Inorganic oxide article having a thin, durable anti-reflective structure - Patents.com

Abstract

The article exhibits a hardness of 8 GPa or greater when measured at an indentation depth of about 100 nm or a maximum hardness of 9 GPa or greater when measured over an indentation depth range of about 100 nm to about 500 nm, the hardness and maximum hardness being measured by a Berkovich indentation hardness test, and further exhibits a single-sided photopic average reflectance of less than 1%. [Solution] An article comprising an inorganic oxide substrate having opposite major surfaces; and an optical film structure disposed on the first major surface of the substrate, the optical film structure comprising one or more of a silicon-containing oxide, a silicon-containing nitride, and a silicon-containing oxynitride, and having a physical thickness of about 50 nm to less than 500 nm.

Description

Description of Related Applications

[0001] This application claims the benefit of priority under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application No. 62 / 765,081, filed Aug. 17, 2018, the content of which is relied upon and incorporated herein by reference in its entirety.

[0002] This application is a divisional application of Japanese Patent Application No. 2021-507941, filed Aug. 14, 2019.

Technical Field

[0003] The present disclosure relates to an inorganic oxide article having a thin durable antireflection structure and a method for manufacturing the same, and more particularly, to an article having a thin multilayer antireflection coating.

Background Art

[0004] To protect devices within an electrical product, to provide a user interface and / or a display for input, and / or to provide many other functions, cover articles are often used. Such products include portable devices such as smartphones, smartwatches, mp3 players, and tablet computers. Cover articles include architectural articles, transportation articles (e.g., interior and exterior displays and non-display articles used in automotive applications, trains, airplanes, ships, etc.), electrical appliance articles, or any article that would benefit from a degree of transparency, scratch resistance, abrasion resistance, or a combination thereof. These applications often require scratch resistance and strong optical performance characteristics regarding maximum light transmittance and minimum reflectance. Further, for some cover applications, it is beneficial that the color shown or perceived in reflection and / or transmission does not change appreciably when the viewing angle is changed. In display applications, this is because if the reflected or transmitted color changes appreciably with the viewing angle, the user of the product may perceive a change in the color or brightness of the display, thereby reducing the perceived quality of the display. In other applications, the color change may negatively affect the aesthetic appearance or other functional aspects of the device.

[0005] These display and non-display articles are often used in applications with implementation constraints (e.g., portable devices). In particular, many of these applications can benefit significantly from a reduction in overall thickness, even a few percent reduction. In addition, many applications using such display and non-display articles benefit from low manufacturing costs, e.g., by minimizing raw material costs, minimizing process complexity, and improving yield. Smaller packaging with performance attributes of optical and mechanical properties comparable to existing display and non-display articles can also meet the desire for reduced manufacturing costs (e.g., by less raw material costs, reducing the number of layers in an anti-reflection structure, etc.).

[0006] The optical performance of a cover article can be improved by using various anti-reflection coatings; however, known anti-reflection coatings are susceptible to wear and abrasion. Such wear can compromise any improvement in optical performance achieved by the anti-reflection coating. For example, optical filters are often manufactured from multilayer coatings having different refractive indices and are made from optically transparent dielectric materials (e.g., oxides, nitrides, and fluorides). Most typical oxides used in such optical filters are materials with a large bandgap, which do not have the mechanical properties, such as hardness, required for use in portable devices, architectural articles, transportation articles, or consumer electronics. Most nitrides and diamond-like coatings will not exhibit a high hardness value, which is associated with improved wear resistance, and such materials do not exhibit a desirable transmittance for such applications.

[0007] Wear damage can include reciprocating sliding contact with an opposing object (e.g., a finger). In addition, wear damage can generate heat, which can decompose chemical bonds in the film material and cause delamination and another type of damage to the cover glass. Wear damage is generally experienced over a longer period than a single event that causes scratching, so the coated material disposed to experience wear damage may also oxidize, further reducing the durability of the coating. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] Accordingly, there is a need for a new cover article having abrasion resistance, acceptable or improved optical performance, and a thinner optical structure, and a method of manufacturing the same. MEANS FOR SOLVING THE PROBLEMS

[0009] According to some embodiments of the present disclosure, an article is provided that includes an inorganic oxide substrate having opposing major surfaces; and an optical film structure disposed on a first major surface of the inorganic oxide substrate, the optical film structure including one or more of a silicon-containing oxide, a silicon-containing nitride, and a silicon-containing oxynitride and having a physical thickness of from about 50 nm to less than 500 nm. The article exhibits a hardness of 8 GPa or greater as measured at an indentation depth of about 100 nm or a maximum hardness of 9 GPa or greater as measured over an indentation depth range of from about 100 nm to about 500 nm, and the hardness and maximum hardness are measured by a Berkovich indenter hardness test. Further, the article exhibits a single-sided specular average reflectance of less than 1%.

[0010] According to some embodiments of the present disclosure, an article is provided that includes an inorganic oxide substrate having opposing major surfaces; and an optical film structure disposed on a first major surface of the inorganic oxide substrate, the optical film structure having a physical thickness of from about 50 nm to less than 500 nm and including a plurality of alternating high refractive index layers and low refractive index layers and a capping low refractive index layer, with a first low refractive index layer on the first major surface. Each layer includes one or more of a silicon-containing oxide, a silicon-containing nitride, and a silicon-containing oxynitride. The refractive index of the low refractive index layer is within the range of the refractive index of the inorganic oxide substrate such that the refractive index of the low refractive index layer is less than about 1.8, and the high refractive index layer has a refractive index greater than 1.8. The high refractive index layer exhibits a maximum hardness of 18 GPa or greater as measured by a Berkovich indenter hardness test over an indentation depth of from about 100 nm to about 500 nm on a hardness test laminate having a high refractive index layer disposed thereon with a physical thickness of about 2 micrometers (microns or μm) on the inorganic oxide substrate. Further, the article exhibits a single-sided specular average reflectance of less than 1%.

[0011] According to some embodiments of the present disclosure, an inorganic oxide substrate having opposite main surfaces; and an optical film structure disposed on a first main surface of the inorganic oxide substrate, the optical film structure having a plurality of alternating high refractive index layers and low refractive index layers and a capping low refractive index layer having a physical thickness of from about 50 nm to less than 500 nm and having a first low refractive index layer on the first main surface thereof are provided. Each layer includes one or more of a silicon-containing oxide, a silicon-containing nitride, and a silicon-containing oxynitride. The refractive index of the low refractive index layer is within the range of the refractive index of the inorganic oxide substrate such that the refractive index of the low refractive index layer is less than about 1.8, and the high refractive index layer has a refractive index greater than 1.8. The optical film structure further includes a high refractive index layer of 30% or more by volume. Further, the article exhibits a single-sided specular average reflectance of less than 1%.

[0012] According to some embodiments of the present disclosure, an inorganic oxide substrate having opposite main surfaces; and an optical film structure disposed on a first main surface of the inorganic oxide substrate, the optical film structure having a plurality of alternating high refractive index layers and low refractive index layers and a capping low refractive index layer having a first low refractive index layer on the first main surface of the substrate are provided. The refractive index of the low refractive index layer is within the range of the refractive index of the inorganic oxide substrate such that the refractive index of the low refractive index layer is less than about 1.8, and the high refractive index layer has a refractive index greater than 1.8. The article exhibits a hardness of 8 GPa or more as measured at an indentation depth of about 100 nm or a maximum hardness of 9 GPa or more as measured over an indentation depth range of from about 100 nm to about 500 nm, and this hardness and maximum hardness are measured by a Berkovich indenter hardness test. The optical film structure further includes a high refractive index layer of 35% or more by volume. The article exhibits a single-sided specular average reflectance of less than 1%. The high refractive index layer exhibits a maximum hardness of 18 GPa or more as measured by a Berkovich indenter hardness test over an indentation depth of from about 100 nm to about 500 nm on a hardness test laminate in which a high refractive index layer having a physical thickness of about 2 micrometers is disposed on the inorganic oxide substrate. Further, the article has an a * value of from about -10 to +2 upon reflection, and a b * value of from -10 to +2 upon reflection, and this a *Value and b * Each of the values is measured on the optical film structure at a normal incidence illumination angle.

[0013] Additional features and advantages are described in the following detailed description, some of which will be readily apparent to those skilled in the art from that description, or will be recognized by practicing the embodiments as described herein, including the following detailed description, the claims, and the accompanying drawings.

[0014] It will be understood that both the foregoing general description and the following detailed description are exemplary only and are intended to provide an overview or framework for understanding the nature and characteristics of the claims.

[0015] The accompanying drawings, which are incorporated herein and constitute a part hereof, are included to provide a further understanding. The drawings illustrate one or more embodiments and, together with the description, serve to explain the principles and operation of the disclosure by way of example. It should be understood that the various features of the disclosure disclosed herein can be used in any and all combinations. By way of non-limiting example, the various features of the disclosure may be combined with each other according to the following embodiments.

[0016] These and other features, aspects, and advantages of the present disclosure will be better understood when the following detailed description of the disclosure is read with reference to the accompanying drawings.

Brief Description of the Drawings

[0017]

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DETAILED DESCRIPTION OF THE INVENTION

[0018] In the following detailed description, for purposes of illustration and not limitation, exemplary embodiments disclosing specific details are set forth in order to provide a thorough understanding of the various principles of the present disclosure. However, it will be apparent to those skilled in the art having the benefit of this disclosure that the present disclosure may be practiced in other embodiments that depart from the specific details disclosed herein. Further, descriptions of well-known devices, methods, and materials may be omitted so as not to obscure the description of the various principles of the present disclosure. Finally, wherever applicable, like reference numerals refer to like elements.

[0019] Ranges can be expressed herein as from "about" a particular value and / or to "about" another particular value. As used herein, the term "about" means that the quantity, size, formulation, parameter, and other quantities and characteristics are not and need not be exact, but reflect tolerances, conversion factors, rounding, measurement error, and other factors known to those of ordinary skill in the art, and may, as appropriate, be approximate and / or larger or smaller. When the term "about" is used in describing a value or the endpoint of a range, the present disclosure is to be understood as including the recited particular value or endpoint. Whether or not the numerical or range endpoints herein are prefaced with "about", such numerical or range endpoints are intended to include both embodiments that are modified by "about" and those that are not modified by "about". It is further understood that each of the endpoints of those ranges is significant both in relation to the other endpoint and independently of the other endpoint.

[0020] As used herein, the terms "substantially", "substantially", and variations thereof are intended to indicate that the recited feature is equal to or approximately equal to a certain value or description. For example, a "substantially flat" surface is intended to indicate a surface that is flat or approximately flat. Further, "substantially" is intended to indicate that two values are equal or approximately equal. In some embodiments, "substantially" may indicate values within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.

[0021] Directional terms used herein - for example, up, down, right, left, front, back, top, bottom - are used only with respect to the drawn figures and are not intended to imply absolute orientation.

[0022] Unless otherwise specified, it is never intended that any of the methods described herein be construed as requiring that the steps be performed in a particular order. Thus, where a method claim does not actually recite the order to be followed by its steps, or where the steps are not otherwise specifically recited in the claims or the specification as being limited to a particular order, no order should be implied in any respect. This applies to any possible ambiguous criteria for interpretation, including logical issues regarding the arrangement of steps or the flow of operations; the plain meaning derived from grammatical construction or punctuation; and the number or type of embodiments described in the specification.

[0023] As used herein, a noun includes plural referents unless clearly indicated otherwise. Thus, for example, a reference to "a component" includes embodiments having two or more such components unless clearly indicated otherwise.

[0024] Embodiments of the present disclosure relate to inorganic oxide articles having a thin durable anti-reflective structure and methods of manufacturing the same, and more particularly to articles having a thin multi-layer anti-reflective coating exhibiting abrasion resistance, low reflectivity, and colorless transmittance and / or reflectivity. Embodiments of these articles have a total physical thickness of less than 500 nm while maintaining the hardness, abrasion resistance, and optical properties relevant to the intended use of these articles (e.g., as covers, housings, and substrates for display devices, interior and exterior automotive components, etc.).

[0025] Referring to FIG. 1, an article 100 according to one or more embodiments may include a substrate 110 and an anti-reflection coating 120 (also referred to herein as an “optical film structure”) disposed on the substrate. The substrate 110 includes opposite main surfaces 112, 114 and opposite secondary surfaces 116, 118. The anti-reflection coating 120 is shown in FIG. 1 as being disposed on the first main surface 112; however, the anti-reflection coating 120 may be disposed on, in addition to, or instead of, the first main surface 112, on the second main surface 114 and / or on one or both of the opposite secondary surfaces. The anti-reflection coating 120 forms an anti-reflection surface 122.

[0026] The anti-reflection coating 120 includes at least one layer of at least one type of material. The term “layer” may include a single layer or one or more sub-layers. Such sub-layers may be in direct contact with each other. The sub-layers may be formed of 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 continuous layers and / or one or more discontinuous intermittent layers (i.e., layers having different materials formed adjacent to each other). A layer or sub-layer may be formed by an individual deposition process or a continuous deposition process. In one or more embodiments, the layer may be formed using only a continuous deposition process or, alternatively, only an individual deposition process.

[0027] As used herein, the term “disposed” includes the processes of coating, depositing, and / or forming a material on a surface. The disposed material may constitute a layer as defined herein. The phrase “disposed on” includes examples of forming a material on a surface such that the material is in direct contact with the surface, and examples of forming a material on a surface with one or more intervening materials disposed between the material and the surface. The intervening material may constitute a layer as defined herein.

[0028] According to one or more embodiments, the anti-reflection coating 120 of the article 100 (e.g., as shown and described with respect to FIG. 1) can be characterized by abrasion resistance according to the Alumina SCE test. As used herein, the "Alumina SCE test" is performed by subjecting a sample to a commercially available 800 grit alumina abrasive paper (10 mm × 10 mm) with a total mass of 0.7 kg for 50 polishing cycles using a stroke length of approximately 1 inch (about 2.54 cm) driven by a Taber Industries 5750 linear polisher. Next, according to the Alumina SCE test, and in accordance with principles understood by those skilled in the art in the field of the present disclosure, the abrasion resistance is characterized by measuring the specular reflectance removal (SEC) value reflected from the polished sample. More specifically, the SEC is a measure of the diffuse reflection from the surface of the anti-reflection coating 120, measured using a Konica-Minolta CM700D having an aperture of 6 mm in diameter. According to some embodiments, the anti-reflection coating 120 of the article 100 can exhibit SEC values of less than 0.4%, less than 0.2%, less than 0.18%, less than 0.16%, and even less than 0.08% obtained from the Alumina SCE test. In contrast, commercially available anti-reflection coatings (such as 6-layer Nb 2 O 5 / SiO 2 multilayer coatings, etc.) have SEC values after abrasive paper polishing of greater than 0.6%. Polishing-induced damage increases the surface roughness and results in an increase in diffuse reflection (i.e., the SEC value). Lower SEC values indicate less severe damage and improved abrasion resistance.

[0029] The antireflection coating 120 and the article 100 may be described in terms of the hardness measured by the Berkovich indenter hardness test. Further, those skilled in the art will understand that the wear resistance of the antireflection coating 120 and the article 100 is related to the hardness of these elements. As used herein, the "Berkovich indenter hardness test" includes measuring the hardness of the material on the surface by indenting the surface with a diamond Berkovich indenter. This Berkovich indenter hardness test involves indenting the antireflection surface 122 of the article 100 or the surface of the antireflection coating 120 (or any one or more surfaces of the layers within the antireflection coating) with a diamond Berkovich indenter to form an indentation to a depth of indentation in the range of about 50 nm to about 1000 nm (or the total thickness of the antireflection coating or layer, whichever is smaller), and generally using the methods described in Oliver, W.C. and Pharr, G.M., "An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments", 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, to measure the hardness from this indentation at various points along the entire depth of indentation range, along a particular segment of this depth of indentation (e.g., in the depth range of about 100 nm to about 500 nm), or at a particular depth of indentation (e.g., at a depth of 100 nm, at a depth of 500 nm, etc.).Furthermore, when hardness is measured over an indentation depth range (e.g., a depth range from about 100 nm to about 500 nm), the result can be reported as the maximum hardness within a defined range, where the maximum value is selected from the measured values taken at each depth within that range. As used herein, both "hardness" and "maximum hardness" refer to the hardness value as measured, rather than the average of the hardness values. Similarly, when hardness is measured at a particular indentation depth, the hardness value obtained from a Berkovich indenter hardness test is given for that particular indentation depth.

[0030] Typically, in nanoindentation measurement methods (such as using a Berkovich indenter) of a coating that is harder than the underlying substrate below, the measured hardness initially appears to increase due to the occurrence of a plastic region at shallow indentation depths, and then reaches a maximum value or a flat region at deeper indentation depths. Thereafter, the hardness begins to decrease at even deeper indentation depths due to the effect of the underlying substrate. The same effect is seen when a substrate having increased hardness compared to the coating is used; however, the hardness increases at deeper indentation depths due to the effect of the underlying substrate.

[0031] The indentation depth range and the hardness values within a specific indentation depth range can be selected to specify the particular hardness response of the optical film structure and its layers described herein, without the effect of the underlying substrate. When measuring the hardness of an optical film structure (when disposed on a substrate) with a Berkovich indenter, the region of permanent strain (plastic region) of the material is related to the hardness of the material. During indentation, the elastic stress field extends far beyond the region of permanent strain. As the indentation depth increases, the apparent hardness and elastic modulus are affected by the stress field interaction with the underlying substrate. The effect of the substrate on the hardness occurs at deeper indentation depths (i.e., typically depths deeper than about 10% of the thickness of the optical film structure or layer). Furthermore, it is an even more troublesome issue that a specific minimum load is used to cause full plasticity during the indentation process. Prior to that specific minimum load, the hardness generally shows a tendency to increase.

[0032] At small indentation depths (which may be characterized as small loads) (e.g., up to about 50 nm), the apparent hardness of the material appears to increase dramatically with indentation depth. This small indentation depth regime does not represent a true measure of hardness; instead, it reflects the onset of the plastic regime described above, which is related to the finite radius of curvature of the indenter. At intermediate indentation depths, the apparent hardness approaches a maximum level. At greater indentation depths, the influence of the substrate becomes more pronounced as the indentation depth increases. Once the indentation depth exceeds about 30% of the thickness of the optical film structure or layer thickness, the hardness will begin to decrease dramatically.

[0033] As described above, one of ordinary skill in the art can consider various test-related considerations to ensure that the hardness and maximum hardness values of the coating 120 and the article 100 obtained from the Berkovich indenter hardness test represent these elements rather than being unduly influenced by, for example, the substrate 110. Further, one of ordinary skill in the art can also recognize that the embodiments of the present disclosure surprisingly exhibit high hardness values associated with the anti-reflection coating 120 despite its relatively small thickness (i.e., less than 500 nm). In fact, as evidenced by the examples described below in a later section, the hardness of the high refractive index (RI) layer 130B within the anti-reflection coating (see, for example, FIGS. 2A and 2B), despite its relatively low thickness value associated with these layers, can significantly affect the overall hardness and maximum hardness of the anti-reflection coating 120 and the article 100. This is unexpected due to the test-related considerations described above. These considerations detail how the measured hardness is directly affected by the thickness of the coating, such as the anti-reflection coating 120. Generally, as the thickness of a coating (on a thicker substrate) decreases and as the volume of a harder material within the coating (e.g., compared to other layers within a coating of lower hardness) decreases, it would be predicted that the measured hardness of that coating would tend towards the hardness of the underlying substrate. Nevertheless, the article 100 of the present disclosure, such as including the anti-reflection coating 120 (and as exemplified by the examples outlined in more detail below), surprisingly exhibits significantly higher hardness values compared to the underlying substrate and thus exhibits a unique combination of coating thickness (less than 500 nm), volume ratio of the higher hardness material, and optical properties.

[0034] In some embodiments, the anti-reflective coating 120 of the article 100 may exhibit a hardness of greater than about 8 GPa when measured for the anti-reflective surface 122 by a Berkovich indenter hardness test at an indentation depth of about 100 nm. The anti-reflective coating 120 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, about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, or about 15 GPa or greater when measured by a Berkovich indenter hardness test at an indentation depth of about 100 nm. The article 100, including the anti-reflective coating 120 and any additional coatings as described herein, may exhibit a hardness of about 8 GPa or greater, about 10 GPa or greater, or about 12 GPa or greater when measured for the anti-reflective surface 122 by a Berkovich indenter hardness test at an indentation depth of about 100 nm. Such measured hardness values may be exhibited by the anti-reflective coating 120 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, a maximum hardness value of about 8 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 about 15 GPa or greater when measured 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).

[0035] The antireflection coating 120 may have at least one layer made of a material having a maximum hardness of about 18 GPa or more, about 19 GPa or more, about 20 GPa or more, about 21 GPa or more, about 22 GPa or more, about 23 GPa or more, about 24 GPa or more, about 25 GPa or more, and all hardness values in between, as measured by a Berkovich indenter hardness test over an indentation depth from about 100 nm to about 500 nm (measured at the surface of such a layer, e.g., the surface of the second high RI layer 130B in FIG. 2A). These measurements are performed on a hardness test laminate including the designated layer of the antireflection coating 120 at a physical thickness of about 2 micrometers, disposed on the substrate 110, to minimize the hardness measurement effect related to the thickness described above. The maximum hardness of such a layer may be in the range of about 18 GPa to about 26 GPa as measured by a Berkovich indenter hardness test over an indentation depth from about 100 nm to about 500 nm. Such maximum hardness values may be indicated by the material of at least one layer (e.g., the high RI layer 130B as shown in FIG. 2A) over an indentation depth of about 50 nm or more or about 100 nm or more (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 greater than the hardness of the substrate (which can be measured at the surface opposite the antireflection surface). Similarly, the hardness value may be indicated by the material of at least one layer (e.g., the high RI layer 130B as shown in FIG. 2A) over an indentation depth of about 50 nm or more or about 100 nm or more (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 at least one layer (e.g., the high RI layer 130B) can also be observed at a specific indentation depth (e.g., 100 nm, 200 nm, etc.) over the measured indentation depth range.

[0036] Optical interference between the reflected wave from the interface between the antireflection coating 120 and air and the reflected wave from the interface between the antireflection coating 120 and the substrate can result in spectral reflectance and / or transmittance oscillations that create the apparent color in the article 100. As used herein, the term "transmittance" is defined as the percentage of incident light power within a given wavelength range that passes through a material (e.g., an article, a substrate, or its optical film or portion). The term "reflectance" is similarly defined as the percentage of incident light power within a given wavelength range that is reflected from a material (e.g., an article, a substrate, or its optical film or portion). In one or more embodiments, the spectral resolution for characterizing transmittance and reflectance is less than 5 nm or 0.02 eV. The color will be more apparent in reflection. Angular color is shifted in reflection with the viewing angle due to a shift in the spectral reflectance oscillation with the incident illumination angle. The angular color shift in transmittance with the viewing angle is also due to the same shift in the spectral transmittance oscillation with the incident illumination angle. The observed color and angular color shift with the incident illumination angle are often distracting or unpleasant for the user of the device, particularly under illumination with sharp spectral characteristics, such as fluorescent illumination and some LED illuminations. The angular color shift in transmittance can also contribute to the angular color shift in reflection and vice versa. The factors contributing to the angular color shift in transmittance and / or reflection can include a color shift away from a certain white point that may be caused by material absorption (somewhat independent of the angle) defined by a particular light source or test system or an angular color shift due to the viewing angle.

[0037] Vibrations may be described in terms of amplitude. As used herein, the term "amplitude" includes the change from the maximum value to the minimum value in reflectivity or transmittance. The phrase "average amplitude" includes the change from the maximum value to the minimum value in reflectivity or transmittance averaged within the optical wavelength region. As used herein, the "optical wavelength region" includes a wavelength range from about 400 nm to about 800 nm (and more specifically, from about 450 nm to about 650 nm). According to some embodiments, the optical wavelength range further includes the infrared spectrum from 800 nm to 1000 nm.

[0038] Embodiments of the present disclosure include an anti-reflection coating (e.g., anti-reflection coating 120 or optical film structure 120) for providing improved optical performance with respect to colorlessness and / or color shift at smaller angles when viewed at various incident illumination angles from normal incidence under different light sources.

[0039] One aspect of the present disclosure relates to an article that exhibits colorlessness in reflection and / or transmission even when viewed at different incident illumination angles under a light source. In one or more embodiments, the article exhibits a color shift in reflection and / or transmission of about 5 or less, or about 2 or less, between a reference illumination angle and any incident illumination angle within the ranges provided herein. As used herein, the phrase "color shift" (angle or reference point) refers to the change in both a and b in the Commission Internationale de l'Eclairage (CIE) L * , a * , b * measurement color system. Unless otherwise specified, it should be understood that the L * coordinates of the articles described herein are the same at any angle or reference point and do not affect the color shift. For example, the color shift due to angle is given by the following equation (1): * both changes in a * and b.

[0040]

Equation

[0041] can be determined using, where a * 1 , and b * 1 represent 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 represent the a * and b * coordinates of the article when viewed at an incident illumination angle, on the premise that the incident illumination angle is different from the reference illumination angle, and in some cases, about 1 degree or more, about 2 degrees or more, about 5 degrees or more, about 10 degrees or more, about 15 degrees or more, or about 20 degrees or more different from the reference illumination angle. In some cases, a color shift due to the angle in reflection and / or transmission is exhibited by the article when viewed at various incident illumination angles from the reference illumination angle under a light source. In some cases, the color shift due to the angle in reflection and / or transmission is 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, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, or 0.1 or less. In some embodiments, the color shift due to the angle may be about 0. Standard light sources as determined by the CIE include A light source (representing tungsten filament illumination), B light source (daylight simulation light source), C light source (daylight simulation light source), D series light sources (representing natural illumination), and F series light sources (representing various types of fluorescent illumination). In a specific example, the article exhibits a color shift due to the angle in reflection and / or transmission of about 2 or less when viewed at an incident illumination angle from the reference illumination angle under a CIE F2, F10, F11, F12, or D65 light source, or more specifically, under a CIE F2 light source.

[0042] The reference illumination angle, on the premise that the difference between the incident illumination angle and the reference illumination angle is about 1 degree or more, 2 degrees or more, about 5 degrees or more, about 10 degrees or more, about 15 degrees or more, or about 20 degrees or more, 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. The incident illumination angle may be away from normal incidence with respect to the reference illumination angle, in the range of about 5 degrees to about 80 degrees, about 5 degrees to about 75 degrees, about 5 degrees to about 70 degrees, about 5 degrees to about 65 degrees, about 5 degrees to about 60 degrees, about 5 degrees to about 55 degrees, about 5 degrees to about 50 degrees, about 5 degrees to about 45 degrees, about 5 degrees to about 40 degrees, about 5 degrees to about 35 degrees, about 5 degrees to about 30 degrees, about 5 degrees to about 25 degrees, about 5 degrees to about 20 degrees, about 5 degrees to about 15 degrees, and all ranges and sub-ranges therebetween. The article may exhibit color shift due to the angles in reflection and / or transmission described herein at all incident illumination angles in the range of about 2 degrees to about 80 degrees, or about 5 degrees to about 80 degrees, or about 10 degrees to about 80 degrees, or about 15 degrees to about 80 degrees, or about 20 degrees to about 80 degrees when the reference illumination angle is normal incidence. In some embodiments, the article may exhibit color shift due to the angles in reflection and / or transmission described herein at all incident illumination angles in the range of about 2 degrees to about 80 degrees, or about 5 degrees to about 80 degrees, or about 10 degrees to about 80 degrees, or about 15 degrees to about 80 degrees, or 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, about 5 degrees or more, about 10 degrees or more, about 15 degrees or more, or about 20 degrees or more. In one example, the article may exhibit a color shift due to the angles in reflection and / or transmission of 2 or less at any incident illumination angle in the range of about 2 degrees to about 60 degrees, about 5 degrees to about 60 degrees, or about 10 degrees to about 60 degrees away from a reference illumination angle equal to normal incidence.In other examples, the article may exhibit color shift due to angle in reflection and / or transmission of 2 or less when the reference illumination angle is 10 degrees and the incident illumination angle is at any angle in the range of about 12 degrees to about 60 degrees, about 15 degrees to about 60 degrees, or about 20 degrees to about 60 degrees away from the reference illumination angle.

[0043] In some embodiments, the color shift due to angle may be measured at all angles between a reference illumination angle (e.g., normal incidence) in the range of about 20 degrees to about 80 degrees and the incident illumination angle. In other words, the color shift due to angle may be measured at all angles in the range of about 0 degrees to about 20 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 60 degrees, or about 0 degrees to about 80 degrees, and may be less than about 5, or less than about 2.

[0044] In one or more embodiments, the article 100 has a distance between the transmitted color or reflection coordinates from a reference point or reference point color shift of less than about 5, or less than about 2, under a light source (which may include an A light source (representing tungsten filament illumination), a B light source (daylight simulation light source), a C light source (daylight simulation light source), a D-series light source (representing natural illumination), and an F-series light source (representing various types of fluorescent illumination)) in reflection and / or transmission such that the CIE L * , a * , b *It shows the color in the color measurement system. In a specific example, the article shows a color shift in reflection and / or transmission of about 2 or less when viewed from the reference illumination angle to the incident illumination angle under the CIE F2, F10, F11, F12 or D65 light source, or more specifically under the CIE F2 light source. In other words, the article shows the transmitted color (or transmitted color coordinates) and / or the reflected color (or reflected color coordinates) measured on the anti-reflection surface 122 having a reference point color shift of less than about 2 from the reference point as defined herein. Unless otherwise specified, the transmitted color or transmitted color coordinates are measured on two surfaces of the article, including the anti-reflection surface 122 of the article and the opposite bare surface (i.e., 114). Unless otherwise specified, the reflected color or reflected color coordinates are measured only on the anti-reflection surface 122 of the article.

[0045] In one or more embodiments, the reference point is the CIE L * , a * , b * starting point (0, 0) (or color coordinates a * = 0, b * = 0) in the color measurement system, the color coordinates (a * = -2, b * = -2) or the transmittance or reflected color coordinates of the substrate. Unless otherwise specified, it should be understood that the L * coordinates of the articles described herein are the same as the reference point and do not affect the color shift. When the reference point color shift of the article is defined with respect to the substrate, the transmitted color coordinates of the article are compared with the transmitted color coordinates of the substrate, and the reflected color coordinates of the article are compared with the reflected color coordinates of the substrate.

[0046] In one or more specific embodiments, the reference point color shift of the transmitted color and / or the reflected color may be less than 1 or even less than 0.5. In one or more specific embodiments, the reference point color shift of the transmitted color and / or the reflected color may be in the ranges and sub-ranges of 1.8, 1.6, 1.4, 1.2, 0.8, 0.6, 0.4, 0.2, 0 and all between them. When the reference point is the color coordinates a * = 0, b * = 0, the reference point color shift is given by Equation (2):

[0047]

Number

[0048] is calculated by. When the reference point is the color coordinate a * = -2, b * = -2, the reference point color deviation is given by Equation (3):

[0049]

Number

[0050] is calculated by. When the reference point is the color coordinate of the substrate, the reference point color deviation is given by Equation (4):

[0051]

Number

[0052] is calculated by.

[0053] In some embodiments, the article 100 may indicate the transmitted color (or transmitted color coordinates) and the reflected color (or reflected color coordinates) such that the reference point color deviation is less than 2 when the reference point is one of the color coordinates of the substrate, color coordinate a * = 0, b * = 0, and color coordinate a * = -2, b * = -2.

[0054] In some embodiments, the article 100 has a b in reflection in the range of about -10 to about +2, about -7 to about 0, about -6 to about -1, about -6 to about 0, or about -4 to about 0 in the CIE L * , a * , b * color measurement system at a substantially normal angle of incidence (i.e., about 0 degrees or within 10 degrees of normal). *may indicate a value (measured only on the anti-reflective surface 122). In other embodiments, the article 100 has, for all incident illumination angles in the range of from about 0 to about 60 degrees (or from about 0 to about 40 degrees, or from about 0 to about 30 degrees), CIE L * *, a * *, b * in the colorimetric system, a b value in the range of from about -10 to about +10, from about -8 to about +8, or from about -5 to about +5 in reflection (measured only on the anti-reflective surface 122) may be indicated. * * (measured only on the anti-reflective surface 122).

[0055] In some embodiments, the article 100 has, at a substantially normal angle of incidence (i.e., about 0 degrees or within 10 degrees of normal), CIE L * *, a * *, b * in the colorimetric system, a b value in the range of from about -2 to about 2, from about -1 to about 2, from about -0.5 to about 2, from about 0 to about 2, from about 0 to about 1, from about -2 to about 0.5, from about -2 to about 1, from about -1 to about 1, or from about 0 to about 0.5 in transmission (measured on the anti-reflective surface of the article and the opposite bare surface) may be indicated. In other embodiments, the article has, for all incident illumination angles in the range of from about 0 to about 60 degrees (or from about 0 to about 40 degrees, or from about 0 to about 30 degrees), CIE L * *, a * *, b * *, a * in the colorimetric system, a b value in the range of from about -2 to about 2, from about -1 to about 2, from about -0.5 to about 2, from about 0 to about 2, from about 0 to about 1, from about -2 to about 0.5, from about -2 to about 1, from about -1 to about 1, or from about 0 to about 0.5 in transmission may be indicated. * *

[0056] In some embodiments, the article 100 has, at a substantially normal angle of incidence (i.e., about 0 degrees or within 10 degrees of normal), CIE L * *, a * *, b * in the colorimetric system, an a value in the range of from about -2 to about 2, from about -1 to about 2, from about -0.5 to about 2, from about 0 to about 2, from about 0 to about 1, from about -2 to about 0.5, from about -2 to about 1, from about -1 to about 1, or from about 0 to about 0.5 in transmission.* may indicate a value (measured on the anti-reflective surface of the article and the opposite bare surface). In other embodiments, the article has a CIE L * *, * a * *, and b * * value in the transmission within a range of from about -2 to about 2, from about -1 to about 2, from about -0.5 to about 2, from about 0 to about 2, from about 0 to about 1, from about -2 to about 0.5, from about -2 to about 1, from about -1 to about 1, or from about 0 to about 0.5 for all incident illumination angles in the range of about 0 to about 60 degrees (or about 0 to about 40 degrees, or about 0 to about 30 degrees).

[0057] In some embodiments, article 100 has an a * and / or b * * value in the transmission within a range of from about -1.5 to about 1.5 (e.g., -1.5 to -1.2, -1.5 to -1, -1.2 to 1.2, -1 to 1, -1 to 0.5, or -1 to 0) for incident illumination angles in the range of from about 0 to about 60 degrees under light sources D65, A, and F2 (measured on the anti-reflective surface and the opposite bare surface).

[0058] In some embodiments, article 100 has an a * *, * a * *, and b * * value in the reflection within a range of from about -10 to about +5, -5 to about +5 (e.g., -4.5 to +4.5, -4.5 to +1.5, -3 to 0, -2.5 to -0.25), or from about -4 to +4 at a substantially perpendicular angle of incidence (i.e., about 0 degrees or within 10 degrees of perpendicular) in the CIE L * *, * a * *, and b * * value in the reflection within a range of from about -5 to about +15 (e.g., -4.5 to +14) or from about -3 to +13 for incident illumination angles in the range of from about 0 to about 60 degrees in the CIE L

[0059] The article 100 of one or more embodiments, or the anti-reflection surface 122 of one or more articles, may exhibit a clear visual average light transmittance of 94% or more (e.g., 94% or more, 95% or more, 96% or more, 96.5% or more, 97% or more, 97.5% or more, 98% or more, 98.5% or more, or 99% or more) over the optical wavelength range from about 400 nm to about 800 nm. In some embodiments, the article 100, or the anti-reflection surface 122 of one or more articles, may exhibit an average light reflectance of 2% or less (e.g., 1.5% or less, 1% or less, 0.75% or less, 0.5% or less, or 0.25% or less) over the optical wavelength range from about 400 nm to about 800 nm. These light transmittance and light reflectance values may be observed over the entire optical wavelength range or a selected range of its optical wavelength range (e.g., a 100 nm wavelength range, 150 nm wavelength range, 200 nm wavelength range, 250 nm wavelength range, 280 nm wavelength range, or 300 nm wavelength range within the optical wavelength range). In some embodiments, these light reflectance and transmittance values may be total reflectance or total transmittance (considering the reflectance or transmittance at both the anti-reflection surface 122 and the opposite major surface 114). Unless otherwise specified, the average reflectance or transmittance is measured at an incident illumination angle of 0 degrees (however, such measurements may be made at an incident illumination angle of 45 degrees or 60 degrees).

[0060] The article 100 of one or more embodiments, or the antireflection surface 122 of one or more articles, may exhibit an average light transmittance of about 87% or more (e.g., about 87% or more, about 88% or more, about 89% or more, about 90% or more, about 91% or more, about 92% or more, about 93% or more, about 94% or more, or about 95% or more) over an optical wavelength region in the infrared spectrum from about 800 nm to about 1000 nm, from about 900 nm to 1000 nm, or from 930 nm to 950 nm. In these embodiments, the article 100, or the antireflection surface 122 of one or more articles, may exhibit an average light reflectance of about 2% or less, about 1% or less, or about 0.5% or less (e.g., about 1.5% or less, about 1% or less, about 0.75% or less, about 0.5% or less, or about 0.25% or less) over an optical wavelength region in the range from about 400 nm to about 800 nm. These light transmittance and light reflectance values may be observed over the entire optical wavelength region or a selected range of its optical wavelength region (e.g., a 100 nm wavelength range, a 150 nm wavelength range, a 200 nm wavelength range, a 250 nm wavelength range, a 280 nm wavelength range, or a 300 nm wavelength range within the optical wavelength region). In some of these embodiments, the light reflectance and transmittance values may be total reflectance or total transmittance (considering the reflectance or transmittance at both the antireflection surface 122 and the opposite major surface 114). Unless otherwise specified, the average reflectance or transmittance of these embodiments is measured at an incident illumination angle of 0 degrees (however, such measurements may be made at an incident illumination angle of 45 degrees or 60 degrees).

[0061] In some embodiments, the article 100 of one or more embodiments, or the anti-reflective surface 122 of one or more articles, may exhibit a visible specular average reflectance of 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 0.4% or less, about 0.3% or less, or about 0.2% or less over the optical wavelength region. These specular average reflectance values may be shown 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, "visible specular average reflectance" mimics the response of the human eye by weighting the reflectance versus wavelength spectrum according to the sensitivity of the human eye. The visible specular average reflectance may also be defined as the luminance of the reflected light, or the tristimulus Y value, according to known conventions, for example, the conventions of the CIE color space. This visible specular average reflectance is defined in Equation (5) as the spectral reflectance R(λ) multiplied by the TIFF0007679410000005.tif7114

[0062] as defined in Equation (5):

[0063]

Number

[0064] In some embodiments, the antireflective surface 122 of one or more articles (i.e., when measuring the antireflective surface 122 by single-sided measurement only) may exhibit a visible specular average reflectance of about 2% or less, about 1.8% or less, about 1.5% or less, about 1.2% or less, about 1% or less, about 0.9% or less, about 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, or about 0.2% or less. In a "single-sided" measurement as described in the present disclosure, the reflectance from the second major surface (e.g., surface 114 shown in FIG. 1) is removed by coupling this surface to a refractive index matching absorber. In some cases, while showing a maximum reflectance color shift over the total incident illumination angle range from about 5 degrees to about 60 degrees (with a reference illumination angle of normal incidence) using a D65 light source of less than about 5.0, less than about 4.0, less than about 3.0, less than about 2.0, less than about 1.5, or less than about 1.25, a visible specular average reflectance range is shown. 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. Those values are the maximum change in a * value (a * 最高 -a * 最低 ), the maximum change in b * value (b * 最高 -b * 最低 ), the maximum change in both b * and a * values, or the maximum change in the quantity √((a * 最高 -a * 最低 ) 2 +(b * 最高 -b * 最低 ) 2 ).

[0065] substrate The substrate 110 may include an inorganic oxide material and may include an amorphous substrate, a crystalline substrate, or a combination thereof. In one or more embodiments, the substrate has a refractive index in the range of 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.

[0066] A suitable substrate 110 may exhibit a modulus of elasticity (or Young's modulus) in the range of about 30 GPa to about 120 GPa. In some cases, the modulus of elasticity of the substrate is in the range of about 30 GPa to about 110 GPa, about 30 GPa to about 100 GPa, about 30 GPa to about 90 GPa, about 30 GPa to about 80 GPa, about 30 GPa to about 70 GPa, about 40 GPa to about 120 GPa, about 50 GPa to about 120 GPa, about 60 GPa to about 120 GPa, about 70 GPa to about 120 GPa, and all ranges and sub-ranges between the foregoing values. The Young's modulus of the substrate itself as recited in the present disclosure refers to the value measured by the general type of resonant ultrasound spectroscopy technique described in ASTM E2001-13 entitled "Standard Guide for Resonant Ultrasound Spectroscopy for Defect Detection in Both Metallic and Non-metallic Parts".

[0067] In one or more embodiments, the amorphous substrate may include glass, which may or may not be strengthened. Examples of suitable glasses include soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali aluminoborosilicate glass. In some variations, the glass may be free of thoria. In one or more alternative embodiments, the substrate 110 may include a crystalline substrate, such as a glass ceramic or ceramic substrate (which may or may not be strengthened), or may include a single crystal structure, such as sapphire. In one or more particular embodiments, the substrate 110 includes an amorphous base (e.g., glass) and a crystalline cladding (e.g., a sapphire layer, a polycrystalline alumina layer, and / or a spinel (MgAl 2 O 4 ) layer).

[0068] 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 transparent, transmissive, and free of light scattering. In such embodiments, the substrate may exhibit an average light transmittance over an optical wavelength region of about 85% or more, about 86% or more, about 87% or more, about 88% or more, about 89% or more, about 90% or more, about 91% or more, or about 92% or more. In one or more alternative embodiments, the substrate 110 may be opaque or exhibit an average light transmittance over an optical wavelength region 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 total reflectance or total transmittance (considering reflectance or transmittance at both major surfaces of the substrate), or may be observed at one side of the substrate (i.e., only for the anti-reflective surface 122 without considering the opposite side). Unless otherwise specified, the average reflectance or transmittance is measured at an incident illumination angle of 0 degrees (however, such measurements may be made at an incident illumination angle of 45 degrees or 60 degrees). The substrate 110 may optionally exhibit a color, such as white, black, red, blue, green, yellow, orange, etc.

[0069] In addition 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, the edges of the substrate 110 may be thicker compared to more central regions of the substrate 110. The length, width, and physical thickness of the substrate 110 may also vary according to the use or application of the article.

[0070] The substrate 110 may be provided using a variety of different processes. For example, if the substrate 110 includes an amorphous substrate, such as glass, various forming methods include the float glass process, the rolling process, the up-draw process, and the down-draw process, such as the fusion draw process and the slot draw process.

[0071] Once formed, the substrate 110 may be strengthened to form a strengthened substrate. As used herein, the term "strengthened substrate" may refer to, for example, a substrate that has been chemically strengthened by ion exchange of smaller ions within the surface of the substrate with larger ions. However, other strengthening methods known in the art, such as thermal strengthening, or the use of a mismatch in the coefficient of thermal expansion between multiple portions of the substrate to create a region of compressive stress and a central region of tensile stress, may be used to form the strengthened substrate.

[0072] If the substrate is chemically strengthened by an ion exchange process, the ions within the surface layer of the substrate are replaced - i.e., exchanged - by larger ions having the same valence or oxidation state. The ion exchange process is typically performed by immersing the substrate in a molten salt bath containing larger ions to be exchanged for smaller ions within the substrate. The parameters of the ion exchange process, including but not limited to the composition and temperature of the bath, the immersion time, the number of times the substrate is immersed in one (or multiple) salt baths, the use of multiple salt baths, and any additional processes (such as slow cooling, washing, etc.), will generally be determined by the composition of the substrate, the desired compressive stress (CS), and the desired depth (or depth of the layer) of the compressive stress (CS) layer of the substrate resulting from the strengthening operation, as will be recognized by those skilled in the art. As an example, the ion exchange of a glass substrate containing an alkali metal can be performed by immersion in a salt, such as, but not limited to, at least one molten bath containing nitrates, sulfates, and chlorides of larger alkali metal ions. The temperature of the molten salt bath is typically in the range of about 380°C to about 450°C, while the immersion time can range from about 15 minutes to about 40 hours. However, different temperatures and immersion times than those described above may also be used.

[0073] In addition, non-limiting examples of the ion exchange process in which a glass substrate is immersed in a number of ion exchange baths, with a cleaning step and / or a slow cooling step being performed between multiple immersions, include a number of successive ion exchange treatments including immersion in a plurality of salt baths of different concentrations, by which the glass substrate is strengthened, claiming priority from U.S. Provisional Patent Application No. 61 / 079,995, filed Jul. 11, 2008, U.S. Patent Application No. 12 / 500,650, filed Jul. 10, 2009, entitled "Glass with Compressive Surface for Consumer Applications", and the glass substrate is strengthened by ion exchange in a first bath diluted by outflow ions and subsequent immersion in a second bath having outflow ions of a lower concentration than the first bath, claiming priority from U.S. Provisional Patent Application No. 61 / 084,398, filed Jul. 29, 2008, described in U.S. Patent No. 8,312,739, issued Nov. 20, 2012, entitled "Dual Stage Ion Exchange for Chemical Strengthening of Glass", by Christopher M. Lee et al. U.S. Patent Application No. 12 / 500,650 and U.S. Patent No. 8,312,739 are hereby incorporated by reference in their entirety.

[0074] The degree of chemical strengthening achieved by ion exchange can be quantified based on the parameters of center tension (CT), peak CS, depth of compression (DOC, the point along the thickness where compression changes to tension), and depth of layer (DOL). Peak CS is the maximum observed compressive stress, which may be measured near the surface of the substrate 110 or at various depths within the strengthened glass. The peak CS value is the measured CS at the surface of the strengthened substrate (CS Smay include. In other embodiments, the peak CS is measured below the surface of the strengthened substrate. Compressive stress (including surface CS) is measured by a surface stress meter (FSM) using a commercially available instrument such as the FSM-6000 manufactured by Orihara Seisakusho Co., Ltd. (Japan). Surface stress measurement depends on the precise measurement of the stress-optical coefficient (SOC) related to the birefringence of the glass. Next, the SOC is measured according to Procedure C (glass disk method) described in ASTM standard C770-16, entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient", the content of which is hereby incorporated by reference in its entirety. As used herein, DOC means the depth at which the stress in the chemically strengthened alkali aluminosilicate glass described herein changes from compression to tension. DOC can be measured by FSM or by a scattered light polarimeter (SCALP) depending on the ion exchange treatment. When the stress in the glass article is caused by the exchange of potassium ions into the glass article, FSM is used to measure DOC. When the stress is caused by the exchange of sodium ions into the glass article, SCALP is used to measure DOC. When the stress in the glass article is caused by the exchange of both potassium ions and sodium ions into the glass, DOC is measured by SCALP. This is because the exchange depth of sodium ions represents DOC, and the exchange depth of potassium ions is considered to represent a change in the magnitude of the compressive stress (not a change in stress from compression to tension); the exchange depth of potassium ions in such a glass article is measured by FSM. The maximum CT value is measured using a scattered light polarimeter (SCALP) known in the art. The refractive near-field (RNF) method or SCALP may be used to measure (plot on a graph, visually display, or precisely show in other ways) the complete stress profile. When the RNF method is used to measure the stress profile, the maximum CT value given by SCALP is utilized by the RNF method.Specifically, the stress profile measured by the RNF method is force balanced and calibrated against the maximum CT value provided by the SCALP measurement. This 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 hereby incorporated by reference in its entirety. Specifically, the RNF method includes the steps of placing a glass article adjacent to a reference block, generating a polarization-switching light beam that is switched between orthogonal polarizations at a rate from 1 Hz to 50 Hz, measuring the output power of the polarization-switching light beam, and generating a polarization-switching reference signal, wherein the measured amounts of the outputs of the orthogonal polarizations are within 50% of each other. This method further includes the step of transmitting the polarization-switching light beam through the glass sample and the reference block at different depths in the glass sample, and then relaying the transmitted polarization-switching light beam to a signal light detector using a relay optical system, wherein the signal light detector generates a polarization-switching detector signal. This method also includes the steps of dividing the detector signal by the reference signal to form a normalized detector signal, and determining a profile indicative of the characteristics of the glass sample from the normalized detector signal.

[0075] In some embodiments, the strengthened substrate 110 may have a peak CS of 250 MPa or more, 300 MPa or more, 400 MPa or more, 450 MPa or more, 500 MPa or more, 550 MPa or more, 600 MPa or more, 650 MPa or more, 700 MPa or more, 750 MPa or more, or 800 MPa or more. The strengthened substrate has a DOC of 10 μm or more, 15 μm or more, 20 μm or more (e.g., 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or more), and / or a CT of 10 MPa or more, 20 MPa or more, 30 MPa or more, 40 MPa or more (e.g., 42 MPa, 45 MPa, or 50 MPa or more), but may have a CT of less than 100 MPa (e.g., 95, 90, 85, 80, 75, 70, 65, 60, 55 MPa or less). In one or more particular embodiments, the strengthened substrate has one or more of the following: a peak CS greater than 500 MPa, a DOC greater than 15 μm, and a CT greater than 18 MPa.

[0076] Exemplary glasses that can be used for the substrate include alkali aluminosilicate glass compositions or alkali aluminoborosilicate glass compositions, although other glass compositions are also contemplated. Such glass compositions can be chemically strengthened by an ion exchange process. One exemplary glass composition is SiO 2 , B 2 O 3 and Na 2 O, where (SiO 2 +B 2 O 3 )≧66 mol% and Na 2 O≧9 mol%. In some embodiments, the glass composition contains about 6 wt% or more of aluminum oxide. In some embodiments, the substrate includes a glass composition having one or more alkaline earth oxides such that the content of the alkaline earth oxides is about 5 wt% or more. In some embodiments, a suitable glass composition further includes at least one of K 2 O, MgO, or CaO. In some embodiments, the glass composition used for the substrate may include 61-75 mol% of SiO 2 , 7-15 mol% of Al 2 O 3 , 0-12 mol% of B 2 O 3 , 9-21 mol% of Na 2 O, 0-4 mol% of K 2 O, 0-7 mol% of MgO, and 0-3 mol% of CaO.

[0077] Further exemplary glass compositions suitable for the substrate include 60-70 mol% of SiO 2 , 6-14 mol% of Al 2 O 3 , 0-15 mol% of B 2 O 3 , 0-15 mol% of Li 2 O, 0-20 mol% of Na 2 O, 0-10 mol% of K 2 O, 0-8 mol% of MgO, 0-10 mol% of CaO, 0-5 mol% of ZrO 2, 0 to 1 mol% of SnO 2 , 0 to 1 mol% of CeO 2 , less than 50 ppm of As 2 O 3 , and less than 50 ppm of Sb 2 O 3 containing, where 12 mol% ≤ (Li 2 O + Na 2 O + K 2 O) ≤ 20 mol%, and 0 mol% ≤ (MgO + CaO) ≤ 10 mol%.

[0078] Another exemplary glass composition suitable for the substrate is 63.5 to 66.5 mol% of SiO 2 , 8 to 12 mol% of Al 2 O 3 , 0 to 3 mol% of B 2 O 3 , 0 to 5 mol% of Li 2 O, 8 to 18 mol% of Na 2 , 0 to 5 mol% of K 2 O, 1 to 7 mol% of MgO, 0 to 2.5 mol% of CaO, 0 to 3 mol% of ZrO 2 , 0.05 to 0.25 mol% of SnO 2 , 0.05 to 0.5 mol% of CeO 2 , less than 50 ppm of As 2 O 3 , and less than 50 ppm of Sb 2 O 3 containing, where 14 mol% ≤ (Li 2 O + Na 2 O + K 2 O) ≤ 18 mol%, and 2 mol% ≤ (MgO + CaO) ≤ 7 mol%.

[0079] In some embodiments, an alkali aluminosilicate glass composition suitable for the substrate 110 includes alumina, at least one alkali metal, and in some embodiments, more than 50 mol% of SiO 2 , in other embodiments, 58 mol% or more of SiO 2 , and in still other embodiments, 60 mol% or more of SiO 2 where the ratio (Al 2 O3 +B 2 O 3 ) / Σ modifier (i.e., the total of the modifiers) is greater than 1, where the ratios of these components are expressed in mol%, and the modifier is an alkali metal oxide. In a particular embodiment, this glass composition comprises 58 to 72 mol% of SiO 2 , 9 to 17 mol% of Al 2 O 3 , 2 to 12 mol% of B 2 O 3 , 8 to 16 mol% of Na 2 O, and 0 to 4 mol% of K 2 O, where the ratio (Al 2 O 3 +B 2 O 3 ) / Σ modifier (i.e., the total of the modifiers) is greater than 1.

[0080] In some embodiments, the substrate 110 comprises 64 to 68 mol% of SiO 2 , 12 to 16 mol% of Na 2 O, 8 to 12 mol% of Al 2 O 3 , 0 to 3 mol% of B 2 O 3 , 2 to 5 mol% of K 2 O, 4 to 6 mol% of MgO, and 0 to 5 mol% of CaO, with 66 mol% ≦ SiO 2 +B 2 O 3 +CaO ≦ 69 mol%, Na 2 O + K 2 O + B 2 O 3 +MgO + CaO + SrO > 10 mol%, 5 mol% ≦ MgO + CaO + SrO ≦ 8 mol%, (Na 2 O + B 2 O 3 ) - Al 2 O 3 ≦ 2 mol%, 2 mol% ≦ Na 2 O - Al 2 O 3 ≦ 6 mol%, and 4 mol% ≦ (Na 2 O + K 2 O) - Al 2 O 3It may include an alkali aluminosilicate glass composition that is ≦10 mol%.

[0081] In some embodiments, substrate 110 may include an alkali aluminosilicate glass composition having 2 mol% or more of Al 2 O 3 and / or ZrO 2 , or having 4 mol% or more of Al 2 O 3 and / or ZrO 2 .

[0082] When substrate 110 includes a crystalline substrate, the substrate may include a single crystal, and the single crystal may include Al 2 O 3 . Such a single crystal substrate is called sapphire. Other suitable materials for the crystalline substrate include polycrystalline alumina layers and / or spinel (MgAl 2 O 4 ).

[0083] Optionally, crystalline substrate 110 may include a glass-ceramic substrate, which may or may not be strengthened. Examples of suitable glass-ceramics include Li 2 O·Al 2 O 3 ·SiO 2 -based (i.e., LAS-based) glass-ceramics, MgO·Al 2 O 3 ·SiO 2 -based (i.e., MAS-based) glass-ceramics, and / or glass-ceramics having a main crystal phase including β-quartz solid solution, β-spodumene solid solution, cordierite, and lithium disilicate. The glass-ceramic substrate may be strengthened using the chemical strengthening process disclosed herein. In one or more embodiments, the MAS-based glass-ceramic substrate can be strengthened in a Li 2 SO 4 molten salt, whereby an exchange of Mg + for 2Li 2+ can occur.

[0084] The substrate 110 according to one or more embodiments may have a physical thickness ranging from about 50 μm to about 5 mm. The physical thickness of the exemplary substrate 110 ranges from about 50 μm to about 500 μm (e.g., 50, 100, 200, 300, 400, or 500 μm). Further, the physical thickness of the exemplary substrate 110 ranges from about 500 μm to about 1000 μm (e.g., 500, 600, 700, 800, 900, or 1000 μm). 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 can be treated by acid polishing or other methods to eliminate or reduce the effect of surface scratches.

[0085] antireflection coating As shown in FIG. 1, the anti-reflection coating 120 of the article 100 may include a plurality of layers 120A, 120B, 120C. In some embodiments, one or more layers are disposed on the side opposite to the anti-reflection coating 120 of the substrate 110 (i.e., on the main surface 114) (not shown). In some embodiments of the article 100, the layer 120C as shown in FIG. 1 can perform the function of a capping layer (e.g., the capping layer 131 as shown in FIGS. 2A and 2B and described in the following column).

[0086] The physical thickness of the antireflection coating 120 may be in the range from about 50 nm to less than about 500 nm. In some cases, the physical thickness of the antireflection coating 120 is from about 10 nm to less than about 500 nm, from about 50 nm to less than about 500 nm, from about 75 nm to less than about 500 nm, from about 100 nm to less than about 500 nm, from about 125 nm to less than about 500 nm, from about 150 nm to less than about 500 nm, from about 175 nm to less than about 500 nm, from about 200 nm to less than about 500 nm, from about 225 nm to less than about 500 nm, from about 250 nm to less than about 500 nm, from about 300 nm to less than about 500 nm, from about 350 nm to less than about 500 nm, from about 400 nm to less than about 500 nm, from about 450 nm to less than about 500 nm, in the range from about 200 nm to about 450 nm, and in all ranges and sub-ranges therebetween.For example, the physical thickness of the antireflection coating 120 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 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 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 430 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.

[0087] In one or more embodiments, as shown in FIGS. 2A and 2B, the anti-reflection coating 120 of the article 100 may include a period 130 that includes two or more layers. In one or more embodiments, the two or more layers may be characterized as having different refractive indices from each other. In some embodiments, the period 130 includes a first low-RI layer 130A and a second high-RI layer 130B. The difference in refractive index between the first low-RI layer 130A and the second high-RI layer 130B may be about 0.01 or more, 0.05 or more, 0.1 or more, or even 0.2 or more. In some implementations, the refractive index of the first low-RI layer 130A is within the refractive index of the substrate 110 such that the refractive index of the first low-RI layer 130A is less than about 1.8, and the high-RI layer 130B has a refractive index greater than 1.8.

[0088] As shown in FIG. 2A, the anti-reflection coating 120 may include a plurality of periods (130). One period includes a first low-RI layer 130A and a second high-RI layer 130B. Thus, when a plurality of periods are provided, the first low-RI layer 130A (shown for illustration as "L") and the second high-RI layer 130B (shown for illustration as "H") alternate in the following layer order: L / H / L / H or H / L / H / L, so that the first low-RI layer and the second high-RI layer appear alternately along the physical thickness of the anti-reflection coating 120. In the example shown in FIG. 2A, the anti-reflection coating 120 includes three periods such that there are three pairs of low-RI and high-RI layers 130A and 130B, respectively. In the example of FIG. 2B, the anti-reflection coating 120 includes two periods such that there are two pairs of low-RI and high-RI layers 130A and 130B, respectively. In some embodiments, the anti-reflection coating 120 may include up to 25 periods. For example, the anti-reflection coating 120 may include from about 2 to about 20 periods, from about 2 to about 15 periods, from about 2 to about 10 periods, from about 2 to about 12 periods, from about 3 to about 8 periods, or from about 3 to about 6 periods.

[0089] In the embodiment of the article 100 shown in FIGS. 2A and 2B, the antireflection coating 120 may comprise an additional capping layer 131, which may comprise a material having a lower refractive index than the second high RI layer 130B. In some embodiments, the refractive index of the capping layer 131 is the same as or substantially the same as the refractive index of the low RI layer 130A.

[0090] As used herein, the terms "low RI" and "high RI" refer to the relative value of the RI of each layer with respect to the RI of another layer within the antireflection coating 120 (e.g., low RI < high RI). In one or more embodiments, the term "low RI", when used for the first low RI layer 130A or the capping layer 131, includes a range from about 1.3 to about 1.7. In one or more embodiments, the term "high RI", when used for the high RI layer 130B, includes a range from about 1.6 to about 2.5. In some cases, the low RI and high RI ranges may overlap; however, in most cases, the layers of the antireflection coating 120 have a general relationship with respect to RI of low RI < high RI.

[0091] Exemplary materials suitable for use in the antireflection coating 120 include SiO 2 , Al 2 O 3 , GeO 2 , SiO, AlO x N y , AlN, oxygen-doped SiN x , SiN x , SiO x N y , Si u , Al v O x N y , TiO 2 , ZrO 2 , TiN, MgO, HfO 2 , Y 2 O 3 , ZrO 2 , diamond-like carbon, and MgAl 2 O 4 are included.

[0092] Some examples of suitable materials for use in the low RI layer 130A include SiO 2 , Al 2 O 3 , GeO 2 , SiO, AlO x N y , SiO x N y , Si u Al v O x N y , MgO, and MgAl 2 O 4 The nitrogen content in the materials (e.g., materials such as Al 2 O 3 and MgAl 2 O 4 in) for use in the first low RI layer 130A (i.e., the layer 130A in contact with the substrate 110) may be minimized. In some embodiments, the low RI layer 130A in the anti-reflection coating 120 and, if present, the capping layer 131 may include one or more of silicon-containing oxides (e.g., silicon dioxide), silicon-containing nitrides (e.g., oxide-doped silicon nitride, silicon nitride, etc.), and silicon-containing oxynitrides (e.g., silicon oxynitride). In some embodiments of the article 100, the low RI layer 130A and the capping layer 131 include a silicon-containing oxide, e.g., SiO 2 .

[0093] Some examples of materials suitable for use in the high RI layer 130B include Si u Al v O x N y , AlN, oxygen-doped SiN x , SiN x , Si 3 N 4 , AlO x N y , SiO x N y , HfO 2 , TiO 2 , ZrO 2 , Y 2 O 3 , ZrO2 , Al 2 O 3 , and diamond-like carbon. The material of the high RI layer 130B, in particular, SiN x or AlN x The oxygen content in the material may be minimized. The above materials may be hydrogenated up to about 30% by mass. In some embodiments, the high RI layer 130B in the antireflection coating 120 may include one or more of silicon-containing oxides (e.g., silicon dioxide), silicon-containing nitrides (e.g., oxide-doped silicon nitride, silicon nitride, etc.), and silicon-containing oxynitrides (e.g., silicon oxynitride). In some embodiments of the article 100, the high RI layer 130B is a silicon-containing nitride, e.g., Si 3 N 4 If a material having an intermediate refractive index is desired between the high RI layer and the low RI layer, some embodiments may utilize AlN and / or SiO x N y . The hardness of the high RI layer may be specifically characterized. In some embodiments, the maximum hardness of the high RI layer 130B, as measured by a Berkovich indenter hardness test over an indentation depth from about 100 nm to about 500 nm (i.e., on a hardness test laminate having a 2 micrometer thick material layer of the layer 130B disposed on the substrate 110), may be about 18 GPa or more, about 20 GPa or more, about 22 GPa or more, about 24 GPa or more, about 26 GPa or more, and all values in between.

[0094] In one or more embodiments, at least one of the layers of the antireflection coating 120 of the article 100 may have a specific optical thickness range. As used herein, "optical thickness" is (n *Determined by (d), where "n" refers to the RI of the sublayer and "d" refers to the physical thickness of that layer. In one or more embodiments, at least one of the layers of the anti-reflection coating 120 may have an optical thickness in the range of about 2 nm to about 200 nm, about 10 nm to about 100 nm, or about 15 nm to about 100 nm. In some embodiments, each of all the layers in the anti-reflection coating 120 may have an optical thickness in the range of about 2 nm to about 200 nm, about 10 nm to about 100 nm, or about 15 nm to about 100 nm. In some cases, at least one layer of the anti-reflection coating 120 has an optical thickness of about 50 nm or more. In some cases, each of the low RI layers 130A has an optical thickness in the range of about 2 nm to about 200 nm, about 10 nm to about 100 nm, or about 15 nm to about 100 nm. In other cases, each of the high RI layers 130B has an optical thickness in the range of about 2 nm to about 200 nm, about 10 nm to about 100 nm, or about 15 nm to about 100 nm. In some embodiments, each of the high RI layers 130B has an optical thickness in the range of about 2 nm to about 500 nm, or about 10 nm to about 490 nm, or about 15 nm to about 480 nm, or about 25 nm to about 475 nm, or about 25 nm to about 470 nm, or about 30 nm to about 465 nm, or about 35 nm to about 460 nm, or about 40 nm to about 455 nm, or about 45 nm to about 450 nm, and any and all partial ranges therebetween. In some embodiments, for the capping layer 131 (see FIGS. 2A, 2B and 3), or the configuration without the capping layer 131, the outermost low RI layer 130A has a physical thickness of less than about 100 nm, less than about 90 nm, less than about 85 nm, or less than about 80 nm.

[0095] As described above, the embodiments of the article 100 are made such that one or more of the physical thicknesses within the layers of the anti-reflection coating 120 are minimized. In one or more embodiments, the physical thicknesses of the high RI layer 130B and / or the low RI layer 130A are minimized such that they total less than 500 nm. In one or more embodiments, the total physical thickness of the high RI layer 130B, the low RI layer 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 450 nm, less than 440 nm, less than 430 nm, less than 425 nm, less than 420 nm, less than 410 nm, less than 400 nm, less than 350 nm, less than 300 nm, less than 250 nm, or less than 200 nm, and all total thickness values that are less than 500 nm and greater than 10 nm.For example, the total physical thickness of the high RI layer 130B, the low RI layer 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 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 430 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.

[0096] In one or more embodiments, the total physical thickness of the high RI layer 130B may be characterized. For example, in some embodiments, the total physical thickness of the high RI layer 130B is about 90 nm or more, about 100 nm or more, about 150 nm or more, about 200 nm or more, about 250 nm or more, or about 300 nm or more, but may be less than 500 nm. This total physical thickness is the calculated total of the physical thicknesses of the individual high RI layers 130B in the anti-reflection coating 120, even if there are intervening low RI layers 130A or other layers. In some embodiments, the total physical thickness of the high RI layer 130B, which may also include a high hardness material (e.g., nitride or oxynitride), may be more than 30% of the total physical thickness (or, referred to in terms of volume) of the anti-reflection coating. For example, the total physical thickness (or volume) of the high RI layer 130B may be about 30% or more, about 35% or more, about 40% or more, about 45% or more, about 50% or more, about 55% or more, or even about 60% or more of the total physical thickness (or volume) of the anti-reflection coating 120.

[0097] In some embodiments, the antireflection coating 120 exhibits a specular average light reflectance of 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.25% or less, or 0.2% or less across the optical wavelength region when measured at the antireflection surface 122 (e.g., when reflections from the uncoated back surface of the article 100 (e.g., 114 in FIG. 1) are removed by using a refractive index matching oil on the back surface bonded to the absorber, or other known methods). In some cases, the antireflection coating 120 may exhibit such an average light reflectance across other wavelength ranges, such as from about 450 nm to about 650 nm, from about 420 nm to about 680 nm, from about 420 nm to about 700 nm, from about 420 nm to about 740 nm, from about 420 nm to about 850 nm, or from about 420 nm to about 950 nm. In some embodiments, the antireflection surface 122 exhibits a specular average light transmittance of about 90% or more, 92% or more, 94% or more, 96% or more, or 98% or more across its optical wavelength region. In some embodiments, the antireflection surface 122 exhibits a specular average light transmittance of about 87% or more, 88% or more, 89% or more, 90% or more, 91% or more, 92% or more, 93% or more, 94% or more, or 95% or more across the optical wavelength region of the infrared spectrum from 800 nm to 1000 nm, from 900 nm to 1000 nm, or from 930 nm to 950 nm. Unless otherwise specified, the average reflectance or transmittance is measured at an incident illumination angle of 0 degrees (however, such measurements may be made at an incident illumination angle of 45 degrees or 60 degrees).

[0098] As shown in FIG. 3, the article 100 may comprise one or more additional coatings 140 disposed on the anti-reflection coating. 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 / 690904, filed November 30, 2012, entitled "PROCESS FOR MAKING OF GLASS ARTICLES WITH OPTICAL AND EASY-TO-CLEAN COATINGS", which is hereby incorporated by reference in its entirety. This easy-to-clean coating may have a physical thickness in the range of about 5 nm to about 50 nm and may include known materials such as fluorinated silanes. In some embodiments, the easy-to-clean coating has a physical thickness in the range of about 1 nm to about 40 nm, about 1 nm to about 30 nm, about 1 nm to about 25 nm, about 1 nm to about 20 nm, about 1 nm to about 15 nm, about 1 nm to about 10 nm, about 5 nm to about 50 nm, about 10 nm to about 50 nm, about 15 nm to about 50 nm, about 7 nm to about 20 nm, about 7 nm to about 15 nm, about 7 nm to about 12 nm, or about 7 nm to about 10 nm, and all ranges and sub-ranges therebetween.

[0099] The additional coating 140 may include a scratch-resistant coating. Exemplary materials used for this scratch-resistant coating may include inorganic carbides, nitrides, oxides, diamond-like materials, or combinations thereof. Examples of suitable materials for this scratch-resistant coating include metal oxides, metal nitrides, metal oxynitrides, 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 for the scratch-resistant coating include Al 2 O 3 、AlN、AlO x N y 、Si 3 N 4 、SiOx N y 、 Si u Al v O x N y 、 diamond, diamond-like carbon, Si x C y 、 Si x O y C z 、 ZrO 2 、 TiO x N y 、 and combinations thereof would be included.

[0100] In some embodiments, the additional coating 140 may include a combination of a material that is easy to clean and a scratch-resistant material. In one example, the combination includes a material that is easy to clean and diamond-like carbon. Such an additional coating 140 may have a physical thickness in the range of about 5 nm to about 20 nm. The components of the additional coating 140 may be provided in separate layers. For example, the diamond-like carbon material may be disposed as a first layer, and the material that is easy to clean may be disposed as a second layer on top of the first layer of diamond-like carbon. The physical thicknesses of the first layer and the second layer may be within the ranges given previously 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 about 4 nm to about 15 nm (or more specifically about 10 nm), and the second layer of the material that is easy to clean may have a physical thickness of about 1 nm to about 10 nm (or more specifically about 6 nm). This diamond-like coating may include tetrahedral amorphous carbon (Ta-C), Ta-C:H, and / or Ta-C-H.

[0101] A further aspect of the present disclosure relates to a method of forming an article 100 (e.g., as shown in FIGS. 1 - 3) described herein. In some embodiments, the method includes providing a substrate having a major surface within a coating chamber, creating 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 including at least one of a wash - friendly coating and a scratch - resistant coating as positioned 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 either within the same coating chamber or within separate coating chambers without breaking the vacuum.

[0102] In one or more embodiments, the method may include loading the substrate onto a carrier used to move the substrate into and out of different coating chambers under load - lock conditions such that the vacuum is maintained when the substrate is moved.

[0103] The antireflection coating 120 (e.g., including layers 130A, 130B, and 131) and / or the additional coating 140 may be formed using various deposition methods, such as vacuum evaporation techniques, chemical vapor deposition methods (e.g., plasma-assisted chemical vapor deposition (PECVD), low-pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, and plasma-assisted atmospheric pressure chemical vapor deposition), physical vapor deposition methods (e.g., reactive or non-reactive sputtering or laser ablation), thermal or electron beam evaporation, and / or atomic layer deposition. Liquid-based methods, such as spraying or slot coating, may also be used. When vacuum deposition is utilized, an in-line process may be used to form the antireflection coating 120 and / or the additional coating 140 in one deposition operation. In some cases, vacuum deposition can be performed by a line PECVD source. In some implementations of this method, and in the article 100 manufactured by this method, the antireflection coating 120 can be prepared using a sputtering method (e.g., a reactive sputtering method), a chemical vapor deposition (CVD) method, a plasma-assisted chemical vapor deposition method, or some combination of these processes. In one implementation, the antireflection coating 120 including the low RI layer 130A and the high RI layer 130B can be prepared according to a reactive sputtering method. According to some embodiments, the antireflection coating 120 (including the low RI layer 130A, the high RI layer 130B, and the capping layer 131) of the article 100 is manufactured using a reactive sputtering method in a metal mode within a rotary drum coater. The conditions of this reactive sputtering method are defined by careful experiments to achieve the desired combination of hardness, refractive index, light transmittance, thin color, and controlled film stress.

[0104] In some embodiments, the method may include controlling the physical thickness of the anti-reflection coating 120 (e.g., including its layers 130A, 130B, and 131) and / or the additional coating 140 so that it does not vary by more than about 4% from the target physical thickness of each layer along at least about 80% of the area of the anti-reflection surface 122, or at any point along the area of the substrate. In some embodiments, the physical thickness of the anti-reflection coating 120 and / or the additional coating 140 is controlled so that it does not vary by more than about 4% along at least about 95% of the area of the anti-reflection surface 122.

[0105] In some embodiments of the article 100 shown in FIGS. 1-3, the anti-reflection coating 120 is characterized by a residual stress of from less than about +50 MPa (tensile) to about -1000 MPa (compressive). In some implementations of the article 100, the anti-reflection coating 120 is characterized by a residual stress of from about -50 MPa to about -1000 MPa (compressive), or from about -75 MPa to about -800 MPa (compressive). Unless otherwise specified, the residual stress in the anti-reflection coating 120 is obtained by measuring the curvature of the substrate 110 before and after deposition of the anti-reflection coating 120 and then calculating the residual film stress using Stoney's equation according to principles known and understood by those of ordinary skill in the art of the present disclosure.

[0106] The article 100 disclosed herein (e.g., as shown in FIGS. 1-3) may be incorporated into a device article, such as a device article having a display (or a display device article) (e.g., a consumer electronic device including a mobile phone, a tablet, a computer, a navigation system, a wearable device (e.g., a wristwatch), etc.), an augmented reality display, a head-up display, an eyewear-based display, a building device article, a transportation device article (e.g., an automobile, a train, an aircraft, a ship, etc.), a consumer product device article, or any device article that benefits from a degree of transparency, scratch resistance, abrasion resistance, or a combination thereof. Exemplary device articles incorporating any of the articles disclosed herein (e.g., according to the article 100 shown in FIGS. 1-3) are shown in FIGS. 4A and 4B. Specifically, FIGS. 4A and 4B show a housing 402 having a front face 404, a back face 406, and a side face 408; electrical components (not shown) at least partially or entirely inside the housing, including at least a control device, a memory, and a display 410 on or adjacent to the front face of the housing; and a consumer electronic device 400 having a cover substrate 412 on or over the front face of the housing as if on 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 part of the housing or a cover glass is made from the article disclosed herein.

[0107] According to some embodiments, an article 100 (such as shown in FIGS. 1 - 3) may be incorporated within a vehicle interior having a vehicle interior system as shown in FIG. 5. More specifically, article 100 may be used in connection with various vehicle interior systems. A vehicle interior 540 is shown including three different examples of vehicle interior systems 544, 548, 552. Vehicle interior system 544 includes a center console base 556 having a surface 560 that includes a display 564. Vehicle interior system 548 includes a dashboard base 568 having a surface 572 that includes a display 576. The dashboard base 568 typically includes an instrument panel 580 that may also include a display. Vehicle interior system 552 includes a handle base 584 having a surface 588 and a display 592. In one or more examples, the vehicle interior system may include a base that is any part of the vehicle interior including an armrest, a pillar, a seatback, a floorboard, a headrest, a door panel, or a surface. It will be understood that the article 100 described herein may be used interchangeably with each of the vehicle interior systems 544, 548, and 552.

[0108] According to some embodiments, an article 100 (such as shown in FIGS. 1 - 3) may or may not be integrated with an electronic display or an electrically active device and may be used in a passive optical element, such as a lens, a window, a lighting cover, glasses, or sunglasses.

[0109] Referring back to FIG. 5, each of the displays 564, 576, and 592 may comprise a housing having a front, a back, and sides. At least one electrical component is at least partially internal to the housing. The display element is on or adjacent to the front of the housing. The article 100 (see FIGS. 1-3) is disposed on the display element. The article 100 may be used on or in relation to any part of the vehicle interior, including an armrest, a pillar, a seatback, a floorboard, a headrest, a door panel, or a surface, as previously described. According to various examples, the displays 564, 576, and 592 may be a vehicle image display system or a vehicle infotainment system. It will be understood that the article 100 may be incorporated into various displays and structural components of an autonomous vehicle and that the description provided herein in relation to conventional vehicles is not limiting.

Example

[0110] The following examples will further clarify various embodiments.

[0111] Example 1 A glass substrate having a nominal composition of 69 mol% SiO 2 , 10 mol% Al 2 O 3 , 15 mol% Na 2 O, and 5 mol% MgO was provided, and an anti-reflection coating having five layers was disposed on the glass substrate as shown in FIG. 2B and Table 1 below to form a as-manufactured sample of Example 1. The anti-reflection coating of each of the as-manufactured samples in this example (e.g., such as corresponding to the anti-reflection coating 120 outlined in the present disclosure) was deposited using a reactive sputtering method.

[0112] For the modeled sample of Example 1 ("Example 1-M"), it was assumed that a glass substrate having the same composition as the glass substrate used for the as-manufactured sample of this example was used. Further, it was assumed that each antireflection coating of this modeled sample had layer materials and physical thicknesses as shown in Table 1 below. The optical properties reported for all examples were measured at near-normal incidence unless otherwise specified.

[0113] [Table 1]

[0114] Example 2 69 mol% SiO 2 10 mol% Al 2 O 3 15 mol% Na 2 O, and 5 mol% MgO was provided, and an antireflection coating having five layers was disposed on the glass substrate as shown in FIG. 2B and Table 2 below to form an as-manufactured sample of Example 2. Each antireflection coating of the as-manufactured sample in this example (e.g., such as corresponding to the antireflection coating 120 outlined in the present disclosure) was deposited using a reactive sputtering method.

[0115] For the modeled sample of Example 2 ("Example 2-M"), it was assumed that a glass substrate having the same composition as the glass substrate used for the as-manufactured sample of this example was used. Further, it was assumed that each antireflection coating of this modeled sample had layer materials and physical thicknesses as shown in Table 2 below.

[0116] [Table 2]

[0117] Example 3 69 mol% SiO 2 10 mol% Al 2 O 3 15 mol% Na2 A glass substrate having a nominal composition of 69 mol% SiO₂, 10 mol% Al₂O₃, 15 mol% Na₂O, and 5 mol% MgO was provided, and as shown in FIG. 2B and Table 3 below, a sample as manufactured in Example 3 was formed by disposing an antireflection coating having five layers on the glass substrate. Each antireflection coating of the as-manufactured samples in this example (e.g., such as corresponding to the antireflection coating 120 outlined in the present disclosure) was deposited using a reactive sputtering method.

[0118] For the modeled sample of Example 3 ("Example 3-M"), it was assumed that a glass substrate having the same composition as the glass substrate used for the as-manufactured sample of this example was used. Further, it was assumed that each antireflection coating of this modeled sample had layer materials and physical thicknesses as shown in Table 3 below.

[0119] [Table 3]

[0120] Example 3A 69 mol% SiO₂ 2 10 mol% Al 2 ₂O₃ 3 15 mol% Na 2 ₂O, and 5 mol% MgO was provided, and as shown in FIG. 2B and Table 3A below, a sample as manufactured in Example 3A was formed by disposing an antireflection coating having five layers on the glass substrate. Each antireflection coating of the as-manufactured samples in this example (e.g., such as corresponding to the antireflection coating 120 outlined in the present disclosure) was deposited using a reactive sputtering method.

[0121] For the modeled sample of Example 3A ("Example 3-M"), it was assumed that a glass substrate having the same composition as the glass substrate used for the as-manufactured sample of this example was used. Further, it was assumed that each antireflection coating of this modeled sample had layer materials and physical thicknesses as shown in Table 3A below.

[0122]

Table 3A

[0123] Example 4 69 mol% of SiO 2 、10 mol% of Al 2 O 3 、15 mol% of Na 2 O, and 5 mol% of MgO was provided with a glass substrate having a nominal composition, and as shown in FIG. 2A and Table 4 below, an antireflection coating having 7 layers was disposed on the glass substrate to form a as-manufactured sample of Example 4. Each antireflection coating of the as-manufactured samples in this example (e.g., such as corresponding to the antireflection coating 120 outlined in the present disclosure) was deposited using a reactive sputtering method.

[0124] The modeled sample of Example 4 ("Example 4-M") was assumed to use a glass substrate having the same composition as the glass substrate used for the as-manufactured sample of this example. Further, each antireflection coating of this modeled sample was assumed to have a layer material and a physical thickness as shown in Table 4 below.

[0125]

Table 4

[0126] Example 5 69 mol% of SiO 2 、10 mol% of Al 2 O 3 、15 mol% of Na 2A glass substrate having a nominal composition of O and 5 mol% of MgO was provided, and as shown in FIG. 2B and Table 5A below, a sample as manufactured in Example 5 was formed by disposing an antireflection coating having five layers on the glass substrate. Each antireflection coating of the as-manufactured samples in this example (e.g., such as corresponding to the antireflection coating 120 outlined in the present disclosure) was deposited using a reactive sputtering method.

[0127] For the modeled sample of Example 5 ("Example 5-M"), it was assumed that a glass substrate having the same composition as the glass substrate used for the as-manufactured sample of this example was used. Further, it was assumed that each antireflection coating of this modeled sample had layer materials and physical thicknesses as shown in Table 5A below.

[0128] [Table 5A]

[0129] Example 5A 69 mol% of SiO 2 、10 mol% of Al 2 O 3 、15 mol% of Na 2 O, and a glass substrate having a nominal composition of 5 mol% of MgO was provided, and as shown in FIG. 2B and Table 5B below, a sample as manufactured in Example 5A was formed by disposing an antireflection coating having five layers on the glass substrate. Each antireflection coating of the as-manufactured samples in this example (e.g., such as corresponding to the antireflection coating 120 outlined in the present disclosure) was deposited using a reactive sputtering method.

[0130] For the modeled sample of Example 5A ("Example 5-M"), it was assumed that a glass substrate having the same composition as the glass substrate used for the as-manufactured sample of this example was used. Further, it was assumed that each antireflection coating of this modeled sample had layer materials and physical thicknesses as shown in Table 5B below.

[0131]

Table 5B

[0132] Referring now to FIG. 6, a plot of hardness versus indentation depth is provided for the as-manufactured articles of Examples 1, 2, 3, 4, 5 and 5A. The data shown in FIG. 6 were generated using a Berkovich indenter hardness test on the samples of Examples 1-5A. As is apparent from FIG. 6, the hardness values peak at an indentation depth of 150 to 250 nm. Further, the as-manufactured samples of Examples 4, 5 and 5A exhibited the highest hardness values at indentation depths of 100 nm and 500 nm, and the highest maximum hardness values within the indentation depth range of 100 nm to 500 nm.

[0133] Referring now to FIG. 7, a plot of the first surface reflection color coordinates measured or predicted for the samples generally described above in Examples 1-5A at near-normal incidence is provided. As is apparent from FIG. 7, there is a fairly good correlation between the color coordinates shown by the as-manufactured samples and the modeled samples from each of the examples. Further, the color coordinates shown by the samples shown in FIG. 7 represent a limited color shift associated with the anti-reflection coatings of the present disclosure.

[0134] Example 6 Example 6 relates to two sets of modeled samples. Specifically, the modeled samples of Example 6 ("Example 3-M" and "Example 6-M") were assumed to use a glass substrate having the same composition as the glass substrate used for the as-manufactured samples of this example. Note that the modeled sample of Example 3-M in Example 6 has the same configuration as the antireflection coating used in Example 3, i.e., it uses Example 3-M. However, the sample of Example 6-M has a configuration of an antireflection coating that is similar but has a thicker low RI layer in contact with the substrate. More specifically, each antireflection coating of the modeled samples was assumed to have layer materials and physical thicknesses as shown in Table 6 below. As is clear from the data shown in Table 6, the samples of Example 6-M exhibit a lower average reflectance in bright light (i.e., Y value) compared to the modeled samples of Example 3-M.

[0135]

Table 6

[0136] Referring now to FIG. 8, a plot of specular component elimination (SCE) values is provided for the samples of the previous examples, specifically Examples 1-5, as obtained from samples on which the Alumina SCE Test was performed. Further, SCE values are also reported from a comparative article ("Comparative Example 1"), which article comprises the same substrates as used in Examples 1-5 and has a conventional antireflection coating comprising niobia and silica. In particular, the samples from Examples 1-5 of the present disclosure (i.e., Examples 1-5) exhibited SCE values of about 0.2% or less, which were three times (or more) lower than the SCE values reported for the comparative sample (Comparative Example 1). As described above, lower SCE values indicate less severe wear-related damage.

[0137] Referring now to FIG. 9, SiN that corresponds to the high RI layer 130B according to the present disclosure xA plot of hardness (GPa) vs. indentation depth (nm) is given for a hardness test laminate of a high refractive index layer material made from (i.e., a material suitable for the high RI layer 130B as shown in FIGS. 2A and 2B). In particular, the plot of FIG. 9 is for a substrate that matches those in Examples 1-5A and SiN having a thickness of about 2 micrometers in order to minimize the influence of the substrates and other test-related articles previously described in this disclosure. x Obtained using a Vickers indenter hardness test for a test laminate including a high RI layer made from x . As a result, the hardness values observed in FIG. 9 for the 2-micrometer-thick samples indicate the actual intrinsic material hardness of the much thinner high RI layers used in the antireflection coating 120 of this disclosure.

[0138] Example 7 69 mol% SiO 2 10 mol% Al 2 O 3 15 mol% Na 2 O, and 5 mol% MgO, and by disposing an antireflection coating having 5 layers (Examples 7, 7A, and 7B) and 7 layers (Example 7C) on the glass substrate as shown in FIGS. 2A and 2B and Table 7 below, as-manufactured samples of Example 7 (“Examples 7, 7A, 7B, and 7C”) were formed. The antireflection coating of each of the as-manufactured samples in this example (e.g., such as matching the antireflection coating 120 outlined in this disclosure) was deposited using a reactive sputtering method. The selected optical and mechanical properties of the samples in this example are also given below in Table 7.

[0139]

Table 7

[0140] Referring now to FIG. 10, there is provided a plot of the first surface reflectance transmittance (%) versus wavelength (i.e., from 350 nm to 950 nm) measured at approximately normal incidence of the samples outlined above in Example 7 (Examples 7, 7A, 7B, and 7C), or predicted therefor. As is apparent from FIG. 10, each of the samples in this example exhibits an average transmittance of greater than 96% in the visible spectrum from 450 nm to 650 nm, and an average transmittance of 87% or greater in the infrared spectrum from 800 nm to 950 nm, from 800 nm to 950 nm, and from 930 nm to 950 nm.

[0141] As used herein, the "AlO x N y ", "SiO x N y " and "Si u Al x O y N z " materials include various aluminum oxynitride, silicon oxynitride, and silicon aluminum oxynitride materials as would be understood by one of ordinary skill in the art of the present disclosure, as described according to specific numerical values and ranges for the subscripts "u", "x", "y", and "z". That is, it is common to describe a solid in "integer form", e.g., Al 2 O 3 . A description in "atomic fraction form" of equivalent meaning, e.g., Al 2 O 3 equal to, Al 0.4 O 0.6It is also common to describe solids using. 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. The description of atomic fraction is described in many general textbooks, and the description of atomic fraction is often used to describe alloys. For example, see (i) Charles Kittel, Introduction to Solid State Physics, seventh edition, John Wiley & Sons, Inc., NY, 1996, pp. 661 - 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.

[0142] Again, referring to the "AlO x N y ", "SiO x N y ", and "Si u Al x O y N z " materials, these subscripts allow those skilled in the art to refer to these materials as types of materials without specifying the values of the specific subscripts. Without specifying the values of the specific subscripts, generally for alloys, for example, for aluminum oxide, one can talk about Al v O x . Describing Al v O x means Al 2 O 3 or Al 0.4 O 0.6can all be represented. If v + x is selected such that the sum is 1 (i.e., v + x = 1), then, by extension, the formula would be a description of atomic fraction. Similarly, for more complex mixtures, such as Si u Al x O y N z can be described, and here too, if the sum u + v + x + y equals 1, it would be a case of atomic fraction description.

[0143] Once again, referring to the "AlO x N y ", "SiO x N y ", and "Si u Al x O y N z " materials in this disclosure, with these notations, one skilled in the art can easily compare these materials with others. That is, the atomic fraction formula is sometimes easier to use for comparison. For example, an exemplary alloy consisting of (Al 2 O 3 ) 0.3 (AlN) 0.7 is closely equal to the formula descriptions Al 0.448 O 0.31 N 0.241 and Al 367 O 254 N 198 Another exemplary alloy consisting of (Al 2 O 3 ) 0.4 (AlN) 0.6 is closely equal to the formula descriptions Al 0.438 O 0.375 N 0.188 and Al 37 O 32 N 16 The atomic fraction formulas Al 0.448 O 0.31 N 0.241 and Al 0.438 O 0.375 N 0.188 are relatively easy to compare with each other. For example, the atomic fraction of Al decreased by only 0.01, the atomic fraction of O increased by only 0.065, and the atomic fraction of N decreased by only 0.053. The integer formula description Al367 O 254 N 198 and Al 37 O 32 N 16 To compare them, more detailed calculations and considerations are needed. Therefore, it may be preferable to use the description of the atomic fraction formula of the solid. Nevertheless, since it includes any alloy containing Al, O, and N atoms, the use of Al v O x N y is common.

[0144] As would be understood by those skilled in the art in the field of the present disclosure regarding any of the previous materials (e.g., AlN) for the optical film 80, each of the subscripts "u", "x", "y", and "z" can vary from 0 to 1, the sum of those subscripts is 1 or less, and the remainder of the composition is the first element (e.g., Si or Al) in the material. In addition, those skilled in the art will recognize that "Si u Al x O y N z " can be made such that "u" is equal to zero, and that the material can be described as "AlO x N y ". Furthermore, the previous composition of the optical film 80 excludes combinations of subscripts that would result in a pure elemental form (e.g., pure silicon, pure aluminum metal, oxygen gas, etc.). Finally, those skilled in the art will recognize that the previous composition may include other elements (e.g., hydrogen) that are not explicitly shown, thereby resulting in a non-stoichiometric composition (e.g., SiN x versus Si 3 N 4 ). Therefore, the previous material for the optical film can represent the available space within the SiO 2 -Al 2 O 3 -SiN x -AlN or SiO 2 -Al 2 O 3 -Si 3 N 4 -AlN phase diagram.

[0145] Without substantially departing from the spirit and various principles of the present disclosure, many changes and modifications can be made to the above-described embodiments of the present disclosure. All such modifications and changes are intended to be included within the scope of the present disclosure and protected by the following claims. For example, various features of the present disclosure may be combined according to the following embodiments.

[0146] Embodiment 1 An inorganic oxide substrate having opposite main surfaces, and An optical film structure disposed on a first main surface of the inorganic oxide substrate, the optical film structure having a physical thickness of from about 50 nm to less than 500 nm and comprising one or more of a silicon-containing oxide, a silicon-containing nitride, and a silicon-containing oxynitride, An article comprising The article exhibits a hardness of 8 GPa or more as measured at an indentation depth of about 100 nm or a maximum hardness of 9 GPa or more as measured over an indentation depth range of from about 100 nm to about 500 nm, the hardness and the maximum hardness being measured by a Berkovich indenter hardness test, and further the article exhibits a single-sided bright-field average reflectance of less than 1%.

[0147] Embodiment 2 The article exhibits a hardness of 10 GPa or more as measured at an indentation depth of about 100 nm or a maximum hardness of 11 GPa or more as measured over an indentation depth range of from about 100 nm to about 500 nm, the hardness and the maximum hardness being measured by a Berkovich indenter hardness test, the physical thickness of the optical film structure is from about 200 nm to about 450 nm, and further the article exhibits a single-sided bright-field average reflectance of less than 0.6%, the article of Embodiment 1.

[0148] Embodiment 3 The article has an a * value of from about -10 to +5 upon reflection, and a b * value of from -10 to +2 upon reflection, the a * value and the b *Each of the values is measured on the optical film structure at a substantially normal incidence illumination angle, for the article of Embodiment 1 or Embodiment 2.

[0149] Embodiment 4 The article has an a value of from about -4 to +4 by reflection, and a b value of from -6 to -1 by reflection, and each of the a value and the b value is measured on the optical film structure at a substantially normal incidence illumination angle, for the article of Embodiment 1 or Embodiment 2. * and a b value of from -6 to -1 by reflection, * and each of the a value * and the b value * is measured on the optical film structure at a substantially normal incidence illumination angle, for the article of Embodiment 1 or Embodiment 2.

[0150] Embodiment 5 The article shows a maximum hardness of about 12 GPa or more as measured by a Berkovich indenter hardness test over a penetration depth range of from about 100 nm to about 500 nm, for any one of the articles of Embodiments 1 to 4.

[0151] Embodiment 6 The optical film structure has a residual stress in the range of from about -1000 MPa (compression) to about +50 MPa (tension), for any one of the articles of Embodiments 1 to 5.

[0152] Embodiment 7 The optical film structure contains a silicon-containing oxide and a silicon-containing nitride, the silicon-containing oxide is silicon oxide, and the silicon-containing nitride is silicon nitride, for any one of the articles of Embodiments 1 to 6.

[0153] Embodiment 8 The inorganic oxide substrate is made of a glass selected from the group consisting of soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali aluminoborosilicate glass, for any one of the articles of Embodiments 1 to 7.

[0154] Embodiment 9 The glass is chemically strengthened and has a compressive stress (CS) layer with a peak CS of 250 MPa or more, and the CS layer extends into the chemically strengthened glass to a compressive depth (DOC) of about 10 micrometers or more from the first major surface. An article according to Embodiment 8.

[0155] Embodiment 10 An article according to any one of Embodiments 1 to 9, further comprising any one or more of a cleaning - easy coating, a diamond - shaped coating, and a scratch - resistant coating disposed on the optical film structure.

[0156] Embodiment 11 An article according to any one of Embodiments 1 to 10, wherein the article exhibits a specular reflectance elimination (SEC) value of 0.2% or less as measured according to the Alumina SCE test.

[0157] Embodiment 12 An inorganic oxide substrate having major surfaces opposite to each other, and An optical film structure disposed on the first major surface of the inorganic oxide substrate, the optical film structure having a physical thickness of about 50 nm to less than 500 nm, and having a plurality of alternating high - refractive - index layers and low - refractive - index layers and a capping low - refractive - index layer with a first low - refractive - index layer on the first major surface. An article comprising Each layer contains one or more of a silicon - containing oxide, a silicon - containing nitride, and a silicon - containing oxynitride. The refractive index of the low - refractive - index layer is within the range of the refractive index of the substrate such that the refractive index of the low - refractive - index layer is less than about 1.8, and the high - refractive - index layer has a refractive index of more than 1.8. The high - refractive - index layer exhibits a maximum hardness of 18 GPa or more as measured by a Vickers indenter hardness test over an indentation depth of about 100 nm to about 500 nm on a hardness test laminate having a physical thickness of about 2 micrometers of the high - refractive - index layer disposed on the inorganic oxide substrate. Furthermore, the article exhibits a single - side bright - field average reflectance of less than 1%. An article.

[0158] Embodiment 13 The maximum hardness exhibited by the high refractive index layer is 22 GPa or more as measured by a Berkovich indenter hardness test over an indentation depth ranging from about 100 nm to about 500 nm on the hardness test laminate in which the high refractive index layer having a physical thickness of about 2 micrometers is disposed on the inorganic oxide substrate, the physical thickness of the optical film structure is from about 200 nm to about 450 nm, and further the article is an article of Embodiment 12 that exhibits a single-sided bright-field average reflectance of less than 0.6%.

[0159] Embodiment 14 The article has an a * value of about -10 to +5 upon reflection, and a b * value of -10 to +2 upon reflection, and each of the a * value and the b * value is measured for the optical film structure at a substantially normal incidence illumination angle, and is an article of Embodiment 12 or Embodiment 13.

[0160] Embodiment 15 The article has an a * value of about -4 to +4 upon reflection, and a b * value of -6 to -1 upon reflection, and each of the a * value and the b * value is measured for the optical film structure at a substantially normal incidence illumination angle, and is an article of Embodiment 12 or Embodiment 13.

[0161] Embodiment 16 The optical film structure has a residual stress in the range of about -1000 MPa (compression) to about +50 MPa (tension), and is an article of any one of Embodiments 12 to 15.

[0162] Embodiment 17 The inorganic oxide substrate is made of a glass selected from the group consisting of soda-lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali aluminoborosilicate glass, and is an article of any one of Embodiments 12 to 16.

[0163] Embodiment 18 The article of Embodiment 17, wherein the glass is chemically strengthened and has a compressive stress (CS) layer with a peak CS of 250 MPa or more, and the CS layer extends into the chemically strengthened glass to a compressive depth (DOC) of about 10 micrometers or more from the first major surface.

[0164] Embodiment 19 The article of any one of Embodiments 12 to 18, further comprising any one or more of an easily cleanable coating, a diamond-like coating, and a scratch-resistant coating disposed on the optical film structure.

[0165] Embodiment 20 The article of any one of Embodiments 12 to 19, wherein the plurality of alternating high refractive index layers and low refractive index layers are at least four layers, each layer contains one or more of a silicon-containing oxide and a silicon-containing nitride, the silicon-containing oxide is silicon oxide, and the silicon-containing nitride is silicon nitride.

[0166] Embodiment 21 The article of any one of Embodiments 12 to 20, wherein the physical thickness of the high refractive index layer adjacent to the capping low refractive index layer is about 70 nm or more, and the physical thickness of the capping low refractive index layer is about 80 nm or more.

[0167] Embodiment 22 The article of any one of Embodiments 12 to 21, wherein the article exhibits a specular reflection elimination (SEC) value of 0.2% or less as measured according to the Alumina SCE test.

[0168] Embodiment 23 An inorganic oxide substrate having opposite major surfaces, and An optical film structure disposed on the first major surface of the inorganic oxide substrate, the optical film structure having a physical thickness of about 50 nm to less than 500 nm and having a plurality of alternating high refractive index layers and low refractive index layers and a capping low refractive index layer with a first low refractive index layer on the first major surface of the substrate. An article comprising, each layer contains one or more of a silicon-containing oxide, a silicon-containing nitride, and a silicon-containing oxynitride, the refractive index of the low refractive index layer is within the range of the refractive index of the inorganic oxide substrate such that the refractive index of the low refractive index layer is less than about 1.8, and the high refractive index layer has a refractive index greater than 1.8, the optical film structure further contains the high refractive index layer in an amount of 30% or more by volume, furthermore, the article exhibits a single-sided specular average reflectance of less than 1%, an article.

[0169] Embodiment 24 The optical film structure of the article according to Embodiment 23 further contains the high refractive index layer in an amount of 50% or more by volume.

[0170] Embodiment 25 wherein the article has an a * value of about -10 to +5 upon reflection, and a b * value of -10 to +2 upon reflection, and each of the a * value and the b * value is measured for the optical film structure at a substantially normal incidence illumination angle, an article according to Embodiment 23 or Embodiment 24.

[0171] Embodiment 26 wherein the article has an a * value of about -4 to +4 upon reflection, and a b * value of -6 to -1 upon reflection, and each of the a * value and the b * value is measured for the optical film structure at a substantially normal incidence illumination angle, an article according to Embodiment 23 or Embodiment 24.

[0172] Embodiment 27 The optical film structure of any one of Articles according to Embodiments 23 to 26 has a residual stress in the range of about -1000 MPa (compression) to about +50 MPa (tension).

[0173] Embodiment 28 The article according to any one of Embodiments 23 to 27, wherein the inorganic oxide substrate is made of a glass selected from the group consisting of soda-lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali aluminoborosilicate glass.

[0174] Embodiment 29 The article according to Embodiment 28, wherein the glass is chemically strengthened and has a compressive stress (CS) layer having a peak CS of 250 MPa or more, and the CS layer extends into the chemically strengthened glass to a compressive depth (DOC) of about 10 micrometers or more from the first major surface.

[0175] Embodiment 30 The article according to any one of Embodiments 23 to 29, further comprising at least one of an easily cleanable coating, a diamond-like coating, and a scratch-resistant coating disposed on the optical film structure.

[0176] Embodiment 31 The article according to any one of Embodiments 23 to 30, wherein the plurality of alternating high refractive index layers and low refractive index layers are at least four layers, each layer containing one or more of a silicon-containing oxide and a silicon-containing nitride, the silicon-containing oxide is silicon oxide, and the silicon-containing nitride is silicon nitride.

[0177] Embodiment 32 The article according to any one of Embodiments 23 to 31, wherein the high refractive index layer adjacent to the capping low refractive index layer has a physical thickness of about 70 nm or more, and the capping low refractive index layer has a physical thickness of about 80 nm or more.

[0178] Embodiment 33 The article according to any one of Embodiments 23 to 32, wherein the article exhibits a specular reflectance elimination (SEC) value of 0.2% or less as measured according to the Alumina SCE test.

[0179] Embodiment 34 An inorganic oxide substrate having major surfaces opposite to each other, and An optical film structure disposed on a first major surface of the inorganic oxide substrate, the optical film structure having a plurality of alternating high refractive index layers and low refractive index layers and a capping low refractive index layer with a first low refractive index layer on the first major surface of the substrate, An article comprising, The refractive index of the low refractive index layer is within the range of the refractive index of the substrate such that the refractive index of the low refractive index layer is less than about 1.8, and the high refractive index layer has a refractive index greater than 1.8, The article exhibits a hardness of 8 GPa or more as measured at an indentation depth of about 100 nm or a maximum hardness of 9 GPa or more as measured over an indentation depth range from about 100 nm to about 500 nm, and the hardness and the maximum hardness are measured by a Berkovich indenter hardness test, The article exhibits a one-sided bright-field average reflectance of less than 1%, The optical film structure further includes the high refractive index layer at 35% or more by volume, The high refractive index layer exhibits a maximum hardness of 18 GPa or more as measured by a Berkovich indenter hardness test over an indentation depth from about 100 nm to about 500 nm on a hardness test laminate in which the high refractive index layer having a physical thickness of about 2 micrometers is disposed on the inorganic oxide substrate, Furthermore, the article has an a * value of about -10 to +5 by reflection, and a b * value of -10 to +2 by reflection, and each of this a * value and b * value is measured for the optical film structure at a normal incidence illumination angle, article.

[0180] Embodiment 35 The article according to Embodiment 34, wherein the high refractive index layer exhibits a maximum hardness of 21 GPa or more as measured by a Berkovich indenter hardness test over an indentation depth from about 100 nm to about 500 nm on a hardness test laminate in which the high refractive index layer having a physical thickness of about 2 micrometers is disposed on the inorganic oxide substrate.

[0181] Embodiment 36 The article of Embodiment 34 or Embodiment 35, which shows a specular component elimination (SEC) value of 0.2% or less when measured according to the Alumina SCE test.

[0182] Embodiment 37 The article of any one of Embodiments 1 to 11, which shows a one-sided average transmittance of 87% or more in the infrared spectrum from 900 nm to 1000 nm.

[0183] Embodiment 38 The article of any one of Embodiments 12 to 22, which shows a one-sided average transmittance of 87% or more in the infrared spectrum from 900 nm to 1000 nm.

[0184] Embodiment 39 The article of any one of Embodiments 23 to 33, which shows a one-sided average transmittance of 87% or more in the infrared spectrum from 900 nm to 1000 nm.

[0185] Embodiment 40 The article of any one of Embodiments 34 to 36, which shows a one-sided average transmittance of 87% or more in the infrared spectrum from 900 nm to 1000 nm.

[0186] Embodiment 41 A housing having a front surface, a back surface, and side surfaces, An electrical component that is at least partially inside the housing and includes a control device, a memory, and a display on or adjacent to the front surface of the housing, and A cover substrate disposed on the display, A household electronic device comprising: A household electronic device, wherein at least one of a part of the housing or the cover substrate is made of the article of any one of Embodiments 1 to 40.

[0187] Hereinafter, preferred embodiments of the present invention will be described item by item.

[0188] Embodiment 1 An inorganic oxide substrate having opposing major surfaces, and an optical film structure disposed on a first major surface of the inorganic oxide substrate, the optical film structure having a physical thickness of from about 50 nm to less than 500 nm and comprising one or more of a silicon-containing oxide, a silicon-containing nitride, and a silicon-containing oxynitride, An article comprising: The article exhibits a hardness of 8 GPa or more as measured at an indentation depth of about 100 nm or a maximum hardness of 9 GPa or more as measured over an indentation depth range of from about 100 nm to about 500 nm, the hardness and the maximum hardness being measured by a Berkovich indenter hardness test, and the article further exhibits a single-sided bright-field average reflectance of less than 1%.

[0189] Embodiment 2 The article exhibits a hardness of 10 GPa or more as measured at an indentation depth of about 100 nm or a maximum hardness of 11 GPa or more as measured over an indentation depth range of from about 100 nm to about 500 nm, the hardness and the maximum hardness being measured by a Berkovich indenter hardness test, the physical thickness of the optical film structure is from about 200 nm to about 450 nm, and the article further exhibits a single-sided bright-field average reflectance of less than 0.6%, the article according to Embodiment 1.

[0190] Embodiment 3 The article has an a * value of from about -10 to +5 upon reflection, and a b * value of from -10 to +2 upon reflection, each of the a * value and the b * value being measured on the optical film structure at a substantially normal incidence illumination angle, the article according to Embodiment 1 or 2.

[0191] Embodiment 4 The article has an a * value of from about -4 to +4 upon reflection, and a b * value of from -6 to -1 upon reflection, the a * value and the b *Each of the values is measured on the optical film structure at a substantially normal incidence illumination angle, the article according to Embodiment 1 or 2.

[0192] Embodiment 5 The article according to any one of Embodiments 1 to 4, wherein the article exhibits a maximum hardness of about 12 GPa or more as measured by a Berkovich indenter hardness test over a penetration depth range of about 100 nm to about 500 nm.

[0193] Embodiment 6 The article according to any one of Embodiments 1 to 5, wherein the optical film structure has a residual stress in the range of about -1000 MPa (compression) to about +50 MPa (tension).

[0194] Embodiment 7 The article according to any one of Embodiments 1 to 6, wherein the optical film structure includes a silicon-containing oxide and a silicon-containing nitride, the silicon-containing oxide is silicon oxide, and the silicon-containing nitride is silicon nitride.

[0195] Embodiment 8 The article according to any one of Embodiments 1 to 7, wherein the inorganic oxide substrate is made of a glass selected from the group consisting of soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali aluminoborosilicate glass.

[0196] Embodiment 9 The article according to Embodiment 8, wherein the glass is chemically strengthened and has a compressive stress (CS) layer with a peak CS of 250 MPa or more, and the CS layer extends into the chemically strengthened glass to a compressive depth (DOC) of about 10 micrometers or more from the first major surface.

[0197] Embodiment 10 The article according to any one of Embodiments 1 to 9, further comprising at least one of an easily cleanable coating, a diamond-like coating, and an abrasion-resistant coating disposed on the optical film structure.

[0198] Embodiment 11 The article according to any one of Embodiments 1 to 10, wherein the article exhibits a specular light removal (SEC) value of 0.2% or less as measured according to the Alumina SCE test.

[0199] Embodiment 12 An inorganic oxide substrate having opposite main surfaces, and An optical film structure disposed on the first main surface of the inorganic oxide substrate, having a physical thickness of about 50 nm to less than 500 nm, and having a plurality of alternating high refractive index layers and low refractive index layers and a capping low refractive index layer with a first low refractive index layer on the first main surface. An article comprising: Each layer contains one or more of silicon-containing oxides, silicon-containing nitrides, and silicon-containing oxynitrides. The refractive index of the low refractive index layer is within the range of the refractive index of the substrate such that the refractive index of the low refractive index layer is less than about 1.8, and the high refractive index layer has a refractive index greater than 1.8. The high refractive index layer shows a maximum hardness of 18 GPa or more as measured by a Berkovich indenter hardness test over an indentation depth of about 100 nm to about 500 nm on a hardness test laminate having a physical thickness of about 2 micrometers of the high refractive index layer disposed on the inorganic oxide substrate. Furthermore, the article exhibits a single-sided bright-field average reflectance of less than 1%.

[0200] Embodiment 13 The article according to Embodiment 12, wherein the maximum hardness exhibited by the high refractive index layer is 22 GPa or more as measured by a Berkovich indenter hardness test over an indentation depth of about 100 nm to about 500 nm on the hardness test laminate having a physical thickness of about 2 micrometers of the high refractive index layer disposed on the inorganic oxide substrate, the physical thickness of the optical film structure is about 200 nm to about 450 nm, and furthermore, the article exhibits a single-sided bright-field average reflectance of less than 0.6%.

[0201] Embodiment 14 The article has an a value of approximately -10 to +5 by reflection, and a b value of -10 to +2 by reflection. Each of the a value and the b value is measured in the optical film structure at a substantially normal incidence illumination angle. The article according to Embodiment 12 or 13. * The article has an a value of approximately -4 to +4 by reflection, and a b value of -6 to -1 by reflection. Each of the a value and the b value is measured in the optical film structure at a substantially normal incidence illumination angle. The article according to Embodiment 12 or 13. * The article has an a value of approximately -4 to +4 by reflection, and a b value of -6 to -1 by reflection. Each of the a value and the b value is measured in the optical film structure at a substantially normal incidence illumination angle. The article according to Embodiment 12 or 13. * The article has an a value of approximately -4 to +4 by reflection, and a b value of -6 to -1 by reflection. Each of the a value and the b value is measured in the optical film structure at a substantially normal incidence illumination angle. The article according to Embodiment 12 or 13. * The article has an a value of approximately -4 to +4 by reflection, and a b value of -6 to -1 by reflection. Each of the a value and the b value is measured in the optical film structure at a substantially normal incidence illumination angle. The article according to Embodiment 12 or 13.

[0202] Embodiment 15 The article has an a value of approximately -4 to +4 by reflection, and a b value of -6 to -1 by reflection. Each of the a value and the b value is measured in the optical film structure at a substantially normal incidence illumination angle. The article according to Embodiment 12 or 13. * The article has an a value of approximately -4 to +4 by reflection, and a b value of -6 to -1 by reflection. Each of the a value and the b value is measured in the optical film structure at a substantially normal incidence illumination angle. The article according to Embodiment 12 or 13. * The article has an a value of approximately -4 to +4 by reflection, and a b value of -6 to -1 by reflection. Each of the a value and the b value is measured in the optical film structure at a substantially normal incidence illumination angle. The article according to Embodiment 12 or 13. * The article has an a value of approximately -4 to +4 by reflection, and a b value of -6 to -1 by reflection. Each of the a value and the b value is measured in the optical film structure at a substantially normal incidence illumination angle. The article according to Embodiment 12 or 13. * The article has an a value of approximately -4 to +4 by reflection, and a b value of -6 to -1 by reflection. Each of the a value and the b value is measured in the optical film structure at a substantially normal incidence illumination angle. The article according to Embodiment 12 or 13.

[0203] Embodiment 16 The optical film structure has a residual stress in the range of approximately -1000 MPa (compression) to approximately +50 MPa (tension). The article according to any one of Embodiments 12 to 15.

[0204] Embodiment 17 The inorganic oxide substrate is made of a glass selected from the group consisting of soda-lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali aluminoborosilicate glass. The article according to any one of Embodiments 12 to 16.

[0205] Embodiment 18 The glass is chemically strengthened and has a compressive stress (CS) layer with a peak CS of 250 MPa or more. The CS layer extends into the chemically strengthened glass to a compressive depth (DOC) of approximately 10 micrometers or more from the first main surface. The article according to Embodiment 17.

[0206] Embodiment 19 The article according to any one of Embodiments 12 to 18, further comprising any one or more of a coating that is easy to clean, a diamond-shaped coating, and a scratch-resistant coating, disposed on the optical film structure.

[0207] Embodiment 20 The article according to any one of Embodiments 12 to 19, wherein the plurality of alternating high refractive index layers and low refractive index layers are at least four layers, each layer contains one or more of a silicon-containing oxide and a silicon-containing nitride, the silicon-containing oxide is silicon oxide, and the silicon-containing nitride is silicon nitride.

[0208] Embodiment 21 The article according to any one of Embodiments 12 to 20, wherein the physical thickness of the high refractive index layer adjacent to the capping low refractive index layer is about 70 nm or more, and the physical thickness of the capping low refractive index layer is about 80 nm or more.

[0209] Embodiment 22 The article according to any one of Embodiments 12 to 21, wherein the article exhibits a specular reflection light removal (SEC) value of 0.2% or less as measured according to the Alumina SCE test.

[0210] Embodiment 23 An inorganic oxide substrate having opposite main surfaces, and An optical film structure disposed on the first main surface of the inorganic oxide substrate, having a physical thickness of about 50 nm to less than 500 nm, and having a plurality of alternating high refractive index layers and low refractive index layers and a capping low refractive index layer with a first low refractive index layer on the first main surface of the substrate. An article comprising Each layer contains one or more of a silicon-containing oxide, a silicon-containing nitride, and a silicon-containing oxynitride. The refractive index of the low refractive index layer is within the range of the refractive index of the inorganic oxide substrate such that the refractive index of the low refractive index layer is less than about 1.8, and the high refractive index layer has a refractive index greater than 1.8. The optical film structure further includes the high refractive index layer having a volume of 30% or more. Furthermore, the article exhibits a single-sided bright-field average reflectance of less than 1%.

[0211] Embodiment 24 The article according to Embodiment 23, wherein the optical film structure further includes the high refractive index layer having a volume of 50% or more.

[0212] Embodiment 25 The article has an a value of about -10 to +5 upon reflection, * and a b value of -10 to +2 upon reflection, * wherein each of the a value * and the b value * is measured on the optical film structure at a substantially perpendicular incident illumination angle, the article according to Embodiment 23 or 24.

[0213] Embodiment 26 The article has an a value of about -4 to +4 upon reflection, * and a b value of -6 to -1 upon reflection, * wherein each of the a value * and the b value * is measured on the optical film structure at a substantially perpendicular incident illumination angle, the article according to Embodiment 23 or 24.

[0214] Embodiment 27 The article according to any one of Embodiments 23 to 26, wherein the optical film structure has a residual stress in the range of about -1000 MPa (compression) to about +50 MPa (tension).

[0215] Embodiment 28 The article according to any one of Embodiments 23 to 27, wherein the inorganic oxide substrate is made of a glass selected from the group consisting of soda-lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali aluminoborosilicate glass.

[0216] Embodiment 29 The article according to embodiment 28, wherein the glass is chemically strengthened and has a compressive stress (CS) layer with a peak CS of 250 MPa or more, and the CS layer extends into the chemically strengthened glass to a compressive depth (DOC) of about 10 micrometers or more from the first major surface.

[0217] Embodiment 30 The article according to any one of embodiments 23 to 29, further comprising at least one of an easily cleanable coating, a diamond-like coating, and a scratch-resistant coating disposed on the optical film structure.

[0218] Embodiment 31 The article according to any one of embodiments 23 to 30, wherein the plurality of alternating high refractive index layers and low refractive index layers are at least four layers, each layer contains one or more of a silicon-containing oxide and a silicon-containing nitride, the silicon-containing oxide is silicon oxide, and the silicon-containing nitride is silicon nitride.

[0219] Embodiment 32 The article according to any one of embodiments 23 to 31, wherein the high refractive index layer adjacent to the capping low refractive index layer has a physical thickness of about 70 nm or more, and the capping low refractive index layer has a physical thickness of about 80 nm or more.

[0220] Embodiment 33 The article according to any one of embodiments 23 to 32, wherein the article exhibits a specular reflection elimination (SEC) value of 0.2% or less as measured according to the Alumina SCE test.

[0221] Embodiment 34 An inorganic oxide substrate having opposite major surfaces, and An optical film structure disposed on the first major surface of the inorganic oxide substrate, the optical film structure having a plurality of alternating high refractive index layers and low refractive index layers and a capping low refractive index layer with a first low refractive index layer on the first major surface of the substrate. An article comprising The refractive index of the low refractive index layer is within the range of the refractive index of the substrate such that the refractive index of the low refractive index layer is less than about 1.8, and the high refractive index layer has a refractive index greater than 1.8. The article exhibits a hardness of 8 GPa or more as measured at an indentation depth of about 100 nm or a maximum hardness of 9 GPa or more as measured over an indentation depth range from about 100 nm to about 500 nm, and the hardness and the maximum hardness are measured by a Berkovich indenter hardness test. The article exhibits a single-sided specular average reflectance of less than 1%. The optical film structure further includes the high refractive index layer in an amount of 35% or more by volume. The high refractive index layer exhibits a maximum hardness of 18 GPa or more as measured by a Berkovich indenter hardness test over an indentation depth from about 100 nm to about 500 nm on a hardness test laminate in which the high refractive index layer having a physical thickness of about 2 micrometers is disposed on the inorganic oxide substrate. Furthermore, the article has an a * value of about -10 to +5 upon reflection and a b * value of -10 to +2 upon reflection, and each of the a * value and the b * value is measured for the optical film structure at a normal incidence illumination angle.

[0222] Embodiment 35 The article according to Embodiment 34, wherein the high refractive index layer exhibits a maximum hardness of 21 GPa or more as measured by a Berkovich indenter hardness test over an indentation depth from about 100 nm to about 500 nm on a hardness test laminate in which the high refractive index layer having a physical thickness of about 2 micrometers is disposed on the inorganic oxide substrate.

[0223] Embodiment 36 The article according to Embodiment 34 or 35, wherein the article exhibits a specular light removal (SEC) value of 0.2% or less as measured according to the Alumina SCE test.

[0224] Embodiment 37 The article according to any one of Embodiments 1 to 11, wherein the article exhibits a one-sided average transmittance of 87% or more in the infrared spectrum from 900 nm to 1000 nm.

[0225] Embodiment 38 The article according to any one of Embodiments 12 to 22, wherein the article exhibits a one-sided average transmittance of 87% or more in the infrared spectrum from 900 nm to 1000 nm.

[0226] Embodiment 39 The article according to any one of Embodiments 23 to 33, wherein the article exhibits a one-sided average transmittance of 87% or more in the infrared spectrum from 900 nm to 1000 nm.

[0227] Embodiment 40 The article according to any one of Embodiments 34 to 36, wherein the article exhibits a one-sided average transmittance of 87% or more in the infrared spectrum from 900 nm to 1000 nm.

[0228] Embodiment 41 A housing having a front surface, a back surface, and side surfaces, An electric component that is at least partially inside the housing and includes a control device, a memory, and a display on or adjacent to the front surface of the housing, and A cover substrate disposed on the display, A household electronic device comprising: A household electronic device, wherein at least one of a part of the housing or the cover substrate is made of the article according to any one of Embodiments 1 to 40.

[0229] Embodiment 42 An inorganic oxide substrate having opposite main surfaces, and An optical film structure disposed on the first main surface of the inorganic oxide substrate, the optical film structure having a physical thickness of about 50 nm to less than 500 nm and including one or more of a silicon-containing oxide, a silicon-containing nitride, and a silicon-containing oxynitride, An article comprising: The article exhibits a hardness of 8 GPa or more when measured at an indentation depth of about 100 nm, or a maximum hardness of 9 GPa or more when measured over an indentation depth range from about 100 nm to about 500 nm, and the hardness and the maximum hardness are measured by a Berkovich indenter hardness test. Furthermore, the article exhibits a single-sided specular average reflectance of less than 1%.

[0230] Embodiment 43 The article has an a value of about -10 to +5 upon reflection, * and a b value of -10 to +2 upon reflection, * where each of the a value * and the b value * is measured for the optical film structure at a substantially normal incidence illumination angle, the article according to Embodiment 42.

[0231] Embodiment 44 The article has an a value of about -4 to +4 upon reflection, * and a b value of -6 to -1 upon reflection, * where each of the a value * and the b value * is measured for the optical film structure at a substantially normal incidence illumination angle, the article according to Embodiment 42.

[0232] Embodiment 45 The optical film structure has a residual stress in the range of about -1000 MPa (compression) to about +50 MPa (tension), the article according to any one of Embodiments 42 to 44.

[0233] Embodiment 46 The optical film structure includes a silicon-containing oxide and a silicon-containing nitride, the silicon-containing oxide is silicon oxide, and the silicon-containing nitride is silicon nitride, the article according to any one of Embodiments 42 to 45.

[0234] Embodiment 47 The article according to any one of Embodiments 42 to 46, further comprising any one or more of an easily cleanable coating, a diamond-shaped coating, and an abrasion-resistant coating disposed on the optical film structure.

[0235] Embodiment 48 The article according to any one of Embodiments 42 to 47, wherein the article exhibits a specular reflectance removal (SEC) value of 0.2% or less as measured according to the Alumina SCE test.

[0236] Embodiment 49 The article according to any one of Embodiments 42 to 48, wherein the inorganic oxide substrate is a glass-ceramic substrate.

[0237] Embodiment 50 A housing having a front surface, a back surface, and side surfaces, An electrical component that is at least partially inside the housing and includes a control device, a memory, and a display on or adjacent to the front surface of the housing, and A cover substrate disposed on the display, A household electronic device comprising: A household electronic device, wherein at least one of a part of the housing or the cover substrate is made of the article according to any one of Embodiments 42 to 49.

[0238] Embodiment 51 An inorganic oxide substrate having opposite main surfaces, and An optical film structure disposed on a first main surface of the inorganic oxide substrate, the optical film structure having a physical thickness of from about 50 nm to less than 500 nm and having a plurality of alternating high refractive index layers and low refractive index layers and a capping low refractive index layer with a first low refractive index layer on the first main surface of the substrate, An article comprising: Each layer contains one or more of a silicon-containing oxide, a silicon-containing nitride, and a silicon-containing oxynitride, The refractive index of the low refractive index layer is within the range of the refractive index of the inorganic oxide substrate such that the refractive index of the low refractive index layer is less than about 1.8, and the high refractive index layer has a refractive index greater than 1.8. The optical film structure further includes the high refractive index layer at 30% or more by volume. Furthermore, the article exhibits a single-sided specular average reflectance of less than 1%.

Explanation of Signs

[0239] 100 Article 110 Substrate 112, 114 Main surfaces 116, 118 Cover surfaces 120 Anti-reflection coating 120A, 120B, 120C Multiple layers 122 Anti-reflection surface 130 Multiple periods 130A Low RI layer 130B High RI layer 131 Capping layer 140 Additional coating 400 Household electronic device 402 Housing 404 Front surface 406 Rear surface 408 Side surface 410, 564, 576, 592 Display 412 Cover substrate 540 Vehicle interior 544, 548, 552 Vehicle interior system 556 Center console base 560, 572, 588 Surface 568 Dashboard base 580 Instrument panel 586 Handle base

Claims

1. an inorganic oxide substrate having opposing major surfaces; an optical film structure disposed on a first major surface of the inorganic oxide substrate, the optical film structure having a physical thickness of from 50 nm to less than 500 nm, the optical film structure having a plurality of alternating high and low refractive index layers and a capping low refractive index layer with a first low refractive index layer on the first major surface of the inorganic oxide substrate; An article comprising: each low refractive index layer comprises a silicon-containing oxide and each high refractive index layer comprises a silicon-containing nitride or a silicon-containing oxynitride; the article exhibits a hardness of 8 GPa or greater measured at an indentation depth of 100 nm, or a maximum hardness of 9 GPa or greater measured over an indentation depth range of 100 nm to 300 nm, the hardness and maximum hardness being measured by Berkovich indentation hardness testing; the high refractive index layer adjacent to the capping low refractive index layer has an optical thickness of 45 nm to 450 nm and is the thickest layer of the optical film structure; The article, wherein the first low refractive index layer is in direct contact with a first major surface of the inorganic oxide substrate.

2. The article of claim 1 , wherein the inorganic oxide substrate comprises a glass ceramic or a glass selected from the group consisting of soda-lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali aluminoborosilicate glass.

3. The article of claim 1 or 2, further comprising one or more of an easy-to-clean coating, a diamond-like coating, and a scratch-resistant coating disposed on the optical film structure.

4. 4. The article of claim 1, wherein the article exhibits a single-sided photopic average reflectance of less than 2%.

5. The article has a reflectance of -10 to +5. ＊ value, and b from -10 to +2 in reflection ＊ The value of a ＊ value and the b ＊ 5. The article of claim 1, wherein each of the values ​​is measured at approximately a normal incidence illumination angle on the optical film structure.

6. a housing having a front, a back, and sides; electrical components at least partially within the housing, the electrical components including a controller, memory, and a display on or adjacent to a front surface of the housing; and a cover substrate disposed over the display; A household electronic device comprising: A consumer electronic device, wherein at least one of a portion of the housing or the cover substrate comprises an article according to any one of claims 1 to 5.

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