. In some aspects, the CIE b x values of

coated articles

101, 201, and/or 301 can be within the following ranges: 0 to about-6, about-0.5 to about-4, about-1 to about-2, or any range or subrange therebetween. In some aspects, the CIE a x values of the

coated articles

101, 201, and/or 301 can be about 2 or less, about 1 or less, about 0 or less, about-0.5 or less, or about-1 or less. In some aspects, the coated article may have a CIE a x value of less than 0, e.g., within the following ranges: about 0 to about-6, about-0.5 to about-4, about-1 to about-2, or any range or subrange therebetween. In some aspects, the CIE a x values of

coated articles

101, 201, and/or 301 can be within the following ranges: about 2 to about-2, about 1 to about-1, about 0.5 to about-0.5, or any range or subrange therebetween.

Throughout the present disclosure, the abrasion resistance of the coating of the coated article was measured in a medium abrasion test using a Taber abrasion tester according to ISO9211-4:2012 with 4 layers of cheesecloth at a load of 750g at 23 ℃ and 50% relative humidity. In some aspects, the coating 113 of the

coated article

101, 201, and/or 301 is subjected to 10,000 cycles in a moderate wear test. In a further aspect, the second surface area 117 may include a contact angle of about 70 ° or more, about 75 ° or more, or 80 ° or more after 10,000 cycles in a moderate wear test. In a further aspect, after 10,000 cycles in the moderate wear test, the coated article may include CIE a x values and CIE b x values within one or more of the ranges discussed above.

In some aspects, the substrate 103 may comprise a glass-based substrate and/or a ceramic-based substrate, and may include one or more compressive stress regions. In some aspects, the compressive stress region may be formed by chemical strengthening. Chemical strengthening involves an ion exchange process in which ions in the surface layer are replaced by or exchanged with larger ions of the same valence or oxidation state. The method of chemical strengthening will be discussed later. The compressive stress region may extend to a depth referred to as a compression depth in a portion of the first portion and/or the second portion. As used herein, compressive depth means the depth at which the stress of the chemically strengthened substrate and/or portions described herein changes from compressive to tensile stress. The depth of compression is measured by a surface stress meter or scattered light polarizer (SCALP), depending on the ion exchange treatment and the thickness of the article being measured, wherein the values reported herein are derived using SCALP-5 manufactured by glass company of Estonia. In the case where stress in the substrate and/or the portion is generated by exchanging sodium ions into the substrate, a surface stress meter (for example, FSM-6000 (Orihara industrial limited (japan)) is used to measure the compression depth. Unless otherwise indicated, compressive stress (including surface CS) is measured by a surface stress meter (FSM) using a commercially available instrument (e.g., FSM-6000 manufactured by Orihara). Surface stress measurements rely on accurate measurement of Stress Optical Coefficient (SOC) associated with birefringence of glass. Unless otherwise indicated, SOC is measured according to procedure C (glass disk method) described in ASTM Standard C770-16 (2020), entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," the contents of which are incorporated herein by reference in their entirety. Where stress is generated by exchanging sodium ions into the substrate and the article being measured is thicker than about 400 μm, the SCALP is used to measure compression depth and Center Tension (CT). In the case where the stress in the substrate and/or portion is generated by exchanging potassium and sodium ions into the substrate and/or portion and the measured article is thicker than about 400 μm, the compression depth and CT are measured by the SCALP. Without wishing to be bound by theory, sodium exchange depth indicates compression depth, while potassium ion exchange depth may indicate a change in magnitude of compressive stress (but not a change in stress from compression to tension). Refractive near field (RNF, RNF method is described in U.S. patent No. 8,854,623, entitled "Systems and methods for measuring a profile characteristic of a glass sample," which is incorporated herein by reference in its entirety), methods can also be used to derive a graphical representation of stress distribution. When deriving a graphical representation of the stress distribution using the RNF method, the maximum central tension value provided by the SCALP is utilized in the RNF method. The graphical representation of the stress distribution derived by the RNF is force balanced and calibrated according to the maximum center tension value provided by the SCALP measurement. As used herein, "depth of layer" (DOL) means the depth to which ions have been exchanged into a substrate and/or portion (e.g., sodium, potassium). Throughout this disclosure, when the maximum center tension cannot be measured directly by the SCALP (e.g., when the article being measured is thinner than about 400 μm), the maximum center tension can be approximated by the product of the maximum compressive stress and the compressive depth divided by the difference between the thickness of the substrate and twice the compressive depth, where the compressive stress and the compressive depth are measured by the FSM.

In some aspects, the substrate 103 including the glass-based portion and/or the ceramic-based portion may include a first compressive stress region located at the first major surface 105 that may extend from the first major surface 105 to a first compressive depth. In some aspects, the substrate 103 including the first glass-based and/or ceramic-based portion can include a second compressive stress region located at the first major surface 107 that can extend from the second major surface 107 to a second compressive depth. In some aspects, the first compression depth and/or the second compression depth as a percentage of the substrate thickness 109 may be about 1% or more, about 5% or more, about 10% or more, about 30% or less, about 25% or less, or about 20% or less. In some aspects, the first compression depth and/or the second compression depth as a percentage of the substrate thickness 109 may be within the following range: about 1% to about 30%, about 5% to about 25%, about 10% to about 30%, about 10% to about 25%, about 10% to about 20%, or any range or subrange therebetween. In some aspects, the first compression depth and/or the second compression depth as a percentage of the substrate thickness 109 may be about 10% or less, for example, about 1% to about 10%, about 3% to about 8%, about 5% to about 8%, or any range or subrange therebetween. In a further aspect, the first compression depth may be substantially equal to the second compression depth. In some aspects, the first depth of compression and/or the second depth of compression may be about 1 μm or more, about 10 μm or more, about 30 μm or more, about 50 μm or more, about 200 μm or less, about 150 μm or less, about 100 μm or less, or about 60 μm or less. In some aspects, the first compression depth and/or the second compression depth may be within the following ranges: about 1 μm to about 200 μm, about 10 μm to about 150 μm, about 30 μm to about 100 μm, about 50 μm to about 60 μm, or any range or subrange therebetween.

In some aspects, the first compressive stress region may include a maximum first compressive stress. In some aspects, the second compressive stress region may include a maximum second compressive stress. In further aspects, the maximum first depth of compression and/or the maximum second depth of compression may be about 100 megapascals (MPa) or more, about 300MPa or more, about 500MPa or more, about 600MPa or more, about 700MPa or more, about 1,500MPa or less, about 1,200MPa or less, about 1,000MPa or less, or about 800MPa or less. In a further aspect, the maximum first compression depth and/or the maximum second compression depth may be within the following range: about 100MPa to about 1,500MPa, about 300MPa to about 1,200MPa, about 500MPa to about 1,000MPa, about 600MPa to about 1,000MPa, about 700MPa to about 800MPa, about 500MPa to about 800MPa, or any range or subrange therebetween.

In some aspects, the substrate 103 may include a first depth layer of one or more alkali metal ions associated with the first compressive stress region. In some aspects, the substrate 103 may include a second depth layer of one or more alkali metal ions associated with a second compressive stress region. As used herein, the one or more alkali metal ions of the deep layer of one or more alkali metal ions may include sodium, potassium, rubidium, cesium, and/or francium. In some aspects, the one or more alkali ions of the first depth layer of one or more alkali ions and/or the second depth layer of one or more alkali ions comprise potassium. In some aspects, the first depth layer and/or the second depth layer may be about 1% or more, about 5% or more, about 10% or more, about 40% or less, about 35% or less, about 30% or less, about 25 or less, or about 20% or less as a percentage of the substrate thickness 109. In some aspects, the percentage of the first depth layer and/or the second depth layer as substrate thickness 109 may be within the following range: about 1% to about 40%, about 1% to about 35%, about 5% to about 30%, about 10% to about 25%, about 10% to about 20%, or any range or subrange therebetween. In some aspects, the first depth layer of one or more alkali metal ions and/or the second depth layer of one or more alkali metal ions may be about 10% or less as a percentage of the substrate thickness 109, for example, about 1% to about 10%, about 3% to about 8%, about 5% to about 8%, or any range or subrange therebetween. In some aspects, the first depth layer of one or more alkali metal ions and/or the second depth layer of one or more alkali metal ions may be about 1 μm or more, about 10 μm or more, about 30 μm or more, about 50 μm or more, about 200 μm or less, about 150 μm or less, about 100 μm or less, or about 60 μm or less. In some aspects, the first depth layer of one or more alkali metal ions and/or the second depth layer of one or more alkali metal ions may be within the following ranges: about 1 μm to about 200 μm, about 10 μm to about 150 μm, about 30 μm to about 100 μm, about 50 μm to about 60 μm, or any range or subrange therebetween.

In some aspects, the substrate 103 may include a first tensile stress region. In some aspects, the first tensile stress region may be positioned between the first compressive stress region and the second compressive stress region. In some aspects, the first tensile stress region may include a maximum first tensile stress. In further aspects, the maximum first tensile stress may be about 10MPa or more, about 20MPa or more, about 30MPa or more, about 100MPa or less, about 80MPa or less, or about 60MPa or less. In a further aspect, the maximum first tensile stress may be within the following range: about 10MPa to about 100MPa, about 20MPa to about 80MPa, about 30MPa to about 60MPa, or any range or subrange therebetween.

Aspects of the present disclosure may include consumer electronics. The consumer electronic product may include a housing comprising a front surface, a back surface, and a side surface. The consumer electronic product may further comprise an electronic component at least partially within the housing. The electronic components may include a controller, a memory, and a display. The display may be located at or adjacent to the front surface of the housing. The display may include a Liquid Crystal Display (LCD), an electrophoretic display (EPD), an organic light emitting diode display (OLED), or a Plasma Display Panel (PDP). The consumer electronic product may include a cover substrate disposed over the display. In some aspects, at least one of a portion of the housing or the cover substrate comprises a coated article as discussed herein. Consumer electronics may include portable electronic devices, such as smartphones, tablet computers, wearable devices, or laptop computers. The consumer electronics may include, for example, a cover lens disposed on the camera. In some aspects, the cover lens may comprise a coated article discussed by the present disclosure. In a further aspect, the coating of the coated article can be used as an easy-to-clean coating.

The coated articles disclosed herein can be incorporated into another article, such as an article (or display article) having a display (e.g., consumer electronics devices including mobile phones, tablet computers, navigation systems, wearable devices (e.g., watches), etc.), architectural articles, transportation articles (e.g., automobiles, trains, aircraft, marine vessels, etc.), appliance articles, or any article that can benefit from some transparency, abrasion resistance, or a combination thereof. Exemplary articles incorporating any of the coated articles disclosed herein are shown in fig. 5-6. In particular, fig. 5-6 illustrate a consumer electronic device 500 comprising a housing 502, the housing 502 having a front surface 504, a back surface 506, and side surfaces 508. Although not shown, the consumer electronic device may include electronic components at least partially or entirely within the housing. For example, the electronic components include at least a controller, a memory, and a display. As shown in fig. 5-6, the display 510 may be located at or adjacent to the front surface of the housing 502. The consumer electronic device can include a cover substrate 512 at or on the front surface of the housing 502 such that it is located over the display 510. In some aspects, at least one of the cover substrate 512 or a portion of the housing 502 can comprise any of the coated articles disclosed herein.

Fig. 4 shows a vehicle interior 401 that includes three different vehicle

interior systems

400, 440, and 480. The vehicle interior system 400 includes a dashboard base 410 having a curved surface 420, including a display shown as curved display 430. The dashboard base 410 generally includes a dashboard 415, which dashboard 415 may also include a curved display. The vehicle interior system 440 includes a center console base 450 having a curved surface 460, including a display shown as curved display 470. The vehicle interior system 480 includes a fascia base 485 having a curved surface 490 and a display, shown as curved display 495. Any of these vehicle interior systems may include the

coated articles

101, 201, and/or 301 discussed herein. In some aspects, the vehicle interior system includes a base that is an armrest, a post, a seat back, a floor, a headrest, a door panel, or any portion of the vehicle interior that includes a curved surface. Although fig. 4 shows an automobile interior, aspects of the vehicle interior system may be incorporated into any type of vehicle, such as trains, automobiles (e.g., cars, trucks, buses, etc.), seagoing vessels (boats, ships, submarines, etc.), and aircraft (e.g., drones, planes, jet planes, helicopters, etc.), including human joystick vehicles, semi-autonomous vehicles, and fully autonomous vehicles.

Aspects of methods of making coated articles and/or substrates according to the present disclosure will be discussed with reference to the flowchart in fig. 13 and the exemplary method steps shown in fig. 14-16. Exemplary aspects of manufacturing the coated

articles

101, 201, and/or 301 shown in fig. 1-3 will now be discussed with reference to the flowcharts in fig. 14-16 and 13. In a first step 1301 of the method of the present disclosure, the method may provide for a substrate 103 to start. In some aspects, the substrate 103 may be provided by purchasing or otherwise obtaining the substrate or by forming the substrate. In some aspects, the substrate 103 may comprise a glass-based substrate and/or a ceramic-based substrate. In a further aspect, the glass-based substrate and/or ceramic-based substrate may be provided by shaping them using a variety of ribbon shaping processes (e.g., slot draw, drop down, fusion drop down, pull up, press roll, heavy pull, or float process). In a further aspect, the ceramic-based substrate may be provided by heating a glass-based substrate to crystallize one or more ceramic crystals. In some aspects, the substrate 103 may be strengthened by one or more compressive stress regions, e.g., chemical strengthening or thermal strengthening, as discussed above. The substrate 103 can include a first major surface 105 and a second major surface 107 opposite the first major surface 105 with a substrate thickness 109 defined therebetween.

After step 1301, as shown in fig. 14, the method may proceed to step 1303, which includes: one or more layers 223 are disposed on the substrate 103 (e.g., the first major surface 105). As shown, a precursor 1401 may be disposed on the first major surface 105 of the substrate 103 to form one or more layers 223. In some aspects, one or more layers may be set using the following method: chemical Vapor Deposition (CVD) (e.g., low pressure CVD, plasma Enhanced CVD (PECVD)), physical Vapor Deposition (PVD) (e.g., sputtering, evaporation, molecular beam epitaxy, ion plating), atomic Layer Deposition (ALD), spray pyrolysis, chemical bath deposition, sol-gel deposition. For example, step 1303 may use PECVD and/or PVD under the conditions discussed below for

steps

1305 and 1307, respectively, with minor modifications to accommodate the composition of the materials being set. The one or more layers may include one or more of the materials discussed above for the one or more layers 223. In some aspects, one or more layers may be used as an antireflective stack.

After

step

1301 or 1303, as shown in fig. 15, the method may proceed to step 1305, which includes the following: the coating is provided using a premised Plasma Enhanced Chemical Vapor Deposition (PECVD). In some aspects, as shown in fig. 15, step 1305 may occur in a PECVD apparatus 1501 including a reaction chamber 1521. In a further aspect, as shown, a Radio Frequency (RF) generator 1503 may be connected to the electrode 1517 for plasma generation through the matching network 1505. For example, the RF generator 1503 may oscillate at 13.56 megahertz (MHz). In a further aspect, the RF generator 1503 may be connected to a power supply 1507, the power supply 1507 comprising about 2 kilowatts (kW) or more, about 4kW or more, about 10kW or less, or about 7kW or less, such as between about 2kW and about 10kW, about 4kW and about 7kW, or any range or subrange therebetween, of nameplate power. In a further aspect, a Direct Current (DC) bias voltage can be applied to the substrate 103 by a potential difference 1509 established between ground and a substrate holder 1531 on which the substrate 103 is disposed (e.g., the second major surface 107 of the substrate 103 can contact a surface 1533 of the substrate holder 1531). In a still further aspect, a Direct Current (DC) bias voltage may be applied to the substrate. In still further aspects, the DC bias may be about-100 volts (V) or less, about-200V or less, about-250V or less, about-400V or more, about-350V or more, or about-300V or more. In a further aspect, the DC bias may be in the following range: about-100V to about-400V, about-200V to about-350V, about-250V to about-300V, or any range or subrange therebetween. In some aspects, the reaction chamber 1521 may be maintained at a temperature of about 50 ℃ or more, about 100 ℃ or more, about 130 ℃ or less, about 300 ℃ or less, about 200 ℃ or less, or about 170 ℃ or less. In some aspects, the reaction chamber may be maintained at a temperature within the range of: about 50 ℃ to about 300 ℃, about 100 ℃ to about 200 ℃, about 130 ℃ to about 170 ℃, or any range or subrange therebetween. In some aspects, the reaction chamber may be at an absolute pressure of about 1Pa (Pa) or less, about 0.1Pa or less, about 0.01Pa or less, or about 0.005Pa or less under vacuum.

In some aspects, as shown in fig. 15, a working gas comprising a precursor may be fed through inlet 1511 in direction 1513 (e.g., from precursor source 1527 toward electrode 1517). In a further aspect, the working gas may be introduced at an absolute working pressure of about 1MPa or more, about 5MPa or more, about 10MPa or more, about 100MPa or less, about 60MPa or less, about 30Pa or less, or about 20MPa or less. In a further aspect, the absolute operating pressure may be within the following range: about 1GPa to about 100GPa, about 5GPa to about 60GPa, about 5GPa to about 30GPa, about 10GPa to about 20GPa, or any range or subrange therebetween. In a further aspect, the precursor includes hydrogen, carbon, and silicon. In a still further aspect, the precursor may also include at least one of oxygen or nitrogen. In a still further aspect, the precursor may include a molecule comprising each of the above atoms, for example, an alkylsilane having an amino functionality or an alkylsilane having a glycidyl, epoxy or other functionality. In a still further aspect, the precursor may include hydrocarbons, orthosilicates, and hydrogen. As used herein, a hydrocarbon consists of hydrogen and carbon, for example, an alkane, alkene, or alkyne. Exemplary aspects of the hydrocarbon include methane. In a still further aspect, the hydrocarbon may comprise an alkane, and the orthosilicate may comprise an alkylsilicate. Exemplary aspects of the precursor include methane, tetraethyl orthosilicate (TEOS), and hydrogen. In a further aspect, the working gas may include an inert gas in addition to the precursor. For example, the inert gas may include helium, neon, argon, and/or krypton. In a further aspect, the working gas may include a ratio based on standard cubic centimeters (sccm), for example, 1 part methane to 10 parts hydrogen under 2 parts argon (Ar), wherein the argon has been bubbled through an orthosilicate (e.g., TEOS). For example, argon may be bubbled through an orthosilicate (e.g., TEOS) at an elevated temperature (e.g., about 40 ℃ to about 100 ℃, about 50 ℃ to about 60 ℃) and the vapor pressure of the orthosilicate may be in the following range: about 1 kilopascal (kPa) to about 15kPa, about 2kPa to about 8kPa, about 3kPa to about 5kPa, or any range or subrange therebetween. In still further aspects, the sccm-based hydrogen to methane ratio may be about 5 or more, about 8 or more, about 20 or less, about 15 or less, or about 12 or less. In a further aspect, the sccm-based hydrogen to methane ratio may be in the following range: about 5 to about 20, about 8 to about 15, about 8 to about 12, or any range or subrange therebetween. In still further aspects, the sccm-based TEOS methane ratio may be about 0.3 or more, about 0.5 or more, about 0.7 or more, about 1 or more, about 8 or less, about 4 or less, about 2 or less, or about 1.5 or less. In a still further aspect, the sccm-based TEOS methane ratio may be in the following range: about 0.3 to about 8, about 0.5 to about 4, about 0.7 to about 2, about 1 to about 1.5, or any range or subrange therebetween.

In some aspects, as shown in fig. 15, a working gas can be fed through the inlet 1511 and through the electrode 1517 to generate the plasma 1523. In a further aspect, as shown, the working gas may be fed through a showerhead diffuser 1515, which showerhead diffuser 1515 may distribute the gas through a plurality of openings 1519, wherein one or more of the plurality of openings are surrounded by an electrode 1517. In some aspects, the plasma may provide a coating on the substrate 103, as indicated by arrow 1525. In a further aspect, the coating can be disposed directly on (i.e., in contact with) the first major surface 105 of the substrate 103. In a further aspect, as indicated by the dashed lines, one or more layers 223 can be disposed on the substrate (e.g., from step 1303) such that the coating will contact the one or more layers 223 while still disposed on the first major surface 105 of the substrate 103.

After

step

1301 or 1303, as shown in fig. 16, the method may proceed to step 1307, which includes: physical Vapor Deposition (PVD) is used to provide the coating. PVD can include sputtering, evaporation, molecular beam epitaxy, and/or ion plating. In some aspects, PVD may include sputtering, for example, DC magnetron sputtering. In a further aspect, as shown in fig. 16, sputtering can be performed using a sputtering apparatus 1601, the sputtering apparatus 1601 comprising a sputtering target 1603 and a substrate 103 positioned in a reaction chamber 1621. In a still further aspect, the substrate 103 can be positioned and/or secured on the substrate holder 1631, for example, wherein the second major surface 107 of the substrate 103 contacts the outer surface 1633 of the substrate holder. In a still further aspect, the sputtering target 1603 can be positioned and/or secured to a target holder 1641.

In still further aspects, the sputter target can include a carbon source (e.g., graphite) and/or a silicon source. In a further aspect, as shown in fig. 16, a working gas may be fed through inlet 1611 in direction 1613 (e.g., from precursor source 1615). The working gas can include and/or form ions 1617, which ions 1617 can strike the outer surface 1605 of the sputtering target 1603 as indicated by arrows 1619 to eject material 1623 from the sputtering target as indicated by arrows 1625. In a still further aspect, material 1623 may be reactive with the working gas, as indicated by 1627, and disposed on substrate 103, as indicated by arrow 1629. In a still further aspect, the working gas may include an inert gas and a precursor. In a still further aspect, the precursor may include one or more of the materials discussed above with respect to the precursor with reference to step 1305. For PVD, an exemplary aspect of the hydrocarbon for the working gas is acetylene. In a still further aspect, the coating may be disposed directly on (i.e., in contact with) the first major surface 105 of the substrate 103. In a still further aspect, as indicated by the dashed lines, one or more layers 223 can be disposed on the substrate (e.g., from step 1303) such that the coating will contact the one or more layers 223 while still disposed on the first major surface 105 of the substrate 103.

After

steps

1305 or 1307, the method can proceed to step 1309 which includes assembling the coated article. In some aspects, the coated article may be incorporated into another article. As discussed above, the coated article may be incorporated into a display device, for example, as a cover lens. As discussed above with reference to fig. 4, the coated article may be incorporated into a vehicle interior system as part of a display. It should be appreciated that the coated article may be incorporated into any of the articles or applications discussed above. After

steps

1305, 1307, or 1309, a method of manufacturing a substrate and/or coating an article according to the present disclosure of the flowchart in fig. 13 may be completed at step 1311.

In some aspects, methods of making coated articles according to aspects of the present disclosure may proceed sequentially along

steps

1301, 1303, 1305, 1309, and 1311 of the flowchart in fig. 13, as discussed above. In some aspects, for example, arrow 1302 may follow from step 1301 to step 1305 if substrate 103 already includes one or more layers disposed thereon in step 1301 or if coating 113 is to be disposed directly on substrate 103 in step 1305. In some aspects, for example, if PVD is to be used instead of PECVD to provide the coating, and the substrate 103 already includes one or more layers disposed thereon in step 1301, or if the coating 113 is to be disposed directly on the substrate 103 in step 1307, then arrow 1304 may follow from step 1301 to step 1307. In some aspects, for example, if PVD is to be used instead of PECVD to provide a coating, arrow 1310 may follow from step 1303 to step 1307. In some aspects, for example, if the method is complete after the coating 113 is disposed in step 1305, arrow 1306 may follow from step 1305 to step 1311. In some aspects, for example, if the method is complete after the coating 113 is disposed in step 1307, arrow 1308 can follow from step 1307 to step 1311. Any of the above options may be combined to make a coated article according to aspects of the present disclosure.

Examples

Various aspects will be further elucidated by the following examples. Examples A-C and AA-BB include a glass-based substrate (composition 1:63.6SiO with the following nominal composition in mol% ₂ ；15.7Al ₂ O ₃ ；10.8Na ₂ O；6.2Li ₂ O；1.16ZnO；0.04SnO ₂ The method comprises the steps of carrying out a first treatment on the surface of the 2.5P ₂ O ₅ ) The substrate thickness 109 is 700 μm. Examples a-C follow the above with layers and/or coatings comprising the materials set forth in table 1The method of layer description deals with. The coatings of examples A-C and BB were set using PECVD with a 13.56 megahertz (MHz) RF generator and a-300V Direct Current (DC) bias applied to the substrate, wherein the generator was powered by a 6 kilowatt (kW) power supply and the reaction chamber was maintained at 16 millipascals (mPa) (absolute) at 150 ℃. For examples A-C, methane (CH) ₄ ) Hydrogen (H) ₂ ) Working gases of tetraethyl orthosilicate (TEOS) and argon (Ar) were introduced into the reaction chamber, wherein the working pressure was 15 Pa (absolute). Specifically, the working gas used in examples A-C consisted of 1 standard cubic centimeter (sccm) of methane/10 sccm of hydrogen, 2sccm of argon, wherein the argon was bubbled through TEOS at 50℃, wherein the vapor pressure of TEOS was 3.3kPa. As used herein, sccm refers to the equivalent flow rate at a temperature of 23℃and a pressure of 101 kilopascals (kPa). For embodiment BB, the working gas comprises methane (CH ₄ ) Hydrogen (H) ₂ ) And argon (Ar), wherein the working pressure is 15Pa (absolute), and the ratio is 1sccm methane/10 sccm hydrogen and 2sccm argon.

In example a, the coating comprises a coating thickness of 125nm and is disposed directly on the substrate (i.e., the coating contacts the substrate). Example a includes a contact angle of 120 °. Example BB is a comparative example comprising a diamond-like coating (DLC) exhibiting a contact angle of 56.4 °.

For example a, the surface of the coating (i.e., the second surface area) included a surface roughness Ra of 15nm, a surface roughness Rz of 263nm, a surface roughness Rq of 18nm, a skewness Rsk of 0.164, and a kurtosis of 2.85. These properties indicate that the coating is hydrophobic and that the surface profile of the coating is skewed to a lower height and is relatively flat. Fig. 7 schematically shows a Scanning Electron Microscope (SEM) image of the coating surface of example a. As shown in fig. 7, the raised structures form a porous surface, which reduces the surface area accessible on the micrometer scale. The porosity of the coating was calculated based on fig. 7, as discussed above. Example a included a porosity of 32%.

Example AA is a comparative example comprising an uncoated substrate. Fig. 8 shows the transmittance on the vertical axis 803 (i.e., y-axis) versus the wavelength of light on the horizontal axis 801 (i.e., x-axis). The transmittance distribution for example a is shown as curve 807, while the transmittance distribution for example AA is shown as curve 805. As shown in fig. 8, the transmittance of example a (curve 807) was greater than the transmittance of example AA (curve 805) at each optical wavelength measured. For example, at 500nm, example a includes a transmittance of about 93%, while example AA includes a transmittance of about 91.5%. Example a included an average transmittance of about 93.5% averaged over an optical wavelength of 400nm to 700 nm. As such, the coating may increase the light transmittance of the coated article (example a) relative to the uncoated substrate (example AA), and the coated article may have a light transmittance at 500nm and an average light transmittance of greater than 91%, greater than 92%, greater than about 93%.

Fig. 9 shows the reflectivity on the vertical axis 903 (i.e., the y-axis) versus the optical wavelength on the horizontal axis 801 (i.e., the x-axis). The reflection curve for example a is shown as curve 905. For each wavelength of light measured, the reflectance is less than 2%. For example, example A has a reflectivity of about 1.4% at 500 nm. On average over wavelengths of light from 400nm to 700nm, example a includes an average reflectance of about 1.5%.

FIG. 10 shows absorbance on the vertical axis 1003 (left side) and the vertical axis 1013 (right side in cm ^-1 In units) to the optical wavelength on the horizontal axis 801. Curve 1005 represents the absorbance of example a and curve 1015 represents the extinction coefficient of example a. As shown in fig. 10, the absorbance was less than 2% for all measured optical wavelengths. Curve 1005 decreases as the optical wavelength increases from about 400nm to about 480 nm. At 500nm, example a included an absorbance of about 1.17%. Example a included an average absorbance of about 0.60% averaged over an optical wavelength of 400nm to 700 nm. As shown in fig. 10, the reflectance was less than 5% for all measured optical wavelengths. Curve 1015 is from about 0.01cm at 380nm ^-1 Monotonically decreasing to about 0.0002cm at 780nm ^-1 . At 500nm, example A included an extinction coefficient of about 0.0077%. On average over an optical wavelength of 400nm to 700nm, example a includes an average extinction coefficient of about 0.006.

Fig. 11 shows refractive index on the vertical axis 1103 (i.e., y-axis) versus optical wavelength on the horizontal axis 801 (i.e., x-axis). The curve 1105 represents the refractive index of example a. As shown in fig. 11, the refractive index of example a monotonically linearly decreases from 380nm to 780nm, from about 1.44 at 380nm to about 1.16 at 780 nm. At 500nm, example A included a refractive index of 1.365. On average over an optical wavelength of 400nm to 700nm, example a includes an average refractive index of about 1.326.

The coating of example a was analyzed using energy dispersive X-ray analysis (EDX), indicating that the coating included 13.5 atomic% C, 56.6 atomic% O, and 18.3 atomic% Si, with the balance being less than 10 atomic% elements. As discussed above, EDX results do not include hydrogen. These results correspond to an atomic ratio of 1 part carbon to about 4.2 parts oxygen and 1.36 parts silicon. For example, if the composition of the above elements is scaled to 100 atomic% of the coating, the composition (based on no hydrogen) will be about 15.3 atomic% C, 64.0 atomic% O, and 20.7 atomic% Si.

Example a was subjected to the medium wear test described above. After 10,000 cycles, the coating of example a remained intact. After 10,000 cycles, the coated surface of example a included a contact angle of 70 ℃.

Table 1: material disposed on a substrate

Examples	A	B	C
				Coating layer	125nm	5nm	10nm
Layer
	5	--	85nm SiO ₂	78nm SiO ₂
Layer 4					--	111nm NbO _x	113nm Nb ₂ O ₅
	Layer 3	--	38nm SiO ₂	39nm SiO ₂
Layer 2					--	11.5nm NbO _x	11.7nm Nb ₂ O ₅
	Layer 1	--	25nm SiO ₂	25nm SiO ₂

As shown in table 1, examples B-C include five layers between the coating and the substrate. The material of these layers is the same for examples B and C, i.e. layers 1 to 5 are deposited on silicon dioxide (SiO ₂ ) With niobium oxide (Nb) ₂ O ₅ ) Alternating between, where x is between 1 and 2.5. The thickness of layers 1-4 is substantially the same between examples B and C. The thickness of layer 5 in example C was about 7nm less than in example B, but the coating in example C was about 5nm thicker than in example B. The total thickness of the material disposed on the substrate in examples B-C was about 275nm. The coatings of examples B and C had a refractive index of 1.36 at 500 nm.

The CIE color coordinates of examples B and C are presented in table 2. Examples B and C both include negative a (i.e., a < 0) and B (i.e., B < 0), which results in a blue color. The CIE a and B values of example B are greater than example C, which gives example B a stronger blue (e.g. cyan) than example C. Embodiments B and C each include B values greater than-2 (e.g., about-2 to about 2, -2 to 0) and a values greater than-2 (e.g., about-2 to about 2, -2 to 0). Examples B and C include values of L greater than 1.5, i.e., between 1.5 and 2.

TABLE 2 CIE color coordinates

Examples	B	C
			L*	1.696	1.818
a*	-1.946	-0.406
			b*	-1.457	-0.602

Fig. 12 shows reflectivity on the vertical axis 1203 (i.e., y-axis) versus optical wavelength on the horizontal axis 1201 (i.e., x-axis). Curve 1205 corresponds to the reflectivity of embodiment B, and curve 1207 corresponds to the reflectivity of embodiment C. As shown in fig. 12, embodiment B includes a reflectivity of less than 0.02% at about 620nm, and embodiment C includes a reflectivity of less than 0.02% at about 440 nm. The reflection curves for examples B and C each include two minima at about 430nm to about 440nm and about 620nm to about 630 nm. Between these minima, embodiment C includes a reflectivity of less than 0.3%, while embodiment B includes a reflectivity of about 0.32% or less. From about 425nm to about 650nm, examples B and C have a reflectance of less than about 0.32%. For example B, the average reflectance over the optical wavelength of 400nm to 700nm was about 0.32%. For example C, the average reflectance over the optical wavelength of 400nm to 700nm was about 0.41%.

The above observations can be combined to provide coated articles having contact angles with deionized water of 90 ° or greater. The coated article may include a substrate including a glass-based material and/or a ceramic-based material, which may provide good dimensional stability, good impact resistance, and/or good puncture resistance. The substrate comprising glass-based material and/or ceramic-based material may comprise one or more compressive stress regions, which may further provide increased impact resistance and/or increased puncture resistance.

Directional terms such as up, down, right, left, front, rear, top, bottom as used herein are made with reference only to the drawings being drawn and are not intended to imply absolute orientation.

It is to be understood that the various disclosed aspects may be directed to features, elements, or steps described in connection with the particular aspects. It will also be appreciated that features, elements, or steps, although described with respect to one aspect, may be interchanged or combined in various alternative aspects not shown in the figures or arranged in the figures.

It will be further understood that, as used herein, the terms "a," "an," or "the" mean "at least one," and should not be limited to "only one," unless explicitly indicated to the contrary. For example, reference to "a component" includes aspects having two or more such components unless the context clearly indicates otherwise. Likewise, "a plurality of" is intended to mean "more than one".

As used herein, the term "about" means that the amounts, sizes, formulations, parameters, and other amounts and characteristics are not, and need not be, exact, but may be approximated and/or greater or lesser according to the following requirements: reflecting tolerances, scaling factors, rounding off, measurement errors and the like, as well as other factors known to those skilled in the art. Ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, aspects include from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. Whether a numerical value or endpoint of a range in the specification expresses "about," the numerical value or endpoint of the range is intended to include two aspects: one modified by "about" and one not modified by "about". It will also be appreciated that each range end value is significant, either with respect to the other end value or independent of the other end value.

The terms "substantially", "essentially" and variations thereof as used herein are intended to indicate that the feature being described is equal to or approximately equal to a value or description. For example, a "substantially planar" surface is intended to mean a planar or near-planar surface. Further, as defined above, "substantially" is intended to mean that the two values are equal or approximately equal. In some aspects, "substantially similar" may mean values within about 10% of each other, e.g., within about 5% of each other or within about 2% of each other.

Unless explicitly stated otherwise, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that any specific order be inferred.

While various features, elements, or steps of a particular aspect may be disclosed using the transitional word "comprising", it should be understood that alternative aspects are implied, including those aspects that may use the transitional word "consisting of … …" or "consisting essentially of … …". Thus, for example, implications for alternative aspects of a device comprising a+b+c include aspects in which the device consists of a+b+c and aspects in which the device consists essentially of a+b+c. As used herein, the terms "comprising" and "including" and variations thereof are to be interpreted as synonymous and open-ended, unless otherwise indicated.

The features of the aspects and aspects described above are exemplary and may be provided alone or in combination with any one or more of the features of the other aspects provided herein without departing from the scope of the present disclosure.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present disclosure without departing from the spirit or scope of the disclosure. Accordingly, it is intended that the present disclosure cover the modifications and variations of this disclosure provided they come within the scope of the appended claims and their equivalents.

Claims

1. A coated article, comprising:

a substrate comprising a first major surface; and

a coating disposed on the substrate, the coating comprising a surface having a contact angle with deionized water of 90 ° or more, the coating having a refractive index less than the refractive index of the substrate, and the coating comprising an interpenetrating network of hydrogenated amorphous carbon and amorphous silicon oxide.

2. The coated article of claim 1, wherein the refractive index of the coating is in the range of about 1.3 to about 1.4.

3. The coated article of any of claims 1-2, wherein the refractive index of the coating is less than 1.37.

4. The coated article of any of claims 1-3, wherein the thickness of the coating is in the range of about 0.1 nanometers to about 200 nanometers.

5. The coated article of claim 4, wherein the thickness of the coating is in the range of about 1 nm to about 50 nm.

6. The coated article of any one of claims 1-5, wherein the contact angle is in a range of about 100 ° to about 140 °.

7. The coated article of any of claims 1-6, wherein the surface of the coating comprises a surface roughness Ra in a range of about 10 nanometers to about 20 nanometers.

8. The coated article of any of claims 1-7, wherein the surface of the coating comprises a surface roughness Rz in the range of about 100 nanometers to about 300 nanometers.

9. The coated article of any of claims 1-8, wherein the surface of the coating comprises a skewness Rsk in the range of 0 to about 0.3.

10. The coated article of any of claims 1-9, wherein the surface of the coating comprises a kurtosis Rku of less than 3.

11. The coated article of any one of claims 1-10, wherein the coated article comprises a transmittance of 91% or more at 500 nm.

12. The coated article of claim 11, wherein the transmittance of the coated article at 500 nm is greater than the transmittance of a substrate without the coating at 500 nm.

13. The coated article of any one of claims 1-12, wherein the coated article has an average transmittance of about 91% or more over an optical wavelength of 400 nm to 700 nm.

14. The coated article of claim 13, wherein the average transmittance of the coated article is in the range of about 92 percent to about 95 percent.

15. The coated article of any of claims 1-14, wherein the average reflectivity of the surface of the coating averages about 2.0% or less over an optical wavelength of 400 nm to 700 nm.

16. The coated article of claim 15, wherein the average reflectivity of the surface of the coating is in the range of about 0.5% to about 1.5%.

17. The coated article of any one of claims 1-16, wherein the coating comprises about 0.01cm at about 500 nanometers ^-1 Or less.

18. As in claims 1-17The coated article of any one of claims, wherein the average extinction coefficient averages about 0.001cm over an optical wavelength of 400 nm to about 700 nm ^-1 To about 0.004cm ^-1 Within a range of (2).

19. The coated article of any one of claims 1-18, wherein the coating has a porosity in the range of about 5% to about 50%.

20. The coated article of any one of claims 1-19, wherein the surface of the coating is an outer surface of the coated article.

21. The coated article of any of claims 1-20, wherein the coating contacts the first major surface of the substrate.

22. The coated article of any of claims 1-20, further comprising a layer disposed between the coating and the substrate, the layer comprising one or more of silicon oxide, silicon nitride, titanium oxide, or niobium oxide.

23. The coated article of claim 22, wherein the layer comprises a plurality of layers that function as an antireflective stack.

24. The coated article of claim 23, wherein the refractive index of the coating is about 0.05 or more less than an outermost layer of the plurality of layers.

25. The coated article of claim 23, wherein the refractive index of the coating is about 0.1 or more less than an outermost layer of the plurality of layers.

26. The coated article of any one of claims 1-25, wherein the contact angle of the coating is about 70 ° or more after the surface of the coating is abraded with cheesecloth for 10,000 cycles according to ISO 9211-4:2012.

27. The coated article of any one of claims 1-26, wherein the coated article comprises a CIE b x value in the range of about 0 to about-6.

28. The coated article of claim 27, wherein the coated article comprises a CIE a x value in the range of about 0 to about-6.

29. The coated article of any one of claims 1-28, wherein the coating is fluorine-free.

30. The coated article of any one of claims 1-29, wherein the coating is nitrogen-free.

31. The coated article of any one of claims 1-29, wherein the coating comprises amorphous silicon nitride.

32. The coated article of any one of claims 1-31, wherein the coating comprises a silicon to carbon atomic ratio of about 0.7 to about 2.

33. The coated article of any one of claims 1-32, wherein the coating comprises an oxygen to carbon atomic ratio of about 2 to about 5.

34. The coated article of any of claims 1-33, wherein the coating comprises a dynamic coefficient of friction of about 0.3 or less.

35. The coated article of any of claims 1-34, wherein the substrate comprises a glass-based material or a ceramic-based material.

36. The coated article of claim 35, wherein the substrate is a cover lens of a display and the coating is used as an easy-to-clean coating.

37. The coated article of claim 35, wherein the display is a component of a vehicle interior system.

38. A method of forming a coated article, comprising:

a coating is disposed on a substrate using plasma enhanced chemical vapor deposition on a precursor comprising hydrogen, carbon, and silicon, the precursor further comprising at least one of oxygen or nitrogen, wherein a contact angle of a surface of the coating with deionized water is 90 ° or more, a refractive index of the coating is less than a refractive index of the substrate, and the coating comprises an interpenetrating network of hydrogenated amorphous carbon and at least one of amorphous silicon oxide or amorphous silicon nitride.

39. A method of forming a coated article, comprising:

a coating is disposed on a substrate using physical vapor deposition on a precursor comprising hydrogen, carbon, and silicon, the precursor further comprising at least one of oxygen or nitrogen, wherein a contact angle of a surface of the coating with deionized water is 90 ° or more, a refractive index of the coating is less than a refractive index of the substrate, and the coating comprises an interpenetrating network of hydrogenated amorphous carbon and at least one of amorphous silicon oxide or amorphous silicon nitride.

40. The method of any of claims 38-39, wherein the precursors comprise methane, hydrogen, and orthosilicate.

41. The method of any one of claims 38-40, wherein the refractive index of the coating is in the range of about 1.3 to about 1.4.

42. The method of any of claims 38-40, wherein the refractive index of the coating is less than 1.37.

43. The method of any one of claims 38-42, wherein the coating has a thickness in a range of about 0.1 nanometers to about 200 nanometers.

44. The method of claim 43, wherein said thickness of said coating is in the range of about 1 nanometer to about 50 nanometers.

45. The method of any one of claims 38-44, wherein the contact angle is in the range of about 100 ° to about 140 °.

46. The method of any one of claims 38-45, wherein the surface of the coating comprises a surface roughness Ra in a range of about 10 nanometers to about 20 nanometers.

47. The method of any one of claims 38-46, wherein the surface of the coating comprises a surface roughness Rz in the range of about 100 nanometers to about 300 nanometers.

48. The method of any one of claims 38-47, wherein the surface of the coating comprises a skewness Rsk in the range of 0 to about 0.3.

49. The method of any one of claims 38-48, wherein the surface of the coating comprises a kurtosis Rku of less than 3.

50. The method of any of claims 38-49, wherein the coating comprises a silicon to carbon atomic ratio of about 0.7 to about 2.

51. The method of any one of claims 38-50, wherein the coating comprises an oxygen to carbon atomic ratio of about 2 to about 5.

52. The method of any of claims 38-51, wherein the coating comprises a dynamic coefficient of friction of about 0.3 or less.

53. The method of any one of claims 38-52, wherein the substrate comprises a glass-based material or a ceramic-based material.

54. The method of any of claims 38-53, wherein the coated article comprises a transmittance at 500nm of 92% or more.

55. The method of claim 54, wherein the transmittance at 500nm of the coated article is greater than the transmittance at 500nm of a substrate without the coating.

56. The method of any one of claims 38-55, wherein the average transmittance of the coated article averages about 91% or more over an optical wavelength of 400 nm to 700 nm.

57. The method of claim 56, wherein said average transmittance of said coated article is in the range of about 92 percent to about 95 percent.

58. The method of any one of claims 38-57, wherein the average reflectivity of the surface of the coating averages about 2.0% or less over an optical wavelength of 400 nm to 700 nm.

59. The method of claim 58, wherein said average reflectivity of said surface of said coating is in the range of about 0.5% to about 1.5%.

60. The method of any one of claims 38-59, wherein the coating comprises about 0.01cm at about 500 nanometers ^-1 Or less.

61. The method of any one of claims 38-60, wherein the average extinction coefficient averages about 0.001cm over an optical wavelength of 400 nm to about 700 nm ^-1 To about 0.004cm ^-1 Within a range of (2).

62. The method of any one of claims 38-61, wherein the porosity of the coating is in the range of about 5% to about 50%.

63. The method of any one of claims 38-62, wherein the coating comprises the contact angle of about 70 ° or greater after the surface is abraded with cheesecloth for 10,000 cycles according to ISO 9211-4:2012.

64. The method of any one of claims 38-63, wherein the coated article comprises a CIE b x value in the range of about 0 to about-6.

65. The method of claim 64, wherein the coated article comprises a CIE a value in the range of about 0 to about-6.

66. The method of any of claims 38-65, wherein the coating contacts the substrate.

67. The method of any one of claims 38-65, further comprising disposing one or more layers prior to disposing the coating, wherein the one or more layers comprise one or more of silicon oxide, silicon nitride, titanium oxide, or niobium oxide.

68. The method of claim 67, wherein the layers comprise a plurality of layers that function as an anti-reflective stack.

69. The method of claim 67, wherein the refractive index of the coating is about 0.05 or more less than the outermost layer of the plurality of layers.

70. The method of claim 67, wherein the refractive index of the coating is about 0.1 or more less than the outermost layer of the plurality of layers.

71. The method of any one of claims 38-70, wherein the coating is fluorine-free.

72. The method of any one of claims 38-71, wherein the coating is nitrogen-free.