Three-material Anti-reflective coating and articles with the same

Abstract

An article is described herein that includes: a substrate having a major surface; and an anti-reflective coating on the major surface that comprises a plurality of layers. The coating comprises a low refractive index (RI) capping layer of SiO2 and periods of an alternating low RI layer and one or more high RI layers, one of the low RI layers in direct contact with the major surface, and the capping layer on the periods. One of the periods comprises at least two high RI layers, a layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2, and a layer comprising SiNx or AlOxNy. The article exhibits one or more of: (i) a first-surface photopic average reflectance (Y) of ≤ 0.18, (ii) a first-surface reflected color chroma (C*) of ≤ 3.5 at all incidence angles of 0⁰-60⁰, where C* = √(a*2 + b*2), and (iii) a two-surface transmittance T(940 nm) of ≥ 88%.

Description

Attorney Docket No.: SP24-275THREE-MATERIAL ANTI-REFLECTIVE COATING AND ARTICLES WITH THE SAMECLAIM OF PRIORITY

[0001] This application claims the benefit of priority under 35 U. S. C. § 119 of U. S.Provisional Application Serial No. 63 / 730,114, filed on December 10, 2024, the content of which is relied upon and incorporated herein by reference in its entirety.FIELD OF THE DISCLOSURE

[0002] The disclosure relates to low reflectance, anti-reflective structures with high durability and articles having such structures, including such articles and structures with chemical resistance, low average visible reflectance, abrasion resistance, and controlled color over a range of viewing angles, along with high hardness.BACKGROUND

[0003] Cover articles are often used to protect devices within electronic products, to provide a user interface for input and / or display, and / or for many other functions. Such products include mobile devices, for example smart phones, smart watches, mp3 players and computer tablets. Cover articles also include architectural articles, transportation articles (e.g., interior and exterior display and non-display articles used in automotive applications, trains, aircraft, sea craft, etc.), appliance articles, or any article that may benefit from some transparency, scratch-resistance, abrasion resistance or a combination thereof. These applications often demand scratch-resistance and strong optical performance characteristics, in terms of maximum light transmittance and minimum reflectance.

[0004] Furthermore, for some cover applications it is beneficial that the color exhibited or perceived, in reflection and / or transmission, does not change appreciably as the viewing angle is changed. In display applications, this is because, if the color in reflection or transmission changes with viewing angle to an appreciable degree, the user of the product will perceive a change in color or brightness of the display, which can diminish the perceived quality of the display. In other applications, changes in color may negatively impact the aesthetic appearance or other functional aspects of the device.

[0005] As for durability and reliability, cover applications can have specific abrasion and damage resistance requirements. For example, laptop and tablet cover applications oftenAttorney Docket No.: SP24-275require no visible delamination from scratch, wear, and exposure to moisture and chemicals that occur during typical daily usage. As another example, automotive interior display cover applications can require no visible delamination from similar or even more stringent scratch, wear and exposure levels over substantially longer durations, e.g., 10 years of service, and under more challenging environmental conditions, e.g., -40°C to 85°C temperature extremes, 95% relative humidity, and exposure to dust and various chemicals. Further, conventional articles with anti-reflective structures can exhibit acceptable optical performance, but often with lower-than-acceptable mechanical performance and resistance to chemicals.

[0006] Accordingly, there is a need for articles and structures with chemical resistance, low average visible reflectance, abrasion resistance, and controlled color over a range of viewing angles, along with high hardness. This need and other needs are addressed by the present disclosure.SUMMARY

[0007] According to some embodiments of the disclosure, an article is provided that includes: a substrate having a first and second major surface, the first and second major surfaces opposing one another; and an anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface, wherein the anti-reflective coating comprises a plurality of layers. Further, the anti-reflective coating comprises a capping layer and a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, wherein one of the low refractive index layers is in direct contact with the major surface of the substrate, wherein the capping layer comprises at least one low refractive index layer of SiO disposed on the plurality of periods. In addition, at least one of the plurality of periods comprises at least two high refractive index layers, the at least two high refractive index layers comprise a first layer comprising NbOxNy, Nb2O5, TiCh, TJVOV or HfCh, and a second layer comprising SiNx, SiOxNy, or AlOxNy. Further, the article exhibits one or more of: (i) a first surface photopic average reflectance (Y) value of less than or equal to 0.18, (ii) a first surface reflected color chroma (C*) value, where C* = √(a*2+ b*2) in the (L*, a*, b*) colorimetry system and C* is less than or equal to 3.5 under an International Commission on Illumination illuminant measured for all light incident angles in a range from 0 degrees to 60 degrees at the anti-reflective surface, and (iii) a two-surface transmittance T(940) at a wavelength of 940 nm of greater than or equal to 88%, wherein T(940) is measured with a bare second major surface of the substrate.Attorney Docket No.: SP24-275

[0008] According to some embodiments of the disclosure, an article is provided that includes: a substrate having a first and second major surface, the first and second major surfaces opposing one another; and an anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface, wherein the anti-reflective coating comprises a plurality of layers. Further, the anti-reflective coating comprises a capping layer and a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, wherein one of the low refractive index layers is in direct contact with the major surface of the substrate, wherein the capping layer comprises at least one low refractive index layer of SiC>2 disposed on the plurality of periods. In addition, at least one of the plurality of periods comprises at least two high refractive index layers, the at least two high refractive index layers comprise a first layer comprising NbOxNy, Nb2O5, TiCh, TJVOV or HfCh, and a second layer comprising SiNx, SiOxNy, or AlOxNy. Further, the capping layer comprises at least one layer with a refractive index of greater than 1.45.

[0009] According to some embodiments of the disclosure, an article is provided that includes: a substrate having a first and second major surface, the first and second major surfaces opposing one another; and an anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface, wherein the anti-reflective coating comprises a plurality of layers. Further, the anti-reflective coating comprises a capping layer and a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, wherein one of the low refractive index layers is in direct contact with the major surface of the substrate, wherein the capping layer comprises at least one low refractive index layer of SiO disposed on the plurality of periods. In addition, at least one of the plurality of periods comprises at least two high refractive index layers, the at least two high refractive index layers comprise a first layer comprising NbOxNy, Nb2O5, TiCh, TJVOV or HfCh, and a second layer comprising SiNx, SiOxNy, or AlOxNy. Further, the anti-reflective coating directly below the capping layer comprises either: a first sequence of layers given by (1) SiNxor SiOxNy, and (2) NbiO? or NbOxNy,or, a second sequence of layers given by (1) SiNxor SiOxNy, (2) a tie layer of SiO2 or SiOxNy, and (3) Nb2O5or NbOxNy, wherein the tie layer of SiO2 or SiOxNyhas a physical thickness of less than 5nm.Attorney Docket No.: SP24-275

[0010] According to some embodiments of the disclosure, an article is provided that includes: a substrate having a first and second major surface, the first and second major surfaces opposing one another; and an anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface. The anti-reflective coating comprises a capping layer and a plurality of layers, the plurality of layers comprising a low refractive index layer, a first high refractive index layer, and a second high refractive index layer. Each of the first and second high refractive index layers has a refractive index value greater than 1.9, and the first and second high refractive index layers have different refractive index values. Further, the low refractive index layer has a refractive index value greater than 1.45.

[0011] Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.

[0012] It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework to understanding the nature and character of the claims.

[0013] The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s) and, together with the description, serve to explain, by way of example, principles and operation of the disclosure. It is to be understood that various features of the disclosure disclosed in this specification and in the drawings can be used in any and all combinations. By way of non-limiting examples, the various features of the disclosure may be combined with one another according to the following embodiments.BRIEF DESCRIPTION OF THE DRAWINGS

[0014] These and other features, aspects and advantages of the present disclosure are better understood when the following detailed description of the disclosure is read with reference to the accompanying drawings, in which:

[0015] FIG. 1 A is a side, cross-sectional view of an article, according to one or more embodiments;

[0016] FIG. IB is a side, cross-sectional view of an article, according to one or more embodiments;Attorney Docket No.: SP24-275

[0017] FIG. 1C is a side, cross-sectional view of an article, according to one or more embodiments;

[0018] FIG. ID is a side, cross-sectional view of an article, according to one or more embodiments;

[0019] FIG. IE is a side, cross-sectional view of an article, according to one or more embodiments;

[0020] FIG. IF is a side, cross-sectional view of an article, according to one or more embodiments;

[0021] FIG. 1G is a side, cross-sectional view of an article, according to one or more embodiments;

[0022] FIG. 1H is a side, cross-sectional view of an article, according to one or more embodiments;

[0023] FIG. 2A is a plan view of an exemplary electronic device incorporating any of the articles disclosed herein;

[0024] FIG. 2B is a perspective view of the exemplary electronic device of FIG. 2A;

[0025] FIG. 3 is a perspective view of a vehicle interior with vehicular interior systems that may incorporate any of the articles disclosed herein;

[0026] FIG. 4 is a perspective view of a laptop that may incorporate any of the articles disclosed herein;

[0027] FIGS. 5A-5D are optical micrographs at 50x and 200x of the anti-reflective surface of articles with an example Nb₂O₅ / SiNx / SiO₂ anti-reflective coating, as subjected to abrasion with a Taber Abrader system and before and after 15 minutes of exposure to petroleum jelly (Vaseline®), according to one or more embodiments of the disclosure;

[0028] FIGS. 5E-5J are optical micrographs at 50x and 200x of the anti-reflective surface of articles with an example Nb₂O₅ / SiNx / SiO₂ anti-reflective coating, as subjected to abrasion with a Taber Abrader system and before and after 15 minutes and 80 hours of exposure to petroleum jelly (Vaseline®), according to one or more embodiments of the disclosure;

[0029] FIG. 6 is a Weibull distribution chart of the failure strength levels of the example articles of FIGS. 5A-5J, as tested with a Ring-on- Ring test, according to embodiments of the disclosure;

[0030] FIG. 6A is a plot of radial stress vs. load for the example articles of FIG. 6, as modeled using a finite element analysis methodology;

[0031] FIG. 6B is a plot of nanoindentation elastic modulus and hardness data for an article of the disclosure, as measured through a Berkovich Hardness Test;Attorney Docket No.: SP24-275

[0032] FIGS. 7A and 8A are plots of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of respective comparative articles;

[0033] FIGS. 7B and 8B are plots of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of respective comparative articles;

[0034] FIGS. 7C and 8C are plots of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees on the anti-reflective surface of respective comparative articles;

[0035] FIGS. 7D and 8D are plots of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 90 degrees on the anti-reflective surface of respective comparative articles;

[0036] FIGS. 9A, 10A, 11A, 12A, 13A, 14A, 15A,16A,17A, and 18A are plots of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of respective articles of the disclosure;

[0037] FIGS. 9B, 10B, 11B, 12B, 13B, 14B, 15B,16B, 17B, and 18B are plots of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of respective articles of the disclosure;

[0038] FIGS. 9C, 10C, 11C, 12C, 13C, 14C, 15C,16C, 17C, and 18C are plots of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees on the anti-reflective surface of respective articles of the disclosure;

[0039] FIGS. 9D, 10D, 11D, 12D, 13D, 14D, 15D, 16D, 17D, and 18D are plots of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 90 degrees on the anti-reflective surface of respective articles of the disclosure; and

[0040] FIG. 19 is a table summarizing optical and mechanical properties of two comparative articles and ten articles configured according to the disclosure.DETAILED DESCRIPTION

[0041] In the following detailed description, for purposes of explanation and not limitation, example embodiments disclosing specific details are set forth to provide a thorough understanding of various principles of the present disclosure. However, it will be apparent to one having ordinary skill in the art, having had the benefit of the present disclosure, that the present disclosure may be practiced in other embodiments that depart from the specific details disclosed herein. Moreover, descriptions of well-known devices,Attorney Docket No.: SP24-275methods and materials may be omitted so as not to obscure the description of various principles of the present disclosure. Finally, wherever applicable, like reference numerals refer to like elements.

[0042] Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. As used herein, the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. When the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to. Whether or not a numerical value or end-point of a range in the specification recites “about,” the numerical value or end-point of a range is intended to include two embodiments: one modified by “about,” and one not modified by “about.” It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0043] The terms “substantial,” “substantially,” and variations thereof as used herein are intended to note that a described feature is equal or approximately equal to a value or description. For example, a “substantially planar” surface is intended to denote a surface that is planar or approximately planar. Moreover, “substantially” is intended to denote that two values are equal or approximately equal. In some embodiments, “substantially” may denote values within about 10% of each other, for example within about 5% of each other, or within about 2% of each other.

[0044] Directional terms as used herein - for example “up”, “down”, “right”, “left”, “front”, “back”, “top”, “bottom” - are made only with reference to the figures as drawn and are not intended to imply absolute orientation.

[0045] Unless otherwise expressly stated, 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 an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.Attorney Docket No.: SP24-275

[0046] As used herein, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a “component” includes embodiments having two or more such components, unless the context clearly indicates otherwise.

[0047] The disclosure generally relates to low reflectance, anti-reflective structures with high durability and articles having such structures, including such articles and structures with chemical resistance, low average visible reflectance, abrasion resistance, and controlled color over a range of viewing angles, along with high hardness. Embodiments of these articles possess anti-reflective optical structures with two or more high refractive index materials, at least one low refractive index material, and, in some implementations, while maintaining the hardness, abrasion resistance, chemical resistance and optical properties associated with the intended applications for these articles (e.g., as covers, housings and substrates for display devices, interior and exterior automotive components, etc.).

[0048] According to some implementations of the articles of the disclosure, the anti-reflective structures include at least different high refractive index materials and at least one low refractive index material and are not prone to delamination upon exposure to abrasion, foreign objects and / or chemicals. In contrast, current, commercially available anti-reflective structures typically employ a less-complex, two-material system (e.g., SiCh / NbiO?) and are more prone to delamination upon exposure to application-related abrasion, foreign object and / or chemicals.

[0049] Another advantage of the articles and anti-reflective structures of the disclosure is that they can enable low reflectance, abrasion resistance, and high hardness through a unique combination of three materials (i.e., at least two high refractive index materials and at least one low refractive index material) having a relatively low total thickness (< 2500 nm) and number of layers (e.g., less than 40 layers). In some implementations, the anti-reflective structures employ a combination of SiNx, SiOxNy, NbOxNy, Nb2O5and SiO materials, recognizing that SiNxis a high refractive index material that can provide high hardness, and that NbOxNyand NbjO?. and SiO and SiOxNy, are high and low refractive index materials, respectively, that can contribute to desired optical properties. In some aspects of the articles of the disclosure, SiOxNycan exhibit a relatively high (> 1.9) or relatively medium (1.5 to 1.9) refractive index values under certain oxygen and nitrogen levels. In some embodiments, SiOxNyhaving a refractive index of 1.5 to 1.9 can be substituted for one or more layers of SiO2 in the layer stack structure. This substitution enhances the overall surface hardness ofAttorney Docket No.: SP24-275the coating and coated article. Suitable alternatives for the SiNymaterial include AlOxNyand suitable alternatives for the Nb O? material include TiO?. NbOxNy, Ta? O? and HfO?.

[0050] Further, implementations of the anti-reflective structures of the disclosure have improved combinations of optical performance and abrasion resistance. Key preferred structural attributes enabling this improved performance include higher capping layer index (greater than 1.45 or 1.46), the insertion of a thin SiNxlayer above the softer materials of Nb? O? and NbOxNy, minimization of the thickness of the thickest layer of high index material with a refractive index >2.2 (e.g. Nb? O?. NbOxNyor TiO?). Key preferred combined mechanical and optical attributes include maximum hardness greater than 9 GPa, first-surface photopic average reflectance of less than 0.25%, a two-surface transmittance of greater than 88% at 940 nm wavelength, and a first-surface reflected color for the entire angular range from 0 to 60 degrees angle of incidence (AOI) or 0 to 90 degrees AOI having a* held within a range from -5 to -0.2 and b* held within a range from -6 to +0.6.

[0051] Each of the anti-reflective (AR) coating structures of the disclosure can optionally include an additional low-friction layer, hydrophobic layer, or oleophobic layer, typically coated on the outermost air- facing surface of the AR coating. Such a coating may be a silane, a siloxane, a fluorosilane, or similar layer, and may impart easy-to-clean properties to the surface of the coating. Such a layer is typically <10 nm thick and has minimal effect on the optical performance of the overall AR structure / coating or AR-coated article. Thus, such a layer is not included in the specific anti-reflective structure / coating designs (as detailed below) and is not considered an “optical layer” as part of the AR structure / coating for the purpose of counting optical layers in the AR structure / coating. Preferred substrates for the AR structure / coating of the disclosure are inorganic glasses, especially thermally strengthened and chemically strengthened inorganic glasses. Thus, the glass substrate, AR structure / coating stack, and optional additional layer (e.g., low-friction, oleophobic and / or hydrophobic layer) can be combined to form the coated article of the disclosure, with the first-surface reflectance and color values detailed in the Tables below being applicable to the entire coated article.

[0052] Referring to FIGS. 1A-1H, the article 100 according to one or more embodiments may include a substrate 110, and an anti-reflective coating 130 (also referred herein as an “optical film structure”) disposed on the substrate. The substrate 110 includes opposing major surfaces 112, 114 and opposing minor surfaces 116, 118. The anti-reflective coating 130 is shown in FIG. 1A as being disposed on a first opposing major surface 112; however, the anti-reflective coating 130 may be disposed on the second opposing major surface 114Attorney Docket No.: SP24-275 and / or one or both of the opposing minor surfaces 116, 118, in addition to or instead of being disposed on the first opposing major surface 112. The anti-reflective coating 130 forms an anti-reflective surface 122.

[0053] Referring again to FIGS. 1A-1H, the anti-reflective coating 130 includes a plurality of layers. More specifically, the anti-reflective coating 130 comprises one or more capping layers 131 and a plurality of periods 132. Each period 132 includes an alternating low refractive index layer 130A and one or more high refractive index layers 130B. Further, in some embodiments, one of the low refractive index layers 130A is in direct contact with the major surface 112 of the substrate 110 and the capping layer 131 (or layers 131) comprises at least one low refractive index layer of SiC>2 disposed on the plurality of periods 132. In addition, as shown in FIGS. 1A-1H, at least one of the plurality of periods 132 includes at least two high refractive index layers 130B, preferably of different materials. For example, one of these high refractive index layers 130B can be NbjO',. TiO?. Ta? O', or HfO? and another of these high refractive index layers 130B can be SiNx, SiOxNy, or AlOxNy.

[0054] The term “layer” may include a single layer or may include one or more sub-layers. Such sub-layers may be in direct contact with one another. The sub-layers may be formed from the same material or two or more different materials. In one or more alternative embodiments, such sub-layers may have intervening layers of different materials disposed therebetween. In one or more embodiments a layer may include one or more contiguous and uninterrupted layers and / or one or more discontinuous and interrupted layers (i.e., a layer having different materials formed adjacent to one another). A layer or sub-layers may be formed by a discrete deposition or a continuous deposition process. In one or more embodiments, the layer may be formed using only continuous deposition processes, or, alternatively, only discrete deposition processes.

[0055] As used herein, the term “dispose” includes coating, depositing and / or forming a material onto a surface. The disposed material may constitute a layer, as defined herein. The phrase “disposed on” includes the instance of forming a material onto a surface such that the material is in direct contact with the surface and also includes the instance where the material is formed on a surface, with one or more intervening material(s) between the disposed material and the surface. The intervening material(s) may constitute a layer, as defined herein.

[0056] According to one or more embodiments, the anti-reflective coating 130 of the article 100 (e.g., as shown and described in connection with FIGS. 1A-1H) can be characterized with abrasion resistance according to the Alumina SCE Test. As used herein, the “AluminaAttorney Docket No.: SP24-275SCE Test” is conducted by subjecting a sample to a commercial 800 grit alumina sandpaper (10 mm x 10 mm) with a total weight of 0.35 kg (350 g) for 500 or 1500 abrasion cycles at 60 cycles / min, using an ~2” stroke length (50 mm) powered by a Taber Industries 5750 linear abrader. Abrasion resistance is then characterized, according to the Alumina SCE Test, by measuring reflected specular component excluded (SCE) values (also referred herein as “reflected haze”) from the abraded samples according to principles understood by those with ordinary skill in the field of the disclosure. More particularly, SCE is a relative measure of the change in diffuse reflection off of the surface of the anti-reflection coating 130 between as-abraded and non-abraded portions of the sample, and as measured using a Konica-Minolta CM700D with a 6 mm diameter aperture. According to some implementations, the anti-reflective coating 130 of the articles 100 can exhibit SCE values, as obtained from the Alumina SCE Test, of less than 2%, less than 1.8%, less than 1.6%, less than 1.4%, less than 1.2%, less than 1%, less than 0.8%, less than 0.6%, less than 0.4%, or even less than 0.2%. Abrasion-induced damage increases the surface roughness leading to the increase in diffuse reflection (i.e., SCE values). Lower SCE values indicates less severe damage, indicative of improved abrasion resistance.

[0057] According to embodiments, the anti-reflective coating 130 of the article 100 (e.g., as shown and described in connection with FIGS. 1A-1H) can be characterized with chemical resistance according to the Delamination Test. More specifically, the anti-reflective coating 130 of the article 100 can exhibit no visible delamination after testing according to the Delamination Test with exposure of the anti-reflective surface 122 to petroleum jelly for 15 minutes, or longer up to 80 hours. Without being bound by theory, according to some embodiments, the anti-reflective coating 130 of the article 100 can exhibit no visible delamination after testing according to the Delamination Test with exposure of the anti-reflective surface 122 to any of sweat (alkaline and acidic representations), ambient moisture, tap water, salt water, common household chemicals, and common sunscreen brands (e.g., Neutrogena® SPF45), for 15 minutes, or longer up to 80 hours.

[0058] As used herein, the “Delamination Test” is conducted by subjecting a sample to an Hl 8 abradant (e.g., a non-resilient, vitrified Wearaser, as supplied by Taber Industries) at a total weight of 1 kg (1000 g) for one half abrasion cycle at 20 cycles / min, using an ~1” stroke length powered by a Taber Industries 5750 linear abrader. Damage to the sample is then inspected under an optical microscope and ‘preimages’ are recorded at different locations at 50x and 200x magnifications. After the damage is created, one of the commonly used chemicals by a consumer is applied on the scratches of the samples (e.g., petroleum jellyAttorney Docket No.: SP24-275(Vaseline®) such that the chemical penetrates through the anti-reflective coating of the given sample. To ensure that the chemical has penetrated the anti-reflective coating, the chemical is applied onto the scratch area in a circular motion moving along the length of the scratch back and forth for about 25-30 times. After a duration (e.g., short duration of 15 minutes, long duration of 80 hours), the applied chemical is wiped off in a circular motion with a clean, soft wipe cloth or tissue. The tested sample is then cleaned using isopropyl alcohol to remove any additional chemical residue and inspected again under an optical microscope. Post-tested images are recorded at 50x and 200x magnification. The ‘pre’ and ‘post’ images are then compared to evaluate the delamination behavior of the given sample and its anti-reflective coating configuration.

[0059] The anti-reflective coating 130 and the article 100 (see FIGS. 1A-1H) maybe described in terms of a hardness measured by a Berkovich Indenter Hardness Test. Further, those with ordinary skill in the art can recognize that abrasion resistance of the anti-reflective coating 130 and the article 100 can be correlated to the hardness of these elements. As used herein, the “Berkovich Indenter Hardness Test” includes measuring the hardness of a material on a surface thereof by indenting the surface with a diamond Berkovich indenter. The Berkovich Indenter Hardness Test includes indenting the anti -reflective surface 122 of the article 100 or the surface of the anti-reflective coating 130 (or the surface of any one or more of the layers in the anti-reflective coating) with the diamond Berkovich indenter to form an indent to an indentation depth in the range from about 50 nm to about 1000 nm (or the entire thickness of the anti-reflective coating or layer, whichever is less) and measuring the hardness from this indentation at various points along the entire indentation depth range, along a specified segment of this indentation depth (e.g., in the depth range from about 100 nm to about 500 nm), or at a particular indentation depth (e.g., at a depth of 100 nm, at a depth of 500 nm, etc.) generally using the methods set forth in Oliver, W. C.; Pharr, G. M. An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. See J. Mater. Res., Vol. 7, No. 6, 1992, 1564-1583; and Oliver, W. C. and Pharr, G. M, “Measurement of Hardness and Elastic Modulus by Instrument Indentation: Advances in Understanding and Refinements to Methodology”, J. Mater. Res., Vol. 19, No. 1, 2004, 3-20. Further, when hardness is measured over an indentation depth range (e.g., in the depth range from about 100 nm to about 500 nm), the results can be reported as a maximum hardness within the specified range, wherein the maximum is selected from the measurements taken at each depth within that range. As used herein, “hardness” and “maximum hardness” both refer to as-measured hardness values, notAttorney Docket No.: SP24-275averages of hardness values. Similarly, when hardness is measured at an indentation depth, the value of the hardness obtained from the Berkovich Indenter Hardness Test is given for that particular indentation depth.

[0060] Typically, in nanoindentation measurement methods (such as by using a Berkovich indenter) of a coating that is harder than the underlying substrate, the measured hardness may appear to increase initially due to development of the plastic zone at shallow indentation depths and then increases and reaches a maximum value or plateau at deeper indentation depths. Thereafter, hardness begins to decrease at even deeper indentation depths due to the effect of the underlying substrate. Where a substrate having an increased hardness compared to the coating is utilized, the same effect can be seen; however, the hardness increases at deeper indentation depths due to the effect of the underlying substrate.

[0061] The indentation depth range and the hardness values at certain indentation depth range(s) can be selected to identify a particular hardness response of the optical film structures and layers thereof, described herein, without the effect of the underlying substrate. When measuring hardness of the optical film structure (when disposed on a substrate) with a Berkovich indenter, the region of permanent deformation (plastic zone) of a material is associated with the hardness of the material. During indentation, an elastic stress field extends well beyond this region of permanent deformation. As indentation depth increases, the apparent hardness and modulus are influenced by stress field interactions with the underlying substrate. The substrate influence on hardness occurs at deeper indentation depths (i.e., typically at depths greater than about 10% of the optical film structure or layer thickness). Moreover, a further complication is that the hardness response utilizes a certain minimum load to develop full plasticity during the indentation process. Prior to that certain minimum load, the hardness shows a generally increasing trend.

[0062] At small indentation depths (which also may be characterized as small loads) (e.g., up to about 50 nm), the apparent hardness of a material appears to increase dramatically versus indentation depth. This small indentation depth regime does not represent a true metric of hardness but instead, reflects the development of the aforementioned plastic zone, which is related to the finite radius of curvature of the indenter. At intermediate indentation depths, the apparent hardness approaches maximum levels. At deeper indentation depths, the influence of the substrate becomes more pronounced as the indentation depths increase. Hardness may begin to drop dramatically once the indentation depth exceeds about 30% of the optical film structure thickness or the layer thickness.Attorney Docket No.: SP24-275

[0063] As noted above, those with ordinary skill in the art can consider various test-related considerations in ensuring that the hardness and maximum hardness values of the anti-reflective coating 130 and article 100 (see FIGS. 1A-1H) obtained from the Berkovich Indenter Hardness Test are indicative of these elements, rather than being unduly influenced by the substrate 110, for example. Further, those with ordinary skill in the art can also recognize that embodiments of the disclosure surprisingly demonstrate high hardness values associated with the anti-reflective coating 130 despite the relatively low thickness of the coating 130 (i.e., < 2500 nm). Indeed, as evidenced by the Examples detailed below in subsequent sections, the hardness of certain of the high RI layer(s) 130B within an anti-reflective coating 130, can significantly influence the overall hardness and maximum hardness of the anti -reflective coating 130 and article 100, despite the relatively low thickness values associated with these layers. This is surprising because of the above test-related considerations, which detail how measured hardness is directly influenced by the thickness of a coating, for example the anti-reflective coating 130. In general, as a coating (over a thicker substrate) is reduced in thickness, and as the volume of harder material (e.g., as compared to other layers within the coating having a lower hardness) in the coating decreases, it would be expected that the measured hardness of the coating will trend toward the hardness of the underlying substrate. Nevertheless, embodiments of the articles 100 of the disclosure, as including the anti-reflective coating 130 (and as also exemplified by the Examples outlined in detail below), surprisingly exhibit significantly high hardness values in comparison to the underlying substrate, thus demonstrating a unique combination of coating thickness (< 500 nm), volumetric fraction of higher hardness material and optical properties.

[0064] In some embodiments, the anti-reflective coating 130 of the article 100 (see FIGS.1A-1H) may exhibit a hardness of greater than about 8 GPa, as measured on the anti-reflective surface 122, by a Berkovich Indenter Hardness Test at an indentation depth of about 100 nm. The antireflective coating 130 may exhibit a hardness of about 8 GPa or greater, about 8.5 GPa or greater, about 9 GPa or greater, about 9.5 GPa or greater, about 10 GPa or greater, about 10.5 GPa or greater, about 11 GPa or greater, about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, about 15 GPa or greater, or any hardness value or range of hardness values within the foregoing ranges by a Berkovich Indenter Hardness Test at an indentation depth of about 100 nm. The article 100, including the antireflective coating 130 and any additional coatings, as described herein, may exhibit a hardness of about 8 GPa or greater, about 9 GPa or greater, about 10 GPa or greater, about 11 GPa or greater, or about 12 GPa or greater, as measured on the anti-reflective surface 122, byAttorney Docket No.: SP24-275a Berkovich Indenter Hardness Test at an indentation depth of about 100 nm or greater. Such measured hardness values may be exhibited by the anti-reflective coating 130 and / or the article 100 over an indentation depth of about 50 nm or greater or about 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm). Similarly, maximum hardness values of about 8 GPa or greater, about 8.5 GPa or greater, about 9 GPa or greater, about 9.5 GPa or greater, about 10 GPa or greater, about 10.5 GPa or greater, about 11 GPa or greater, about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, about 15 GPa or greater, or any hardness value or range of hardness values within the foregoing ranges by a Berkovich Indenter Hardness Test may be exhibited by the anti-reflective coating and / or the article over an indentation depth of about 50 nm or greater or about 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm).

[0065] In addition, it is evident that certain of the anti-reflective coatings 130 of the articles 100, such as depicted in FIGS. 1A-1H and made according to the Examples below with laboratory grade sputtering equipment, demonstrate hardness values that range from 7.88 GPa to 8.05 GPa at an indentation depth of 100 nm. Without being bound by theory, it is also believed that production grade sputtering equipment (e.g., in-line reactive sputtering or metal mode reactive sputtering equipment) can be employed to generate comparable anti-reflective coatings 130 of the articles 100, as made according to the Examples below, with hardness values of about 8 GPa or greater, about 8.5 GPa or greater, about 9 GPa or greater, about 10 GPa or greater, about 11 GPa or greater, about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, or even about 15 GPa or greater. Further, it is believed that the hardness results associated with the anti-reflective coatings 130 of the Examples are likely to trend significantly higher with production grade sputtering equipment because it is understood that the production grade equipment can deposit anti-reflective coatings with higher power densities than laboratory grade sputtering equipment.

[0066] In some implementations of the article 100 (see FIGS. 1A-1H), the anti-reflective coating 130 may have at least one layer made of material itself having a maximum hardness (as measured on the surface of such a layer, e.g., a surface of one or more of the high RIAttorney Docket No.: SP24-275layers 130B) of about 18 GPa or greater, about 19 GPa or greater, about 20 GPa or greater, about 21 GPa or greater, about 22 GPa or greater, about 23 GPa or greater, about 24 GPa or greater, about 25 GPa or greater, and all hardness values therebetween, as measured by the Berkovich Indenter Hardness Test over an indentation depth from about 100 nm to about 500 nm. These measurements are made on a hardness test stack comprising the designated layer of the anti-reflective coating 130 at a physical thickness of about 2 microns, as disposed on a substrate 110, to minimize the thickness-related hardness measurement effects described earlier. The maximum hardness of such a layer may be in the range from about 18 GPa to about 26 GPa, as measured by the Berkovich Indenter Hardness Test over an indentation depth from about 100 nm to about 500 nm. Such maximum hardness values may be exhibited by the material of at least one layer (e.g., one or more of the high RI layer(s) 130B, as shown in FIGS. 1A-1H) over an indentation depth of about 50 nm or greater or 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm). In one or more embodiments, the article 100 exhibits a hardness that is greater than the hardness of the substrate (which can be measured on the opposite surface from the anti-reflective surface). Similarly, hardness values may be exhibited by the material of at least one layer (e.g., one or more of the high RI layer(s) 130B, as shown in FIGS. 1A-1H) over an indentation depth of about 50 nm or greater or about 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm). In addition, these hardness and / or maximum hardness values associated with the at least one layer (e.g., the high RI layer(s) 130B) can also be observed at particular indentation depths (e.g., at 100 nm, 200 nm, etc.) over the measured indentation depth ranges.

[0067] According to some implementations of the articles 100 depicted in FIGS. 1A-1H, the coated article (i.e., as including the anti-reflective coating 130) at the anti-reflective surface 122 may exhibit an elastic modulus (or Young’s modulus) in the range from about 30 GPa to about 120 GPa. In some instances, the elastic modulus of the article 100 may be in the range from about 70 GPa to about 140 GPa, from about 70 GPa to about 130 GPa, from about 70 GPa to about 120 GPa, from about 70 GPa to about 110 GPa, and all ranges and sub-ranges therebetween. According to some embodiments, the elastic modulus of the articleAttorney Docket No.: SP24-275100 at the anti-reflective surface 122 may be greater than 80 GPa, greater than 85 GPa, greater than 90 GPa, greater than 95 GPa, greater than 100 GPa, greater than 105 GPa, greater than 110 GPa, or any modulus value or sub-range of values between the foregoing values.

[0068] Referring again to the article 100 depicted in FIGS. 1A-1H, optical interference between reflected waves from the interface between the anti-reflective coating 130 and air, and from the interface between the anti-reflective coating 130 and substrate 110 (e.g., at the major surface 112), can lead to spectral reflectance and / or transmittance oscillations that create apparent color in the article 100. As used herein, the term “transmittance” is defined as the percentage of incident optical power within a given wavelength range transmitted through a material (e.g., the article, the substrate or the optical film structure or portions thereof). The term “reflectance” is similarly defined as the percentage of incident optical power within a given wavelength range that is reflected from a material (e.g., the article, the substrate, or the optical film structure or portions thereof). In one or more embodiments, the spectral resolution of the characterization of the transmittance and reflectance is less than 5 nm or 0.02 eV. The color may be more pronounced in reflection. The angular color shifts in reflection with viewing angle due to a shift in the spectral reflectance oscillations with incident illumination angle. Angular color shifts in transmittance with viewing angle are also due to the same shift in the spectral transmittance oscillation with incident illumination angle. The observed color and angular color shifts with incident illumination angle are often distracting or objectionable to device users, particularly under illumination with sharp spectral features for example fluorescent lighting and some LED lighting. Angular color shifts in transmission may also play a factor in angular color shift in reflection and vice versa. Factors in angular color shifts in transmission and / or reflection may also include angular color shifts due to viewing angle or color shifts away from a certain white point that may be caused by material absorption (somewhat independent of angle) defined by a particular illuminant or test system.

[0069] The oscillations may be described in terms of amplitude. As used herein, the term “amplitude” includes the peak-to-valley change in reflectance or transmittance.The phrase “average amplitude” includes the peak-to-valley change in reflectance or transmittance averaged within the optical wavelength regime. Unless otherwise noted, the “optical wavelength regime” includes the wavelength range from about 400 nm to about 800 nm (and more specifically from about 450 nm to about 650 nm). In some implementations,Attorney Docket No.: SP24-275the articles 100 of the disclosure can also demonstrate high average transmittance in an infrared wavelength range from about 900 nm to 1000 nm.

[0070] The articles 100 of this disclosure (see FIGS. 1A-1H) include an anti-reflective coating (e.g., anti-reflective coating 130) to provide improved optical performance, in terms of colorlessness and / or smaller angular color shifts when viewed at varying incident illumination angles from normal incidence under different illuminants.

[0071] One aspect of this disclosure pertains to an article that exhibits colorlessness in reflectance and / or transmittance even when viewed at different incident illumination angles under an illuminant. In one or more embodiments, the article 100 exhibits an angular color shift in reflectance and / or transmittance of about 8 or less, about 7 or less, about 6 or less, about 5 or less, about 4 or less, about 3 or less, about 2.5 or less, about 2.1 or less, or about 2 or less, between a reference illumination angle and an incident illumination angle, e.g., from a reference illumination angle of 0 degrees to an incident illumination angle of 60 degrees. As used herein, the phrase “angular color shift” refers to the change in both a* and b*, under the CIE L*, a*, b* colorimetry system in reflectance and / or transmittance. It should be understood that unless otherwise noted, the L* coordinate of the articles described herein are the same at any angle or reference point and do not influence color shift. For example, angular color shift may be determined using the following Equation (1):(1) √((a*2-a*1)2+(b*2-b*1)2)with a*i, and b*i representing the a* and b* coordinates of the article when viewed at a reference illumination angle (which may include normal incidence) and a*2, and b*2 representing the a* and b* coordinates of the article when viewed at an incident illumination angle, provided that the incident illumination angle is different from the reference illumination angle and in some cases differs from the reference illumination angle by about 1 degree or more, 2 degrees or more, or about 5 degrees or more, or about 10 degrees or more, or about 15 degrees or more, or about 20 degrees or more. In some instances, an angular color shift in reflectance and / or transmittance of about 8 or less (e.g., 5 or less, 4 or less, 3 or less, 2.5 or less, or 2 or less) is exhibited by the article 100 when viewed at various incident illumination angles from a reference illumination angle, under an illuminant. In some instances, the angular color shift in reflectance and / or transmittance is about 2.1 or less, about 2.0 or less, about 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1 or less, 0.5 or less, 0.25 or less, or 0.1 or less. In someAttorney Docket No.: SP24-275embodiments, the angular color shift may be about 0. The illuminant can include standard illuminants as determined by the CIE, including A illuminants (representing tungsten-filament lighting), B illuminants (daylight simulating illuminants), C illuminants (daylight simulating illuminants), D series illuminants (representing natural daylight), and F series illuminants (representing various types of fluorescent lighting). In specific examples, the articles 100 exhibit an angular color shift in reflectance and / or transmittance of about 2 or less when viewed at incident illumination angle from the reference illumination angle under a CIE F2, F10, Fll, F12 or D65 illuminant or more specifically under a CIE F2 illuminant.

[0072] The reference illumination angle may include normal incidence (i.e., 0 degrees), or 5 degrees from normal incidence, 10 degrees from normal incidence, 15 degrees from normal incidence, 20 degrees from normal incidence, 25 degrees from normal incidence, 30 degrees from normal incidence, 35 degrees from normal incidence, 40 degrees from normal incidence, 50 degrees from normal incidence, 55 degrees from normal incidence, or 60 degrees from normal incidence, provided the difference between the reference illumination angle and the difference between the incident illumination angle and the reference illumination angle is about 1 degree or more, 2 degrees or more, or about 5 degrees or more, or about 10 degrees or more, or about 15 degrees or more, or about 20 degrees or more. The incident illumination angle may be, with respect to the reference illumination angle, in the range from about 5 degrees to about 80 degrees, from about 5 degrees to about 70 degrees, from about 5 degrees to about 65 degrees, from about 5 degrees to about 60 degrees, from about 5 degrees to about 55 degrees, from about 5 degrees to about 50 degrees, from about 5 degrees to about 45 degrees, from about 5 degrees to about 40 degrees, from about 5 degrees to about 35 degrees, from about 5 degrees to about 30 degrees, from about 5 degrees to about 25 degrees, from about 5 degrees to about 20 degrees, from about 5 degrees to about 15 degrees, and all ranges and sub-ranges therebetween, away from normal incidence. The article may exhibit the angular color shifts in reflectance and / or transmittance described herein at and along all the incident illumination angles in the range from about 2 degrees to about 80 degrees, or from about 5 degrees to about 80 degrees, or from about 10 degrees to about 80 degrees, or from about 15 degrees to about 80 degrees, or from about 20 degrees to about 80 degrees, when the reference illumination angle is normal incidence. In some embodiments, the article may exhibit the angular color shifts in reflectance and / or transmittance described herein at and along all the incident illumination angles in the range from about 2 degrees to about 80 degrees, or from about 5 degrees to about 80 degrees, or from about 10 degrees to about 80 degrees, or from about 15 degrees to about 80 degrees, orAttorney Docket No.: SP24-275from about 20 degrees to about 80 degrees, when the difference between the incident illumination angle and the reference illumination angle is about 1 degree or more, 2 degrees or more, or about 5 degrees or more, or about 10 degrees or more, or about 15 degrees or more, or about 20 degrees or more. In one example, the article may exhibit an angular color shift in reflectance and / or transmittance of 2 or less at any incident illumination angle in the range from about 2 degrees to about 60 degrees, from about 5 degrees to about 60 degrees, or from about 10 degrees to about 60 degrees away from a reference illumination angle equal to normal incidence. In other examples, the article may exhibit an angular color shift in reflectance and / or transmittance of 2 or less when the reference illumination angle is 10 degrees and the incident illumination angle is any angle in the range from about 12 degrees to about 60 degrees, from about 15 degrees to about 60 degrees, or from about 20 degrees to about 60 degrees away from the reference illumination angle.

[0073] In some embodiments, the angular color shift (AC) may be measured at all angles between a reference illumination angle (e.g., normal incidence) and an incident illumination angle in the range from about 0 degrees to about 60 degrees for the articles 100 of the disclosure (see FIGS. 1A-1H). In such implementations, the angular color shift (AC) may be determined using the following Equation (1A):(1A) √((a*max-a*min)2+(b*max-b*min)2)with a *max, a*min, b*max, and b*min as the maximum and minimum color coordinates in the (L*, a*, b*) colorimetery system for the respective a* and b* coordinates over the incident illumination angle in the range from about 0 degrees to about 60 degrees. In other words, the angular color shift (AC) may be measured and may be about 8 or less, about 7 or less, about 6 or less, about 5 or less, about 4 or less, about 3 or less, about 2.5 or less, about 2.1 or less, or about 2 or less, at all incident angles in the range from about 0 degrees to about 20 degrees, from about 0 degrees to about 30 degrees, from about 0 degrees to about 40 degrees, from about 0 degrees to about 50 degrees, or from about 0 degrees to about 60 degrees.

[0074] In one or more embodiments, the article 100 (see FIGS. 1A-1H) exhibits a color in the CIE L*, a*, b* colorimetry system in reflectance and / or transmittance such that the distance or reference point color shift between the transmittance color or reflectance coordinates from a reference point is about 8 or less, about 7 or less, about 6 or less, about 5 or less, about 4 or less, about 3 or less, about 2.5 or less, or about 2 or less, under an illuminant (which can include standard illuminants as determined by the CIE, including AAttorney Docket No.: SP24-275 illuminants (representing tungsten-filament lighting), B illuminants (daylight simulating illuminants), C illuminants (daylight simulating illuminants), D series illuminants (representing natural daylight), and F series illuminants (representing various types of fluorescent lighting). In specific examples, the articles 100 exhibit an angular color shift in reflectance and / or transmittance of about 8 or less, about 7 or less, about 6 or less, about 5 or less, about 4 or less, about 3 or less, or about 2 or less, when viewed at incident illumination angles from the reference illumination angle under a CIE F2, F10, Fll, F12 or D65 illuminant or more specifically under a CIE F2 illuminant. Stated another way, the article may exhibit a transmittance color (or transmittance color coordinates) and / or a reflectance color (or reflectance color coordinates) measured at the anti-reflective surface 122 having a reference point color shift of about 8 or less, about 7 or less, about 6 or less, about 5 or less, about 4 or less, about 3 or less, or about 2 or less, from a reference point, as defined herein. Unless otherwise noted, the transmittance color or transmittance color coordinates are measured on two surfaces of the article including at the anti-reflective surface 122 and the opposite bare surface of the article (i.e., 114). Unless otherwise noted, the reflectance color or reflectance color coordinates are measured on only the anti -reflective surface 122 of the article.

[0075] In one or more embodiments of the articles 100 of the disclosure (see FIGS. 1 A-1H), the reference point may be the origin (0, 0) in the CIE L*, a*, b* colorimetry system (or the color coordinates a*=0, b* =0), color coordinates (-2, -2) or the transmittance or reflectance color coordinates of the substrate. It should be understood that unless otherwise noted, the L* coordinate of the articles described herein are the same as the reference point and do not influence color shift. Where the reference point color shift of the article is defined with respect to the substrate, the transmittance color coordinates of the article are compared to the transmittance color coordinates of the substrate and the reflectance color coordinates of the article are compared to the reflectance color coordinates of the substrate.

[0076] In one or more specific embodiments, the reference point color shift of the transmittance color and / or the reflectance color may be less than 1 or even less than 0.5. In one or more specific embodiments, the reference point color shift for the transmittance color and / or the reflectance color may be 1.8, 1.6, 1.4, 1.2, 0.8, 0.6, 0.4, 0.2, 0 and all ranges and sub-ranges therebetween. Where the reference point is the color coordinates a*=0, b*=0, the reference point color shift is calculated by Equation (2):(2) reference point color shift = √((a* article)2+ (b* article)2).Attorney Docket No.: SP24-275Where the reference point is the color coordinates a*=-2, b*=-2, the reference point color shift is calculated by Equation (3):(3) reference point color shift =(a* article +2)2+ (b* article +2)2).Where the reference point is the color coordinates of the substrate, the reference point color shift is calculated by Equation (4):(4) reference point color shift = √((a*article - a*substrate)2+ (b*article - b*substrate)2).

[0077] In some embodiments, the article 100 may exhibit a transmittance color (or transmittance color coordinates) and a reflectance color (or reflectance color coordinates) such that the reference point color shift is less than 2 when the reference point is any one of the color coordinates of the substrate, the color coordinates a*=0, b*=0 and the coordinates a*= -2, b*= -2.

[0078] In some embodiments, the article 100 (see FIGS. 1A-1H) may exhibit an a* and / or b* value in single side reflectance (as measured at the anti-reflective surface 122 only) in the range from about -3 to about 0, from about -2.5 to about 0, from about -2 to about 0, or any a* and / or b* value or sub-range within the foregoing ranges, in the CIE L*, a*, b* colorimetry system at a near-normal incident angle (i.e., at about 0 degrees, or within 10 degrees of normal) and / or from 0 degrees to 10 degrees at the anti-reflective surface 122. For example, the article may exhibit a* and b* values in single side reflectance of -3, -2.8. -2.6, -2.4, -2.2, -2.0, -1.8, -1.6, -1.4, -1.2, -1.0, -0.8, -0.6, -0.4, -0.2, 0, and all a* and b* values between these levels.

[0079] Further, according to some embodiments the article 100 (see FIGS. 1A-1H) may exhibit a first surface reflected color chroma (C*) value, where C* = √(a*2+ b*2) in the (L*, a*, b*) colorimetry system and C* is less than or equal to 10.0 under an International Commission on Illumination illuminant measured at a light incidence angle of 8 degrees at the anti-reflective surface 122. For example, the article 100 can exhibit a color chroma (C*) value of less than 10, 9, 8, 7, 6, 5, 4, 3, 2, or even 1.5, at a light incidence angle of 8 degrees at the anti-reflective surface 122. In other implementations, the article 100 can exhibit a color chroma (C*) value of less than 10, 9, 8, 7, 6, 5, 4, 3, 2, or even 1.5, over the entire range of incident angles from 0 to 60 degrees or 0 to 90 degrees at the anti-reflective surface 122.Attorney Docket No.: SP24-275

[0080] The article 100 of one or more embodiments, or the anti -reflective surface 122 of the anti-reflective coating 130 of one or more articles 100 (see FIGS. 1A-1H), may exhibit an average light transmittance over the optical wavelength regime in the range from about 400 nm to about 800 nm (or a photopic average light transmittance) of about 94% or greater (e.g., about 94% or greater, about 95% or greater, about 96% or greater, about 96.5% or greater, about 97% or greater, about 97.5% or greater, about 98% or greater, about 98.5% or greater or about 99% or greater). In some implementations, the article 100 of one or more embodiments, or the anti-reflective surface 122 of one or more articles, may exhibit an average light transmittance of about 88% or greater, 88.5% or greater, 89% or greater, 89.5% or greater, 90% or greater, 90.5% or greater, 91% or greater, and all transmittance values and ranges within the foregoing ranges, over the infrared wavelength regime in the range from about 900 nm to about 1000 nm, or from 930 nm to 950 nm. Further, in some implementations, the article 100 of one or more embodiments, or the anti-reflective surface 122 of one or more articles, may exhibit an average light transmittance of about 85% or greater, 86% or greater, or even 87% or greater, and all transmittance values and ranges within the foregoing ranges, over the infrared wavelength regime in the range from about 930 nm to 950 nm, e.g., at -940 nm.

[0081] In some embodiments, the article 100, or the anti-reflective surface 122 of the anti-reflective coating 130 of one or more articles 100 (see FIGS. 1A-1H), may exhibit a first-surface visible photopic average reflectance of about 1.5% or less, about 1.25% or less, about 1% or less, about 0.9% or less, about 0.8% or less, about 0.7% or less, about 0.6% or less, about 0.5% or less, about 0.45% or less, about 0.4% or less, about 0.35% or less, about 0.3% or less, about 0.25% or less, about 0.2% or less, about 0.15% or less, about 0.13% or less. These photopic average reflectance values may be exhibited at incident illumination angles in the range from about 0° to about 20°, from about 0°to about 40°, or from about 0° to about 60°. As used herein, “photopic average reflectance” mimics the response of the human eye by weighting the reflectance versus wavelength spectrum according to the human eye’s sensitivity. Photopic average reflectance may also be defined as the luminance, or tristimulus Y value of reflected light, according to known conventions for example CIE color space conventions. The photopic average reflectance is defined in Equation (5) as the spectral reflectance, W multiplied by the illuminant spectrum, IW and the CIE’s color matching function yW, related to the eye’s spectral response:Attorney Docket No.: SP24-275(5) ⟨Rp⟩ = ΣnmR(λ) × I(λ) × y(λ)

[0082] In some embodiments, the anti-reflective surface 122 of one or more articles 100, as depicted in FIGS. 1A-1H (i.e., when measuring the anti-reflective surface 122 only through a single-sided measurement), may exhibit a visible photopic average reflectance of about 1% or less, 0.9% or less, 0.7% or less, about 0.5% or less, about 0.45% or less, about 0.4% or less, about 0.35% or less, about 0.3% or less, about 0.25% or less, about 0.2% or less, about 0.15% or less, or about 0.13% or less. In such “single-sided” or “first- surface” measurements as described in this disclosure, the reflectance from the second major surface (e.g., surface 114 shown in FIGS. 1A-1H) is removed by coupling this surface to an index-matched absorber. In some cases, the visible photopic average reflectance ranges are exhibited while simultaneously exhibiting a maximum reflectance color shift (i.e., AC as described above in Equation 1A), over the entire incident illumination angle range from about 5 degrees to about 60 degrees (with the reference illumination angle being normal incidence) using D65 illumination, of less than about 8, less than about 7, less than about 6, less than about 5, less than about 4, less than about 3, less than about 2, less than about 1.5, or less than about 1.25. These maximum reflectance color shift values represent the lowest color point value measured at any angle from about 5 degrees to about 60 degrees from normal incidence, subtracted from the highest color point value measured at any angle in the same range.

[0083] Substrate

[0084] The substrate 110 may include a translucent substrate material, such as an inorganic oxide material. Further, the substrate 100 may include an amorphous substrate, a crystalline substrate or a combination thereof. In one or more embodiments, the substrate exhibits a refractive index in the range from about 1.45 to about 1.55, e.g., 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, and all refractive indices therebetween.

[0085] Suitable substrates 110 may exhibit an elastic modulus (or Young’s modulus) in the range from about 30 GPa to about 120 GPa. In some instances, the elastic modulus of the substrate may be in the range from about 30 GPa to about 110 GPa, from about 30 GPa to about 100 GPa, from about 30 GPa to about 90 GPa, from about 30 GPa to about 80 GPa, from about 30 GPa to about 70 GPa, from about 40 GPa to about 120 GPa, from about 50 GPa to about 120 GPa, from about 60 GPa to about 120 GPa, from about 70 GPa to about 120 GPa, and all ranges and sub-ranges therebetween. The Young's modulus values for the substrate itself as recited in this disclosure refer to values as measured by a resonantAttorney Docket No.: SP24-275ultrasonic spectroscopy technique of the general type set forth in ASTM E2001-13, titled “Standard Guide for Resonant Ultrasound Spectroscopy for Defect Detection in Both Metallic and Non-metallic Parts.”

[0086] In one or more embodiments, the amorphous substrate may include glass, which may be strengthened or non- strengthened. Examples of suitable glass include soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass and alkali aluminoborosilicate glass. In some variants, the glass may be free of lithia. In one or more alternative embodiments, the substrate 110 may include crystalline substrates for example glass-ceramic, or ceramic, substrates (which may be strengthened or non-strengthened) or may include a single crystal structure, for example sapphire. In one or more specific embodiments, the substrate 110 includes an amorphous base (e.g., glass) and a crystalline cladding (e.g., sapphire layer, a polycrystalline alumina layer and / or or a spinel (MgAhCh) layer).

[0087] The substrate 110 may be substantially planar or sheet-like, although other embodiments may utilize a curved or otherwise shaped or sculpted substrate. The substrate 110 may be substantially optically clear, transparent and free from light scattering. In such embodiments, the substrate may exhibit an average light transmission over the optical wavelength regime of about 85% or greater, about 86% or greater, about 87% or greater, about 88% or greater, about 89% or greater, about 90% or greater, about 91% or greater or about 92% or greater. In one or more alternative embodiments, the substrate 110 may be opaque or exhibit an average light transmission over the optical wavelength regime of less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, or less than about 0%. In some embodiments, these light reflectance and transmittance values may be a total reflectance or total transmittance (taking into account reflectance or transmittance on both major surfaces of the substrate) or may be observed on a single side of the substrate (i.e., on the anti-reflective surface 122 only, without taking into account the opposite surface). Unless otherwise specified, the average reflectance or transmittance is measured at an incident illumination angle of 0 degrees (however, such measurements may be provided at incident illumination angles of 45 degrees or 60 degrees). The substrate 110 may optionally exhibit a color, for example white, black, red, blue, green, yellow, orange, etc.

[0088] Additionally, or alternatively, the physical thickness of the substrate 110 may vary along one or more of its dimensions for aesthetic and / or functional reasons. For example, theAttorney Docket No.: SP24-275edges of the substrate 110 may be thicker as compared to more central regions of the substrate 110. The length, width and physical thickness dimensions of the substrate 110 may also vary according to the application or use of the article 100.

[0089] The substrate 110 may be provided using a variety of different processes. For instance, where the substrate 110 includes an amorphous substrate for example glass, various forming methods can include float glass processes, rolling processes, updraw processes, and down-draw processes, for example fusion draw and slot draw.

[0090] Once formed, a substrate 110 may be strengthened to form a strengthened substrate. As used herein, the term “strengthened substrate” may refer to a substrate that has been chemically strengthened, for example through ion-exchange of larger ions for smaller ions in the surface of the substrate. However, other strengthening methods known in the art, for example thermal tempering, or utilizing a mismatch of the coefficient of thermal expansion between portions of the substrate to create compressive stress and central tension regions, may be utilized to form strengthened substrates.

[0091] Where the substrate is chemically strengthened by an ion exchange process, the ions in the surface layer of the substrate are replaced by - or exchanged with - larger ions having the same valence or oxidation state. Ion exchange processes are typically carried out by immersing a substrate in a molten salt bath containing the larger ions to be exchanged with the smaller ions in the substrate. It will be appreciated by those skilled in the art that parameters for the ion exchange process, including, but not limited to, bath composition and temperature, immersion time, the number of immersions of the substrate in a salt bath (or baths), use of multiple salt baths, additional steps for example annealing, washing, and the like, are generally determined by the composition of the substrate and the desired compressive stress (CS), depth of compressive stress (CS) layer (or depth of layer) of the substrate that result from the strengthening operation. By way of example, ion exchange of alkali metal-containing glass substrates may be achieved by immersion in at least one molten bath containing a salt for example, but not limited to, nitrates, sulfates, and chlorides of the larger alkali metal ion. The temperature of the molten salt bath typically is in a range from about 380°C up to about 450°C, while immersion times range from about 15 minutes up to about 40 hours. However, temperatures and immersion times different from those described above may also be used.

[0092] In addition, non-limiting examples of ion exchange processes in which glass substrates are immersed in multiple ion exchange baths, with washing and / or annealing steps between immersions, are described in U. S. Patent Application No. 12 / 500,650, filed July 10,Attorney Docket No.: SP24-2752009, by Douglas C. Allan et al., entitled “Glass with Compressive Surface for Consumer Applications”, claiming priority from U. S. Provisional Patent Application No. 61 / 079,995, filed July 11, 2008, in which glass substrates are strengthened by immersion in multiple, successive, ion exchange treatments in salt baths of different concentrations; and U. S. Patent No. 8,312,739, by Christopher M. Lee et al., issued on November 20, 2012, and entitled “Dual Stage Ion Exchange for Chemical Strengthening of Glass,” claiming priority from U. S. Provisional Patent Application No. 61 / 084,398, filed July 29, 2008, in which glass substrates are strengthened by ion exchange in a first bath diluted with an effluent ion, followed by immersion in a second bath having a smaller concentration of the effluent ion than the first bath. The contents of U. S. Patent Application No. 12 / 500,650 and U. S. Patent No. 8,312,739 are incorporated herein by reference in their entirety.

[0093] The degree of chemical strengthening achieved by ion exchange may be quantified based on the parameters of central tension (CT), peak CS, depth of compression (DOC, which is the point along the thickness wherein compression changes to tension), and depth of ion layer (DOL). Peak CS, which is a maximum observed compressive stress, may be measured near the surface of the substrate 110 or within the strengthened glass at various depths. A peak CS value may include the measured CS at the surface (CSs) of the strengthened substrate. In other embodiments, the peak CS is measured below the surface of the strengthened substrate. Compressive stress (including surface CS) is measured by surface stress meter (FSM) using commercially available instruments such as the FSM-6000, manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurements rely upon the accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. SOC in turn is measured according to Procedure C (Glass Disc Method) described in ASTM standard C770-16, entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety. As used herein, DOC means the depth at which the stress in the chemically strengthened alkali aluminosilicate glass article described herein changes from compressive to tensile. DOC may be measured by FSM or a scattered light polariscope (SCALP) depending on the ion exchange treatment. Where the stress in the glass article is generated by exchanging potassium ions into the glass article, FSM is used to measure DOC. Where the stress is generated by exchanging sodium ions into the glass article, SCALP is used to measure DOC. Where the stress in the glass article is generated by exchanging both potassium and sodium ions into the glass, the DOC is measured by SCALP, since it is believed the exchange depth of sodium indicates the DOC and the exchange depthAttorney Docket No.: SP24-275of potassium ions indicates a change in the magnitude of the compressive stress (but not the change in stress from compressive to tensile); the exchange depth of potassium ions in such glass articles is measured by FSM. Maximum CT values are measured using a scattered light polariscope (SCALP) technique known in the art. Refracted near-field (RNF) method or SCALP may be used to measure (graph, depict visually, or otherwise map out) the complete stress profile. When the RNF method is utilized to measure the stress profile, the maximum CT value provided by SCALP is utilized in the RNF method. In particular, the stress profile measured by RNF is force balanced and calibrated to the maximum CT value provided by a SCALP measurement. The 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. In particular, the RNF method includes placing the glass article adjacent to a reference block, generating a polarization-switched light beam that is switched between orthogonal polarizations at a rate of from 1 Hz to 50 Hz, measuring an amount of power in the polarization-switched light beam and generating a polarization-switched reference signal, wherein the measured amounts of power in each of the orthogonal polarizations are within 50% of each other. The method further includes transmitting the polarization-switched light beam through the glass sample and reference block for different depths into the glass sample, then relaying the transmitted polarization-switched light beam to a signal photodetector using a relay optical system, with the signal photodetector generating a polarization-switched detector signal. The method also includes dividing the detector signal by the reference signal to form a normalized detector signal and determining the profile characteristic of the glass sample from the normalized detector signal.

[0094] In some embodiments, a strengthened substrate 110 can have a peak CS of 250 MPa or greater, 300 MPa or greater, 400 MPa or greater, 450 MPa or greater, 500 MPa or greater, 550 MPa or greater, 600 MPa or greater, 650 MPa or greater, 700 MPa or greater, 750 MPa or greater, or 800 MPa or greater. The strengthened substrate may have a DOC of 10 pm or greater, 15 pm or greater, 20 pm or greater (e.g., 25 pm, 30 pm, 35 pm, 40 pm, 45 pm, 50 pm or greater) and / or a CT of 10 MPa or greater, 20 MPa or greater, 30 MPa or greater, 40 MPa or greater (e.g., 42 MPa, 45 MPa, or 50 MPa or greater) but less than 100 MPa (e.g., 95, 90, 85, 80, 75, 70, 65, 60, 55 MPa or less). In one or more specific embodiments, the strengthened substrate has one or more of the following: a peak CS greater than 500 MPa, a DOC greater than 15 pm, and a CT greater than 18 MPa.

[0095] Example glasses that may be used in the substrate may include alkali aluminosilicate glass compositions or alkali aluminoborosilicate glass compositions, thoughAttorney Docket No.: SP24-275other glass compositions are contemplated. Such glass compositions are capable of being chemically strengthened by an ion exchange process. One example glass composition comprises SiO2, B2O3and Na2O, where (SiO2+ B2O3) > 66 mol. %, and Na2O > 9 mol. %. In some embodiments, the glass composition includes about 6 wt.% aluminum oxide or more. In some embodiments, the substrate includes a glass composition with one or more alkaline earth oxides, such that a content of alkaline earth oxides is about 5 wt.% or more. Suitable glass compositions, in some embodiments, further comprise at least one of K2O, MgO, or CaO. In some embodiments, the glass compositions used in the substrate can comprise 61-75 mol.% SiO2; 7-15 mol.% Al2O3; 0-12 mol.% B2O3; 9-21 mol.% Na2O; 0-4 mol.% K2O; 0-7 mol.% MgO; and 0-3 mol.% CaO.

[0096] A further example glass composition suitable for the substrate comprises: 60-70 mol.% SiO2; 6-14 mol.% Al2O3; 0-15 mol.% B2O3; 0-15 mol.% Li2O; 0-20 mol.% Na2O; 0-10 mol.% K2O; 0-8 mol.% MgO; 0-10 mol.% CaO; 0-5 mol.% ZrO2; 0-1 mol.% SnO2; 0-1 mol.% CeO2; less than 50 ppm AS2O3; and less than 50 ppm Sb2O3; where 12 mol.% < (IA2O + Na2O + K2O) < 20 mol.% and 0 mol.% < (MgO + CaO) < 10 mol.%.

[0097] A still further example glass composition suitable for the substrate comprises: 63.5-66.5 mol.% SiO2; 8-12 mol.% Al2O3; 0-3 mol.% B2O3; 0-5 mol.% Li2O; 8-18 mol.% Na2O; 0-5 mol.% K2O; 1-7 mol.% MgO; 0-2.5 mol.% CaO; 0-3 mol.% ZrO2; 0.05-0.25 mol.% SnO2; 0.05-0.5 mol.% CeO2; less than 50 ppm AS2O3; and less than 50 ppm Sb2O3; where 14 mol.% < (Li2O + Na2O + K2O) < 18 mol.% and 2 mol.% < (MgO + CaO) < 7 mol.%.

[0098] In some embodiments, an alkali aluminosilicate glass composition suitable for the substrate 110 comprises alumina, at least one alkali metal and, in some embodiments, greater than 50 mol.% SiO2, in other embodiments 58 mol.% SiO2or more, and in still other embodiments 60 mol.% SiO2or more, wherein the ratio (Al2O3+ B2O3) / Σmodifiers (i.e., sum of modifiers) is greater than 1, wherein the components in the ratio are expressed in mol.% and the modifiers are alkali metal oxides. This glass composition, in particular embodiments, comprises: 58-72 mol.% SiO2; 9-17 mol.% Al2O3; 2-12 mol.% B2O3; 8-16 mol.% Na2O; and 0-4 mol.% K2O, wherein the ratio (Al2O3+ B2O3) / Σmodifiers (i.e., sum of modifiers) is greater than 1.

[0099] In some embodiments, the substrate 110 may include an alkali aluminosilicate glass composition comprising: 64-68 mol.% SiCh; 12-16 mol.% Na2O; 8-12 mol.% Al2O3; 0-3 mol.% B2O3; 2-5 mol.% K2O; 4-6 mol.% MgO; and 0-5 mol.% CaO, wherein: 66 mol.% < SiO2 + B2O3 + CaO < 69 mol.%; Na2O + K2O + B2O3 + MgO + CaO + SrO > 10 mol.%; 5Attorney Docket No.: SP24-275mol.% < MgO + CaO + SrO < 8 mol.%; (Na?© + B2O3) — Al2O3< 2 mol.%; 2 mol.% < Na2O - Al2O3< 6 mol.%; and 4 mol.% < (Na2O + K2O) — Al2O3< 10 mol.%.

[0100] In some embodiments, the substrate 110 may comprise an alkali aluminosilicate glass composition comprising: 2 mol% or more of Al2O3and / or ZrO2, or 4 mol% or more of Al2O3and / or ZrO2.

[0101] Where the substrate 110 includes a crystalline substrate, the substrate may include a single crystal, which may include Al2O3. Such single crystal substrates are referred to as sapphire. Other suitable materials for a crystalline substrate include a polycrystalline alumina layer and / or spinel (MgAl2O4).

[0102] Optionally, the crystalline substrate 110 may include a glass-ceramic substrate, which may be strengthened or non-strengthened. Examples of suitable glass-ceramics may include Li2O-Al2O3-SiO2system (i.e., a LAS-System) glass-ceramics, MgO-Al2O3-SiO2system (i.e., an MAS-System) glass-ceramics, and / or glass-ceramics that include a predominant crystal phase including (3-quartz solid solution, -spodumene ss, cordierite, and lithium disilicate. The glass-ceramic substrates may be strengthened using the chemical strengthening processes disclosed herein. In one or more embodiments, MAS-System glass-ceramic substrates may be strengthened in Li2SO4molten salt, whereby an exchange of 2Li+for Mg2+can occur.

[0103] The substrate 110, according to one or more embodiments, can have a physical thickness ranging from about 50 pm to about 5 mm. Example substrate 110 physical thicknesses range from about 50 pm to about 500 pm (e.g., 50, 100, 200, 300, 400 or 500 pm). Further example substrate 110 physical thicknesses range from about 500 pm to about 1000 pm (e.g., 500, 600, 700, 800, 900 or 1000 pm). The substrate 110 may have a physical thickness greater than about 1 mm (e.g., about 2, 3, 4, or 5 mm). In one or more specific embodiments, the substrate 110 may have a physical thickness of 2 mm or less or less than 1 mm. The substrate 110 may be acid polished or otherwise treated to remove or reduce the effect of surface flaws.

[0104] Anti-Reflective Coating

[0105] As shown in FIGS. 1A-1H, the anti-reflective coating 130 of the article 100 includes a plurality of layers, including a capping layer 131 (or layers 131) and a plurality of periods 132. Each period 132 includes an alternating one low refractive (low RI) layer 130A and one or more high refractive index layers (high RI) 130B. In embodiments, at least one low RI layer 130A is in direct contact with a major surface of the substrate 110, e.g., majorAttorney Docket No.: SP24-275surface 112. The capping layer 131 or capping layers 131 can comprise SiO and be disposed on the plurality of periods 132. Further, at least one of the periods 132 includes at least two high RI layers 13 OB, of different materials, and at least one low RI layer 130A. According to some embodiments, each low RI layer 130A has a refractive index of less than 1.7 and each high RI layer 130B has a refractive index of greater than or equal to 1.7, 1.8, 1.9, 2.0, 2.1 or even 2.2 (see, e.g., anti-reflective coating 130 designs of FIGS. 1A-1F, and corresponding description below). According to some embodiments, each low RI layer 130A has a refractive index of less than 1.9 (e.g., as inclusive of SiOxNy), or less than 2.1 in some cases (e.g., as inclusive of SiNx), and each high RI layer 130B has a refractive index of greater than or equal to 1.9, or greater than 2.1 in some cases (see, e.g., anti-reflective coating 130 designs of FIGS. 1G, and 1H, and corresponding description below). In embodiments where one or more of the low RI layers 130A comprises an SiOxNylayer with a refractive index of 1.5 to 1.9, SiOxNyis being substituted for one or more layers of Sith in the anti-reflective coating 130. As SiOxNywith index of 1.5 to 1.9 has a higher hardness than SiO. this substitution increases the overall surface hardness and abrasion resistance of the coating and coated article. In some embodiments, one or more layers may be disposed on the opposite side of the substrate 110 from the anti-reflective coating 130 (i.e., on major surface 114) (not shown).

[0106] The physical thickness of the anti-reflective coating 130 may be in the range from about 50 nm to 2500 nm, about 50 nm to 2250 nm, about 50 nm to 2000 nm, about 50 nm to 1750 nm, about 50 nm to 1500 nm, about 50 nm to about 1250 nm, about 50 nm to 1000 nm, about 50 nm to less than 500 nm, about 50 nm to less than 450 nm or from about 50 nm to less than about 300 nm. In some instances, the physical thickness of the anti-reflective coating 120 may be in the range from about 10 nm to less than 500 nm, from about 50 nm to less than 500 nm, from about 75 nm to less than 500 nm, from about 100 nm to less than 500 nm, from about 125 nm to less than 500 nm, from about 150 nm to less than 500 nm, from about 175 nm to less than 500 nm, from about 200 nm to less than 500 nm, from about 225 nm to less than 500 nm, from about 250 nm to less than 500 nm, from about 300 nm to less than 500 nm, from about 350 nm to less than 500 nm, from about 400 nm to less than 500 nm, from about 450 nm to less than 500 nm, from about 200 nm to about 450 nm, and all ranges and sub-ranges therebetween. For example, the physical thickness of the anti-reflective coating 130 may be from 10 nm to 490 nm, or from 10 nm to 480 nm, or from 10 nm to 475 nm, or from 10 nm to 460 nm, or from 10 nm to 450 nm, or from 10 nm to 450 nm, or from 10 nm to 430 nm, or from 10 nm to 425 nm, or from 10 nm to 420 nm, or from 10 nm to 410 nm, or from 10 nm to 400 nm, or from 10 nm to 350 nm, or from 10 nm to 300Attorney Docket No.: SP24-275 nm, or from 10 nm to 250 nm, or from 10 nm to 225 nm, or from 10 nm to 200 nm, or from 15 nm to 490 nm, or from 20 nm to 490 nm, or from 25 nm to 490 nm, or from 30 nm to 490 nm, or from 35 nm to 490 nm, or from 40 nm to 490 nm, or from 45 nm to 490 nm, or from 50 nm to 490 nm, or from 55 nm to 490 nm, or from 60 nm to 490 nm, or from 65 nm to 490 nm, or from 70 nm to 490 nm, or from 75 nm to 490 nm, or from 80 nm to 490 nm, or from 85 nm to 490 nm, or from 90 nm to 490 nm, or from 95 nm to 490 nm, or from 100 nm to 490 nm, or from 10 nm to 485 nm, or from 15 nm to 480 nm, or from 20 nm to 475 nm, or from 25 nm to 460 nm, or from 30 nm to 450 nm, or from 35 nm to 440 nm, or from 40 nm to 430 nm, or from 50 nm to 425 nm, or from 55 nm to 420 nm, or from 60 nm to 410 nm, or from 70 nm to 400 nm, or from 75 nm to 400 nm, or from 80 nm to 390 nm, or from 90 nm to 380 nm, or from 100 nm to 375 nm, or from 110 nm to 370 nm, or from 120 nm to 360 nm, or from 125 nm to 350 nm, or from 130 nm to 325 nm, or from 140 nm to 320 nm, or from 150 nm to 310 nm, or from 160 nm to 300 nm, or from 170 nm to 300 nm, or from 175 nm to 300 nm, or from 180 nm to 290 nm, or from 190 nm to 280 nm, or from 200 nm to 275 nm.

[0107] As shown in FIGS. 1A-1H, the anti-reflective coating 130 of the article 100 includes a plurality of periods 132, with each period 132 comprising an alternating low RI layer 130A and a high RI layer 130B. At least one of the periods 132 in the anti-reflective coating 130 includes at least two high RI layers 130B, each of different materials, and at least one low RI layer 130A. The difference in the refractive index of each low RI layer 130A and each high RI layer 130B may be about 0.01 or greater, 0.05 or greater, 0.1 or greater or even 0.2 or greater. In some implementations, the refractive index of the low RI layer(s) 130A is within the refractive index of the substrate 110 such that the refractive index of the low RI layer(s) 130A is less than about 1.7, and the high RI layer(s) 130B have a refractive index that is greater than 2.0.

[0108] As noted earlier, and as shown in FIGS. 1A-1H, the anti-reflective coating 130 may include a plurality of periods (132). In some implementations, the anti-reflective coating 130 can be configured such that at least one of the plurality of periods 132 comprises at least two high RI layers 130B, the at least two high RI layers comprise a first high RI layer comprising Nb2O5, NbOxNy, TiCh, TJVOV or HfCh, and a second high RI layer comprising SiNx, SiOxNy, or AlOxNy. In some embodiments, the anti -reflective coating 130 is configured such that at least one of the periods 132 is in contact with the capping layer 131 and the second high RI layer 130B of the at least two high RI layers 130B has a thickness of less than 99 nm.Attorney Docket No.: SP24-275

[0109] According to an embodiment, articles 100, as shown in one or more of FIGS. 1A-1H, are provided that include: a substrate 110 having a first and second major surface 112, 114, the first and second major surfaces 112, 114 opposing one another; and an anti-reflective coating 130 disposed on the first major surface 112 of the substrate 110 and forming an anti-reflective surface 122, wherein the anti-reflective coating 130 comprises a plurality of layers. Further, the anti -reflective coating 130 comprises a capping layer 131 and a plurality of periods 132 such that each period 132 comprises an alternating low refractive index layer 130A and one or more high refractive index layers 130B, wherein one of the low refractive index layers 130A is in direct contact with the major surface 112 of the substrate 110, wherein the capping layer 131 comprises at least one low refractive index layer of SiC>2 disposed on the plurality of periods 132. In addition, at least one of the plurality of periods 132 comprises at least two high refractive index layers 130B, the at least two high refractive index layers 130B comprise a first layer comprising NbOxNy, Nb? O?. TiO?. Ta? O?. or HfO?. and a second layer comprising SiNx, SiOxNy, or AlOxNy. Further, the article 100 exhibits one or more of: (i) a first surface photopic average reflectance (Y) value of less than or equal to 0.18, (ii) a first surface reflected color chroma (C*) value, where C* = ' / (a*2+ b*2) in the (L*, a*, b*) colorimetry system and C* is less than or equal to 3.5 under an International Commission on Illumination illuminant measured for all light incident angles in a range from 0 degrees to 60 degrees at the anti-reflective surface 122, and (iii) a two-surface transmittance T(940) at a wavelength of 940 nm of greater than or equal to 88%, wherein T(940) is measured with a bare second major surface 114 of the substrate 110.

[0110] According to an embodiment, articles 100, as shown in one or more of FIGS. 1A-1H, are provided that include: a substrate 110 having a first and second major surface 112, 114, the first and second major surfaces 112, 114 opposing one another; and an anti-reflective coating 130 disposed on the first major surface 112 of the substrate 110 and forming an anti-reflective surface 122, wherein the anti-reflective coating 130 comprises a plurality of layers. Further, the anti -reflective coating 130 comprises a capping layer 131 and a plurality of periods 132 such that each period 132 comprises an alternating low refractive index layer 130A and one or more high refractive index layers 130B, wherein one of the low refractive index layers 130A is in direct contact with the major surface 112 of the substrate 110, wherein the capping layer 131 comprises at least one low refractive index layer of SiO? disposed on the plurality of periods 132. In addition, at least one of the plurality of periods 132 comprises at least two high refractive index layers 130B, the at least two high refractive index layers 130B comprise a first layer comprising NbOxNy, Nb? O?. TiO?. Ta O?. or HfO?.Attorney Docket No.: SP24-275and a second layer comprising SiNx, SiOxNy, or AlOxNy. Further, the capping layer 131 comprises at least one layer with a refractive index of greater than 1.45.

[0111] According to an embodiment, articles 100, as shown in one or more of FIGS. 1A-1H, are provided that include: a substrate 110 having a first and second major surface 112, 114, the first and second major surfaces 112, 114 opposing one another; and an anti-reflective coating 130 disposed on the first major surface 112 of the substrate 110 and forming an anti-reflective surface 122, wherein the anti-reflective coating 130 comprises a plurality of layers. Further, the anti -reflective coating 130 comprises a capping layer 131 and a plurality of periods 132 such that each period 132 comprises an alternating low refractive index layer 130A and one or more high refractive index layers 130B, wherein one of the low refractive index layers 130A is in direct contact with the major surface 112 of the substrate 110, wherein the capping layer 131 comprises at least one low refractive index layer of SiO disposed on the plurality of periods 132. In addition, at least one of the plurality of periods 132 comprises at least two high refractive index layers 130B, the at least two high refractive index layers 130B comprise a first layer comprising NbOxNy, b2Os, TiO2, TajOv or HfO2, and a second layer comprising SiNxor AlOxNy. Further, the anti-reflective coating 130 directly below the capping layer 131 comprises a sequence of layers given by (1) SiNxor SiOxNy, (2) Nb2O5or NbOxNy, and (3) SiNx, SiOxNy, or Nb2O5.

[0112] For the article 100 depicted in FIG. 1A, the anti-reflective coating 130 includes: a capping layer 131, a first period 132 with a low RI layer 130A (e.g., SiO2) and a high RI layer 130B (e.g., SiNx), and a second period 132 with a low RI layer 130A (e.g., SiO2), a high RI layer 130B (e.g., SiNx) and a high RI layer 130B (e.g., Nb2Os), such that the low RI layers 130A (designated for illustration as “L”) and the high RI layers 130B (designated for illustration as “H”) alternate in the following sequence of layers: substrate110 / L / H / L / H / H / L(capping layer 131), along the physical thickness of the anti-reflective coating 130. In the example in FIG. 1A, the anti-reflective coating 130 includes two periods 132 and a single capping layer 131, i.e., a total of six layers disposed on the substrate 110. In some embodiments of the article 100 depicted in FIG. 1A, the anti-reflective coating 130 comprises less than 7 layers and is further configured such that at least one of the plurality of periods 132 comprises two high RI layers 130B and one low RI layer 130A, the two high RI layers 130B comprising the first high RI layer 130B as b2Os and the second RI layer 130B as SiNx, and the one low RI layer 130A as SiO2. For example, Examples 1, 2, 3, 5, and 6 (see below) employ the design of the anti-reflective coating 130 of FIG. 1A and offer one or more of the advantageous first-surface reflectance, change in color chroma (AC*), and / orAttorney Docket No.: SP24-275two-surface transmittance at 940 nm properties detailed below in Table 9 (see below and corresponding description). The two high RI layers 13 OB enable an improved combination of hardness and optical properties, optimizing the combination of e.g. abrasion resistance and reflectance, by combining a higher hardness material in one of the high RI layers 130B (e.g. SiNx) with a higher refractive index layer in one of the other high RI layers 130B (e.g.Nb2O5).

[0113] For the article 100 depicted in FIG. IB, the anti-reflective coating 130 includes: a capping layer comprising two capping layers 131, a first period 132 with a low RI layer 130A (e.g., SiO2) and a high RI layer 130B (e.g., SiNx), and a second period 132 with a low RI layer 130A (e.g., SiO2), a high RI layer 130B (e.g., SiNx), and a high RI layer 130B (e.g., Nb2Os), such that the low RI layers 130A (designated for illustration as “L”) and the high RI layers 130B (designated for illustration as “H”) alternate in the following sequence of layers: substrate 110 / L / H / L / H / H / L(capping layer 131) / L(capping layer 131), along the physical thickness of the anti-reflective coating 130. In the example in FIG. IB, the anti-reflective coating 130 includes two periods 132 and a capping layer comprising two capping layers 131, i.e., a total of seven layers disposed on the substrate 110. In some embodiments of the article 100 depicted in FIG. IB, the anti-reflective coating 130 comprises less than 8 layers and is further configured such that at least one of the plurality of periods 132 comprises two high RI layers 130B and one low RI layer 130A, the two high RI layers 130B comprising the first high RI layer 130B as SiNxand the second high RI layer 130B as Nb2Os, and the one low RI layer 130A as SiO2. For example, Examples 4 and 7 which have two SiO2capping layers 110 that have different RIs (see below) employ the design of the anti-reflective coating 130 of FIG. IB and offer one or more of the advantageous first-surface reflectance, change in color chroma (AC*), and / or two-surface transmittance at 940 nm properties detailed below in Table 9 (see below and corresponding description). The two capping layers 131 enable an improved combination of hardness and optical properties, e.g., optimizing the combination of abrasion resistance and reflectance, by combining a higher hardness material in one of the capping layers 131 (e.g. SiO2with n=l.46) with a lower refractive index layer in one of the capping layers 131 (e.g. SiO2with n=1.41).

[0114] For the article 100 depicted in FIG. 1C, the anti-reflective coating 130 includes: one capping layer 131, a first period 132 with a low RI layer 130A (e.g., SiO2) and a high RI layer 130B (e.g., SiNx), and a second period 132 with a low RI layer 130A (e.g., SiO2), a high RI layer 130B (e.g., SiNx), a high RI layer 130B (e.g., Nb2Os) and a high RI layer 130B (e.g., SiNx), such that the low RI layers 130A (designated for illustration as “L”) and the high RIAttorney Docket No.: SP24-275layers 130B (designated for illustration as “H”) alternate in the following sequence of layers: substrate 110 / L / H / L / H / H / H / L(capping layer 131), along the physical thickness of the anti-reflective coating 130. In the example in FIG. 1C, the anti-reflective coating 130 includes two periods 132 and one capping layer 131, i.e., a total of seven (7) layers disposed on the substrate 110. In some embodiments of the article 100 depicted in FIG. 1C, the anti-reflective coating 130 comprises less than 9 layers and is further configured such that at least one of the plurality of periods 132 comprises three high RI layers 130B and one low RI layer 130A, the three high RI layers 130B comprising the first high RI layer 130B as SiNx, the second high RI layer 130B as NbjO?. and the third RI layer 130B as SiNx, and the one low RI layer 130A as SiC>2- For example, Example 8 employs the design of the anti-reflective coating 130 of FIG. 1C and offers one or more of the optical and / or mechanical properties shaded in black in FIG. 19 (see below and corresponding description). The sequence of three consecutive high RI layers 130B near the exterior surface 122 of the article 100 enables an improved combination of hardness and optical properties, e.g., optimizing the combination of abrasion resistance and reflectance, by ‘sandwiching’ a higher refractive index layer 130B (e.g. bzOs) between two layers of a higher hardness material 130B (e.g. SiNx).

[0115] For the article 100 depicted in FIG. ID, the anti-reflective coating 130 includes: one capping layer 131, four periods 132, each with a low RI layer 130A (e.g., S1O2) and a high RI layer 130B (e.g., SiNx), and a fifth period 132 with a low RI layer 130A (e.g., SiCh). a high RI layer 130B (e.g., SiNx), a high RI layer 130B (e.g., bzOs) and a high RI layer 130B (e.g., SiNx), such that the low RI layers 130A (designated for illustration as “L”) and the high RI layers 130B (designated for illustration as “H”) alternate in the following sequence of layers: substrate 110 / L / H / L / H / L / H / L / H / L / H / H / H / L(capping layer 131), along the physical thickness of the anti-reflective coating 130. In the example in FIG. ID, the anti-reflective coating 130 includes five periods 132 and one capping layer 131, i.e., a total of thirteen (13) layers disposed on the substrate 110. In some embodiments of the article 100 depicted in FIG. ID, the anti-reflective coating 130 comprises less than 15 layers and is further configured such that at least one of the plurality of periods 132 comprises three high RI layers 130B and one low RI layer 130A, the three high RI layers 130B comprising the first high RI layer 130B as SiNx, the second high RI layer 130B as NbiOv and the third RI layer 130B as SiNx, and the one low RI layer 130A as SiCh. For example, each of Examples 9 and 10 employs the design of the anti-reflective coating 130 of FIG. ID and offers one or more of the optical and / or mechanical properties shaded in black in FIG. 19 (see below and corresponding description). The sequence of three consecutive high RI layers 130B near theAttorney Docket No.: SP24-275exterior surface 122 of the article 100 enables an improved combination of hardness and optical properties, e.g., optimizing the combination of abrasion resistance and reflectance, by ‘sandwiching’ a higher refractive index layer 130B (e.g. Nb2O5) between two layers of a higher hardness material 130B (e.g. SiNx).

[0116] For the article 100 depicted in FIG. IE, the anti-reflective coating 130 includes: one capping layer 131, three periods 132, each with a low RI layer 130A (e.g., SiO or SiOxNy) and a high RI layer 130B (e.g., SiNx), and a fourth period 132 with a low RI layer 130A (e.g., SiCh), a high RI layer 130B (e.g., SiNx), a high RI layer 130B (e.g., Nb2O5) and a high RI layer 130B (e.g., SiNx), such that the low RI layers 130A (designated for illustration as “L”) and the high RI layers 130B (designated for illustration as “H”) alternate in the following sequence of layers: substrate I lO / L / H / L / H / L / H / L / H / H / H / Ltcapping layer 131), along the physical thickness of the anti-reflective coating 130. In the example in FIG. IE, the anti-reflective coating 130 includes four periods 132 and one capping layer 131, i.e., a total of eleven (11) layers disposed on the substrate 110. In some embodiments of the article 100 depicted in FIG. IE, the anti-reflective coating 130 comprises less than 15 layers and is further configured such that at least one of the plurality of periods 132 comprises three high RI layers 130B and one low RI layer 130A, the three high RI layers 130B comprising the first high RI layer 130B as SiNx, the second high RI layer 130B as Nb2O5, and the third RI layer 130B as SiNx, and the one low RI layer 130A as SiC>2 or SiOxNy. For example, each of Examples 11, 13, and 14 employs the design of the anti-reflective coating 130 of FIG. IE and offers one or more of the optical and / or mechanical properties shaded in black in FIG. 19 (see below and corresponding description). The sequence of three consecutive high RI layers 130B near the exterior surface 122 of the article 100 enables an improved combination of hardness and optical properties, e.g., optimizing the combination of abrasion resistance and reflectance, by ‘sandwiching’ a higher refractive index layer 130B (e.g. Nb2O5) between two layers of a higher hardness material 130B (e.g. SiNx).

[0117] For the article 100 depicted in FIG. IF, the anti-reflective coating 130 includes: one capping layer 131, two periods 132, each with a low RI layer 130A (e.g., SiO or SiOxNy) and a high RI layer 130B (e.g., SiNx), and a third period 132 with a low RI layer 130A (e.g., SiC>2 or SiOxNy), a high RI layer 130B (e.g., Nb2O5or NbxOy), a high RI layer 130B (e.g., SiNx), a high RI layer 130B (e.g., Nb2O5or NbxOy), and a high RI layer 130B (e.g., SiNx) such that the low RI layers 130A (designated for illustration as “L”) and the high RI layers 130B (designated for illustration as “H”) alternate in the following sequence of layers: substrate 110 / L / H / L / H / L / H / H / H / H / L(capping layer 131), along the physical thickness of theAttorney Docket No.: SP24-275anti-reflective coating 130. In the example in FIG. IF, the anti-reflective coating 130 includes three periods 132 and one capping layer 131, i.e., a total often (10) layers disposed on the substrate 110. In some embodiments of the article 100 depicted in FIG. IF, the anti-reflective coating 130 comprises less than 13 layers and is further configured such that at least one of the plurality of periods 132 comprises four high RI layers 130B and one low RI layer 130A, the four high RI layers 130B comprising the first high RI layer 130B as NbOxNy, the second high RI layer 130B as SiNx, the third high RI layer 130B as NbOxNy, and the fourth high RI layer 130B as SiNx, and the one low RI layer 130A as SiO2or SiOxNy. For example, Example 12 employs the design of the anti-reflective coating 130 of FIG. IF and offers one or more of the optical and / or mechanical properties shaded in black in FIG. 19 (see below and corresponding description). The sequence of four high RI layers 130B enables an improved combination of hardness and optical properties, e.g., optimizing the combination of abrasion resistance and reflectance, by combining a higher hardness material in one of the layers 130B (e.g., SiNx) with a higher refractive index layer in one of the layers 130B (e.g. Nb2O5or NbOxNy).

[0118] For the article 100 depicted in FIG. 1G, the anti-reflective coating 130 includes: one capping layer 131, eleven periods 132, each with a low RI layer 130A (e.g., SiO2, SiNx, SiOxNy) and a high RI layer 130B (e.g., NbOxNyor Nb2Os), and a twelfth period 132 with a low RI layer 130A (e.g., SiO2or SiOxNy), a high RI layer 130B (e.g., Nb2O5or NbxOy), a high RI layer 130B (e.g., SiNx), a high RI layer 130B (e.g., Nb2O5orNbxOy), and a high RI layer 130B (e.g., SiNx) such that the low RI layers 130A (designated for illustration as “L”) and the high RI layers 130B (designated for illustration as “H”) alternate in the following sequence of layers: substrate 110 + / L / H / L / H / L / H / L / H / L / H / L / H / L / H / L / H / L / H / L / H / L / H / + L / H / H / H / H / L(capping layer 131), along the physical thickness of the anti-reflective coating 130. In the example in FIG. 1G, the anti-reflective coating 130 includes thirteen periods 132 and one capping layer 131, i.e., a total of twenty-eight (28) layers disposed on the substrate 110. In some embodiments of the article 100 depicted in FIG. 1G, the anti-reflective coating 130 comprises less than 30 layers and is further configured such that at least one of the plurality of periods 132 comprises four high RI layers 130B and one low RI layer 130A, the four high RI layers 130B comprising the first high RI layer 130B as NbOxNy, the second high RI layer 130B as SiNx, the third high RI layer 130B as NbOxNy, and the fourth high RI layer 130B as SiNx, and the one low RI layer 130A as SiO2or SiOxNy. For example, Example 15 employs the design of the anti-reflective coating 130 of FIG. 1G and offers one or more of the optical and / or mechanical properties shaded in black in FIG. 19 (see below andAttorney Docket No.: SP24-275corresponding description). The sequence of four high RI layers 130B enables an improved combination of hardness and optical properties, e.g., optimizing the combination of abrasion resistance and reflectance, by combining a higher hardness material in one of the layers 13 OB (e.g. SiNx) with a higher refractive index layer in one of the layers 130B (e.g. NbiO? or NbOxNy).

[0119] For the article 100 depicted in FIG. 1H, the anti-reflective coating 130 includes: one capping layer 131, thirteen periods 132, each with a low RI layer 130A (e.g., SiOi) and a high RI layer 130B (e.g., SiNx), and a fourteenth period 132 with a low RI layer 130A (e.g., SiChor SiOxNy), a high RI layer 130B (e.g., SiNx), a high RI layer 130B (e.g., NbjO? or NbxOy), and a high RI layer 130B (e.g., SiNx) such that the low RI layers 130A (designated for illustration as “L”) and the high RI layers 130B (designated for illustration as “H”) alternate in the following sequence of layers: substrate 110 + / L / H / L / H / L / H / L / H / L / H / L / H / L / H / L / H / L / H / L / H / L / H / L / H / L / H + L / H / H / H / / L(capping layer 131), along the physical thickness of the anti-reflective coating 130. In the example in FIG.1H, the anti-reflective coating 130 includes fourteen periods 132 and one capping layer 131, i.e., a total of thirty-one (31) layers disposed on the substrate 110. In some embodiments of the article 100 depicted in FIG. 1G, the anti-reflective coating 130 comprises less than 35 layers and is further configured such that at least one of the plurality of periods 132 comprises three high RI layers 130B and one low RI layer 130A, the three high RI layers 130B comprising the first high RI layer 130B as SiNx, the second high RI layer 130B as NbOxNy, and the third high RI layer 130B as SiNx, and the one low RI layer 130A as SiO or SiOxNy. The sequence of three consecutive high RI layers 130B near the exterior surface 122 of the article 100 enables an improved combination of hardness and optical properties, e.g., optimizing the combination of abrasion resistance and reflectance, by ‘sandwiching’ a higher refractive index layer 130B (e.g. Nb2O5) between two layers of a higher hardness material 130B (e.g. SiNx). For example, Example 16 employs the design of the anti-reflective coating 130 of FIG. 1H and offers one or more of the optical and / or mechanical properties shaded in black in FIG. 19 (see below and corresponding description).

[0120] The foregoing articles depicted in FIGS. 1A-1H and described above are exemplary of the inventive aspects of the various articles 100 of the disclosure, all of which are inventive over conventional articles with anti-reflective coatings. As noted earlier, embodiments of the articles 100 include at least one low RI layer 130A (e.g., SiCh, SiNx, SiOxNy) and at least two high RI layers 130B (e.g., NbOxNy, Nb2O5, SiNx, or SiOxNy). Some of these embodiments also employ a capping layer 131 with a refractive index greater thanAttorney Docket No.: SP24-2751.45. Some of these embodiments employ a capping layer 131 with two layers, one with a refractive index greater than or equal to 1.45 and the other with a refractive index of less than 1.45. In some embodiments, the anti-reflective coating 130 includes a sequence of layers below the capping layer 131 given by (1) SiNx, SiOxNy(2) NbOxNyor Nb2O5, (3) SiNx, SiOxNyor bzOs. These structural and material composition aspects of the anti-reflective coating 130 influence and advantageously drive an optical combination of mechanical and optical properties as detailed in Table 9 and FIG. 19, described in greater detail below.

[0121] In some implementations of the articles 100 depicted in FIGS. 1A-1H, the anti-reflective coating 130 can have from 1 to 10 periods (i.e., period 132), from 1 to 8 periods, from 1 to 6 periods, from 1 to 4 periods, or from 1 to 3 periods. In some embodiments, the anti-reflective coating 130 may include up to 20 periods (i.e., period 132). For example, the anti-reflective coating 130 may include from about 2 to 20 periods, about 2 to 18 periods, about 2 to 16 periods, about 2 to about 15 periods, from about 2 to about 10 periods, from about 2 to about 8 periods, from about 2 to about 6 periods, from about 3 to about 8 periods, or from about 3 to about 6 periods (i.e., period 132). In some implementations, the anti-reflective coating 130 can have up to 40 layers, 35 layers, 30 layers, 25 layers, 20 layers, 15 layers, 14 layers, 13 layers, 12 layers, 11 layers, 10 layers, 9 layers, 8 layers, 7 layers, 6 layers, or even as low as 5 layers.

[0122] In the embodiments of the article 100 shown in FIGS. 1A-1H, the anti-reflective coating 130 includes one or more capping layers 131, which may include a lower refractive index material than the high RI layer 130B. In some implementations, the refractive index of the capping layer 131 is the same or substantially the same as the refractive index of the low RI layers 130A, and may comprise SiCh. In some embodiments, the capping layer includes two or more capping layers 131. In some embodiments, the capping layer 131 (or layers) has a refractive index of greater than 1.45 or greater than 1.46 and, in some cases, less than 1.7. In some embodiments, the capping layer 131 (or layers) has a refractive index of less than 1.42 and, in some cases, greater than 1.3.

[0123] As used herein, the terms “low RI” and “high RI” refer to the relative values for the RI of each layer relative to the RI of another layer within the anti-reflective coating 130 (e.g., low RI < high RI). In one or more embodiments, the term “low RI” when used with the low RI layer 130A or with the capping layer 131, includes a range from about 1.3 to about 1.7, or from about 1.3 to less than 1.7. In some implementations, the term “low RI” when used with the low RI layer 130A, is inclusive of medium index (e.g., SiOxNy) material, and includes a refractive index range from about 1.5 to about 1.9; and in some cases, the low RIAttorney Docket No.: SP24-275 layer 130A can be inclusive of SiNxmaterial and have a refractive index of about 2.1 or less (e.g., when the high RI layers 130B are much higher in refractive index and comprise NbOxNy or Nb2O5). In one or more embodiments, the term “high RI” when used with the high RI layer 130B, includes a range from about 1.7 to about 2.5, from about 1.8 to about 2.5, from about 1.9 to about 2.5, from about 2.0 to about 2.5, greater than 2.0, from about 2.1 to about 2.5, or greater than 2.5.

[0124] Exemplary materials suitable for use in the anti-reflective coating 130 include: SiO2, Al2O3, GeO2, SiO, AlOxNy, AIN, oxygen-doped SiNx, SiNx, SiOxNy, SiuAlvOxNy, TiO2, ZrO2, TiN, MgO, NbOxNy, Nb2O5, Ta2O5, HfO2, Y2O3, ZrO2, diamond-like carbon, and MgAl2O4.

[0125] Some examples of suitable materials for use in the low RI layer(s) 130A include SiO2, Al2O3, GeO2, SiO, AlOxNy, SiOxNy, SiuAlvOxNy, MgO, and MgAl2O4. In some embodiments, the low RI layer(s) 130A can comprise SiNxin situations when the anti-reflective coating 130 employs high RI layers 130B with particularly high refractive index levels, e.g., Nb2Os and / or NbOxNy. The nitrogen content of the materials for use in the first low RI layer 130A (i.e., the layer 130A in contact with the substrate 110) may be minimized (e.g., in materials for example Al2O3and MgAl2O4). In some embodiments, the low RI layer(s) 130A and a capping layer 131, if present, in the anti-reflective coating 130 can comprise one or more of a silicon-containing oxide (e.g., silicon dioxide), a silicon-containing nitride (e.g., an oxide-doped silicon nitride, silicon nitride, etc.), and a silicon-containing oxynitride (e.g., silicon oxynitride). In some embodiments of the article 100, the low RI layer(s) 130A and the capping layer 131 comprise a silicon-containing oxide, e.g., SiO2.

[0126] As used herein, the “AlOxNy,” “SiOxNy,” and “SiuAlxOyNz” materials in the disclosure include various aluminum oxynitride, silicon oxynitride and silicon aluminum oxynitride materials, as understood by those with ordinary skill in the field of the disclosure, described according to certain numerical values and ranges for the subscripts, “u,” “x,” “y,” and “z”. That is, it is common to describe solids with “whole number formula” descriptions, for example Al2O3. It is also common to describe solids using an equivalent “atomic fraction formula” description for example AI0.4O0.6, which is equivalent to AhOs. In the atomic fraction formula, the sum of all atoms in the formula is 0.4 + 0.6 = 1, and the atomic fractions of Al and O in the formula are 0.4 and 0.6 respectively. Atomic fraction descriptions are described in many general textbooks and atomic fraction descriptions are often used to describe alloys. See, for example: (i) Charles Kittel, Introduction to Solid State Physics,Attorney Docket No.: SP24-275seventh edition, John Wiley & Sons, Inc., NY, 1996,pp. 611-627; (ii) Smart and Moore, Solid State Chemistry, An introduction, Chapman & Hall University and Professional Division, London, 1992, pp. 136-151; and (iii) James F. Shackelford, Introduction to Materials Science for Engineers, Sixth Edition, Pearson Prentice Hall, New Jersey, 2005, pp. 404-418.

[0127] Again referring to the “AlOxNy,” “SiOxNy,” and “SiuAlxOyNz” materials in the disclosure, the subscripts allow those with ordinary skill in the art to reference these materials as a class of materials without specifying particular subscript values. To speak generally about an alloy, for example aluminum oxide, without specifying the particular subscript values, we can speak of A1VOX. The description A1VOXcan represent either Al2O3or AI0.4O0.6- If v + x were chosen to sum to 1 (i.e. v + x = 1), then the formula would be an atomic fraction description. Similarly, more complicated mixtures can be described, for example SiuAlvOxNy, where again, if the sum u + v + x + y were equal to 1, we would have the atomic fractions description case.

[0128] Once again referring to the “AlOxNy,” “SiOxNy,” and “SiuAlxOyNz” materials in the disclosure, these notations allow those with ordinary skill in the art to readily make comparisons to these materials and others. That is, atomic fraction formulas are sometimes easier to use in comparisons. For instance; an example alloy consisting of (A1203)O.3(A1N)O.7 is closely equivalent to the formula descriptions AI0.448O0.31N0.241 and also AI367O254N198. Another example alloy consisting of (A1203)O.4(A1N)O.6 is closely equivalent to the formula descriptions Al0.43sO0.375N0.i88 and AI37O32N16. The atomic fraction formulas Al0.44sO0.31N0.241 and Al0.43sO0.375N0.i88 are relatively easy to compare to one another. For instance, Al is decreased in atomic fraction by 0.01, O is increased in atomic fraction by 0.065 and N is decreased in atomic fraction by 0.053. It takes more detailed calculation and consideration to compare the whole number formula descriptions AI367O254N198 and AI37O32N16. Therefore, it is sometimes preferable to use atomic fraction formula descriptions of solids. Nonetheless, the use of AlvOxNyis general since it captures any alloy containing Al, O and N atoms.

[0129] As understood by those with ordinary skill in the field of the disclosure with regard to any of the foregoing materials (e.g., AIN) for the optical film structure, each of the subscripts, “u,” “x,” “y,” and “z,” can vary from 0 to 1, the sum of the subscripts will be less than or equal to one, and the balance of the composition is the first element in the material (e.g., Si or Al). In addition, those with ordinary skill in the field can recognize that “SiuAlxOyNz” can be configured such that “u” equals zero and the material can be described as “AlOxNy”. Still further, the foregoing compositions for the optical film structure exclude a combination of subscripts that would result in a pure elemental form (e.g., pure silicon, pureAttorney Docket No.: SP24-275 aluminum metal, oxygen gas, etc.). Finally, those with ordinary skill in the art will also recognize that the foregoing compositions may include other elements not expressly denoted (e.g., hydrogen), which can result in non-stoichiometric compositions (e.g., SiNxvs. Si3N4). Accordingly, the foregoing materials for the optical film structure can be indicative of the available space within a SiO2-Al2O3-SiNx-AlN or a SiO2-Al2O3-Si3N4-AlN phase diagram, depending on the values of the subscripts in the foregoing composition representations.

[0130] Some examples of suitable materials for use in the high RI layer(s) 13 OB in the anti-reflective coating 130 of the article 100 (see FIGS. 1A-1H) include SiuAlvOxNy, AIN, oxygen-doped SiNx, SiNx, Si3N4, AlOxNy, SiOxNy, NbOxNy, Nb2O5, Ta? O',. HfO?. TiO?. ZrCh, Y2O3, ZrCh, Al2O3, and diamond-like carbon. Further, according to some implementations, at least two high RI layers 130B within a period 132 of the anti-reflective coating 130 are of different materials (e.g., SiOxNy, SiNxor AlOxNyfor one high RI layer 130B; and NbOxNy, Nb2O5, TiO2, Ta2O5, or HfO2for another high RI layer 130B). Further, according to some implementations, at least three high RI layers 130B within a period 132 of the anti-reflective coating 130 are of different materials (e.g., NbOxNy, Nb2O5, TiO2, Ta2O5, or HfO2for a first high RI layer 130B, SiNxor AlOxNyfor a second high RI layer 130B; and Nb2O5, TiO2, Ta2O5, or HfO2for a third high RI layer 130B). Without being bound by theory, the use of two or more high RI layers 130B having different materials can enable an optimal combination of optical and mechanical properties exhibited by the anti-reflective coating 130, while also ensuring that the article 100 demonstrates chemical resistance (e.g., no delamination observed in the anti-reflective coating 130 after testing in the Delamination Test).

[0131] In one or more embodiments at least one of the layers of the anti-reflective coating 130 of the article 100 may include a specific optical thickness range. As used herein, the term “optical thickness” is determined by (n*d), where "n" refers to the RI of the sub-layer and "d" refers to the physical thickness of the layer. In one or more embodiments, at least one of the layers of the anti-reflective coating 130 may include an optical thickness in the range from about 2 nm to about 200 nm, from about 10 nm to about 100 nm, or from about 15 nm to about 100 nm. In some embodiments, all of the layers in the anti-reflective coating 130 may each have an optical thickness in the range from about 2 nm to about 200 nm, from about 10 nm to about 100 nm, or from about 15 nm to about 100 nm. In some cases, at least one layer of the anti-reflective coating 130 has an optical thickness of about 50 nm or greater. In some cases, each of the low RI layers 130A has an optical thickness in the range from about 2 nm to about 200 nm, from about 10 nm to about 100 nm, or from about 15 nm toAttorney Docket No.: SP24-275about 100 nm. In other cases, each of the high RI layers 13 OB has an optical thickness in the range from about 2 nm to about 200 nm, from about 10 nm to about 100 nm, or from about 15 nm to about 100 nm. In some embodiments, each of the high RI layers 130B has an optical thickness in the range from about 2 nm to about 500 nm, or from about 10 nm to about 490 nm, or from about 15 nm to about 480 nm, or from about 25 nm to about 475 nm, or from about 25 nm to about 470 nm, or from about 30 nm to about 465 nm, or from about 35 nm to about 460 nm, or from about 40 nm to about 455 nm, or from about 45 nm to about 450 nm, and any and all sub-ranges between these values.

[0132] In some embodiments, each of the capping layers 131 (see FIGS. 1A-1H) has a physical thickness of less than about 100 nm, less than about 95 nm, less than about 90 nm, less than about 85 nm, less than 80 nm, or less than 70 nm. In other implementations, each of the capping layers 131 has a physical thickness of more than 60 nm, 70 nm, 80 nm, 90 nm, or even 100 nm. According to some embodiments, each capping layer 131 can have a physical thickness that ranges from 20 nm to 150 nm, 25 nm to 125 nm, 30 nm to 115 nm, 40 nm to 115 nm, 50 nm to 115 nm, and all thickness values between the foregoing ranges.

[0133] As noted earlier, embodiments of the article 100, such as depicted in FIGS. 1A-1H, are configured such that the physical thickness of one or more of the layers of the anti-reflective coating 130 are minimized. In one or more embodiments, the physical thickness of the high RI layer(s) 130B and / or the low RI layer(s) 130A are minimized such that they total less than 500 nm, or less than 450 nm. In one or more embodiments, the combined physical thickness of the high RI layer(s) 130B, the low RI layer(s) 130A and any capping layer 131 is less than 500 nm, less than 490 nm, less than 480 nm, less than 475 nm, less than 470 nm, less than 460 nm, less than about 450 nm, less than 440 nm, less than 430 nm, less than 425 nm, less than 420 nm, less than 410 nm, less than about 400 nm, less than about 350 nm, less than about 300 nm, less than about 250 nm, or less than about 200 nm, and all total thickness values below 500 nm and above 10 nm. For example, the combined physical thickness of the high RI layer(s) 130B, the low RI layer(s) 130A and any capping layer 131 may be from 10 nm to 490 nm, or from 10 nm to 480 nm, or from 10 nm to 475 nm, or from 10 nm to 460 nm, or from 10 nm to 450 nm, or from 10 nm to 450 nm, or from 10 nm to 430 nm, or from 10 nm to 425 nm, or from 10 nm to 420 nm, or from 10 nm to 410 nm, or from 10 nm to 400 nm, or from 10 nm to 350 nm, or from 10 nm to 300 nm, or from 10 nm to 250 nm, or from 10 nm to 225 nm, or from 10 nm to 200 nm, or from 15 nm to 490 nm, or from 20 nm to 490 nm, or from 25 nm to 490 nm, or from 30 nm to 490 nm, or from 35 nm to 490 nm, or from 40 nm to 490 nm, or from 45 nm to 490 nm, or from 50 nm to 490 nm, or from 55 nm to 490Attorney Docket No.: SP24-275nm, or from 60 nm to 490 nm, or from 65 nm to 490 nm, or from 70 nm to 490 nm, or from 75 nm to 490 nm, or from 80 nm to 490 nm, or from 85 nm to 490 nm, or from 90 nm to 490 nm, or from 95 nm to 490 nm, or from 100 nm to 490 nm, or from 10 nm to 485 nm, or from 15 nm to 480 nm, or from 20 nm to 475 nm, or from 25 nm to 460 nm, or from 30 nm to 450 nm, or from 35 nm to 440 nm, or from 40 nm to 430 nm, or from 50 nm to 425 nm, or from 55 nm to 420 nm, or from 60 nm to 410 nm, or from 70 nm to 400 nm, or from 75 nm to 400 nm, or from 80 nm to 390 nm, or from 90 nm to 380 nm, or from 100 nm to 375 nm, or from 110 nm to 370 nm, or from 120 nm to 360 nm, or from 125 nm to 350 nm, or from 130 nm to 325 nm, or from 140 nm to 320 nm, or from 150 nm to 310 nm, or from 160 nm to 300 nm, or from 170 nm to 300 nm, or from 175 nm to 300 nm, or from 180 nm to 290 nm, or from 190 nm to 280 nm, or from 200 nm to 275 nm.

[0134] In one or more embodiments, the combined physical thickness of the low RI layer(s) 130A and capping layer(s) 131 in the anti -reflective coating 130 of the article 100 (see FIGS. 1A-1H) may be characterized. For example, in some embodiments, the combined physical thickness of the low RI layer(s) 130A and capping layer(s) 131 may be about 125 nm or greater, about 130 nm or greater, about 135 nm or greater, or even about 140 nm or greater. The combined physical thickness is the calculated combination of the physical thicknesses of the individual low RI layer(s) 130A and capping layer(s) 131 in the anti-reflective coating 130. In some embodiments, the combined physical thickness of the low RI layer(s) 130A and capping layer(s) 131 (e.g., of SiO2) may be greater than 40% or greater than 50% of the total physical thickness of the anti-reflective coating 130 (or, alternatively referred to in the context of volume). For example, the combined physical thickness (or volume) of the low RI layer(s) 130A and capping layer(s) 131 may be about 35% or greater, about 40% or greater, about 45% or greater, about 50% or greater, about 55% or greater, or even about 60% or greater, of the total physical thickness (or volume) of the anti-reflective coating 130. As would also be recognized by those with ordinary skill, the combined physical thickness of the high RI layers 130B in the anti-reflective coating is the difference between the foregoing combined thicknesses of the low RI layer(s) 130A and capping layer(s) 131 and 100%.

[0135] The articles 100 depicted in FIGS. 1A-1H may include one or more additional coatings disposed on the anti-reflective surface 122 of the anti-reflective coating 130 (not shown in the figures). In one or more embodiments, the additional coating may include an easy-to-clean coating. An example of a suitable easy-to-clean coating is described in U. S. Patent Application No. 13 / 690,904, entitled “PROCESS FOR MAKING OF GLASSAttorney Docket No.: SP24-275ARTICLES WITH OPTICAL AND EASY-TO-CLEAN COATINGS,” filed on November 30, 2012, which is incorporated herein in its entirety by reference. The easy-to-clean coating may have a physical thickness in the range from about 5 nm to about 50 nm and may include known materials for example fluorinated silanes. In some embodiments, the easy-to-clean coating may have a physical thickness in the range from about 1 nm to about 40 nm, from about 1 nm to about 30 nm, from about 1 nm to about 25 nm, from about 1 nm to about 20 nm, from about 1 nm to about 15 nm, from about 1 nm to about 10 nm, from about 5 nm to about 50 nm, from about 10 nm to about 50 nm, from about 15 nm to about 50 nm, from about 7 nm to about 20 nm, from about 7 nm to about 15 nm, from about 7 nm to about 12 nm or from about 7 nm to about 10 nm, and all ranges and sub-ranges therebetween.

[0136] The additional coating outlined above (not shown in FIGS. 1A-1H) may include a scratch resistant coating. Exemplary materials used in the scratch resistant coating may include an inorganic carbide, nitride, oxide, diamond-like material, or combination of these. Examples of suitable materials for the scratch resistant coating include metal oxides, metal nitrides, metal oxynitride, metal carbides, metal oxycarbides, and / or combinations thereof. Exemplary metals include B, Al, Si, Ti, V, Cr, Y, Zr, Nb, Mo, Sn, Hf, Ta and W. Specific examples of materials that may be utilized in the scratch resistant coating may include Al2O3, AIN, AlOxNy, SiNx, SiOxNy, SiuAlvOxNy, diamond, diamond-like carbon, SixCy, SixOyCz, ZrO2, TiOxNyand combinations thereof.

[0137] In some embodiments, the additional coating (not shown in FIGS. 1A-1H) includes a combination of easy-to-clean material and scratch resistant material. In one example, the combination includes an easy-to-clean material and diamond-like carbon. Such additional coatings may have a physical thickness in the range from about 5 nm to about 20 nm. The constituents of the additional coating may be provided in separate layers. For example, the diamond-like carbon material may be disposed as a first layer and the easy-to-clean material can be disposed as a second layer on the first layer of diamond-like carbon. The physical thicknesses of the first layer and the second layer may be in the ranges provided above for the additional coating. For example, the first layer of diamond-like carbon may have a physical thickness of about 1 nm to about 20 nm or from about 4 nm to about 15 nm (or more specifically about 10 nm) and the second layer of easy-to-clean material may have a physical thickness of about 1 nm to about 10 nm (or more specifically about 6 nm). The diamond-like coating may include tetrahedral amorphous carbon (Ta-C), Ta-C: H, and / or a-C-H.

[0138] A further aspect of this disclosure pertains to a method for forming the articles 100 described herein (e.g., as shown in FIGS. 1A-1H). In some embodiments, the methodAttorney Docket No.: SP24-275 includes providing a substrate having a major surface in a coating chamber, forming a vacuum in the coating chamber, forming a durable anti-reflective coating having a physical thickness of about 500 nm or less on the major surface, optionally forming an additional coating comprising at least one of an easy-to-clean coating or a scratch resistant coating, on the anti-reflective coating, and removing the substrate from the coating chamber. In one or more embodiments, the anti-reflective coating and the additional coating are formed in either the same coating chamber or without breaking vacuum in separate coating chambers.

[0139] In one or more embodiments, the method may include loading the substrate on carriers which are then used to move the substrate in and out of different coating chambers, under load lock conditions so that a vacuum is preserved as the substrate is moved.

[0140] The anti-reflective coating 130 (i.e., as including layers 130A, 130B and capping layer(s) 131) and / or any additional coating (e.g., additional coating(s) not shown in FIGS. 1A-1H) may be formed using various deposition methods for example vacuum deposition techniques, for example, chemical vapor deposition (e.g., plasma enhanced chemical vapor deposition (PECVD), low-pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, and plasma-enhanced atmospheric pressure chemical vapor deposition), physical vapor deposition (e.g., reactive or nonreactive sputtering or laser ablation), thermal or e-beam evaporation and / or atomic layer deposition. Liquid-based methods may also be used for example spraying or slot coating. Where vacuum deposition is utilized, inline processes may be used to form the anti-reflective coating 130 and / or the additional coating in one deposition run. In some instances, the vacuum deposition can be made by a linear PECVD source. In some implementations of the method, and articles 100 made according to the method, the anti-reflective coating 130 can be prepared using a sputtering process (e.g., a reactive sputtering process), chemical vapor deposition (CVD) process, plasma-enhanced chemical vapor deposition process, or some combination of these processes. In one implementation, an anti-reflective coating 130 comprising low RI layer(s) 130A and high RI layer(s) 130B can be prepared according to a reactive sputtering process. According to some embodiments, the anti-reflective coating 130 (including low RI layers 130A, high RI layers 130B and capping layer(s) 131) of the article 100 is fabricated using a metal-mode, reactive sputtering in a rotary drum coater. The reactive sputtering process conditions were defined through careful experimentation to achieve the desired combinations of hardness, refractive index, optical transparency, low color and controlled film stress.

[0141] In some embodiments, the method may include controlling the physical thickness of the anti-reflective coating 130 (e.g., including its layers 130A, 130B and 131) and / or theAttorney Docket No.: SP24-275 additional coating so that it does not vary by more than about 4% along about 80% or more of the area of the anti-reflective surface 122 or from the target physical thickness for each layer at any point along the substrate area. In some embodiments, the physical thickness of the anti-reflective layer coating 130 and / or the additional coating is controlled so that it does not vary by more than about 4% along about 95% or more of the area of the anti-reflective surface 122.

[0142] The articles 100 disclosed herein, including their anti-reflective coating 130 (e.g., as shown in FIGS. 1A-1H), may be incorporated into a device article for example a device article with a display (or display device articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, wearable devices (e.g., watches) and the like), augmented-reality displays, heads-up displays, glasses-based displays, architectural device articles, transportation device articles (e.g., automotive, trains, aircraft, sea craft, etc.), appliance device articles, or any device article that benefits from some transparency, scratchresistance, abrasion resistance or a combination thereof. An exemplary device article incorporating any of the articles disclosed herein (e.g., as consistent with the articles 100 depicted in FIGS. 1A-1H) is shown in FIGS. 2A and 2B. Specifically, FIGS. 2A and 2B show a consumer electronic device 200 including a housing 202 having a front 204, a back 206, and side surfaces 208; electrical components (not shown) that are at least partially inside or entirely within the housing and including at least a controller, a memory, and a display 210 at or adjacent to the front surface of the housing; and a cover substrate 212 at or over the front surface of the housing such that it is over the display. In some embodiments, the cover substrate 212 may include any of the articles disclosed herein. In some embodiments, at least one of a portion of the housing or the cover glass comprises the articles disclosed herein.

[0143] According to some embodiments, the articles 100 (e.g., as shown in FIGS. 1A-1H) may be incorporated within a vehicle interior with vehicular interior systems, as depicted in FIG. 3. More particularly, the article 100 may be used in conjunction with a variety of vehicle interior systems. A vehicle interior 340 is depicted that includes three different examples of a vehicle interior system 344, 348, 352. Vehicle interior system 344 includes a center console base 356 with a surface 360 including a display 364. Vehicle interior system 348 includes a dashboard base 368 with a surface 372 including a display 376. The dashboard base 368 typically includes an instrument panel 380 which may also include a display.Vehicle interior system 352 includes a dashboard steering wheel base 384 with a surface 388 and a display 392. In one or more examples, the vehicle interior system may include a base that is an armrest, a pillar, a seat back, a floorboard, a headrest, a door panel, or any portionAttorney Docket No.: SP24-275of the interior of a vehicle that includes a surface. It will be understood that the article 100 described herein can be used interchangeably in each of vehicle interior systems 344, 348 and 352.

[0144] According to some embodiments, the articles 100 (e.g., as shown in FIGS. 1A-1H) may be used in a passive optical element, for example a lens, windows, lighting covers, eyeglasses, or sunglasses, that may or may not be integrated with an electronic display or electrically active device.

[0145] Referring again to FIG. 3, the displays 364, 376 and 392 may each include a housing having front, back, and side surfaces. At least one electrical component is at least partially within the housing. A display element is at or adjacent to the front surface of the housings. The article 100 (see FIGS. 1A-1H) is disposed over the display elements. It will be understood that the article 100 may also be used on, or in conjunction with, the armrest, the pillar, the seat back, the floorboard, the headrest, the door panel, or any portion of the interior of a vehicle that includes a surface, as explained above. According to various examples, the displays 364, 376 and 392 may be a vehicle visual display system or vehicle infotainment system. It will be understood that the article 100 may be incorporated in a variety of displays and structural components of autonomous vehicles and that the description provided herein with relation to conventional vehicles is not limiting.

[0146] Another exemplary device article incorporating any of the articles 100 disclosed herein (e.g., as consistent with the articles 100 depicted in FIGS. 1A-1H) is shown in FIG. 4. Specifically, FIG. 4 shows a laptop 400 including a housing 402 having a front 404 (e.g., a bezel), a back 406, and side surfaces 408; electrical components (not shown) that are at least partially inside or entirely within the housing and including at least a controller, a memory, and a display 410 at or adjacent to the front surface of the housing; and a cover substrate 412 at or over the front surface of the housing such that it is over the display. In some embodiments, the cover substrate 412 may include any of the articles disclosed herein. In some embodiments, at least one of a portion of the housing or the cover glass comprises the articles disclosed herein.EXAMPLES

[0147] Various embodiments will be further clarified by the following examples.Example 1 - AR Coating Design, Chemical Resistance, Optical and Mechanical PropertiesAttorney Docket No.: SP24-275

[0148] The as- fabricated samples of Example 1 (“Ex. 1”) were formed by providing a glass substrate having a nominal composition of 69 mol% SiO2. 10 mol% Al2O3, 15 mol% Na? O. and 5 mol% MgO and disposing an anti-reflective coating having six (6) layers on the glass substrate, as shown in FIG. 1A and Table 1 below. The anti-reflective coating (e.g., as consistent with the anti-reflective coatings 130 outlined in the disclosure) of each of the as-fabricated samples in this Example was deposited using a reactive sputtering process.

[0149] Samples of Example 1 were also modeled, and assumed to employ a glass substrate having the same composition of the glass substrate employed in the as-fabricated samples of this example. Further, the anti-reflective coating of each of the modeled samples was assumed to have the layer materials and physical thickness as shown in Table 1 below. The optical properties of this example, as outlined below in Tables 1A and IB, were modeled or otherwise measured at near-normal incidence, unless otherwise noted.

[0150] As is evident from Table IB, Ex. 1 has a photopic average reflectance at nearnormal incidence below 0.26%. The color is well-controlled, with both a* and b* falling within a range of -3 < a* < 0 and -3 < b* <0 at near-normal incidence. The modeling example, as outlined in Table 1A, illustrates that color with changing incident angle stays within a range of -3 < a* < 3 and -3 < b* < 3 for all viewing angles within the range of 0 to 60 degrees. These color values for the modeled Ex. 1 correspond to a ΔC = sqrt((amax-amin)2+ (bmax-bmin)2) value of AC < 5.5 for this same angular range of 0 to 60 degrees. The value of C* = sqrt (a*2+ b*2) is less than 2.5 for all near-normal light incidence angles from 0 to 10 degrees. This is a very tightly controlled range of color vs. changing incident angle for an anti-reflective (AR) coating with such low average reflectance. As with all experimental examples shown here, the optics of the experimental example can be fine-tuned to more closely match the modeling results with sufficient sputtering deposition recipe optimization.Table 1: Anti-reflective coating attributes for Example 1 Refractive Extinction Physical Index @550 Coefficient Thickness Layer Material nm @550nm (nm) Medium Air 1 01 SiO21.462 0 94.91 2 Nb2O52.369 0 22.09 3 SiNx2.036 0 97.61 4 SiO21.462 0 45.33 5 SiNx 2.036 0 9.68 6 SiO21.462 0 25Substrate Glass 1.506 0 0.7 mmAttorney Docket No.: SP24-275Total Coating Thickness 294.62Attorney Docket No.: SP24-275Table 1 A: Optical properties of modeled Example 1 Incident Photopic average L* a* b* c* Angle reflectance (Y)0 0.251 2.2671 -1.0151 -2.0597 2.296 5 0.2503 2.2608 -1.0814 -1.924 2.207 10 0.2494 2.2526 -1.2605 -1.5448 1.994 15 0.2519 2.2757 -1.4984 -0.9996 1.801 20 0.2645 2.3889 -1.7175 -0.3986 1.763 25 0.2971 2.6839 -1.8326 0.1358 1.838 30 0.3651 3.2982 -1.765 0.4847 1.830 35 0.4914 4.4388 -1.45 0.5362 1.546 40 0.7114 6.4259 -0.8345 0.1759 0.853 45 1.0818 9.6553 0.1184 -0.6292 0.640 50 1.6965 13.8065 0.9867 -1.4779 1.777 55 2.7143 18.8612 1.6255 -2.2238 2.75560 4.4074 24.9751 2.0566 -2.7966 3.471Table IB: Measured optical properties of Example 1 Incident Photopic average L* a* b* Angle reflectance (Y)6 0.28 2.55 -3.05 -0.5320 0.27 2.43 -3.07 0.35 40 0.64 5.74 -0.15 -0.0945 0.97 8.77 1.52 -1.1060 4.15 24.17 3.74 -2.89

[0151] Referring now to FIGS. 5A-5D, optical micrographs at 50x and 200x of the anti-reflective surface of articles with the Nb₂O₅ / SiNx / SiO₂ anti-reflective coating of Table 1 (Ex.1), as subjected to a Delamination Test with abrasion conducted using a Taber Abrader system, are shown before and after 15 minutes of exposure to petroleum jelly (Vaseline®). As is evident from these figures, this example exhibited no delamination at 50x and 200x after being tested with the Delamination Test. Further, similar results (i.e., no delaminations) are observed when this example is subjected to the Delamination Test using other common chemical ingredients, including sweat, tap water, salt water, and common sunscreen formulations.

[0152] Referring now to FIGS. 5E-5J, optical micrographs at 50x and 200x of the anti-reflective surface of articles with the Nb₂O₅ / SiNx / SiO₂ anti-reflective coating of Table 1 (Ex.1), as subjected to a Delamination Test with abrasion conducted using a Taber Abrader system, are shown before and after 15 minutes and 80 hours of exposure to petroleum jelly (Vaseline®). As is evident from these figures, this example exhibited no delamination at 50xAttorney Docket No.: SP24-275and 200x after being tested with the Delamination Test, even after the longer duration test for 80 hours.

[0153] This example also exhibits good mechanical properties, suitable for the various applications detailed earlier in this disclosure. Experimentally measured nanoindentation hardness and elastic modulus values are provided below in Table 1C for samples made according to the AR coating design set forth in this example (see Table 1) and under different reactive sputtering pressure levels, as measured with a Berkovich Hardness Test. Hardness is reported both at 100 nm indentation depth and as a maximum (peak) hardness value for each sample of this example in units of GPa. Maximum hardness may occur at different depths for each sample, and typically depends on the total coating stack thickness. Particularly preferred values from those samples shown below include an elastic modulus greater than 70 GPa, greater than 80 GPa, greater than 85 GPa, or even greater than 86 GPa. Particularly preferred values from those samples shown below include a hardness at 100 nm depth of greater than 6.5 GPa, greater than 7.0 GPa, or even greater than 7.5 GPa.Table 1C: Measured optical properties of Example 1 Example Sample Thickness, Elastic Hardness Max.nm Modulus, @ lOOnm, Hardness,GPa GPa GPa 1 Sample 1 - 1 mTorr 295 86.5 7.88 7.88 1 Sample 2 - 1 mTorr 295 88.5 8.05 8.05 1 Sample 3 - 3 mTorr 295 83.3 7.2 7.2 1Sample 4 - 5 mTorr 295 83.2 7.2 7.2

[0154] Referring now to FIG. 6, a Weibull distribution chart is provided of the failure strength levels of the example articles of FIGS. 5A-5J (Ex. 1), as tested with a Ring-on-Ring Test with a displacement rate of 1.2 mm / min at 23°C and 50% room humidity with a load ring diameter as 25.4 mm and support ring diameter of 12.7 mm. Failure load as measured in the Ring-on-Ring Test correlates to stress in the glass of a glass wafer being tested, and a finite element model (FEA) was used to convert load to stress, as described below in connection with FIG. 6A, to present a more accurate representation of Ring-on-Ring Test behavior than beam theory. As is evident from FIG. 6, the surface strength or crack-onset-strain of the coatings of this example (Ex. 1) were evaluated. The anti-reflective coating design of this example shows improved mechanical reliability in terms of a Weibull slope (m) or “Shape”. In particular, the high Weibull modulus (m) value of -149 exhibited by theAttorney Docket No.: SP24-275coatings of this example reflects the high reliability of this design. Further, it is evident from this figure that the characteristic strength value (σ₀) of ~911 MPa (also referred to in the figure as “Scale”) shows that this coating design is 63.2% likely to fail if it is subjected to a stress of 911 MPa. This 911 MPa value can be converted to failure strain of -1.2% using the elastic properties of the coating along with the knowledge of biaxial stress state, as understood by those skilled in the field of the disclosure.

[0155] Referring now to FIG. 6A, a plot of radial stress (MPa) vs. load (kgf) is provided for the transparent article (Ex. 1) of this example, as modeled using a finite element analysis methodology. As noted earlier, an equibiaxial flexure test (Ring-on-Ring Test) was conducted according to this example with a displacement rate of 1.2 mm / min at 23°C and 50% room humidity with a load ring diameter as 25.4 mm and support ring diameter of 12.7 mm, as described in ASTM C1499-23. Failure load measured in the equibiaxial flexure test (Ring-on-Ring Test) correlates to stress in the glass of a glass wafer, substrate or coated article being tested. However, without being bound by theory, it is believed that the use of a numerical model such as finite element model to convert failure load to failure stress presents a more accurate representation of an equibiaxial flexure test (Ring-on-Ring Test) than simply assuming beam (linear) bending theory that further disregards the geometric non-linearity to evaluate stress. ASTM Cl 499-23 stipulates the use of an equibiaxial flexure test (Ring-on-Ring Test) only up to the regime of linear bending behavior, disregarding the geometric nonlinearity. Consequently, a finite element (FE) model was built using commercially available software, ABAQUS, in standard explicit mode. The FE model of the equibixial flexure test (Ring-on-Ring Test) was setup as axisymmetric including geometric non-linearity while neglecting material non-linearity. The shell planar elements were chosen with a solid homogeneous section. The contact between the material being tested and the rings were defined as frictionless while the normal contact was defined as hard contact. The elastic properties of the material being tested and the rings used were also defined. As the displacement is applied to the load ring to simulate the test up to a maximum value, the reaction loads on the ring along with the maximum radial stress on the tension side surface of the plate / sheet / wafer being tested is in the vicinity directly below the load ring is tabulated and plotted, as shown in FIG. 6A.

[0156] Referring again to FIG. 6A, the load (x-axis) corresponds to the radial stress (y-axis) on the surface of the coated glass, wafer or article being tested as obtained from using a finite element analysis with the substrate being 0.7 mm thick. FIG. 6A can also be represented using the following complex polynomial function where applied load is inAttorney Docket No.: SP24-275kilograms force (kgf) between the rings and radial stress is in megapascal (MPa) up to a maximum of 300 kgf load: y = -3.78219E-25x^8 + 6.44038E-21x^7 - 4.63632E-17x^6 + 1.84810E-13x^5 - 4.49643E-10x^4 + 7.00296E-07x^3 - 0.00075x^2 + 0.96340x, where “y” is the radial stress and “x” is the applied load, where “E” means ‘times 10 to the exponent power of the number following the E,’ and where hat symbol (“A”) means ‘to the exponent power of the number following the hat symbol’. These values theoretically align with results (stress) that may be measured through other physical experiments conducted on the samples using a strain gauge or using other optical techniques such as digital image correlation (DIC). Further, the finite element analysis and correction may be validated using strain gauge (or other empirical measurements). Alternatively strain gauge measurements may directly be used for stress and strain data (e.g., failure strain) if such numerical modeling does not align with empirical results.Example 2 - AR Coating Design, and Optical Properties

[0157] Example 2 (“Ex. 2”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 64 mol% SiO?. 16 mol% Al2O3, 11 mol% Na? O. 6 mol% Li? O. 1 mol% ZnO, and 2.5 mol% P2O5 and disposing an anti-reflective coating having six (6) layers on the glass substrate, as shown in FIG. 1A and Table 2 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 2 was designed to have the layer materials and physical thickness as shown in Table 2 below. The optical properties of this example, as outlined below in Table 2A, were modeled at nearnormal incidence, unless otherwise noted.

[0158] As is evident from Table 2A, photopic average reflectance and Lab color results are given vs. incident light angle. As can be seen from the tables, Example 2 has a photopic average reflectance at near-normal incidence below 0.18%. The color is well controlled, with both a* and b* falling with a range of -3 < a* < 0 and -3 < b* < 0 at near normal incidence. The modeling example illustrates that color with changing incident angle stays within a range of -3 < a* < 5 and -3 < b* < 3 for all viewing angles within the range of 0 to 60 degrees. These color values for the modeled Example 2 correspond to a maximum deltaC = sqrt((amax-amin)A2 + (bmax-bmin)A2) value of deltaC < 5.5 for this same angular range of 0 to 60 degrees. The value of C* = sqrt (a*2+ b*2) is less than 2.5 for all near-normal light incidence angles from 0 to 10 degrees. This is a very tightly controlled range of color vs. changing incident angle for an AR coating with such low average reflectance.Attorney Docket No.: SP24-275Table 2: Anti-reflective coating attributes for Example 2Extinction Physical Refractive Coefficient Thickness Layer Material Index @550 nm @550nm (nm) Medium Air 1 01 SiO21.460 0 95.11 2 Nb2O52.366 0 22.32 3 SiNx 2.057 0 93.74 4 SiO21.469 0 41.71 5 SiNx 2.057 0 10.0 6 SiO21.469 0 25.0 Substrate Glass 1.511 0 0.7 mmTotal Coating Thickness 287.9Table 2A: Optical properties of modeled Example 2 Incident Angle Photopic average reflectance (Y) L* a* b* C* 0 0.174 1.572 -0.474 -2.310 2.358 10 0.169 1.525 -0.572 -1.796 1.885 20 0.174 1.575 -0.673 -0.554 0.871 30 0.261 2.360 -0.322 0.700 0.770 40 0.589 5.322 0.974 1.100 1.469 50 1.547 12.906 2.541 -0.254 2.55460 4.219 24.383 3.091 -1.718 3.536Example 3 - AR Coating Design, and Optical Properties

[0159] Example 3 (“Ex. 3”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 64 mol% SiO. 16 mol% Al2O3, 11 mol% Na O. 6 mol% I 2O. 1 mol% ZnO, and 2.5 mol% P2O5 and disposing an anti-reflective coating having six (6) layers on the glass substrate, as shown in FIG. 1A and Table 3 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Low-index SiO2 films having index = 1.41 have been fabricated using reactive sputtering with elevated process pressure, for example through increasing argon or oxygen gas flow during the sputter process. Example 3 was designed to have the layer materials and physical thickness as shown in Table 3 below. The optical properties of this example, as outlined below in Table 3A, were modeled at near-normal incidence, unless otherwise noted.

[0160] As is evident from Table 3A, photopic average reflectance and Lab color results are given vs. incident light angle. As can be seen from the tables, Example 3 has a photopicAttorney Docket No.: SP24-275average reflectance at near-normal incidence below 0.12%. The color is well controlled, with both a* and b* falling with a range of -2 < a* < 0 and -2 < b* < 0 at near normal incidence. The modeling example illustrates that color with changing incident angle stays within a range of -2 < a* < 3 and -2 < b* < 2 for all viewing angles within the range of 0 to 60 degrees. These color values for the modeled Example 3 correspond to a maximum deltaC = sqrt((amax- amin)A2 + (bmax-bmin)A2) value of deltaC < 4.0 for this same angular range of 0 to 60 degrees. The value of C* = sqrt (a*2+ b*2) is less than 2.0 for all near-normal light incidence angles from 0 to 10 degrees. This is a very tightly controlled range of color vs. changing incident angle for an AR coating with such low average reflectance.Table 3: Anti-reflective coating attributes for Example 3Extinction Physical Refractive Coefficient Thickness Layer Material Index (8)550 nm (®550nm (nm) Medium Air 1 01 SiO21.410 0 97.83 2 Nb2O52.366 0 14.24 3 SiNx 2.057 0 106.21 4 SiO21.469 0 40.14 5 SiNx 2.057 0 11.68 6 SiO21.469 0 25.0 Substrate Glass 1.511 0 0.7 mmTotal Coating Thickness 295.1Table 3A: Optical properties of modeled Example 3 Incident Angle Photopic average reflectance (Y) L* a* b* C* 0 0.100 0.905 -0.014 -1.564 1.564 10 0.098 0.885 -0.078 -1.169 1.172 20 0.110 0.989 -0.145 -0.213 0.257 30 0.196 1.772 0.083 0.761 0.766 40 0.498 4.502 0.968 1.112 1.474 50 1.373 11.776 2.203 0.107 2.20560 3.860 23.201 2.598 -1.073 2.811Attorney Docket No.: SP24-275Example 4 - AR Coating Design, and Optical Properties

[0161] Example 4 (“Ex. 4”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 64 mol% SiO?. 16 mol% Al2O3, 11 mol% Na? O. 6 mol% LiaO. 1 mol% ZnO, and 2.5 mol% P2O5 (also referred to as Coming® Gorilla® Glass 5) and disposing an anti-reflective coating having seven (7) layers on the glass substrate, as shown in FIG. 1B and Table 4 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Low-index SiO₂ films having index = 1.41 have been fabricated using reactive sputtering with elevated process pressure, for example through increasing argon or oxygen gas flow during the sputter process. Example 4 was designed to have the layer materials and physical thickness as shown in Table 4 below. The optical properties of this example, as outlined below in Table 4A, were modeled at near-normal incidence, unless otherwise noted.

[0162] As is evident from Table 4A, photopic average reflectance and Lab color results are given vs. incident light angle. As can be seen from the tables, Example 4 has a photopic average reflectance at near-normal incidence below 0.16%. The color is well controlled, with both a* and b* falling with a range of -2 < a* < 0 and -2 < b* < 0 at near normal incidence. The modeling example illustrates that color with changing incident angle stays within a range of -2 < a* < 3 and -2 < b* < 2 for all viewing angles within the range of 0 to 60 degrees. These color values for the modeled Example 4 correspond to a maximum deltaC = sqrt((amax-amin)A2 + (bmax-bmin)A2) value of deltaC < 5.0 for this same angular range of 0 to 60 degrees. The value of C* = sqrt (a*2+ b*2) is less than 2.0 for all near-normal light incidence angles from 0 to 10 degrees. This is a very tightly controlled range of color vs. changing incident angle for an AR coating with such low average reflectance.Attorney Docket No.: SP24-275Table 4: Anti-reflective coating attributes for Example 4Extinction Physical Refractive Coefficient Thickness Layer Material Index @550 nm @550nm (nm) Medium Air 1 01 SiO21.460 0 42.00 2 SiO21.410 0 51.77 3 Nb2O52.366 0 17.92 4 SiNx 2.057 0 100.99 5 SiO21.469 0 40.97 6 SiNx 2.057 0 10.64 7 SiO21.469 0 25.00 Substrate Glass 1.511 0 0.7 mmTotal Coating Thickness 289.3Table 4A: Optical properties of modeled Example 4 Incident Angle Photopic average reflectance (Y) L* a* b* C* 0 0.153 1.381 -0.763 -1.431 1.622 10 0.149 1.348 -0.857 -1.015 1.328 20 0.158 1.425 -0.958 -0.058 0.960 30 0.244 2.199 -0.641 0.751 0.987 40 0.554 4.999 0.574 0.634 0.855 50 1.455 12.316 2.286 -0.868 2.44560 3.998 23.664 2.967 -2.045 3.604Example 5 - AR Coating Design, and Optical Properties

[0163] Example 5 (“Ex. 5”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 64 mol% SiO. 16 mol% Al2O3, 11 mol% Na? O. 6 mol% Li? O. 1 mol% ZnO, and 2.5 mol% P2O5 and disposing an anti-reflective coating having six (6) layers on the glass substrate, as shown in FIG. 1A and Table 5 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 5 was designed to have the layer materials and physical thickness as shown in Table 5 below. The optical properties of this example, as outlined below in Table 5A, were modeled at nearnormal incidence, unless otherwise noted.

[0164] As is evident from Table 5A, photopic average reflectance and Lab color results are given vs. incident light angle. As can be seen from the tables, Example 5 has a photopic average reflectance at near-normal incidence below 0.35%. Further, this example has a two- surface transmittance T(940) greater than 90% at a wavelength of 940nm, when the antiAttorney Docket No.: SP24-275reflective coating is present on only one surface of the substrate and the 2ndsurface of the substrate is uncoated. The color is well controlled, with both a* and b* falling with a range of -2 < a* < 0 and -5 < b* < 0 at near normal incidence. The modeling example illustrates that color with changing incident angle stays within a range of -2 < a* < 3 and -5 < b* < 4 for all viewing angles within the range of 0 to 60 degrees. These color values for the modeled Example 5 correspond to a maximum deltaC = sqrt((amax-amin)^2 + (bmax-bmin)^2) value of deltaC < 9.0 for this same angular range of 0 to 60 degrees. The value of C* = sqrt (a*2+ b*2) is less than 5.0 for all near-normal light incidence angles from 0 to 10 degrees. This is a very tightly controlled range of color vs. changing incident angle for a thin AR coating with less than 9 layers, a total thickness less than 450nm, and a low average reflectance, while also having a T(940) value greater than 90%.Table 5: Anti-reflective coating attributes for Example 5Extinction Physical Refractive Coefficient Thickness Layer Material Index @550 nm @550nm (nm) Medium Air 1 01 SiO21.460 0 101.52 2 Nb2O52.366 0 15.88 3 SiNx 2.057 0 115.25 4 SiO21.469 0 43.12 5 SiNx 2.057 0 17.59 6 SiO21.469 0 25.00 Substrate Glass 1.511 0 0.7 mmTotal Coating Thickness 318.4Table 5A: Optical properties of modeled Example 5 Incident Angle Photopic average reflectance (Y) L* a* b* C* 0 0.313 2.828 -1.373 -4.291 4.505 10 0.294 2.656 -1.257 -3.670 3.879 20 0.264 2.387 -0.654 -2.174 2.270 30 0.313 2.823 0.696 -0.335 0.772 40 0.626 5.658 2.310 1.888 2.983 50 1.629 13.403 2.074 3.397 3.98060 4.438 25.069 0.853 2.877 3.001Attorney Docket No.: SP24-275 Example 6 - AR Coating Design, and Optical Properties

[0165] Example 6 (“Ex. 6”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 64 mol% SiO. 16 mol% Al2O3, 11 mol% Na O. 6 mol% IJ2O. 1 mol% ZnO, and 2.5 mol% P2O5 and disposing an anti-reflective coating having six (6) layers on the glass substrate, as shown in FIG. 1A and Table 6 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Low-index SiO2 films having index = 1.41 have been fabricated using reactive sputtering with elevated process pressure, for example through increasing argon or oxygen gas flow during the sputter process. Example 6 was designed to have the layer materials and physical thickness as shown in Table 6 below. The optical properties of this example, as outlined below in Table 6A, were modeled at near-normal incidence, unless otherwise noted.

[0166] As is evident from Table 6A, photopic average reflectance and Lab color results are given vs. incident light angle. As can be seen from the tables, Example 6 has a photopic average reflectance at near-normal incidence below 0.22%. Further, this example has a two-surface transmittance T(940) greater than 91% at a wavelength of 940nm, when the anti-reflective coating is present on only one surface of the substrate and the 2ndsurface of the substrate is uncoated. The color is well controlled, with both a* and b* falling with a range of -1 < a* < 0 and -4 < b* < 0 at near normal incidence. The modeling example illustrates that color with changing incident angle stays within a range of -2 < a* < 3 and -4 < b* < 3 for all viewing angles within the range of 0 to 60 degrees. These color values for the modeled Example 6 correspond to a maximum deltaC = sqrt((amax-amin)^2 + (bmax-bmin)^2) value of deltaC < 8.0 for this same angular range of 0 to 60 degrees. The value of C* = sqrt (a*2+ b*2) is less than 4.0 for all near-normal light incidence angles from 0 to 10 degrees. This is a very tightly controlled range of color vs. changing incident angle for a thin AR coating with less than 9 layers, a total thickness less than 550nm, and a low average reflectance, while also having a T(940) value greater than 90%.Attorney Docket No.: SP24-275Table 6: Anti-reflective coating attributes for Example 6Extinction Physical Refractive Coefficient Thickness Layer Material Index @550 nm @550nm (nm) Medium Air 1 01 SiO21.410 0 103.19 2 Nb2O52.366 0 8.01 3 SiNx2.057 0 128.28 4 SiO21.469 0 44.63 5 SiNx 2.057 0 16.79 6 SiO21.469 0 229.53 Substrate Glass 1.511 0 0.7 mmTotal Coating Thickness 530.4Table 6A: Optical properties of modeled Example 6 Incident Angle Photopic averagereflectance (Y) L* a* b* c* 0 0.209 1.890 -0.901 -3.766 3.872 10 0.193 1.740 -0.922 -3.223 3.352 20 0.165 1.486 -0.762 -1.978 2.119 30 0.196 1.766 -0.096 -0.539 0.548 40 0.442 3.988 1.189 1.159 1.660 50 1.286 11.175 2.580 2.788 3.79860 3.814 23.045 2.715 2.412 3.632Example 7 - AR Coating Design, and Optical Properties

[0167] Example 7 (“Ex. 7”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 64 mol% SiO. 16 mol% Al2O3, 11 mol% Na O. 6 mol% I 2O. 1 mol% ZnO, and 2.5 mol% P2O5 and disposing an anti-reflective coating having seven (7) layers on the glass substrate, as shown in FIG. IB and Table 7 below. Further, the anti-reflective coating of each of the modeled example s also used refractive index dispersions from experimentally fabricated thin films. Low-index SiO2 films having index = 1.41 have been fabricated using reactive sputtering with elevated process pressure, for example through increasing argon or oxygen gas flow during the sputter process. Example 7 was designed to have the layer materials and physical thickness as shown in Table 7 below. The optical properties of this example, as outlined below in Table 7A, were modeled at near-normal incidence, unless otherwise noted.Attorney Docket No.: SP24-275

[0168] As is evident from Table 7A, photopic average reflectance and Lab color results are given vs. incident light angle. As can be seen from the tables, Example 7 has a photopic average reflectance at near-normal incidence below 0.25%. Further, this example has a two-surface transmittance T(940) greater than 90% at a wavelength of 940nm, when the anti-reflective coating is present on only one surface of the substrate and the 2ndsurface of the substrate is uncoated. The color is well controlled, with both a* and b* falling with a range of -1 < a* < 0 and -5 < b* < 0 at near normal incidence. The modeling example illustrates that color with changing incident angle stays within a range of -2 < a* < 3 and -5 < b* < 4 for all viewing angles within the range of 0 to 60 degrees. These color values for the modeled Example 7 correspond to a maximum deltaC = sqrt((amax-amm)A2 + (bmax-bmm)A2) value of deltaC < 8.0 for this same angular range of 0 to 60 degrees. The value of C* = sqrt (a*2+ b*2) is less than 9.0 for all near-normal light incidence angles from 0 to 10 degrees. This is a very tightly controlled range of color vs. changing incident angle for a thin AR coating with less than 9 layers, a total thickness less than 400nm, and a low average reflectance, while also having a T(940) value greater than 90%.Table 7: Anti-reflective coating attributes for Example 7Extinction Physical Refractive Coefficient Thickness Layer Material Index (8)550 nm (®550nm (nm) Medium Air 1 01 SiO21.460 0 42.00 2 SiO21.410 0 57.23 3 Nb2O52.366 0 12.12 4 SiNx2.057 0 121.72 5 SiO21.469 0 42.26 6 SiNx 2.057 0 17.49 7 SiO21.469 0 25.00 Substrate Glass 1.511 0 0.7 mmTotal Coating Thickness 317.8Attorney Docket No.: SP24-275Table 7A: Optical properties of modeled Example 7 Incident Angle Photopic average reflectance (Y) L* a* b* c* 0 0.231 2.089 -0.787 -4.178 4.252 10 0.215 1.944 -0.687 -3.565 3.630 20 0.192 1.737 -0.161 -2.084 2.090 30 0.245 2.214 0.999 -0.261 1.033 40 0.546 4.933 2.324 1.944 3.030 50 1.490 12.546 2.015 3.704 4.21760 4.158 24.188 0.750 3.172 3.259Comparative Example 1

[0169] The as-fabricated samples of the comparative example (“Comp. Ex. 1”) were formed by providing a glass substrate having a nominal composition of 69 mol% SiO. 10 mol% Al2O3, 15 mol% Na O. and 5 mol% MgO and disposing an anti-reflective coating having six (6) layers on the glass substrate, as shown in Table 8 below. The anti-reflective coating of this comparative example was deposited using a reactive sputtering process.

[0170] Samples of Comp. Ex. 1 were also modeled, and assumed to employ a glass substrate having the same composition of the glass substrate employed in the as-fabricated samples of this comparative example. Further, the anti-reflective coating of each of the modeled samples was assumed to have the layer materials and physical thickness as shown in Table 8 below. The optical properties of this example, as outlined below in Tables 8A and 8B, were modeled or otherwise measured at near-normal incidence, unless otherwise noted. In addition, transmittance data was modeled and measured for samples of Comp. Ex. 1. The modeled data included 1-sided transmittance values of 91.28%, 91.10%, 90.92%, 90.74%, and 90.57% at wavelengths of 930 nm, 935 nm, 940 nm, 945 nm, and 950 nm, respectively. The measured data included 1-sided transmittance values of 88.40%, 88.29%, 88.17%, 88.04%, 87.91% and 87.77% at wavelengths of 930 nm, 934 nm, 938 nm, 942 nm, 946 nm, and 950 nm, respectively.

[0171] As is evident from Tables 8-8B, Comp. Ex. 1 has a photopic average reflectance at near-normal incidence below 0.25%. The color falls within a range of 0 < a* < 2 and -6< b* <-2 at near normal incidence. The modeling example illustrates that color with changing incident angle stays within a range of -2 < a* < 2 and -6 < b* < 1 for all viewing angles within the range of 0 to 60 degrees. These color values for the modeled Comp. Ex. 1 correspond to a AC = sqrt((amax-amin)2+ (bmax-bmin)2) value of AC < 5.0 for this same angular range of 0 to 60 degrees.Attorney Docket No.: SP24-275

[0172] Referring now to FIG. 7A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Comp. Ex. 1. Referring to FIG. 7B, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Comp. Ex. 1. Also referring to FIGS. 7C and 7D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Comp. Ex. 1.

[0173] Although Comp. Ex. 1 demonstrates optical properties that can work for some applications, it does not demonstrate all of the preferred combination of optical properties of the inventive examples in this disclosure (e.g., reflectance, T(940), and controlled color ranges). In addition, Comp. Ex. 1 employs a SiO capping layer with a refractive index of 1.448, which is lower than dense SiO having a refractive index greater than 1.46. The lower index capping layer of Comp. Ex. 1 is an element that enables it to achieve low reflectance optical properties. However, as unexpectedly realized by embodiments of this disclosure, such a low index SiO will generally lead to a worse abrasion resistance, due to the lower density and lower hardness of these low index SiO layers. Inventive examples of this disclosure (Exs. 1-2, 4-5, and 8-17) employ a SiO capping layer with indices >1.46, which is expected to lead to improved abrasion performance.

[0174] Moreover, inventive examples of this disclosure (Exs. 8-17) uniquely rely on the insertion of a thin SiNxlayer above the softer NbiO? or NbOxNylayers in the coating stack. In some embodiments, the thin SiNx layer need not be in direct contact with the softer Nb2O5or NbOxNylayers instead there may be intervening layers in between the thin SiNxlayer and the softer NbjO? or NbOxNylayers. The placement of the thin SiNxlayer above the softer NbjO? or NbOxNylayers with or without intervening layers contributes to mechanical protection of the softer Nb2O5or NbOxNylayers, and improved abrasion resistance of the overall coating stack structure. Intervening layers located between the thin SiNxlayer and the softer Nb2O5or NbOxNylayers or between any other layers in the coating stack may be referred to as ‘tie layers’. These tie layers can be beneficial to improve adhesion and / or optical properties. The tie layers may comprise, for example, SiO or SiOxNylayers between any nitride and any oxide layer in the coating stack. The tie layers may have a thickness less than 30 nm, less than 20 nm, less than 10 nm, less than 5 nm, less than 2 nm, about 1 nm, or less than 1 nm. An inventive example of this disclosure (see Ex. 17) makes use of a ~1 nm SiO2 tie layer disposed between the SiNx and Nb2O5 layers, which is believed to improve the optical and mechanical properties of the overall structure, through lowering optical absorption andAttorney Docket No.: SP24-275improving adhesion associated with the interface where the tie layer is placed. Further, inventive examples of this disclosure (Exs. 9-13, Ex. 16-17) exhibit a first surface reflected color having a maximum a* value less than -0.2 for the entire range of incidence angles from 0-60 degrees, which is preferred for minimizing visible color changes from a green hue to a red hue with changing user viewing angles. Further, inventive examples of this disclosure (Ex. 9-17) exhibit a first surface reflected color having a maximum b* value less than +0.6 for the entire range of incidence angles from 0-60 degrees and for the entire range from 0-90 degrees, which is preferred for minimizing visible color changes from a blue hue to a yellow hue with changing user viewing angles. Further, inventive examples of this disclosure (Ex. 8-11, Ex. 13-17) exhibit T(940) values of greater than 88%, greater than 89%, greater than 90%, greater than 91%, or even greater than 92%, when measured through 2 surfaces of an inventive article having one coated and one uncoated surface. These T(940) values are preferred for optimizing infrared sensor functions, such as camera autofocus, auto driver monitoring, or range sensing functions.Table 8: Anti-reflective coating attributes for Comp. Ex. 1 Extinction Physical Refractive Coefficient Thickness Layer Material Index @550 nm @550nm (nm) Medium Air 1 01 SiO21.448 0 96.72 2 Nb2O52.345 0 22.37 3 SiNx2.054 0 99.97 4 SiO21.448 0 44.67 5 SiNx 2.054 0 11.6 6 SiO21.448 0 25 Substrate Glass 1.511 0 0.7 mmTotal Coating Thickness 300.3Table 8A: Optical properties of modeled Comp. Ex. 1 Incident Photopic average L* a* b*Angle reflectance (Y)0 0.199 1.798 0.4045 -3.6503 5 0.1978 1.7868 0.3211 -3.4763 10 0.1953 1.7639 0.0888 -2.9839 15 0.1952 1.7633 -0.243 -2.2539 20 0.2042 1.8443 -0.6059 -1.4007 25 0.2323 2.0985 -0.9284 -0.550630 0.2947 2.6617 -1.1502 0.1745Attorney Docket No.: SP24-27535 0.4137 3.7366 -1.2283 0.6597 40 0.6239 5.6354 -1.1326 0.787 45 0.9807 8.8293 -0.7827 0.393 50 1.576 13.0832 -0.1851 -0.4236 55 2.5664 18.2161 0.3148 -1.231960 4.2218 24.3917 0.7172 -1.9184Table 8B: Measured optical properties of Comp. Ex. 1 Incident Photopic average L* a* b*Angle reflectance (Y)6 0.22 2.01 1.99 -5.02Summary of Optical Properties of Examples 1-7 and Comparative Example 1

[0175] Table 9 below provides a summary of optical properties of Exs. 1-7 and Comp. Ex.1. As is evident from the data, Exs. 2-4 exhibit lower first-surface reflectance (Y) values at an angle of incidence of 8 degrees (or 6 degrees) as compared to Comp. Ex. 1, which exhibits a reflectance (Y) value of 0.196%. Further, Exs. 1-4 exhibit lower first-surface reflectance color chroma (C*) values at an angle of incidence of 8 degrees (or 6 degrees) as compared to Comp. Ex. 1, which exhibits a reflectance color chroma (C*) value of 3.3%. In addition, Ex.3 exhibits a lower maximum change in color chroma (C*) over an incident angle range from 0 to 60 degrees (AC*) as compared to Comp. Ex. 1, which exhibits a maximum change in color chroma of 4.85% (AC*). Finally, Exs.l and 3-7 exhibit higher two-surface transmittance values at a wavelength of 940 nm as compared to Comp. Ex. 1, which exhibits a transmittance of 86% (T(940)).Table 9: A summary of the optical properties of modeled Exs. 1-7 and Comparative Ex. 12-surface, Modeled 1st surface reflectance metrics coating on 1 side Examples _ (8 deg.) _ (0-60 deg) onlyY c* delta C T(940) Ex. r 0.28 (6°) 3.09 (6°) 7.54 86.19 Ex. 1 0.25 (6°) 2.09 5.14 90.42 Ex. 2 0.17 2.05 5.1 85.6 Ex. 3 0.098 1.31 3.84 86.6 Ex. 4 0.15 1.42 4.88 86.1 Ex. 5 0.30 4.1 8.69 90.2 Ex. 6 0.198 3.53 7.5 91.2Ex. 7 0.22 3.85 8.62 90.2Attorney Docket No.: SP24-275| Comp, Ex, 1 | _ 0,196 _ | 3,3 | 4,85 | ~86 | * The reported values for Ex. 1 in this row were experimentally determined; the values in the remaining rows were modeled.Comparative Example 2

[0176] The as-fabricated samples of Comparative Example 2 (“Comp. Ex. 2”) were formed by providing a glass substrate having a nominal composition of 69 mol% SiO. 10 mol% Al2O3, 15 mol% Na? O. and 5 mol% MgO and disposing an anti-reflective coating having five (5) layers on the glass substrate, as shown in Table 10 below. The anti -reflective coating of each of the as-fabricated samples of this comparative example was deposited using a reactive sputtering process.

[0177] Samples of Comp. Ex. 2 were also modeled, and assumed to employ a glass substrate having the same composition of the glass substrate employed in the as-fabricated samples of this comparative example. Further, the anti-reflective coating of each of the modeled samples was assumed to have the layer materials and physical thickness as shown in Table 10 below. The optical properties of this example, as outlined below in Tables 10A and 10B, were modeled or otherwise measured at near-normal incidence, unless otherwise noted.

[0178] As is evident from Tables 10-10B, Comp. Ex. 2 has a photopic average reflectance at near-normal incidence below 0.12%. The color falls within a range of -1 < a* <1 and -3 < b* <0 at near normal incidence. The modeling example illustrates that color with changing incident angle stays within a range of -1 < a* <1 and -3 < b* <2 for all viewing angles within the range of 0 to 60 degrees. These color values for the modeled Comp. Ex. 2 correspond to a AC = sqrt((amax-amin)2+ (bmax-bmin)2) value of AC <2.5 for this same angular range of 0 to 60 degrees. This is a very tightly controlled range of color vs. changing incident angle for an anti-reflective (AR) coating with such low average reflectance.

[0179] Referring now to FIG. 8A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Comp. Ex. 2. Referring to FIG. 8B, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Comp. Ex. 2. Also referring to FIGS. 8C and 8D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Comp. Ex. 2.

[0180] Although Comp. Ex. 2 demonstrates optical properties that can work for some applications, it does not demonstrate all of the preferred combination of optical properties ofAttorney Docket No.: SP24-275the inventive examples in this disclosure (e.g., reflectance, T(940), and controlled color ranges). In addition, Comp. Ex. 2 employs a SiO2capping layer with a refractive index of 1.448, which is lower than dense SiC>2 having a refractive index greater than 1.46. The lower index capping layer of Comp. Ex. 2 is an element that enables it to achieve low reflectance optical properties. However, as unexpectedly realized by embodiments of this disclosure, such a low index SiO will generally lead to a worse abrasion resistance, due to the lower density and lower hardness of these low index SiO2layers. Comp. Ex. 2 also employs multiple layers of Nb2O2. an individual layer of Nb2O2with thickness greater than 50nm, and a total thickness of Nb2O2greater than lOOnm in the coating stack. These structural features and use of high amounts of Nb2Os have been shown to correlate to poor mechanical performance, e.g., in abrasion and delamination tests.

[0181] Furthermore, the inventive examples of this disclosure (Exs. 1-2, 4-5, and 8-17) employ a SiO2capping layer with indices >1.46, which is expected to lead to improved abrasion performance. Further, inventive examples of this disclosure (Exs. 8-17) employ only a single layer of Nb2O2or NbOxNy(e.g. only a single layer of material having refractive index higher than 2.2), and this single layer of material with index higher than 2.2 has a limited thickness of less than 50nm, less than 40nm, less than 30nm, less than 25nm, less than 20nm, or even less than 18nm. This minimization of Nb2O2orNbOxNymaterial (or minimization of material having index greater than 2.2) allows greater usage of high index materials with higher hardness (e.g. SiNx or SiOxNy), which improves the overall hardness and abrasion resistance of the inventive articles relative to Comp. Ex. 2. The use of a small amount of Nb2Os or NbOxNymaterial in Ex. 8-17 still imparts a significant improvement in optical properties that is difficult or impossible to achieve using only a 2-material (e.g. SiO2and SiNxonly) AR coating. Further, inventive examples of this disclosure (Exs. 8-17) uniquely rely on the insertion of a thin SiNxlayer above the softer Nb2Os or NbOxNylayers in the coating stack.Table 10: Anti-reflective coating attributes for Comp. Ex. 2 Extinction Physical Refractive Coefficient Thickness Layer Material Index @550 nm @550nm (nm) Medium Air 1 01 SiO21.448 0 88.08 2 Nb2O52.345 0 113.23 3 SiO21.448 0 37.954 Nb2O52.345 0 12.4Attorney Docket No.: SP24-2755 SiO21.448 0 25 Substrate Glass 1.511 0 0.7 mmTotal Coating Thickness 277.7Table 10A: Optical properties of modeled Comp. Ex. 2 Incident Photopic average L* a* lrAngle reflectance (Y)0 0.1004 0.9067 -0.2904 -0.9431 5 0.0999 0.902 -0.2759 -0.8802 10 0.0996 0.8997 -0.2341 -0.6965 15 0.1037 0.9367 -0.1711 -0.4053 20 0.1192 1.0764 -0.0999 -0.0275 25 0.1566 1.4147 -0.041 0.4071 30 0.2316 2.092 -0.0188 0.8551 35 0.3672 3.3172 -0.054 1.2511 40 0.5994 5.4145 -0.155 1.501 45 0.9863 8.8765 -0.2892 1.4257 50 1.6246 13.3793 -0.3227 0.7068 55 2.6785 18.7074 -0.2905 0.013460 4.4275 25.0373 -0.1976 -0.5852Table 10B: Measured optical properties of Comp. Ex. 2 Incident Photopic average L* a* lrAngle reflectance (Y)6 0.08 0.75 0.19 -2.51Example 8 - AR Coating Design, and Optical Properties

[0182] Example 8 (“Ex. 8”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 59.09 mol% SiOi.4.08 mol% B2O3, 17.94 mol% Al2O3, 8.79 mol% Na2O, 0.07 mol% K2O, 8.00 mol% Li2O, 1.23 mol% MgO, 0.01 mol% ZnO, 0.10 mol% TiO2, 0.02 mol% CaO, 0.04 mol% SnO2, and 0.66 mol% P2O5 and disposing an anti-reflective coating having seven (7) layers on the glass substrate, as shown in FIG. 1C and Table 11 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 8 was designed to have the layer materials and physical thickness as shown in Table 11 below.

[0183] Referring now to FIG. 9A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 8. Referring to FIG. 9B, a plot is provided of two-surfaceAttorney Docket No.: SP24-275transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 8.

[0184] Also referring to FIGS. 9C and 9D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Ex. 8.

[0185] Referring now to FIG. 6B, a plot is provided of elastic modulus (GPa) and hardness (GPa) data for the articles of this example (Ex. 8), as measured with a Berkovich Indenter Hardness Test as a function of nanoindentation depth (nm). As is evident from this figure, the samples of the Ex. 8 design exhibit a maximum hardness value of 9.7 GPa at a nanoindentation depth of 170 nm.

[0186] More generally, the advantageous combination of optical and mechanical properties for this example is summarized in FIG. 19, as described in further detail below.Attorney Docket No.: SP24-275Table 11: Anti-reflective coating attributes for Example 8 Refractive Extinction Physical Layer Material Index Coefficient Thickness @550nm @550nm (nm)Air 1 01 SiO21.468 0 95.15 2 SiNx 2.070 0.00019 8.0 3 Nb2O52.373 0 16.16 4 SiNx 2.070 0.00019 100.0 5 SiO21.468 0 46.14 6 SiNx 2.070 0.00019 13.91 7 SiO21.468 0 40.0 Substrate Glass 1.522 0 0.4 mmTotal Coating Thickness 319 Example 9 - AR Coating Design, and Optical Properties

[0187] Example 9 (“Ex. 9”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 59.09 mol% SiO2,4.08 mol% B2O3, 17.94 mol% Al2O3, 8.79 mol% Na2O, 0.07 mol% K2O, 8.00 mol% Li2O, 1.23 mol% MgO, 0.01 mol% ZnO, 0.10 mol% TiO2, 0.02 mol% CaO, 0.04 mol% SnO2, and 0.66 mol% P2O5 and disposing an anti-reflective coating having thirteen (13) layers on the glass substrate, as shown in FIG. ID and Table 12 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 9 was designed to have the layer materials and physical thickness as shown in Table 12 below.

[0188] Referring now to FIG. 10A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 9. Referring to FIG. 10B, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 9.

[0189] Also referring to FIGS. 10C and 10D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Ex. 9.

[0190] More generally, the advantageous combination of optical and mechanical properties for this example is summarized in FIG. 19, as described in further detail below.Attorney Docket No.: SP24-275Table 12: Anti-reflective coating attributes for Example 9 Refractive Extinction Physical Layer Material Index Coefficient Thickness @550nm @550nm (nm)Air 1 01 SiO21.468 0 90.9 2 SiNx 2.062 0.00012 8.1 3 Nb2O52.373 0 22.3 4 SiNx 2.062 0.00012 75.9 5 SiO21.468 0 8.0 6 SiNx 2.062 0.00012 11.3 7 SiO21.468 0 194.6 8 SiNx 2.062 0.00012 20.4 9 SiO21.468 0 27.1 10 SiNx 2.062 0.00012 131.1 11 SiO21.468 0 28.6 12 SiNx 2.062 0.00012 20.5 13 SiO21.468 0 25.1 Substrate Glass 1.522 0 0.4 mmTotal Coating Thickness 663.9 Example 10 - AR Coating Design, and Optical Properties

[0191] Example 10 (“Ex. 10”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 59.09 mol% SiO2, 4.08 mol% B2O3, 17.94 mol% Al2O3, 8.79 mol% Na2O, 0.07 mol% K2O, 8.00 mol% Li2O, 1.23 mol% MgO, 0.01 mol% ZnO, 0.10 mol% TiO2, 0.02 mol% CaO, 0.04 mol% SnO2, and 0.66 mol% P2O3and disposing an anti-reflective coating having thirteen (13) layers on the glass substrate, as shown in FIG. ID and Table 13 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 10 was designed to have the layer materials and physical thickness as shown in Table 13 below.

[0192] Referring now to FIG. 11A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 10. Referring to FIG. 1 IB, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 10.Attorney Docket No.: SP24-275

[0193] Also referring to FIGS. 11C and 1 ID, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Ex. 10.

[0194] More generally, the advantageous combination of optical and mechanical properties for this example is summarized in FIG. 19, as described in further detail below.Table 13: Anti-reflective coating attributes for Example 10 Refractive Extinction Physical Layer Material Index Coefficient Thickness @550nm @550nm (nm)Air 1 01 SiO21.468 0 90.4 2 SiNx 2.062 0.00012 8.0 3 Nb2O52.373 0 16.0 4 SiNx 2.062 0.00012 85.0 5 SiO21.468 0 21.4 6 SiNx 2.062 0.00012 8.0 7 SiO21.468 0 174.9 8 SiNx 2.062 0.00012 17.9 9 SiO21.468 0 33.3 10 SiNx 2.062 0.00012 148.9 11 SiO21.468 0 35.2 12 SiNx 2.062 0.00012 17.7 13 SiO21.468 0 25.1 Substrate Glass 1.522 0 0.4 mmTotal Coating Thickness 681.6 Example 11 - AR Coating Design, and Optical Properties

[0195] Example 11 (“Ex. 11”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 59.09 mol% SiO2, 4.08 mol% B2O3, 17.94 mol% Al2O3, 8.79 mol% Na2O, 0.07 mol% K2O, 8.00 mol% Li2O, 1.23 mol% MgO, 0.01 mol% ZnO, 0.10 mol% TiO2, 0.02 mol% CaO, 0.04 mol% SnO2, and 0.66 mol% P2Os and disposing an anti-reflective coating having eleven (11) layers on the glass substrate, as shown in FIG. IE and Table 14 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 11 was designed to have the layer materials and physical thickness as shown in Table 14 below.Attorney Docket No.: SP24-275

[0196] Referring now to FIG. 12A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 11. Referring to FIG. 12B, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 11.

[0197] Also referring to FIGS. 12C and 12D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Ex. 11.

[0198] More generally, the advantageous combination of optical and mechanical properties for this example is summarized in FIG. 19, as described in further detail below.Table 14: Anti-reflective coating attributes for Example 11 Refractive Extinction Physical Layer Material Index Coefficient Thickness @550nm @550nm (nm)Air 1 01 SiO21.468 0 88.1 2 SiNx2.062 0.00012 13.9 3 Nb2O52.373 0 22.5 4 SiNx 2.062 0.00012 81.8 5 SiO21.468 0 211.4 6 SiNx 2.062 0.00012 22.65 7 SiO21.468 0 33.8 8 SiNx 2.062 0.00012 148.9 9 SiO21.468 0 39.5 10 SiNx 2.062 0.00012 16.3 11 SiO21.468 0 60.0 Substrate Glass 1.522 0 0.4 mmTotal Coating Thickness 738.9 Example 12 - AR Coating Design, and Optical Properties

[0199] Example 12 (“Ex. 12”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 59.09 mol% SiO2, 4.08 mol% B2O3, 17.94 mol% Al2O3, 8.79 mol% Na2O, 0.07 mol% K2O, 8.00 mol% Li2O, 1.23 mol% MgO, 0.01 mol% ZnO, 0.10 mol% TiO2, 0.02 mol% CaO, 0.04 mol% SnO2, and 0.66 mol% P2O3and disposing an anti-reflective coating having ten (10) layers on the glass substrate, as shown in FIG. IF and Table 15 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions fromAttorney Docket No.: SP24-275experimentally fabricated thin films. Example 12 was designed to have the layer materials and physical thickness as shown in Table 15 below.

[0200] Referring now to FIG. 13 A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 12. Referring to FIG. 13B, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 12.

[0201] Also referring to FIGS. 13C and 13D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Ex. 12.

[0202] More generally, the advantageous combination of optical and mechanical properties for this example is summarized in FIG. 19, as described in further detail below.Table 15: Anti-reflective coating attributes for Example 12 Refractive Extinction Physical Layer Material Index Coefficient Thickness @550nm @550nm (nm)Air 1 01 SiO21.468 0 85.2 2 SiNx 2.070 0.00019 8.0 3 NbOxNy2.348 0 49.2 4 SiNx 2.070 0.00019 22.2 5 NbOxNy2.348 0 27.1 6 SiOxNy 1.592 0 188.2 7 SiNx 2.070 0.00019 17.0 8 SiOxNy 1.592 0 70.4 9 SiNx 2.070 0.00019 9.2 10 SiO21.468 0 30.2 Substrate Glass 1.522 0 0.4 mmTotal Coating Thickness 506.7 Example 13 - AR Coating Design, and Optical Properties

[0203] Example 13 (“Ex. 13”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 59.09 mol% SiO2, 4.08 mol% B2O3, 17.94 mol% Al2O3, 8.79 mol% Na2O, 0.07 mol% K2O, 8.00 mol% Li2O, 1.23 mol% MgO, 0.01 mol% ZnO, 0.10 mol% TiO2, 0.02 mol% CaO, 0.04 mol% SnO2, and 0.66 mol% P2Os and disposing an anti-reflective coating having eleven (11) layers on the glass substrate, as shown in FIG. IE and Table 16 below. Further, the anti-reflectiveAttorney Docket No.: SP24-275coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 13 was designed to have the layer materials and physical thickness as shown in Table 16 below.

[0204] Referring now to FIG. 14A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 13. Referring to FIG. 14B, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 13.

[0205] Also referring to FIGS. 14C and 14D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Ex. 13.

[0206] More generally, the advantageous combination of optical and mechanical properties for this example is summarized in FIG. 19, as described in further detail below.Table 16: Anti-reflective coating attributes for Example 13 Refractive Extinction Physical Layer Material Index Coefficient Thickness @550nm @550nm (nm)Air 1 01 SiO21.468 0 91.8 2 SiNx 2.040 0 8.0 3 Nb2O52.373 0 22.5 4 SiNx 2.062 0.00012 87.5 5 SiOxNy 1.549 0 183.3 6 SiNx 2.062 0.00012 18.2 7 SiOxNy 1.599 0 27.5 8 SiNx 2.062 0.00012 133.6 9 SiO21.468 0 29.8 10 SiNx 2.062 0.00012 20.8 11 SiO21.468 0 25.0 Substrate Glass 1.522 0 0.4mmTotal Coating Thickness 648.0 Example 14 - AR Coating Design, and Optical Properties

[0207] Example 14 (“Ex. 14”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 59.09 mol% SiO2, 4.08 mol% B2O3, 17.94 mol% Al2O3, 8.79 mol% Na2O, 0.07 mol% K2O, 8.00 mol% Li2O, 1.23 mol% MgO, 0.01 mol% ZnO, 0.10 mol% TiO2, 0.02 mol% CaO, 0.04 mol%Attorney Docket No.: SP24-275SnO. and 0.66 mol% P2O5 and disposing an anti-reflective coating having eleven (11) layers on the glass substrate, as shown in FIG. IE and Table 17 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 14 was designed to have the layer materials and physical thickness as shown in Table 17 below.

[0208] Referring now to FIG. 15A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 14. Referring to FIG. 15B, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 14.

[0209] Also referring to FIGS. 15C and 15D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Ex. 14.

[0210] More generally, the advantageous combination of optical and mechanical properties for this example is summarized in FIG. 19, as described in further detail below.Table 17: Anti-reflective coating attributes for Example 14 Refractive Extinction Physical Layer Material Index Coefficient Thickness @550nm @550nm (nm)Air 1 01 SiO21.468 0 93.1 2 SiNx 2.062 0.00012 8.0 3 Nb2O52.373 0 19.8 4 SiNx 2.062 0.00012 89.6 5 SiOxNy 1.601 0 163.6 6 SiNx 2.062 0.00012 16.1 7 SiOxNy 1.601 0 27.6 8 SiNx 2.062 0.00012 142.6 9 SiO21.468 0 30.8 10 SiNx 2.062 0.00012 20.9 11 SiO21.468 0 25.0 Substrate Glass 1.522 0 0.4 mmTotal Coating Thickness 637.0 Example 15 - AR Coating Design, and Optical Properties

[0211] Example 15 (“Ex. 15”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 59.09 mol%Attorney Docket No.: SP24-275SiO2, 4.08 mol% B2O3, 17.94 mol% Al2O3, 8.79 mol% Na2O, 0.07 mol% K2O, 8.00 mol% Li2O, 1.23 mol% MgO, 0.01 mol% ZnO, 0.10 mol% TiO2, 0.02 mol% CaO, 0.04 mol% S11O2. and 0.66 mol% P2O5 and disposing an anti-reflective coating having twenty-eight (28) layers on the glass substrate, as shown in FIG. 1G and Table 18 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 15 was designed to have the layer materials and physical thickness as shown in Table 18 below.

[0212] Referring now to FIG. 16A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 15. Referring to FIG. 16B, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 15.

[0213] Also referring to FIGS. 16C and 16D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Ex. 15.

[0214] More generally, the advantageous combination of optical and mechanical properties for this example is summarized in FIG. 19, as described in further detail below.Attorney Docket No.: SP24-275Table 18: Anti-reflective coating attributes for Example 15 Refractive Extinction Physical Layer Material Index Coefficient Thickness @550nm @550nm (nm)Air 1 01 SiO21.468 0 90.8 2 SiNx 2.070 0.00019 8.1 3 NbOxNy2.348 0 39.2 4 SiNx 2.070 0.00019 13.4 5 NbOxNy2.348 0 52.0 6 SiOxNy 1.851 0 72.4 7 NbOxNy 2.348 0 8.1 8 SiOxNy 1.851 0 63.1 9 NbOxNy 2.348 0 32.4 10 SiOxNy 1.851 0 19.9 11 NbOxNy 2.348 0 55.7 12 SiNx 2.070 0.00019 35.2 13 NbOxNy 2.348 0 11.6 14 SiOxNy 1.851 0 9.3 15 NbOxNy 2.348 0 8.0 16 SiOxNy 1.851 0 70.3 17 NbOxNy 2.348 0 8.0 18 SiOxNy 1.851 0 41.7 19 NbOxNy 2.348 0 8.0 20 SiOxNy 1.851 0 11.1 21 NbOxNy 2.348 0 31.8 22 SiNx 2.070 0.00019 26.3 23 NbOxNy 2.348 0 40.9 24 SiOxNy 1.851 0 56.4 25 NbOxNy 2.348 0 14.7 26 SiOxNy 1.468 0 57.1 27 NbOxNy 2.348 0 9.3 28 SiO21.468 0 28.2 Substrate Glass 1.522 0 0.4 mmTotal Coating Thickness 922.8 Example 16 - AR Coating Design, and Optical Properties

[0215] Example 16 (“Ex. 16”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 59.09 mol% SiO2, 4.08 mol% B2O3, 17.94 mol% Al2O3, 8.79 mol% Na2O, 0.07 mol% K2O, 8.00 mol% Li2O, 1.23 mol% MgO, 0.01 mol% ZnO, 0.10 mol% TiO2, 0.02 mol% CaO, 0.04 mol% SnO2, and 0.66 mol% P2O3and disposing an anti-reflective coating having thirty-one (31)Attorney Docket No.: SP24-275layers on the glass substrate, as shown in FIG. 1H and Table 19 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 16 was designed to have the layer materials and physical thickness as shown in Table 19 below.

[0216] Referring now to FIG. 17A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 16. Referring to FIG. 17B, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 16.

[0217] Also referring to FIGS. 17C and 17D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Ex. 16.

[0218] More generally, the advantageous combination of optical and mechanical properties for this example is summarized in FIG. 19, as described in further detail below.Attorney Docket No.: SP24-275Table 19: Anti-reflective coating attributes for Example 16Refractive Extinction Physical Layer Material Index Coefficient Thickness @550nm @550nm (nm)Air 1 01 SiO21.468 0 89.92 SiNx 2.070 0.00019 8.03 NbOxNy2.348 0 31.64 SiNx 2.070 0.00019 78.35 SiO21.468 0 229.86 SiNx 2.070 0.00019 20.67 SiO21.468 0 56.98 SiNx 2.070 0.00019 39.39 SiO21.468 0 43.010 SiNx 2.070 0.00019 28.811 SiO21.468 0 57.212 SiNx 2.070 0.00019 15.513 SiO21.468 0 32.414 SiNx 2.070 0.00019 7.115 SiO21.468 0 18.216 SiNx 2.070 0.00019 128.017 SiO21.468 0 181.218 SiNx 2.070 0.00019 138.019 SiO21.468 0 51.420 SiNx 2.070 0.00019 12.321 SiO21.468 0 143.322 SiNx 2.070 0.00019 16.223 SiO21.468 0 44.724 SiNx 2.070 0.00019 138.825 SiO21.468 0 27.526 SiNx 2.070 0.00019 9.327 SiO21.468 0 182.128 SiNx 2.070 0.00019 16.929 SiO21.468 0 61.930 SiNx 2.070 0.00019 13.431 SiO21.468 0 204.6 Substrate Glass 1.522 0 0.4 mmTotal Coating Thickness 2126.1Attorney Docket No.: SP24-275Example 17 - AR Coating Design, and Optical Properties

[0219] Example 17 (“Ex. 17”) was modeled using experimentally measured refractive index dispersion values for a glass substrate having a nominal composition of 59.09 mol% SiO2, 4.08 mol% B2O3, 17.94 mol% Al2O3, 8.79 mol% Na2O, 0.07 mol% K2O, 8.00 mol% Li2O, 1.23 mol% MgO, 0.01 mol% ZnO, 0.10 mol% TiO2, 0.02 mol% CaO, 0.04 mol% SnO2, and 0.66 mol% P2Os and disposing an anti-reflective coating having eight (8) layers on the glass substrate, as shown in FIG. 1H (but with a tie layer 3 of SiO2 Inm thick) and Table 17 below. Further, the anti-reflective coating of each of the modeled examples also used refractive index dispersions from experimentally fabricated thin films. Example 17 was designed to have the layer materials and physical thickness as shown in Table 20 below.

[0220] Referring now to FIG. 18A, a plot is provided of first-surface reflectance as a function of wavelength, as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 17. Referring to FIG. 18B, a plot is provided of two-surface transmittance as a function of wavelength as measured at an angle of incidence of 8 degrees on the anti-reflective surface of Ex. 17.

[0221] Also referring to FIGS. 18C and 18D, plots are provided of first-surface reflected color (a*, b*), as measured at angles of incidence from 0 to 60 degrees and 0 to 90 degrees, respectively, on the anti-reflective surface of Ex. 17.

[0222] More generally, the advantageous combination of optical and mechanical properties for this example is summarized in FIG. 19, as described in further detail below.Attorney Docket No.: SP24-275Table 20: Anti-reflective coating attributes for Example 17Refractive Extinction Physical Layer Material Index Coefficient Thickness @550nm @550nm (nm)Air 1 01 SiO21.469 0 91.12 SiNx 1.967 0.00105 8.03 SiO21.469 0 1.04 Nb2O52.367 0 17.05 SiNx2.051 0.00046 96.06 SiO21.467 0 51.07 SiNx 2.051 0.00046 10.98 SiO21.467 0 81.65 Substrate Glass 1.522 0 0.4 mmTotal Coating Thickness 356.6Attorney Docket No.: SP24-275Summary of Optical Properties of Examples 8-17 and Comparative Examples 1 & 2

[0223] Referring now to FIG. 19, a table is provided that summarizes optical and mechanical properties of Comp. Ex. 1 and Comp. Ex. 2, along with Exs. 8-17. The categories and data shaded in black with white text in FIG. 19 represent areas where the inventive examples (one or mor of Exs. 8-17) have preferred optical properties or coating structure, relative to Comp. Exs. 1 and 2.

[0224] As is evident from FIG. 19, the inventive examples (Exs. 8-17) are distinguishable over the comparative examples (Comp. Exs. 1-2) according to one or more of the following attributes:• capping layer refractive index of greater than 1.45, or greater than 1.46, which contributes significantly to abrasion resistance;• a SiNxlayer above a Nb2O5or NbOxNylayer, which also significantly improves abrasion resistance;• only one layer in the coating stack with a refractive index >2.2 (Nb2O5or NbOxNy) • the thickest layer in the coating stack with a refractive index >2.2 (Nb2O5or NbOxNy) having a thickness of less than 50 nm, 40 nm, 30 nm, 25nm, 20nm, or 18 nm, each of which contributes to abrasion resistance;• a maximum hardness of greater than 9 GPa or even greater than 10 GPa; and• a photopic first-surface average reflectance (or average reflectance from 450-650 nm) of less than 0.3%, 0.25%, 0.2%, 0.18%, 0.16%, 0.14, or less than 0.13%, in combination with one or more of:o T(940) with one coated & one uncoated glass surface of greater than 88%, 89%, 90%, 91%, or even 92%;o first-surface reflected color a* value less than -0.2 for all AOI from 0-60°; o first-surface reflected color a* value from -10 to -0.2, -5 to -0.2, or -2 to -0.2, for all AOI from 0-60°;o first-surface reflected color b* value less than 0.8 or less than 0.6 for all AOI from 0-60°;o first-surface reflected color b* value from -10 to 0.8, -5 to 0.5, or -4 to 0, for all AOI from 0-60°;o first-surface reflected color a* value less than 0.2 for all AOI from 0-90°; o first-surface reflected color a* value from -10 to 0.2, -4 to 0.2, or -2 to 0, for all AOI from 0-90°;Attorney Docket No.: SP24-275o first-surface reflected color b* value less than 0.8 or less than 0.6 for all AOI from 0-90°; ando first-surface reflected color b* value from -10 to 0.8, -6 to 0.6, or -5 to 0, for all AOI from 0-90°.

[0225] Many variations and modifications may be made to the above -described embodiments of the disclosure without departing substantially from the spirit and various principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims. For example, the various features of the disclosure may be combined according to the following embodiments.

[0226] Aspect l. An article, comprising:a substrate having a first and second major surface, the first and second major surfaces opposing one another; and an anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface, wherein the anti-reflective coating comprises a plurality of layers, wherein the anti-reflective coating comprises a capping layer and a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, wherein one of the low refractive index layers is in direct contact with the major surface of the substrate, wherein the capping layer comprises at least one low refractive index layer of SiO2 disposed on the plurality of periods, wherein at least one of the plurality of periods comprises at least two high refractive index layers, the at least two high refractive index layers comprise a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2, and a second layer comprising SiNx or SiOxNy, and wherein the article exhibits one or more of: (i) a first surface photopic average reflectance (Y) value of less than or equal to 0.18, (ii) a first surface reflected color chroma (C*) value, where C* = √(a*2+ b*2) in the (L*, a*, b*) colorimetry system and C* is less than or equal to 3.50 under an International Commission on Illumination illuminant measured for all light incident angles in a range from 0 degrees to 60 degrees at a light incidence angle of 8 degrees at the anti-reflective surface, and (iii) a two-surface transmittance T(940) at a wavelength of 940 nm of greater than or equal to 88%, wherein T(940) is measured with a bare second major surface of the substrate.

[0227] Aspect 2. The article of aspect 1, wherein the article exhibits single side reflected color coordinates in the (L*, a*, b*) colorimetry system within the range of -3 < a* < 0 and -3 < b* < 0 under an International Commission on Illumination illuminant for all light incidentAttorney Docket No.: SP24-275angles in a range from 0 degrees to 60 degrees at a light incidence of 8 degrees at the anti-reflective surface.

[0228] Aspect 3. The article of aspect 1, wherein the article exhibits a first surface photopic average reflectance (Y) of less than 0.18.

[0229] Aspect 4. The article of aspect 1, wherein the article exhibits a C* of less than or equal to 3.0 when measured for all light incident angles in a range from 0 degrees to 60 degrees at a light incidence of 8 degrees at the anti-reflective surface.

[0230] Aspect 5. The article of aspect 1, wherein the article exhibits a T(940) of greater than or equal to 88%, wherein T(940) is measured with a bare second major surface of the substrate.

[0231] Aspect 6. The article of aspect 1, wherein the article exhibits a maximum change in C* over an incident angle range from 0-60 degrees (AC*) of less than or equal to 4.0.

[0232] Aspect 7. The article of aspect 1, wherein the capping layer has a refractive index of less than 1.42.

[0233] Aspect 8. The article of aspect 7, wherein the article exhibits a first surface photopic average reflectance (Y) value of less than or equal to 0.18 or a two-surface transmittance T(940) at a wavelength of 940 nm of greater than or equal to 88%, wherein T(940) is measured with a bare second major surface of the substrate.

[0234] Aspect 9. The article of aspect 1, wherein the capping layer comprises at least one layer with a refractive index of greater than or equal to 1.460.

[0235] Aspect 10. The article of aspect 1, wherein the capping layer comprises two layers of SiO2, each layer of SiO2 has a different refractive index, and further wherein one of the layers of SiO2 has a refractive index greater or equal to 1.45 and the other of the layers of SiO2 has a refractive index of less than 1.45.

[0236] Aspect 11. The article of aspect 1, wherein the capping layer has a refractive index of equal to or greater than 1.45.

[0237] Aspect 12. The article of aspect 11, wherein the anti-reflective coating directly below the capping layer comprises a sequence of layers given by (1) SiNx or SiOxNy, (2) Nb2O5 orNbOxNy, and (3) SiNx, SiOxNy, orNb2O5.

[0238] Aspect 13. The article of aspect 1, wherein one of the at least one of the plurality of periods which comprises at least two high refractive index layers including a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2, and a second layer comprising SiNx or SiOxNy further comprises a tie layer of SiO2 or SiOxNy disposed between the first layer and the second layer.Attorney Docket No.: SP24-275

[0239] Aspect 14. The article of aspect 1, wherein the anti-reflective coating directly below the capping layer comprises a sequence of layers given by (1) SiNx or SiOxNy, (2) a tie layer of SiO2 or SiOxNy, (3) Nb2O5 orNbOxNy, and (4) SiNx, SiOxNy, orNb2O5.

[0240] Aspect 15. The article of aspect 13, wherein the tie layer of SiO2 or SiOxNy has a physical thickness of less than 5nm.

[0241] Aspect 16. An article, comprising: a substrate having a first and second major surface, the first and second major surfaces opposing one another; and an anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface, wherein the anti-reflective coating comprises a plurality of layers, wherein the anti-reflective coating comprises a capping layer and a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, wherein one of the low refractive index layers is in direct contact with the major surface of the substrate, wherein the capping layer comprises at least one low refractive index layer of SiO2 disposed on the plurality of periods, wherein at least one of the plurality of periods comprises at least two high refractive index layers, the at least two high refractive index layers comprise a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2, and a second layer comprising SiNx or SiOxNy, and wherein the capping layer comprises at least one layer with a refractive index of greater than 1.45.

[0242] Aspect 17. The article of aspect 16, wherein all low refractive index layers of the anti-reflective coating have a refractive index of greater than 1.45.

[0243] Aspect 18. The article of aspect 16, wherein the anti-reflective coating has a physical thickness of from 50 nm to less than 700 nm.

[0244] Aspect 19. The article of aspect 16, wherein the capping layer comprises two low refractive index layers of SiO2, each of which has a physical thickness of less than 60 nm, and one of which has a refractive index of less than 1.42.

[0245] Aspect 20. The article of aspect 19, wherein the anti-reflective coating comprises at least 7 layers.

[0246] Aspect 21. The article of aspect 16, wherein the article exhibits a first surface photopic average reflectance (Y) of less than 0.18.

[0247] Aspect 22. The article of aspect 16, wherein the article exhibits a first surface reflected chroma (C*) of less than or equal to 3.50 under an International Commission on Illumination illuminant measured for all light incident angles in a range from 0 degrees to 60 degrees at an incident angle of 8 degrees at the anti-reflective surface, where C* = " (a*2 + b*2) in the (L*, a*, b*) colorimetry system.Attorney Docket No.: SP24-275

[0248] Aspect 23. The article of aspect 16, wherein the anti-reflective coating comprises at least one high refractive index layer of Nb2O5 in contact with the capping layer, wherein the article exhibits no visible delamination after exposure to the Delamination Test with exposure of the anti-reflective surface to petroleum jelly for 15 minutes.

[0249] Aspect 24. The article of aspect 16, wherein the anti-reflective coating comprises at least one high refractive index layer of Nb2O5 in contact with the capping layer, wherein the article exhibits no visible delamination after exposure to the Delamination Test with exposure of the anti-reflective surface to petroleum jelly for 80 hours.

[0250] Aspect 25. The article of aspect 16, wherein the article exhibits a Weibull modulus of greater than 50 and a Weibull characteristic strength of more than 900 MPa, as tested in a Ring-on-Ring Test.

[0251] Aspect 26. The article of aspect 16, wherein the article exhibits an elastic modulus of greater than 70 GPa and a hardness of greater than 6.5 GPa, as measured according to a Berkovich Hardness test at an indentation depth of about 100 nm to 500nm from the anti-reflective surface of the anti-reflective coating.

[0252] Aspect 27. The article of aspect 16, wherein one of the at least one of the plurality of periods which comprises at least two high refractive index layers including a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2, and a second layer comprising SiNx or SiOxNy further comprises a tie layer of SiO2 or SiOxNy disposed between the first layer and the second layer.

[0253] Aspect 28. The article of aspect 16, wherein the anti-reflective coating directly below the capping layer comprises a sequence of layers given by (1) SiNx or SiOxNy, (2) a tie layer of SiO2 or SiOxNy, (3) Nb2O5 or NbOxNy, and (4) SiNx, SiOxNy, orNb2O5.

[0254] Aspect 29. The article of aspect 28, wherein the tie layer of SiO2 or SiOxNy has a physical thickness of less than 5nm.

[0255] Aspect 30. An article, comprising: a substrate having a first and second major surface, the first and second major surfaces opposing one another; and an anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface, wherein the anti-reflective coating comprises a plurality of layers, wherein the anti-reflective coating comprises a capping layer and a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, wherein one of the low refractive index layers is in direct contact with the major surface of the substrate, wherein the capping layer comprises at least one low refractive index layer of SiO2 disposed on the plurality of periods, wherein at least one of the plurality ofAttorney Docket No.: SP24-275periods comprises at least two high refractive index layers, the at least two high refractive index layers comprise a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2, and a second layer comprising SiNx or SiOxNy, and further wherein the anti-reflective coating directly below the capping layer comprises either: a first sequence of layers given by (1) SiNx or SiOxNy, and (2) Nb2O5 or NbOxNy,.or a second sequence of layers given by (1) SiNx or SiOxNy, (2) a tie layer of SiO2 or SiOxNy, and (3) Nb2O5 or NbOxNy, wherein the tie layer of SiO2 or SiOxNy has a physical thickness of less than 5nm.

[0256] Aspect 31. The article of aspect 30, wherein the capping layer has a refractive index of equal to or greater than 1.45.

[0257] Aspect 32. The article of aspect 30, wherein the article exhibits a first surface photopic average reflectance (Y) of less than 0.3%, as measured at an incident angle of 8 degrees.

[0258] Aspect 33. The article of aspect 30, wherein the first sequence or the second sequence of the anti-reflective coating has a physical thickness of less than 150 nm.

[0259] Aspect 34 The article of aspect 30, wherein the first sequence or the second sequence of the anti-reflective coating has a physical thickness of from 110 nm to 150 nm.

[0260] Aspect 35. The article of any one of aspects 30-34, wherein the first sequence of layers of the anti-reflective coating further comprises (3) SiNx, SiOxNy, orNb2O5, or the second sequence of. layers of the anti-reflective coating further comprises (4) SiNx, SiOxNy, orNb2O5.

[0261] Aspect 36. The article of any one of aspects 30-35, wherein all low refractive index layers of the anti-reflective coating have a refractive index of equal to or greater than 1.45.

[0262] Aspect 37. The article of any one of aspects 30-36, wherein the (2) NbOxNy or Nb2O5 layer in the first sequence or the (3) NbOxNy or Nb2O5 layer in the second sequence is a single NbOxNy or Nb2O5 layer having a refractive index of greater than 2.2 and a physical thickness of less than 50 nm, and further wherein the single NbOxNy or Nb2O5 layer is the only layer in the anti -reflective coating comprising NbOxNy or Nb2O5.

[0263] Aspect 38. The article of any one of aspects 30-37, wherein the (1) SiNx or SiOxNy layer in the first sequence or the second sequence comprises a physical thickness of less than 20 nm.

[0264] Aspect 39. The article of any one of aspects 30-38, wherein the anti-reflective coating has a physical thickness of from 310 nm to 2500 nm.

[0265] Aspect 40. The article of any one of aspects 30-39, wherein the anti-reflective coating comprises from 7 layers to 40 layers.Attorney Docket No.: SP24-275

[0266] Aspect 41. The article of any one of aspects 30-40, wherein the article exhibits a two-surface transmittance T(940) at a wavelength of 940 nm of greater than 88%, wherein T(940) is measured with a bare second major surface of the substrate.

[0267] Aspect 42. The article of any one of aspects 30-41, wherein the article exhibits single side reflected color coordinates in the (L*, a*, b*) colorimetry system within the range of -5 < a* < +1 and -5 < b* < +5 under an International Commission on Illumination illuminant over an incident angle range from 0 degrees to 60 degrees at the anti-reflective surface.

[0268] Aspect 43. The article of any one of aspects 30-42, wherein one of the at least one of the plurality of periods which comprises at least two high refractive index layers including a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2, and a second layer comprising SiNx or SiOxNy further comprises a tie layer of SiO2 or SiOxNy disposed between the first layer and the second layer.

[0269] Aspect 44. An article, comprising: a substrate having a first and second major surface, the first and second major surfaces opposing one another; and an anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface, wherein the anti-reflective coating comprises a capping layer and a plurality of layers, the plurality of layers comprising a low refractive index layer, a first high refractive index layer, and a second high refractive index layer, wherein each of the first and second high refractive index layers has a refractive index value greater than 1.9, and the first and second high refractive index layers have different refractive index values, and further wherein the low refractive index layer has a refractive index value greater than 1.45.

[0270] Aspect 45. The article of aspect 44, wherein the anti-reflective coating comprises a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, and wherein one of the at least one of the plurality of periods which comprises at least two high refractive index layers including a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2.

[0271] Aspect 46. The article of aspect 44 or aspect 45, wherein the article exhibits one or more of: (i) a first surface photopic average reflectance (Y) value of less than or equal to 0.18, (ii) a first surface reflected color chroma (C*) value, where C* = √(a*2+ b*2) in the (L*, a*, b*) colorimetry system and C* is less than or equal to 3.50 under an International Commission on Illumination illuminant measured for all light incident angles in a range from 0 degrees to 60 degrees at a light incidence angle of 8 degrees at the anti-reflective surface,Attorney Docket No.: SP24-275and (iii) a two-surface transmittance T(940) at a wavelength of 940 nm of greater than or equal to 88%, wherein T(940) is measured with a bare second major surface of the substrate.

[0272] Aspect 47. The article of any one of aspects 44-46, wherein the plurality of layers comprises at least four layers, each layer having a different refractive index value.

[0273] Aspect 48. The article of any one of aspects 44-47, wherein the capping layer comprises two layers, each layer of the capping layer having a different refractive index, and further wherein one of the layers of the capping layer has a refractive index greater than 1.45 and the other of the layers of the capping layer has a refractive index of less than 1.42.

[0274] Aspect 49. The article of any one of aspects 44-48, wherein the article exhibits a hardness of greater than 8 GPa, as measured according to a Berkovich Hardness test at an indentation depth of about 100 nm to 500nm from the anti-reflective surface of the anti-reflective coating.

[0275] Aspect 50. The article of any one of aspects 44-49, wherein the first high refractive index layer and the second high refractive index layer have different hardness values.

[0276] Aspect 51. The article of any one of aspects 44-50, wherein the anti-reflective coating comprises directly below the capping layer either: a first sequence of layers given by (1) the first high refractive index layer and (2) the second high refractive index layer, wherein the first high refractive index layer comprises a higher hardness than the hardness of the second high refractive index layer; or a second sequence of layers given by (1) the first high refractive index layer, (2) a tie layer of a low refractive index layer, wherein the tie layer has a physical thickness of less than 5nm, and (3) the second high refractive index layer, wherein the first high refractive index layer comprises a higher hardness than the hardness of the second high refractive index layer.

[0277] Aspect 52. The article of aspect 51, wherein in the first sequence or the second sequence the first high refractive index layer comprises a lower refractive index than the refractive index of the second high refractive index layer.

[0278] Aspect 53. The article of aspect 51, wherein the first sequence of layers of the anti-reflective coating further comprises (3) a third high refractive index layer, wherein the third high refractive index layer comprises a higher hardness than the hardness of the second high refractive index layer, or the second sequence of layers of the anti-reflective coating further comprises (4) a third high refractive index layer, wherein the third high refractive index layer comprises a higher hardness than the hardness of the second high refractive index layer..

[0279] Aspect 54. The article of aspect 51, wherein the second high refractive index layer of the first sequence or the second sequence comprises is a single NbOxNy or Nb2O5 layerAttorney Docket No.: SP24-275having a refractive index of greater than 2.2 and a physical thickness of less than 50 nm, and further wherein the single NbOxNy or Nb2O5 layer is the only layer in the anti-reflective coating comprising NbOxNy or Nb2O5.

[0280] Aspect 55. The article of aspect 51, wherein the (1) the first high refractive index layer in the first sequence or the second sequence comprises a physical thickness of less than 20 nm.

[0281] Aspect 56. The article of aspect 51, wherein: the first sequence of layers comprises (1) the first high refractive index layer including SiNx or SiOxNy and (2) the second high refractive index layer including Nb2O5 or NbOxNy, and (3) SiNx, SiOxNy, orNb2O5, the second sequence of layers given by (1) the first high refractive index layer including SiNx or SiOxNy, (2) the tie layer including SiO2 or SiOxNy, (3) the second high refractive index layer including Nb2O5 or NbOxNy, and (4) SiNx, SiOxNy, orNb2O5.

[0282] Aspect 57. The article of any one of aspects 44-56, wherein all low refractive index layers of the anti-reflective coating have a refractive index of greater than 1.45.

[0283] Aspect 58. The article of any one of aspects 44-57, wherein the anti-reflective coating has a physical thickness of from 50 nm to less than 700 nm.

[0284] Aspect 59. The article of any one of aspects 44-58, wherein the article exhibits a first surface photopic average reflectance (Y) of less than 0.3%, as measured at an incident angle of 8 degrees.

[0285] Aspect 60. The article of any one of aspects 44-59, wherein the article exhibits single side reflected color coordinates in the (L*, a*, b*) colorimetry system within the range of -5 < a* < +0.25 and -5 < b* < +4 under an International Commission on Illumination illuminant over all incident angles in the range from 0 degrees to 90 degrees at the anti-reflective surface.

[0286] Aspect 61. The article of any one of aspects 44-59, wherein the article exhibits single side reflected color coordinates in the (L*, a*, b*) colorimetry system within the range of -5 < a* < -0.15 and -5 < b* < +4 under an International Commission on Illumination illuminant over all incident angles in the range from 0 degrees to 60 degrees at the anti-reflective surface.

Claims

Attorney Docket No.: SP24-275What is claimed is:

1. An article, comprising:a substrate having a first and second major surface, the first and second major surfaces opposing one another; andan anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface,wherein the anti-reflective coating comprises a plurality of layers,wherein the anti-reflective coating comprises a capping layer and a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, wherein one of the low refractive index layers is in direct contact with the major surface of the substrate, wherein the capping layer comprises at least one low refractive index layer of SiO disposed on the plurality of periods,wherein at least one of the plurality of periods comprises at least two high refractive index layers, the at least two high refractive index layers comprise a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2, and a second layer comprising SiNxor SiOxNy, and wherein the article exhibits one or more of:(i) a first surface photopic average reflectance (Y) value of less than or equal to 0.18, (ii) a first surface reflected color chroma (C*) value, where C* = √(a*2+ b*2) in the (L*, a*, b*) colorimetry system and C* is less than or equal to 3.5 under an International Commission on Illumination illuminant measured for all light incident angles in a range from 0 degrees to 60 degrees at the anti-reflective surface, and(iii) a two-surface transmittance T(940) at a wavelength of 940 nm of greater than or equal to 88%, wherein T(940) is measured with a bare second major surface of the substrate.

2. The article of claim 1, wherein the article exhibits single side reflected color coordinates in the (L*, a*, b*) colorimetry system within the range of -3 < a* < 0 and -3 < b* < 0 under an International Commission on Illumination illuminant for all light incident angles in a range from 0 degrees to 60 degrees at the anti-reflective surface.

3. The article of claim 1, wherein the article exhibits a first surface photopic average reflectance (Y) of less than 0.18.Attorney Docket No.: SP24-2754. The article of claim 1, wherein the article exhibits a C* of less than or equal to 3.0 when measured for all light incident angles in a range from 0 degrees to 60 degrees at the anti-reflective surface.

5. The article of claim 1, wherein the article exhibits a T(940) of greater than or equal to 88%, wherein T(940) is measured with a bare second major surface of the substrate.

6. The article of claim 1, wherein the article exhibits a maximum change in C* over an incident angle range from 0-60 degrees (AC*) of less than or equal to 4.0.

7. The article of claim 1, wherein the capping layer has a refractive index of less than 1.42.

8. The article of claim 7, wherein the article exhibits a first surface photopic average reflectance (Y) value of less than or equal to 0.18 or a two-surface transmittance T(940) at a wavelength of 940 nm of greater than or equal to 88%, wherein T(940) is measured with a bare second major surface of the substrate.

9. The article of claim 1, wherein the capping layer comprises at least one layer with a refractive index of greater than or equal to 1.460.

10. The article of claim 1, wherein the capping layer comprises two layers of SiO2, each layer of SiO2 has a different refractive index, and further wherein one of the layers of SiO2 has a refractive index greater or equal to 1.45 and the other of the layers of SiO2 has a refractive index of less than 1.45.

11. The article of claim 1, wherein the capping layer has a refractive index of equal to or greater than 1.45.

12. The article of claim 1, wherein the anti-reflective coating directly below the capping layer comprises a sequence of layers given by (1) SiNxor SiOxNy, (2) Nb2O5or NbOxNy, and (3) SiNx, SiOxNy, or Nb2O5.

13. The article of claim 1, wherein one of the at least one of the plurality of periods which comprises at least two high refractive index layers including a first layer comprising NbOxNy,Attorney Docket No.: SP24-275Nb2O5, TiO2, Ta2O3, or HfO2, and a second layer comprising SiNxor SiOxNyfurther comprises a tie layer of SiO2 or SiOxNydisposed between the first layer and the second layer.

14. The article of claim 1, wherein the anti-reflective coating directly below the capping layer comprises a sequence of layers given by (1) SiNxor SiOxNy, (2) a tie layer of SiO2 or SiOxNy, (3) Nb2O5or NbOxNy, and (4) SiNx, SiOxNy, or Nb2O5.

15. The article of claim 13, wherein the tie layer of SiO2 or SiOxNyhas a physical thickness of less than 5nm.

16. An article, comprising:a substrate having a first and second major surface, the first and second major surfaces opposing one another; andan anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface,wherein the anti-reflective coating comprises a plurality of layers,wherein the anti-reflective coating comprises a capping layer and a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, wherein one of the low refractive index layers is in direct contact with the major surface of the substrate, wherein the capping layer comprises at least one low refractive index layer of SiO2disposed on the plurality of periods,wherein at least one of the plurality of periods comprises at least two high refractive index layers, the at least two high refractive index layers comprise a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2, and a second layer comprising SiNxor SiOxNy, and wherein the capping layer comprises at least one layer with a refractive index of greater than 1.45.

17. The article of claim 16, wherein all low refractive index layers of the anti-reflective coating have a refractive index of greater than 1.45.

18. The article of claim 16, wherein the anti-reflective coating has a physical thickness of from 50 nm to less than 700 nm.Attorney Docket No.: SP24-27519. The article of claim 16, wherein the capping layer comprises two low refractive index layers of SiO2, each of which has a physical thickness of less than 60 nm, and one of which has a refractive index of less than 1.42.

20. The article of claim 19, wherein the anti-reflective coating comprises at least 7 layers.

21. The article of claim 16, wherein the article exhibits a first surface photopic average reflectance (Y) of less than 0.18.

22. The article of claim 16, wherein the article exhibits a first surface reflected chroma (C*) of less than or equal to 3.5 under an International Commission on Illumination illuminant measured for all light incident angles in a range from 0 degrees to 60 degrees at the anti-reflective surface, where C* = √(a*2+ b*2) in the (L*, a*, b*) colorimetry system.

23. The article of claim 16, wherein the anti-reflective coating comprises at least one high refractive index layer of Nb2O5in contact with the capping layer, wherein the article exhibits no visible delamination after exposure to the Delamination Test with exposure of the anti-reflective surface to petroleum jelly for 15 minutes.

24. The article of claim 16, wherein the anti-reflective coating comprises at least one high refractive index layer of Nb2O5in contact with the capping layer, wherein the article exhibits no visible delamination after exposure to the Delamination Test with exposure of the anti-reflective surface to petroleum jelly for 80 hours.

25. The article of claim 16, wherein the article exhibits a Weibull modulus of greater than 50 and a Weibull characteristic strength of more than 900 MPa, as tested in a Ring-on-Ring Test.

26. The article of claim 16, wherein the article exhibits an elastic modulus of greater than 70 GPa and a hardness of greater than 6.5 GPa, as measured according to a Berkovich Hardness test at an indentation depth of about 100 nm to 500nm from the anti-reflective surface of the anti-reflective coating.Attorney Docket No.: SP24-27527. The article of claim 16, wherein one of the at least one of the plurality of periods which comprises at least two high refractive index layers including a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2and a second layer comprising SiNxor SiOxNyfurther comprises a tie layer of SiO2 or SiOxNydisposed between the first layer and the second layer.

28. The article of claim 16, wherein the anti-reflective coating directly below the capping layer comprises a sequence of layers given by (1) SiNxor SiOxNy, (2) a tie layer of SiO2 or SiOxNy, (3) Nb2O5or NbOxNy, and (4) SiNx, SiOxNy, or Nb2O5.

29. The article of claim 28, wherein the tie layer of SiO2 or SiOxNyhas a physical thickness of less than 5nm.

30. An article, comprising:a substrate having a first and second major surface, the first and second major surfaces opposing one another; andan anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface,wherein the anti-reflective coating comprises a plurality of layers,wherein the anti-reflective coating comprises a capping layer and a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, wherein one of the low refractive index layers is in direct contact with the major surface of the substrate, wherein the capping layer comprises at least one low refractive index layer of SiO2disposed on the plurality of periods,wherein at least one of the plurality of periods comprises at least two high refractive index layers, the at least two high refractive index layers comprise a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2, and a second layer comprising SiNxor SiOxNy, and further wherein the anti-reflective coating directly below the capping layer comprises either:a first sequence of layers given by (1) SiNxor SiOxNy, and (2) Nb2O5or NbOxNy, or a second sequence of layers given by (1) SiNxor SiOxNy, (2) a tie layer of SiO2or SiOxNy, and (3) Nb2O5or NbOxNy, wherein the tie layer of SiO2 or SiOxNyhas a physical thickness of less than 5nm.Attorney Docket No.: SP24-27531. The article of claim 30, wherein the capping layer has a refractive index of equal to or greater than 1.45.

32. The article of claim 30, wherein the article exhibits a first surface photopic average reflectance (Y) of less than 0.3%, as measured at an incident angle of 8 degrees.

33. The article of claim 30, wherein the first sequence or the second sequence of the anti-reflective coating has a physical thickness of less than 150 nm.

34. The article of claim 30, wherein the first sequence or the second sequence of the anti-reflective coating has a physical thickness of from 110 nm to 150 nm.

35. The article of any one of claims 30-34, wherein the first sequence of layers of the anti-reflective coating further comprises (3) SiNx, SiOxNy, or Nb2O5, or the second sequence of layers of the anti-reflective coating further comprises (4) SiNx, SiOxNy, or Nb2O536. The article of any one of claims 30-35, wherein all low refractive index layers of the anti-reflective coating have a refractive index of equal to or greater than 1.45.

37. The article of any one of claims 30-36, wherein the (2) NbOxNyor Nb2O5layer in the first sequence or the (3) NbOxNyor Nb2O5layer in the second sequence is a single NbOxNyor Nb2O5layer having a refractive index of greater than 2.2 and a physical thickness of less than 50 nm, and further wherein the single NbOxNyor Nb2O5layer is the only layer in the anti-reflective coating comprising NbOxNyor Nb2O5.

38. The article of any one of claims 30-37, wherein the (1) SiNxor SiOxNylayer in the first sequence or the second sequence comprises a physical thickness of less than 20 nm.

39. The article of any one of claims 30-38, wherein the anti-reflective coating has a physical thickness of from 310 nm to 2500 nm.

40. The article of any one of claims 30-39, wherein the anti-reflective coating comprises from 7 layers to 40 layers.Attorney Docket No.: SP24-27541. The article of any one of claims 30-40, wherein the article exhibits a two-surface transmittance T(940) at a wavelength of 940 nm of greater than 88%, wherein T(940) is measured with a bare second major surface of the substrate.

42. The article of any one of claims 30-41, wherein the article exhibits single side reflected color coordinates in the (L*, a*, b*) colorimetry system within the range of -5 < a* < +1 and -5 < b* < +5 under an International Commission on Illumination illuminant over an incident angle range from 0 degrees to 60 degrees at the anti-reflective surface.

43. The article of any one of claims 30-42, wherein one of the at least one of the plurality of periods which comprises at least two high refractive index layers including a first layer comprising NbOxNy, Nb2Os, TiO2, TivOv or HfO2, and a second layer comprising SiNxor SiOxNy further comprises a tie layer of SiO2 or SiOxNydisposed between the first layer and the second layer.

44. An article, comprising:a substrate having a first and second major surface, the first and second major surfaces opposing one another; andan anti-reflective coating disposed on the first major surface of the substrate and forming an anti-reflective surface,wherein the anti-reflective coating comprises a capping layer and a plurality of layers, the plurality of layers comprising a low refractive index layer, a first high refractive index layer, and a second high refractive index layer,wherein each of the first and second high refractive index layers has a refractive index value greater than 1.9, and the first and second high refractive index layers have different refractive index values, andfurther wherein the low refractive index layer has a refractive index value greater than 1.45.

45. The article of claim 44, wherein the anti-reflective coating comprises a plurality of periods such that each period comprises an alternating low refractive index layer and one or more high refractive index layers, and wherein one of the at least one of the plurality of periods which comprises at least two high refractive index layers including a first layer comprising NbOxNy, Nb2O5, TiO2, Ta2O3, or HfO2Attorney Docket No.: SP24-27546. The article of claim 44 or claim 45, wherein the article exhibits one or more of:(i) a first surface photopic average reflectance (Y) value of less than or equal to 0.18, (ii) a first surface reflected color chroma (C*) value, where C* = √(a*2+ b*2) in the (L*, a*, b*) colorimetry system and C* is less than or equal to 3.5 under an International Commission on Illumination illuminant measured for all light incident angles in a range from 0 degrees to 60 degrees at the anti-reflective surface, and(iii) a two-surface transmittance T(940) at a wavelength of 940 nm of greater than or equal to 88%, wherein T(940) is measured with a bare second major surface of the substrate.

47. The article of any one of claims 44-46, wherein the plurality of layers comprises at least four layers, each layer having a different refractive index value.

48. The article of any one of claims 44-47, wherein the capping layer comprises two layers, each layer of the capping layer having a different refractive index, and further wherein one of the layers of the capping layer has a refractive index greater than 1.45 and the other of the layers of the capping layer has a refractive index of less than 1.42.

49. The article of any one of claims 44-48, wherein the article exhibits a hardness of greater than 8 GPa, as measured according to a Berkovich Hardness test at an indentation depth of about 100 nm to 500nm from the anti-reflective surface of the anti-reflective coating.

50. The article of any one of claims 44-49, wherein the first high refractive index layer and the second high refractive index layer have different hardness values.

51. The article of any one of claims 44-50, wherein the anti-reflective coating comprises directly below the capping layer either:a first sequence of layers given by (1) the first high refractive index layer and (2) the second high refractive index layer, wherein the first high refractive index layer comprises a higher hardness than the hardness of the second high refractive index layer; ora second sequence of layers given by (1) the first high refractive index layer, (2) a tie layer of a low refractive index layer, wherein the tie layer has a physical thickness of less than 5nm, and (3) the second high refractive index layer, wherein the first high refractive index layer comprises a higher hardness than the hardness of the second high refractive index layer.Attorney Docket No.: SP24-27552. The article of claim 51, wherein in the first sequence or the second sequence the first high refractive index layer comprises a lower refractive index than the refractive index of the second high refractive index layer.

53. The article of claim 51, wherein the first sequence of layers of the anti-reflective coating further comprises (3) a third high refractive index layer, wherein the third high refractive index layer comprises a higher hardness than the hardness of the second high refractive index layer, or the second sequence of layers of the anti-reflective coating further comprises (4) a third high refractive index layer, wherein the third high refractive index layer comprises a higher hardness than the hardness of the second high refractive index layer.

54. The article of claim 51, wherein the second high refractive index layer of the first sequence or the second sequence comprises is a single NbOxNyor Nb2O5layer having a refractive index of greater than 2.2 and a physical thickness of less than 50 nm, and further wherein the single NbOxNyor Nb2Os layer is the only layer in the anti-reflective coating comprising NbOxNyor Nb2O5.

55. The article of claim 51, wherein the (1) the first high refractive index layer in the first sequence or the second sequence comprises a physical thickness of less than 20 nm.

56. The article of claim 51, wherein:the first sequence of layers comprises (1) the first high refractive index layer including SiNxor SiOxNyand (2) the second high refractive index layer including Nb2O5or NbOxNy, and (3) SiNx, SiOxNy, or Nb2O5,the second sequence of layers given by (1) the first high refractive index layer including SiNxor SiOxNy, (2) the tie layer including SiO2 or SiOxNy, (3) the second high refractive index layer including Nb2Os or NbOxNy, and (4) SiNx, SiOxNy, or Nb2O5.

57. The article of any one of claims 44-56, wherein all low refractive index layers of the anti-reflective coating have a refractive index of greater than 1.45.

58. The article of any one of claims 44-57, wherein the anti-reflective coating has a physical thickness of from 50 nm to less than 700 nm.Attorney Docket No.: SP24-27559. The article of any one of claims 44-58, wherein the article exhibits a first surface photopic average reflectance (Y) of less than 0.3%, as measured at an incident angle of 8 degrees.

60. The article of any one of claims 44-59, wherein the article exhibits single side reflected color coordinates in the (L*, a*, b*) colorimetry system within the range of -5 < a* < +0.25 and -5 < b* < +4 under an International Commission on Illumination illuminant over all incident angles in the range from 0 degrees to 90 degrees at the anti-reflective surface.

61. The article of any one of claims 44-59, wherein the article exhibits single side reflected color coordinates in the (L*, a*, b*) colorimetry system within the range of -5 < a* < -0.15 and -5 < b* < +4 under an International Commission on Illumination illuminant over all incident angles in the range from 0 degrees to 60 degrees at the anti-reflective surface.

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