Translucent anti-reflective assemblies for dead-front display applications

Abstract

The cover article (100) for a display panel includes a substrate (110), an inner layer film (130b) disposed on the outer major surface of the substrate (110), and an outer layer film (130a) disposed on the inner layer film. The outer layer film (130a) includes a plurality of alternating high and low refractive index layers. The high refractive index layer (130b) of the outer layer film (130a) includes a metal oxide. The inner layer film (130b) includes one or more absorbing layers (150) having an average extinction coefficient of 1.3 or greater from 400 nm to 700 nm. The one or more absorbing layers (150) are formed from a metal of the metal oxide included in the outer layer film (130a) rather than an oxide. The article exhibits a dead-front color shift of less than 7.0 at incident measurement angles of 0° to 90°, as measured relative to a black matrix material disposed on the substrate (110).

Description

[Technical Field]

[0001] The present disclosure relates to a cover article for a dead-front display, and more particularly to a vehicle interior system including a dead-front cover article with translucent and anti-reflective properties. [Background technology]

[0002] In various applications involving displays, it is desirable to have a display or functional surface that has a dead-front appearance. Generally, a dead-front appearance is a way of concealing a display or functional surface so that there is a seamless transition between the display area and the non-display area, or between the dead-front area of ​​an article and the non-dead-front area or other surface. For example, in a typical display with a glass or plastic cover surface, the edges of the display (or the transition from the display area to the non-display area) are visible even when the display is turned off. However, from an aesthetic or design standpoint, it is often desirable to have a dead-front appearance when the display is turned off, such that the display area and the non-display area appear indistinguishable from one another and the cover surface presents a unified appearance.

[0003] One application where a dead-front appearance is desirable is in automotive interiors, including in-car displays or capacitive touch interfaces, as well as other applications in consumer mobile or home electronics, including mobile devices and home appliances. However, achieving both a good dead-front appearance and a high-quality display when the display is on can be difficult.

[0004] A conventional approach to achieving a dead-front appearance involves depositing a non-conductive black ink on one major surface of a transparent substrate and applying an anti-reflective (AR) coating to the opposite major surface of the substrate. Screen printing or inkjet printing processes and equipment can be used for the black ink layer, while vacuum deposition processes and equipment can be used for the AR coating. Ultimately, the conventional approach is expensive because it requires at least two separate deposition processes using different deposition equipment. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, there is a need for cover articles for dead-front displays, particularly for capacitive touch screen applications such as vehicle interior systems, including dead-front cover articles with translucent and anti-reflective properties that can be manufactured with processes and equipment that result in reduced manufacturing costs. [Means for solving the problem]

[0006] According to one embodiment of the present disclosure, a cover article for a display panel includes a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. The outer layered film includes a plurality of alternating high and low refractive index layers. Each of the high refractive index layers has a refractive index greater than that of each of the low refractive index layers. The high refractive index layer of the outer layered film includes a metal oxide. The inner layered film includes one or more absorbing layers having an average extinction coefficient of 1.3 or greater from 400 nm to 700 nm. The one or more absorbing layers are formed from a metal of the metal oxide included in the outer layered film, rather than an oxide. The article exhibits a dead-front color shift (ΔE) of less than 7.0 at incident measurement angles of 0° to 90°, as measured relative to a black matrix material disposed on the substrate.

[0007] According to another aspect of the present disclosure, a cover article for a display panel includes a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. The outer layered film includes a plurality of alternating high and low refractive index layers. Each of the high refractive index layers has a refractive index greater than that of each of the low refractive index layers. The high refractive index layer of the outer layered film includes Nb2O5. The inner layered film includes one or more absorbing layers containing Nb not in oxide form. The article exhibits a dead-front color shift (ΔE) of less than 7.0 at incident measurement angles of 0° to 90°, as measured relative to a black matrix material disposed on the substrate.

[0008] According to another aspect of the present disclosure, a cover article for a display panel includes a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. The outer layered film includes a plurality of alternating high and low refractive index layers. Each of the high refractive index layers has a refractive index greater than that of each of the low refractive index layers. The high refractive index layer of the outer layered film includes Nb2O5. The inner layered film includes an inner low refractive index layer disposed closest to the substrate; and a plurality of alternating periods, each period including a Nb layer having a first thickness and a low refractive index layer having a second thickness. Each of the low refractive index layers in the inner layered film has a refractive index at 550 nm that is less than that of the Nb layer. The plurality of alternating periods includes at least three periods.

[0009] According to another aspect of the present disclosure, there is provided a cover article for a display panel, comprising: a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other, the substrate comprising a glass, glass ceramic, or ceramic material; an inner layer film disposed on the outer major surface of the substrate; and an outer layer film disposed on the inner layer film. One or both of the inner layer film and the outer layer film comprises one or more absorbing layers. The outer layer film comprises a plurality of alternating high and low refractive index layers. Each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers. Each absorbing layer has at least 10 5 The article exhibits a sheet resistance of Ω / sq. Furthermore, the article exhibits a dead-front color shift (ΔE) of less than 4.0 at incident measurement angles of 0° to 90° as measured relative to a control article comprising a substrate glass, glass-ceramic, or ceramic material and a standard black matrix disposed on the glass, glass-ceramic, or ceramic material.

[0010] According to another aspect of the present disclosure, there is provided a cover article for a display panel, comprising: a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other, the substrate comprising a glass, glass ceramic, or ceramic material; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. The inner layered film comprises a plurality of low refractive index layers and an absorbing layer. The outer layered film comprises a plurality of alternating high refractive index layers and low refractive index layers. Each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers. Additionally, each absorbing layer comprises a metal or metal alloy. Each absorbing layer comprises at least 10 5 They exhibit sheet resistances of Ω / sq and extinction coefficients greater than 0.05 in the visible spectrum from 400 nm to 700 nm.

[0011] According to a further aspect of the present disclosure, there is provided a cover article for a display panel, comprising: a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other, the substrate comprising a glass, glass ceramic, or ceramic material; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. One or both of the inner layered film and the outer layered film comprise one or more absorbing layers. The outer layered film comprises a plurality of alternating high and low refractive index layers. Each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers. Additionally, each absorbing layer comprises a diamond-like carbon (DLC) material. Each absorbing layer comprises at least 10 5 They exhibit sheet resistances of Ω / sq and extinction coefficients of about 0.05 to about 0.4 in the visible spectrum from 400 nm to 700 nm.

[0012] According to another aspect of the present disclosure, there is provided a cover article for a display panel, comprising: a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other, the substrate comprising a glass, glass ceramic, or ceramic material; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. The inner layered film comprises a plurality of low refractive index and one or more absorbing layers. The outer layered film comprises a plurality of alternating high refractive index and low refractive index layers. Each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers. Additionally, each absorbing layer is a silicon-metal alloy, including Si—Al, Si—Sn, Si—Zn, or a combination thereof. Each absorbing layer has at least 10 5 They exhibit sheet resistances of Ω / sq and extinction coefficients greater than 1.0 in the visible spectrum from 400 nm to 700 nm.

[0013] Additional features and advantages will be set forth in the following detailed description, and in part will be readily apparent to those skilled in the art from that description, or may be learned by practicing the embodiments described herein, including the following detailed description, claims, and accompanying drawings.

[0014] It is to be understood that both the foregoing general description and the following detailed description are merely exemplary and are intended to provide an overview or framework for understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding, and are incorporated into and constitute a part of this specification. The drawings illustrate one or more embodiments, and together with the description, serve to explain the principles and operation of the various embodiments. [Brief explanation of the drawings]

[0015] [Figure 1A] 1 is a cross-sectional side view of a cover article according to one or more embodiments described herein. [Figure 1B] 1 is a cross-sectional side view of a cover article according to one or more embodiments described herein. [Figure 1C] 1 is a cross-sectional side view of a cover article according to one or more embodiments described herein. [Figure 1D] 1 is a cross-sectional side view of a cover article according to one or more embodiments described herein. [Figure 2A] 1 is a plot of the inverse of sheet resistance versus film thickness for chromium films of various thicknesses deposited at 23° C. and 325° C. according to an embodiment of the present disclosure. [Figure 2B] 1 is a plot of absorptance versus wavelength for a glass substrate and chromium films of various thicknesses deposited thereon at 23° C., according to an embodiment of the present disclosure; [Figure 2C] 1 is a scanning electron microscope (SEM) image of a chromium film having a thickness of 1.8 nm deposited at 23° C. according to an embodiment of the present disclosure. [Figure 2D] 1 is a scanning electron microscope (SEM) image of a chromium film having a thickness of 1.3 nm deposited at 325° C. according to an embodiment of the present disclosure. [Figure 3A] 1 is a plot of the inverse of sheet resistance versus film thickness for nickel films of various thicknesses deposited at 23° C. and 325° C. according to an embodiment of the present disclosure. [Figure 3B]1 is a plot of absorptance versus wavelength for nickel films of various thicknesses deposited on glass substrates at 23° C. according to an embodiment of the present disclosure. [Figure 4A] 10A and 10B are plots of transmittance versus wavelength for one, two, and three chrome layers at the 0.5 nm thickness level with a thin silica layer deposited between each chrome layer, according to an embodiment of the present disclosure. [Figure 4B] 10A and 10B are plots of transmittance versus wavelength for one, two, and three chrome layers at the 1 nm thickness level with a thin silica layer deposited between each chrome layer, according to an embodiment of the present disclosure. [Figure 4C] 10A and 10B are plots of transmittance versus wavelength for one, two, and three chrome layers at the 2 nm thickness level with a thin silica layer deposited between each chrome layer, according to an embodiment of the present disclosure. [Figure 5] Plots of reflectance, transmittance, and absorptance versus wavelength for exemplary cover articles of the present disclosure employing a chrome absorbing layer. [Figure 6] Plots of reflectance, transmittance, and absorptance versus wavelength for exemplary cover articles of the present disclosure employing a nickel absorbing layer. [Figure 7] 1 is a plot of the refractive index and extinction coefficient (n, k) of a diamond-like carbon (DLC) layer deposited by a plasma-enhanced chemical vapor deposition process according to one embodiment of the present disclosure; [Figure 8A] Plots of reflectance, transmittance, and absorptance versus wavelength for an exemplary cover article of the present disclosure employing a single DLC layer. [Figure 8B] Plots of reflectance, transmittance, and absorptance versus wavelength for an exemplary cover article of the present disclosure employing five DLC layers. [Figure 8C] 1 is a plot of reflectance, transmittance, and absorptance versus wavelength for an exemplary cover article of the present disclosure employing three DLC layers. [Figure 9A] 1 is a plot of reflectance and transmittance versus wavelength for exemplary cover articles of the present disclosure employing a single DLC layer at each of different thickness levels. [Figure 9B]Plot of the reflected color of the first surface at normal incidence measurement angles with a D65 illuminant for the exemplary cover article of FIG. 9A and a comparative cover article using a black matrix material. [Figure 10A] 9B is an optical image of a cover article with one half having the structure of FIG. 9A and the other half using the black matrix material of FIG. 9B according to an embodiment of the present disclosure. [Figure 10B] 9A and 9B, measured at angles of incidence of 0°, 45°, and 90°, according to embodiments of the present disclosure. [Figure 11A] 1 is a plot of the ratio of extinction coefficients (k) at 400 nm / 550 nm and 780 nm / 440 nm for Si—Al films as a function of Si volume fraction, according to an embodiment of the present disclosure. [Figure 11B] 1 is a plot of reflectance versus wavelength for three Si—Al film compositions at two film thicknesses according to an embodiment of the present disclosure. [Figure 11C] 1 is a plot of transmittance versus wavelength for three Si—Al film compositions at two film thicknesses according to an embodiment of the present disclosure. [Figure 11D] 1 is a plot of absorptance versus wavelength for three Si—Al film compositions at two film thicknesses according to an embodiment of the present disclosure. [Figure 12] 1 is a plot of the ratio of extinction coefficients (k) at 400 nm / 550 nm and 780 nm / 440 nm for Si—Zn films as a function of Si volume fraction, according to an embodiment of the present disclosure. [Figure 13] 1 is a plot of the ratio of extinction coefficients (k) at 400 nm / 550 nm and 780 nm / 440 nm for Si—Sn films as a function of Si volume fraction, according to an embodiment of the present disclosure. [Figure 14] Plot of the ratio of extinction coefficients (k) at 400 nm / 550 nm and 780 nm / 440 nm for comparative Si-Cu films as a function of Si volume fraction [Figure 15] Plot of the ratio of extinction coefficients (k) at 400 nm / 550 nm and 780 nm / 440 nm for comparative Si-Cr films as a function of Si volume fraction [Figure 16A]1 is a plot of simulated reflectance, transmittance, and absorptance versus wavelength for an exemplary cover article of the present disclosure employing a Si—Al absorbing layer. [Figure 16B] 16B is a simulated color plot of x and y coordinates on the 1931 CIE scale for the cover article of FIG. 16A according to one embodiment of the present disclosure. [Figure 17] Plot of extinction coefficient (k) and refractive index (n) for Nb films from 380nm to 780nm [Figure 18] 1 is a plot of reflectance, transmittance, and absorptance versus wavelength for an exemplary cover article of the present disclosure that includes a Nb absorbing layer in the inner layered film. [Figure 19] 1 is a plot of reflectance and transmittance versus wavelength for an exemplary cover article of the present disclosure that includes a Nb absorbing layer in the inner layered film. DETAILED DESCRIPTION OF THE INVENTION

[0016] In the following detailed description, for purposes of explanation and not limitation, exemplary embodiments disclosing specific details are set forth to provide a thorough understanding of various principles of the present disclosure. However, it will be apparent to one 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. Furthermore, descriptions of well-known devices, methods, and materials may be omitted so as not to obscure the description of various principles of the present disclosure. Finally, wherever applicable, like reference numerals refer to like elements.

[0017] Ranges can be expressed herein as from "about" one particular value and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Furthermore, when one or both endpoints of a range, or any particular value, are expressed using the term "about," each of such endpoints or values ​​modified by "about" can vary within ±5% of the stated endpoint or value. Similarly, when values ​​are expressed as approximations, for example, by use of the antecedent "about," it will be understood that the particular value forms a separate embodiment. Moreover, it will be understood that each endpoint of a range is significant both in relation to the other endpoint, and independently of the other endpoint.

[0018] Directional terms used herein (e.g., up, down, right, left, front, back, upper, bottom) are made solely with reference to the depicted figures and are not intended to imply absolute directions.

[0019] Unless otherwise expressly stated, it is in no way intended that any method described herein be construed as requiring that its steps be performed in a particular order. Thus, where a method claim does not actually recite the order in which its steps are to be followed, or where the claims or specification do not expressly state that the steps are to be limited to a particular order, no order is intended to be inferred in any respect. This applies regardless of any implicit basis for interpretation, such as: logical considerations regarding the arrangement or operational flow of steps; plain meaning derived from grammatical organization or punctuation; or the number or type of embodiments described in the specification.

[0020] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an "a" "element" includes aspects having two or more such elements unless the context clearly dictates otherwise.

[0021] As used herein, the term "disposing" includes coating, depositing, and / or forming a material on a surface using methods known in the art. The disposed material may constitute a layer, as defined herein. As used herein, the phrase "disposing on" includes forming a material on a surface such that the material is in direct contact with the surface, as well as embodiments in which a material is formed on a surface with one or more intervening materials disposed between the material and the surface. The intervening material(s) may constitute a layer, as defined herein.

[0022] As used herein, the terms "low RI layer" and "high RI layer" refer to the relative refractive index ("RI") values ​​of layers of an optical film structure of a cover article according to the present disclosure (i.e., low RI layer < high RI layer). Thus, a low RI layer has a refractive index value that is lower than a high RI layer. Furthermore, as used herein, "low RI layer" and "low refractive index layer" have the same meaning and are interchangeable. Similarly, "high RI layer" and "high refractive index layer" have the same meaning and are interchangeable.

[0023] As used herein, the term "reinforced substrate" refers to a substrate used in a cover article of the present disclosure that has been strengthened by a method that imparts residual compressive stress. For example, a reinforced substrate can be formed by ion-exchanging larger ions with smaller ions at the surface of the substrate. Additionally, reinforced substrates can be formed using other strengthening methods known in the art, such as heat tempering or using a mismatch in thermal expansion coefficients between portions of the substrate to create compressive stress regions and central tension regions.

[0024] As used herein, the term "transmittance" is defined as the percentage of incident optical power within a given wavelength range that is transmitted through a material (e.g., a cover article, a substrate, or an outer layered film, or a portion thereof). The term "reflectance" is similarly defined as the percentage of incident optical power within a given wavelength range that is reflected from a material (e.g., a cover article, a substrate, or an outer layered film, or a portion thereof). Transmittance and reflectance are measured using a specific linewidth. As used herein, "average transmittance" refers to the average amount of incident optical power transmitted through a material over a defined wavelength range, e.g., an "optical wavelength range," also defined herein as 400 nm to 700 nm. Unless otherwise specified, a suitable interval for average transmittance measurements is 5 nm. As used herein, "average reflectance" refers to the average amount of incident optical power reflected by a material. Unless otherwise specified, reflectance and transmittance measurements provided herein are for light having a normal angle of incidence to the reference material.

[0025] As used herein, "photopic reflectance" mimics the response of the human eye by weighting reflectance or transmittance, respectively, over the wavelength spectrum according to the sensitivity of the human eye. Photopic reflectance may also be defined as the luminance value or tristimulus Y value of reflected light, according to known conventions such as the CIE color space convention. As used herein, "average photopic reflectance" (R) for the wavelength range of 380 nm to 720 nm is used. p ) is defined as the product of the spectral reflectance R(λ) multiplied by the illuminant spectrum I(λ) and the CIE color matching function Υ(λ), in relation to the spectral response of the eye given by equation (1):

[0026]

number

[0027] Additionally, "average reflectance" can be determined across the visible spectrum or other wavelength range according to measurement principles understood by those skilled in the art of this disclosure. Unless otherwise specified, all reflectance values ​​reported or referenced in this disclosure relate to testing through the outer layered film of the cover article and from the major surface of the substrate on which the outer layered film is disposed, e.g., average photopic reflectance of the "first surface," average reflectance of the "first surface" over a particular wavelength range, etc.

[0028] The ease of use of a given display can be related to the total amount of reflectance in the display system. Photopic reflectance is particularly important for displays used in vehicles. Reducing the reflectance of the display system or a cover article over the display can reduce multiple reflections that can create "ghost images" in the display system. Reflectance therefore has an important bearing on the image quality of the display system.

[0029] As used herein, "photopic transmittance" (T p ) is defined as the product of the spectral transmittance T(λ) multiplied by the illuminant spectrum I(λ) and the CIE color matching function Υ(λ), in relation to the spectral response of the eye given by equation (2):

[0030]

number

[0031] Additionally, "average transmittance" can be determined across the visible spectrum or other wavelength range according to measurement principles understood by those skilled in the art of this disclosure. Unless otherwise specified, all transmittance values ​​reported or referenced in this disclosure relate to testing through both the major surface of the substrate and the outer layered film of the cover article, e.g., "two-surface" average photopic transmittance, "two-surface" average transmittance over a particular wavelength range, etc.

[0032] As previously mentioned, the cover articles and materials of the present disclosure are described in terms of their reflectance and transmittance properties. The cover articles and materials of the present disclosure are also described in terms of their absorbance properties, as calculated or expressed from the following equation (3): Transmittance (T) = 100% - Reflectance (R) - Absorption rate (A) (3) Therefore, equation (3) can be used to calculate the absorptance (A) value (interchangeably referred to as "absorption" in this disclosure) using the measured transmittance (T) and reflectance (R) values.

[0033] The thickness and refractive index (n), as well as the extinction coefficient (k) of the materials and articles disclosed herein, unless otherwise noted, were determined using variable angle spectroscopic ellipsometry, which is based on Maxwell's equations and the Fresnel reflection or transmission equations for polarized light, expressed in terms of psi (Ψ) and delta (Δ) according to equation (4): tan(Ψ)·e (iΔ) =ρ=r p / r s (4) where r p and r sis the complex Fresnel reflection coefficient for p-polarized light (in the plane of incidence) and s-polarized light (perpendicular to the plane of incidence) of the sample, where the complex ratio ρ is measured as a function of both wavelength and angle of incidence. The refractive index (n) and extinction coefficient (k) values ​​reported herein were determined for light having a wavelength of 550 nm unless otherwise reported. Additional information regarding variable angle spectroscopic ellipsometry can be found in: "Overview of Variable Angle Spectroscopic Ellipsometry (VASE), Part I: Basic Theory and Typical Applications," Critical Reviews of Optical Science and Technology, Volume CR72, pages 3-28, 1999. Examples of the present disclosure were analyzed using a J.A. Woollam W-200 spectroscopic ellipsometer. It is understood that other instruments and methods, different operating optical ranges, and / or different angles of incidence can also be used to determine the thickness or optical properties of the materials disclosed herein, with the necessary scaling.

[0034] As used herein, "transmitted color" and "reflected color" refer to the CIE L * , a * , b * Color coordinates in the color system (L * , a * , and b * ), refer to the color transmitted through or reflected by the cover articles of the present disclosure. Furthermore, "transmitted color" and "reflected color" refer to the color measured at a given measured angle of incidence (e.g., at 0 degrees (°), 45 degrees, or 90 degrees) and / or over a range of measured angles of incidence, e.g., from 0 degrees to 10 degrees, from 0 degrees to 45 degrees, from 0 degrees to 90 degrees, etc., as measured by the CIE L * , a * , b * It can be given by color coordinates.

[0035] To evaluate dead front appearance, cover articles of the present disclosure can be evaluated for their dead front color shift (ΔE) according to the following formula (5):

[0036]

number

[0037] where L * VA , a * VA , and b * VA is the CIE L of a portion of a display panel equipped with a cover article of the present disclosure. * , a * , b * is the transmission or reflection color coordinate, L * BM , a * BM , and b * BM are CIE L values ​​for some display panels with comparative black matrix ink materials. * , a * , b * These are transmission or reflection color coordinates. Unless otherwise specified, the comparative black matrix ink material is a polymer resin with the following color values: L*=4.79, a*=0.03, and b*=0.18. Furthermore, like the transmission and reflection color values, the dead-front color shift (ΔE) can be evaluated and reported using various measurement angles of incidence and ranges (e.g., 0°, 45°, 90°, 0° to 45°, etc.). Thus, the smaller the dead-front color shift (ΔE) value, the better the dead-front appearance of a given cover article sample.

[0038] Generally, the present disclosure is directed to cover articles that utilize outer and inner layered films disposed on a glass substrate (e.g., Corning® Gorilla Glass® products), a glass-ceramic substrate, or a ceramic substrate. These cover articles can exhibit translucency (e.g., 5-80% transmittance) and anti-reflective properties (e.g., photopic reflectance <4%), as well as a dead-front appearance (e.g., low ΔE color shift, ΔE <7.0 or 4.0). Additionally, the cover articles of the present disclosure can exhibit sheet resistance values ​​suitable to enable their use in capacitive touchscreen applications.

[0039] Furthermore, the cover articles of the present disclosure can be manufactured in a manner that reduces manufacturing costs over conventional dead-front configurations and processes by depositing all layers on one major surface of the substrate using the same deposition equipment (e.g., plasma-enhanced chemical vapor deposition, vacuum metallization, vacuum sputtering, etc.) in a single process sequence. In embodiments, in addition to the antireflective coating stack, an absorber layer is disposed on the substrate, and this absorber layer can be deposited on the substrate using raw materials (e.g., sputtering target, evaporation source material) that are common to one of the layers of the antireflective coating stack to streamline the manufacturing process. Such an absorber layer can be integrated with existing processes for manufacturing antireflective films, thereby reducing implementation costs. The cover articles of the present disclosure can be used in a variety of display applications that benefit from a dead-front appearance (e.g., mobile phone displays, vehicle dashboard displays, consumer electronics displays, etc.).

[0040] Reference will now be made in detail to various embodiments of cover articles (e.g., for display panel applications), examples of which are illustrated in the accompanying FIGS. 1A-1D. Referring to FIG. 1A, a cover article 100 according to one or more embodiments disclosed herein can include a substrate 110, an inner layer film 130b disposed on the substrate, and an outer layer film 130a disposed on the inner layer film 130b. The substrate 110 can include opposing major surfaces 112, 114 and can comprise a glass, glass-ceramic, or ceramic material. In FIG. 1A, the inner layer film 130b is shown disposed on the outer major surface 112, and the outer layer film 130a is shown disposed on the inner layer film 130b; however, in some implementations, the outer layer film and the inner layer film 130a, 130b can be disposed on the inner major surface 114 of the substrate 110 in addition to or instead of being disposed on the outer major surface 112.

[0041] 1A, the outer layered film 130a (also referred to herein as the "anti-reflective layered film 130a" or "AR layered film 130a") forms the outermost surface 122. Furthermore, the outermost surface 122 of the outer layered film 130a can form an air interface and generally defines the edge of the outer layered film 130a as well as the edge of the entire cover article 100 (e.g., if no additional coating, such as an easy-clean coating described herein, is disposed on the outer layered film 130a). The substrate 110 can be substantially transparent, as described herein.

[0042] The outer layered film 130a includes at least one layer of at least one material. The term "layer" can include a single layer or one or more sub-layers. Such sub-layers may be in direct contact with one another. The sub-layers can 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, the layer can include one or more continuous, uninterrupted layers and / or one or more discontinuous, interrupted layers (i.e., layers having different materials formed adjacent to one another). The layers or sub-layers can be formed by any method known in the art, including discrete or continuous deposition processes. In one or more embodiments, the layers can be formed using only continuous deposition processes or only discrete deposition processes.

[0043] The thickness of the outer layered film 130a can be about 0.20 μm or greater. In some examples, the thickness of the outer layered film 130a can be in the range of about 0.20 μm to about 20 μm, about 0.25 μm to about 20 μm, about 0.25 μm to about 15 μm, about 0.25 μm to about 10 μm, about 0.25 μm to about 5 μm, about 0.5 μm to about 10 μm, about 0.5 μm to about 5 μm, about 0.5 μm to about 4 μm, and all thickness values ​​of the outer layered film 130a between these thickness values. For example, the thickness of the outer layered film 130a can be approximately 0.20 μm, 0.25 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.25 μm, 1.5 μm, 1.75 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, and all thickness values ​​therebetween.

[0044] As also shown in FIG. 1A , the outer layered film 130a includes multiple layers (130A, 130B). In one or more embodiments, the outer layered film 130a can include a period including two or more layers. The outer layered film 130a can include one or more such periods. In one or more embodiments, the two or more layers can be characterized by different refractive indices from one another. Each layer within each period can have a different physical thickness from one another (i.e., corresponding layers within successive periods can have different physical thicknesses). In one embodiment, the period 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 can be about 0.01 or more, about 0.05 or more, about 0.1 or more, or even about 0.2 or more.

[0045] As shown in FIG. 1A , according to some embodiments, the cover article 100 can be configured such that the outer layered film 130a can include multiple periods. A single period can include a first low-RI layer 130A and a second high-RI layer 130B. When multiple periods are provided, the first low-RI layer 130A (designated "L" in the figures) and the second high-RI layer 130B (designated "H" in the figures) are alternately arranged in the following layer order: L / H / L / H or H / L / H / L. This makes the first low-RI layer 130A and the second high-RI layer 130B appear to be alternately arranged along the physical thickness of the outer layered film 130a. In the example of FIG. 1A , the outer layered film 130a includes two periods and one additional low-RI layer 130A in the stack according to the following order: L / H / L / H / L. In some embodiments, the outer layered film 130a can include up to 25 periods (also referred to herein as "N" periods, where N is an integer). For example, the outer layered film 130a can include 2 to 20 periods (i.e., N=2-20), 2 to 15 periods, 2 to 12 periods, 2 to 10 periods, 2 to 12 periods, 2 to 8 periods, 2 to 6 periods, or any other period within these ranges. For example, the outer layered film 130a can include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 periods.

[0046] Optionally, as shown in exemplary form in FIG. 1A, additional low RI layers 130A or high RI layers 130B can be disposed on top of the periods of the outer layered film 130a and are therefore considered to be part of the stack of the outer layered film 130a (in such an embodiment, the outer layered film 130a includes an odd number of layers, including multiple periods and additional layers, and the additional layers are either low RI layers 130A or high RI layers 130B).

[0047] Various configurations for the outer layered film 130a are also contemplated herein. For example, as described herein with respect to FIG. 1B, the outer layered film 130a can include one or more absorbing layers 150 that replace at least one of the high-RI layers 130B shown in FIG. 1A. In another example, as described herein with respect to FIG. 1C, one or more absorbing layers 150 may be incorporated into the outer layered film 130a. In such embodiments, the one or more absorbing layers 150 can be disposed between two low-RI layers 130A (i.e., instead of the single high-RI layer 130B shown in FIG. 1A), between two high-RI layers 130B (i.e., instead of the single low-RI layer 130A shown in FIG. 1A), or between a high-RI layer 130B and a low-RI layer 130A. The outer layered film 130a can incorporate one or more absorbent layers 150 in a variety of different locations, and the layer(s) 150 can be adjacent to the high RI layer 130B or the low RI layer 130A. Furthermore, in some embodiments of the cover article 100, as shown in exemplary form in Figure 1D, the outer layered film 130a does not include an absorbent layer 150 (rather, in this embodiment, one or more absorbent layers 150 are included in the inner layered film 130b).

[0048] As used herein, the terms "low RI" and "high RI" refer to the relative values ​​of the refractive index of layers 130A and 130B relative to one another (e.g., low RI < high RI). In one or more embodiments, the term "low RI" as used with low RI layer 130A includes a range of about 1.3 to about 1.7 or 1.75. In one or more embodiments, the term "high RI" as used with high RI layer 130B includes a range of about 1.7 to about 2.6 (e.g., about 1.85 or greater).

[0049] Suitable materials for use in the low RI layer 130A and high RI layer 130B of the outer layered film 130a include: SiO2, Al2O3, GeO2, SiO, AlO x N y , AlN, SiN x , SiO x N y , Si u Alv O x N y , Ta2O5, Nb2O5, TiO2, ZrO2, MgO, MgF2, BaF2, CaF2, SnO2, HfO2, Y2O3, MoO3, DyF3, YbF3, YF3, CeF3, polymers, fluoropolymers, plasma polymerized polymers, siloxane polymers, silsesquioxanes, polyimides, fluorinated polyimides, polyetherimides, polyethersulfones, polyphenylsulfones, polycarbonates, polyethylene terephthalate, polyethylene naphthalate, acrylic polymers, urethane polymers, polymethyl methacrylate, and other materials listed below as suitable for use in scratch resistant layers, and other materials known in the art. Examples of materials suitable for use in low RI layer 130A include SiO2, Al2O3, GeO2, SiO, AlO x N y , SiO x N y , Si u Al v O x N y , MgO, MgAl2O4, MgF2, BaF2, CaF2, DyF3, YbF3, YF3, and CeF3. Examples of materials suitable for use in the high RI layer 130B include SiAl x O y N z , Ta2O5, Nb2O5, AlN x , Si3N4, AlO x N y , SiO x N y , SiN x , SiN x :H y , HfO2, TiO2, ZrO2, Y2O3, Al2O3, MoO3, and diamond-like carbon (DLC). In some embodiments of the cover article 100, each low RI layer 130A comprises SiO or SiO2, and each high RI layer 130B comprises SiN x , Si3N4 or Nb2O5.

[0050] Referring again to the cover article 100 shown in exemplary form in FIGS. 1A-1D, an inner layered film 130b is disposed on the major surface 112 of the substrate 110. In embodiments, the inner layered film 130b includes multiple low refractive index layers 130A and absorbing layers 150. These layers 130A and 150 can be arranged in various orders within the inner layered film 130b, including an alternating arrangement, as shown in FIG. 1A. In some implementations, the inner layered film 130b includes one absorbing layer 150 (see the cover article 100 shown in FIGS. 1B-1D, described below) or multiple absorbing layers 150 (see the cover article 100 shown in FIG. 1A). In some embodiments, the inner layered film 130b includes 1 to 20, 2 to 20, 2 to 15, or 2 to 10 absorbing layers 150; alternatively, the inner layered film 130b can include any number of absorbing layers 150 within the above ranges.

[0051] The absorbent layer 150 used in one or both of the outer layered film 130a and the inner layered film 130b is generally configured to ensure that the cover article 100 (see FIGS. 1A-1D) exhibits translucency, can be used in touchscreen applications (if desired), and can promote anti-reflective properties. Furthermore, the absorbent layer 150 is configured into the outer layered film and the inner layered film 130a, 130b in embodiments of the cover article 100 so that these films are compatible with manufacturing processes and equipment that can form the outer layered film 130a and the inner layered film 130b in a single process sequence using the same equipment.

[0052] For touchscreen performance, if desired, the absorbent layer 150 of the cover article 100 (see FIGS. 1A-1D) must have at least some electrical resistance. In embodiments, each absorbent layer 150 of the cover article 100 has at least 10 3 Ω / sq, 10 4 Ω / sq, 10 5 Ω / sq, 5×10 5 Ω / sq, 10 6 Ω / sq, or even 10 7 For example, each absorber layer 150 may have a sheet resistance of 105 Ω / sq, 5×10 5 Ω / sq, 10 6 Ω / sq, 5×10 6 Ω / sq, 10 7 Ω / sq, 5×10 7 Sheet resistance in ohms / sq and all sheet resistance values ​​between these levels may be given.

[0053] Regarding translucency of the cover article 100 (see FIGS. 1A-1D), embodiments can be configured so that each absorbent layer 150 exhibits a desired degree of light absorptivity. In some embodiments, each absorbent layer 150 in a single-absorbent layer embodiment, or the total number of absorbent layers 150 in a multiple-absorbent layer embodiment, exhibits an average absorptivity of 1% to 80%, 1% to 70%, 1% to 60%, 2% to 60%, or 3% to 50%, as measured across the visible spectrum from 400 nm to 700 nm, and all absorptivity values ​​in between the aforementioned values. In implementations, each absorbent layer 150 exhibits an extinction coefficient (k) of greater than 0.5, 0.75, 1.0, 1.5, 2.0, 3.0, or even 4.0 across the visible spectrum from 400 nm to 700 nm. In some implementations of the cover article 100, each absorbing layer 150 exhibits an extinction coefficient (k) of about 0.05 to about 0.4, about 0.05 to about 0.35, or about 0.05 to about 0.3, all measured over the visible spectrum from 400 nm to 700 nm. In some implementations, each absorbing layer 150 exhibits an extinction coefficient greater than 1.0 and less than or equal to 3.0 (e.g., greater than or equal to 1.25 and less than or equal to 2.75, greater than or equal to 1.3 and less than or equal to 2.7, greater than or equal to 1.4 and less than or equal to 2.6) across the entire visible spectrum. In various embodiments, each absorbent layer 150 used in the cover articles of the present disclosure may exhibit an extinction coefficient of 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5, 0.75, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 4.0, 5.0, 7.5, 10.0, and all extinction coefficient values ​​between the aforementioned values.

[0054] The absorbent layers 150 used in the cover articles 100 of the present disclosure illustratively shown in FIGS. 1A-1D can include, for example, various materials suitable for exhibiting the aforementioned properties. In the cover article 100 shown in FIG. 1A, for example, each absorbent layer 150 can include Nb, Ni, Cr, a Ni-containing alloy, a Cr-containing alloy, or a Ni / Cr alloy. In some embodiments, each absorbent layer 150 of the cover article 100 includes Nb. In some embodiments, each absorbent layer 150 of the cover article 100 includes Cr. In some embodiments, each absorbent layer 150 of the cover article 100 includes Ni. In other implementations of the cover article 100, as shown in FIGS. 1B and 1C, for example, each absorbent layer 150 can include a diamond-like carbon (DLC) material. Any of a variety of DLC materials known to those skilled in the art of the present disclosure can be used for the absorbent layers 150 of these cover articles 100. In further implementations of cover article 100, as shown, for example, in FIG. 1D , each absorber layer 150 is a silicon-metal alloy comprising Si and Al, Sn, or Zn. In some of these implementations, absorber layer 150 does not include any silicides. Furthermore, according to some embodiments, an absorber layer 150 comprising Si—Al has 69% or more Si (by volume); an absorber layer 150 comprising Si—Sn has 60% or more Si; and an absorber layer 150 comprising Si—Zn has 80% or more Si.

[0055] Furthermore, according to some embodiments, the aforementioned materials of the absorber layer 150 can be deposited by the same processes and equipment suitable for depositing the other layers of the outer and inner layered films 130a, 130b (e.g., the low RI layer 130A and the high RI layer 130B), including, but not limited to, plasma enhanced chemical vapor deposition (PECVD), vacuum sputtering, vacuum metallization magnetron sputtering, filtered cathodic vacuum arc (FCVA), ion beam deposition, ion beam sputtering, evaporation, and other deposition processes.

[0056] The thickness of the absorber layers 150 used in the cover article 100 (e.g., shown in FIG. 1A ) of the present disclosure can also be tailored to achieve targeted article-level and absorber layer properties. In some implementations, each absorber layer 150 of the inner layered film 130b of the cover article 100 (see FIG. 1A ) containing Ni, Cr, or a combination thereof has a thickness of less than 2 nm, 1.8 nm, 1.6 nm, 1.4 nm, 1.2 nm, or 1.0 nm. For absorber layers 150 containing Nb, the thickness of each of these layers can be less than 2.0 nm, according to some embodiments, although thicker layers are possible. For absorber layers 150 containing Cr, the thickness of each of these layers can be less than 2.0 nm, according to some embodiments. For absorber layers 150 containing Ni, the thickness of each of these layers can be less than 1.0 nm, according to some embodiments. In embodiments, certain metal-containing absorber layers 150 may be thickness-limited because layers with thicknesses above the percolation threshold may exhibit material coalescence that results in reduced sheet resistance levels, making articles containing them unsuitable for capacitive touchscreen applications. Accordingly, cover article 100 embodiments with such absorber layers 150 (such as Ni- and Cr-based absorber layers) may be configured so that each absorber layer 150 maintains a thickness below its percolation threshold, depending on which metal it is made from.

[0057] 1A , niobium (Nb) has been found to be a particularly advantageous material for use in the absorbing layers 150 of the inner layered film 130b. Accordingly, in an embodiment, each absorbing layer 150 of the inner layered film 130b is composed of Nb (e.g., consists of Nb, consists essentially of Nb). FIG. 17 is a plot of the refractive index and extinction coefficient of Nb over the wavelength range of 380 nm to 780 nm. As shown, the extinction coefficient of Nb ranges from about 1.55 to about 2.45 over the illustrated wavelength range. The extinction coefficient has an average slope of 0.00225 / nm, which is smaller than some of the other materials described herein (e.g., DLC materials, silicon alloys) that make up the absorbing layers 150. In embodiments, one or more absorbing layers are formed from a metal that is also included in the outer layered film 130a and has an average gradient of 0.005 / nm or less (e.g., 0.004 / nm or less, 0.003 / nm or less) from 380 nm to 780 nm. The extinction coefficient distribution of Nb (or other metals) is relatively flat across the visible spectrum, advantageously allowing the article 100 to exhibit a more neutral material in reflection. Also, as shown in FIG. 17 , Nb exhibits a refractive index ranging from about 1.45 to about 1.95 across the illustrated wavelength range. In embodiments, the absorbing layer 150 constructed from Nb has a refractive index higher than the adjacently disposed low RI layer 130A but lower than the high RI layer 130B included in the outer layered film 130a (i.e., n 低RI <n 吸収層 <n 高RI ). In some embodiments incorporating Nb as the material for the absorbing layer 150, the inner layered film 130b can include an alternating stack of low-RI layers 130A and absorbing layers 150. In such embodiments, the alternating stack of low-RI and Nb layers can include repeating periods of layers having the same physical thickness (e.g., each period can include an Nb layer of a first thickness and a low-RI layer 130A of a second thickness). In embodiments, the second thickness of low-RI (e.g., SiO2) is as small as possible while maintaining coating stability and providing adequate isolation of the Nb layer. In such embodiments, the second thickness is 10 nm or less (e.g., 9 nm or less, 8 nm or less, 7 nm or less).

[0058] The transmittance properties of the article 100 can be adjusted by adjusting the number of repeat periods within the inner layered film 130b. In embodiments, the inner layered film 130b can include a repeat thickness of 4 or more periods (of Nb / low RI material). In embodiments, the inner layered film 130b can include 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, or any number of periods therebetween. Such embodiments can further include an innermost layer (the layer closest to the major surface 112) that is a low RI layer 130A that includes a greater thickness than the remaining low RI layers 130A within the inner layered film 130b. It is believed that such a large thickness of low RI material closest to the substrate 110 helps to improve adhesion between the alternating stack of repeating periods and the substrate 110 .

[0059] The electrical resistivity of Nb film varies depending on the thickness of the film. For example, a 0.1 nm thick Nb layer has a resistivity of 10 4It has been shown that Nb layers can exhibit a volume resistivity of Ω / cm. Accordingly, it is believed that Nb layers having thicknesses within the specific ranges provided herein can provide a sheet resistance suitable for touchscreen compatibility. Applicant has observed that Nb absorber layers having thicknesses of up to 0.7 nm do not significantly impair touch panel functionality. Accordingly, in embodiments where touch panel compatibility is desired, the inner layered film 130b can include one or more absorber layers 150, each composed of Nb and having a physical thickness of 0.7 nm or less (e.g., 0.1 nm, 0.2 nm, 0.3 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.7 nm, and all thicknesses between these values). Embodiments may also incorporate Nb absorption layers thicker than 0.7 nm (e.g., 0.8 nm, 0.9 nm, 1.0 nm, 1.5 nm, 1.75 nm, 2.0 nm, or thicker), although it should be understood that such absorption layers may at least partially interfere with the operation of a touch panel (not shown) located below the substrate 110.

[0060] The configuration of the inner layered film 130b will generally vary depending on the application. Requirements such as touch panel compatibility, optical transmittance, and appearance may influence, for example, the number of absorber layers 150 incorporated and the physical thickness of such absorber layers. For example, in an embodiment, the average transmittance desired for the article 100 may be approximately 60% (averaged over 400 nm to 700 nm). To achieve such transmittance while incorporating 0.6 nm thick Nb layers as absorber layers 150 in the inner layered film 130b to maintain touch panel functionality, Applicant has determined that 18 Nb layers are appropriate. That is, according to this illustrative example, the inner layered film 130b includes 18 alternating periods comprising 0.6 nm thick Nb layers and low RI layers (e.g., SiO). In a similar example with the same transmittance requirements but not requiring touch panel compatibility, 12 0.9 nm thick Nb layers (in an alternating stack) have been found to be appropriate. In another similar example with the same transmittance requirements, nine 1.25 nm thick Nb layers (in an alternating stack) were found to be suitable. Thus, if an average transmittance of about 60% is desired, the total thickness of the Nb absorber layers can be about 11 nm (e.g., 10 nm to 12 nm, 10.5 nm to 11.5 nm).

[0061] As another example, in another set of embodiments, when the desired average transmittance (400 nm to 700 nm) is reduced to 30%, 37 Nb layers (in alternating stacks) having a thickness of 0.6 nm were found to be appropriate. When touch functionality is not required, 24 Nb layers (in alternating stacks) having a thickness of 0.9 nm are appropriate, or 18 Nb layers (in alternating stacks) having a thickness of 1.25 nm are appropriate. Thus, when an average transmittance of about 30% is desired, the total thickness of the Nb absorption layers can be about 22 nm (e.g., 20 nm to 24 nm, 21 nm to 23 nm, 21.5 nm to 22.5 nm).

[0062] The above examples provide Nb absorbing layer structures that applicants have found suitable for various transmittance values, with the structure of the inner layered film 130b incorporating alternating stacks including Nb layers of the same thickness. As shown in the above examples, the number and thickness of Nb layers incorporated into the article 100 can determine the light transmittance performance. Various structures of the inner layered film 130b incorporating Nb absorbing layers are contemplated, including structures in which Nb is incorporated outside of the periodic stack structure (e.g., an alternative inner layered film 130b could incorporate an Nb absorbing layer having a non-uniform thickness), and it should be understood that the number and thickness of Nb layers can vary from the above illustrative examples as the stack structure changes.

[0063] Nb is particularly advantageous when other layers within the article 100 also contain Nb. For example, in an embodiment, the outer layered film 130a can include one or more high-RI layers 130B composed of NbO, while the inner layered film 130b can include one or more absorbing layers 150 formed from Nb. Such an embodiment is particularly beneficial in that both the outer layered film 130a and the inner layered film 130b can be constructed using the same raw materials (e.g., evaporation source material, sputtering target) and deposition process (e.g., sputtering, evaporation). As a result, the absorbing layer 150 can be incorporated without introducing additional raw materials into the deposition process and without separately processing each of the inner layered film 130b and the outer layered film 130a. Using the same raw materials and coating process for both the inner layered film 130b and the outer layered film 130a can significantly increase manufacturing throughput and reduce costs in mass production.

[0064] While the preceding discussion of the material for the absorbing layer 150 has focused on Nb as an example, it is contemplated that other materials may be used to form the absorbing layer using the same source materials as the other layers of the outer layered film 130a. Other metals that may be suitable for use as both the outer layered film 130a and one or more absorbing layers of the inner layered film 130b include, but are not limited to, titanium, nickel, chromium, and tungsten. In various embodiments, one or more layers of the outer layered film 130a are comprised of a metal oxide (e.g., NbO, TiO), and the inner layered film 130b includes one or more absorbing layers 150 comprised of a metal of the metal oxide of the outer layered film 130a. In such embodiments, the inner layered film 130b may include such a metal layer without including the metal oxide contained in the outer layered film 130a. Such a metal layer may be periodically stacked with a layer of the same low-RI material used to form the low-RI layer 130A of the outer layered film 130a. As a result, each layer of the inner layered film 130b can be formed from a subset of the chemical (atomic) components used to form each layer of the outer layered film 130a. This arrangement has the advantage that the same deposition source material can be used to deposit the inner layered film 130b and the outer layered film 130a.

[0065] 1C and 1D, the thickness of the absorber layer 150 used in the cover article 100 of the present disclosure can also be adjusted to achieve targeted article-level and absorber layer properties. In some implementations, each absorber layer 150 of the inner layered film 130b of the cover article 100 (see FIGS. 1B and 1C) comprising a DLC material can have a thickness of about 5 nm to 500 nm, 25 nm to 500 nm, or even 50 nm to 500 nm. For example, each absorber layer 150 comprising a DLC material can have a thickness of about 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 50 nm, 75 nm, 100 nm, 125 nm, 150 nm, 175 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, or even 500 nm, and all thickness values ​​therebetween. Compared to absorber layers 150 comprising metals or metal alloys, these absorber layers 150 comprising DLC ​​materials can advantageously be made thicker without sacrificing sheet resistance. However, the practical thickness of absorber layers 150 comprising DLC ​​materials may be limited by resistance to layer cracking (e.g., due to thermal stress) and / or packaging considerations that make thickening the overall structure impractical for a given end use application.

[0066] The thickness of the absorbent layer 150 used in the cover article 100 of the present disclosure (e.g., as shown in FIG. 1D ) can also be adjusted to achieve targeted article-level and absorbent layer properties. In some implementations, each absorbent layer 150 of the inner layered film 130b of the cover article 100 (see FIG. 1D ) comprising Si—Al, Si—Sn, Si—Zn, or a combination thereof has a thickness of less than 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm, 80 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, 15 nm, or 10 nm. For example, each absorber layer 150 comprising a silicon-aluminum, silicon-tin, or silicon-zinc alloy can have a thickness of 145 nm, 140 nm, 135 nm, 130 nm, 125 nm, 115 nm, 105 nm, 100 nm, 90 nm, 75 nm, 50 nm, 25 nm, 10 nm, 8 nm, 6 nm, 5 nm, 2.5 nm, and all thickness values ​​less than 150 nm. Inherently, Si—Al, Si—Sn, and Si—Zn absorber layers 150 can be thickness-limited because layers with thicknesses above the percolation threshold can exhibit material coalescence that results in reduced sheet resistance levels, rendering articles containing them unsuitable for capacitive touchscreen applications. Accordingly, embodiments of cover article 100 including such absorber layers 150 can be configured so that each absorber layer 150 maintains a thickness below its percolation threshold, depending on which metal it is made of.

[0067] 1A-1D, in one or more embodiments, at least one of the layers (e.g., low RI layer 130A, high RI layer 130B, and absorbing layer 150) of outer layered film 130a and inner layered film 130b can include a particular optical thickness range. As used herein, the term "optical thickness" is determined by the product of the layer's physical thickness (d) and refractive index (n) at a wavelength of 550 nm. In one or more embodiments, at least one of the layers of outer layered film 130a can include an optical thickness ranging from about 0.1 nm to about 200 nm, from about 2 nm to about 100 nm, from about 10 nm to about 100 nm, from about 15 nm to about 100 nm, or from about 15 to about 500 nm. In some embodiments, all layers of the outer layered film 130a can each have an optical thickness ranging from about 2 nm to about 200 nm, about 10 nm to about 100 nm, about 15 nm to about 100 nm, or about 15 nm to about 500 nm. In some cases, one or more layers of the outer and inner layered films 130a, 130b have an optical thickness of about 50 nm or greater. In some cases, each of the low RI layers 130A has an optical thickness ranging from about 2 nm to about 200 nm, about 10 nm to about 100 nm, about 15 nm to about 100 nm, or about 15 nm to about 500 nm. In other cases, each of the high RI layers 130B has an optical thickness ranging from about 2 nm to about 200 nm, about 10 nm to about 100 nm, or about 15 nm to about 100 nm.

[0068] In some embodiments of the cover article 100 of the present disclosure, the outermost surface 122 of the outer layered membrane 130a can include a high RI layer 130B (not shown) that also exhibits high hardness. In some embodiments, an additional coating (not shown) can be disposed on the exposed top, air-side high RI layer 130B, or an additional coating can be disposed on the top, low RI layer 130A (as shown in FIGS. 1A-1D). Such additional coatings can include low-friction coatings, oleophobic coatings, or easy-to-clean coatings, as will be understood by those skilled in the art of the present disclosure.

[0069] In one embodiment, the cover article 100 includes one or more additional coatings (not shown in FIGS. 1A-1D ) disposed on the outer layered film 130a. In one or more embodiments, the additional coatings can include an easy-to-clean coating. One example of a suitable easy-to-clean coating is described in U.S. Patent Application No. 13 / 690,904, entitled “Process for Making of Glass Articles with Optical and Easy-to-Clean Coatings,” filed November 30, 2012, and published April 24, 2014, as U.S. Patent Application Publication No. 2014 / 0113083, the entire contents of which are incorporated herein by reference. The easy-to-clean coating can have a thickness ranging from about 5 nm to about 50 nm and can include known materials such as fluorinated silanes. The easy-to-clean coating can alternatively or additionally include a low-friction coating or surface treatment. Exemplary low-friction coating materials can include diamond-like carbon, silanes (e.g., fluorosilanes), phosphonates, alkenes, and alkynes. In some embodiments, the easy-to-clean coating can have a thickness in the range from about 1 nm to about 40 nm, from about 1 nm to about 30 nm, from about 1 nm to about 25 nm, from about 1 nm to about 20 nm, from about 1 nm to about 15 nm, from about 1 nm to about 10 nm, from about 5 nm to about 50 nm, from about 10 nm to about 50 nm, from about 15 nm to about 50 nm, from about 7 nm to about 20 nm, from about 7 nm to about 15 nm, from about 7 nm to about 12 nm, or from about 7 nm to about 10 nm, and all ranges and subranges therebetween.

[0070] The additional coatings used in such cover articles 100 may also include a scratch-resistant layer or layers, again typically made of materials equivalent to the high-RI layer 130B, as would be understood by one skilled in the art of this disclosure. In some embodiments, the additional coating includes a combination of an easy-to-clean material and a scratch-resistant material. In one example, the combination includes an easy-to-clean material and diamond-like carbon. Such additional coatings may have thicknesses ranging from about 5 nm to about 20 nm. The components of the additional coating may be provided in separate layers. For example, the diamond-like carbon may be disposed as a first layer, and the easy-to-clean material may be disposed as a second layer on top of the first layer of diamond-like carbon. The thicknesses of the first and second layers may be within the ranges provided above for the additional coatings. For example, the first layer of diamond-like carbon can have a 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 easy-to-clean material can have a thickness of about 1 nm to about 10 nm (or, more specifically, about 6 nm). The diamond-like coating can include tetrahedral amorphous carbon (Ta—C), Ta—C:H, and / or aCH.

[0071] In one implementation of the cover article 100, as shown in FIG. 1A , the cover article 100 includes a substrate 110 having a thickness of 50 μm to 5000 μm and including an outer major surface 112 and an inner major surface 114, the outer and inner major surfaces 112, 114 facing each other, and the substrate 110 including a glass, glass ceramic, or ceramic material. The cover article 100 also includes an inner layer film 130b disposed on the outer major surface 112 of the substrate 110; and an outer layer film 130a disposed on the inner layer film 130b. The inner layer film 130b includes a plurality of low refractive index layers 130A and an absorbing layer 150. The outer layer film 130a includes a plurality of alternating high refractive index layers 130B and low refractive index layers 130A. Each of the high refractive index layers 130B has a refractive index greater than that of each of the low refractive index layers 130A. Additionally, each absorber layer 150 comprises a metal or metal alloy. Further, in such an embodiment, each absorber layer 150 comprises at least 10 5They exhibit sheet resistances of Ω / sq and extinction coefficients greater than 0.5 in the visible spectrum from 400 nm to 700 nm.

[0072] In some embodiments of the cover article 100, as exemplarily shown in FIG. 1A, the outer layered film 130a comprises two sets of alternating low RI layers 130A (e.g., SiO2) and high RI layers 130B (e.g., SiN x ), and an additional low RI layer 130A (SiO2) disposed on the top high RI layer 130B. Further, the inner layered film 130b includes five sets of alternating low RI layers 130A (SiO2) and absorbing layers 150 (Ni or Cr). Alternative embodiments may include more or fewer low RI layers 130A, high RI layers 130B, and / or absorbing layers 150.

[0073] 1B, 1C, and 1D, the cover article 100 includes an outer layered film 130a and an inner layered film 130b having absorbent layers 150 configured differently than those described above with respect to the cover article 100 of FIG. 1A. FIG. 1B illustrates a cover article 100 in which the inner layered film 130b includes an absorbent layer 150 and the outer layered film 130a includes one or more absorbent layers 150 disposed adjacent to the low RI layer 130A (and thus the absorbent layer 150 is not disposed adjacent to any of the other high RI layers 130B of the outer layered film 130a), while FIG. 1C illustrates an embodiment in which the inner layered film 130b includes an absorbent layer 150 and the outer layered film 130a includes one or more absorbent layers 150 that may be disposed adjacent to the low RI layer 130A, the high RI layer 130B, and / or both the low RI layer 130A and the high RI layer 130B. 1B and 1C, at least one of the absorbent layers 150 included in the cover article 100 is a DLC layer. Furthermore, FIG. 1C shows a cover article 100 in which the inner layered film 130b includes one absorbent layer 150 adjacent to a low RI layer 130A, and the outer layered film 130a includes multiple alternating low RI layers 130A and high RI layers 130B, with the high RI layer 130B in contact with the absorbent layer 150 of the inner layered film 130b. As described herein, in the embodiment of the cover article 100 shown in FIG. 1D, at least one absorbent layer 150 included in the cover article 100 includes a Si—Al, Si—Sn, or Si—Zn alloy.

[0074] 1B and 1C, the cover article 100 can include a substrate 110 having a thickness of 50 μm to 5000 μm, an outer major surface 112, and an inner major surface 114, the outer and inner major surfaces 112, 114 facing each other, and the substrate 110 comprising a glass, glass ceramic, or ceramic material. The cover article 100 also includes an inner layer film 130b disposed on the outer major surface 112 of the substrate 110; and an outer layer film 130a disposed on the inner layer film 130b. One or both of the inner layer film 130b and the outer layer film 130a include one or more absorbing layers 150. The outer layer film 130a includes a plurality of alternating high-refractive-index layers 130B and low-refractive-index layers 130A. Each of the high-refractive-index layers 130B has a refractive index greater than that of each of the low-refractive-index layers 130A. Additionally, each absorber layer 150 includes a diamond-like carbon (DLC) material. Further, in such an embodiment, each absorber layer 150 includes at least 10 5 They exhibit sheet resistances of Ω / sq and extinction coefficients of about 0.05 to about 0.4 in the visible spectrum from 400 nm to 700 nm.

[0075] 1B, the outer layered film 130a includes three sets of alternating layers, each set including a low RI layer 130A (e.g., SiO) or a high RI layer 130B (e.g., NbO) upon which an absorbing layer 150 (DLC material) or a high RI layer 130B is deposited. The outer layered film 130a also includes an additional low RI layer 130A (SiO) disposed on the topmost high RI layer 130B or absorbing layer 150 of one of the alternating layer sets. Furthermore, the inner layered film 130b includes an additional absorbing layer 150 (DLC material).

[0076] 1C, the outer layered film 130a includes four sets of alternating low RI layers 130A (e.g., SiO) or high RI layers 130; and high RI layers 130B (e.g., NbO) and / or absorbing layers 150 (DLC material), and an additional low RI layer 130A (SiO) disposed on the topmost high RI layer 130B or absorbing layer 150. Furthermore, the inner layered film 130b includes an additional absorbing layer 150 (DLC material).

[0077] Referring generally to FIG. 1D , the cover article 100 can include a substrate 110 having a thickness of 50 μm to 5000 μm, an outer major surface 112, and an inner major surface 114, the outer and inner major surfaces 112, 114 facing each other, and the substrate 110 comprising a glass, glass ceramic, or ceramic material. The cover article 100 also includes an inner layer film 130b disposed on the outer major surface 112 of the substrate 110; and an outer layer film 130a disposed on the inner layer film 130b. The inner layer film 130b can include one or more absorbing layers 150. The outer layer film 130a includes a plurality of alternating high-refractive-index layers 130B and low-refractive-index layers 130A. Each of the high-refractive-index layers 130B has a refractive index greater than that of each of the low-refractive-index layers 130A. Additionally, each absorbent layer 150 of the cover article 100 shown in FIG. 1D comprises a silicon-metal alloy, such as Si—Al, Si—Sn, Si—Zn, or a combination thereof. Furthermore, in such an embodiment, each absorbent layer 150 comprises at least 10 5 They exhibit sheet resistances of Ω / sq and extinction coefficients of about 0.05 to about 0.4 in the visible spectrum from 400 nm to 700 nm.

[0078] In some embodiments of the cover article 100, as exemplarily shown in FIG. 1D , the outer layered film 130a includes three sets of alternating layers, each set including a low RI layer 130A (e.g., SiO) and a high RI layer 130B (e.g., NbO). As exemplarily shown in FIG. 1D , the outer layered film 130 can be configured with an outermost low RI layer 130A defining the outermost surface 122 and an innermost high RI layer 130B in contact with the top layer of the inner layered film 130b. Furthermore, the inner layered film 130b includes an absorbing layer 150 (e.g., a Si—Al, Si—Sn, or Si—Zn alloy) as its top layer, and includes a series of low RI layers 130A and high RI layers 130B between the absorbing layer 150 and the substrate 110.

[0079] 1A-1D, the cover article 100 exhibits a first surface average photopic reflectance of less than 4%, for example, at a normal incidence angle of 0° or a near-normal incidence angle of 8°. In embodiments, the cover article 100 may exhibit a first surface average photopic reflectance of less than 4%, less than 3%, less than 2%, less than 1.75%, less than 1.5%, less than 1.25%, or even less than 1.2%. For example, the cover article 100 may exhibit an average photopic reflectance of the first surface at normal and near-normal angles of incidence from 0° to 8° of 3.9%, 3.7%, 3.5%, 3.3%, 3.1%, 3.0%, 2.5%, 2%, 1.9%, 1.8%, 1.7%, 1.6%, 1.5%, 1.4%, 1.3%, 1.2%, 1.1%, 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, and all reflectance values ​​between the aforementioned ranges and subranges.

[0080] 1A-1D, the cover article 100 may exhibit a two-surface average transmittance of 20% to 90%, 30% to 80%, 40% to 80%, 45% to 75%, or 50% to 70% across the visible spectrum from 400 nm to 700 nm, at a normal angle of incidence of 0° or a near-normal angle of incidence of 8°. For example, the cover article 100 may exhibit a two-surface average transmittance of 20%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, and all transmittance values ​​between the aforementioned ranges and subranges across the visible spectrum from 400 nm to 700 nm, at a normal angle of incidence of 0° or a near-normal angle of incidence of 8°.

[0081] 1A-1D, the cover article 100 exhibits a first surface reflected color or a second surface transmitted color (CIE coordinates under illumination from a D65 illuminant) of a* between −20 and +50 and a b* between −50 and +10 for all angles of incidence from 0° to 90°. In some implementations of the cover article 100 of the present disclosure, the first surface reflected color or the second surface transmitted color for all angles of incidence from 0° to 90° is such that a* is between −20 and +50, or between −10 and +40; and b* is between −50 and +10, or between −45 and 0, or between −40 and −10.

[0082] 1A-1D, the cover article 100 exhibits a dead-front color shift (ΔE) of less than 4.0, less than 3.5, or even less than 3.0 at angles of incidence measured from 0° to 90°, as measured relative to a control article comprising a glass, glass-ceramic, or ceramic material of a substrate 110 and a standard black matrix material (known to those skilled in the art of the present disclosure) disposed on the glass, glass-ceramic, or ceramic material of the control article (otherwise manufactured similarly to the cover article 100). For example, the cover article 100 of the present disclosure may exhibit a dead-front color shift (ΔE) of 3.9, 3.7, 3.5, 3.3, 3.1, 2.9, 2.7, 2.5, 2.3, 2.1, 1.9, 1.7, 1.5, and all dead-front color shift values ​​between the aforementioned values, as measured at angles of incidence from 0° to 90°.

[0083] The substrate 110 can include inorganic materials and can include amorphous substrates, crystalline substrates, or combinations thereof. The substrate 110 can be formed from artificial and / or natural materials (e.g., quartz and polymers). For example, in some cases, the substrate 110 can be characterized as organic, specifically a polymer. Examples of suitable polymers include, but are not limited to, thermoplastic resins such as polystyrene (PS) (including styrene copolymers and blends), polycarbonate (PC) (including copolymers and blends), polyesters (including copolymers and blends, including polyethylene terephthalate and polyethylene terephthalate copolymers), polyolefins (PO) and cyclic polyolefins (cyclic PO), polyvinyl chloride (PVC), acrylic polymers such as polymethyl methacrylate (PMMA) (including copolymers and blends), thermoplastic urethanes (TPUs), polyetherimides (PEIs), and blends of these polymers. Other exemplary polymers include epoxy, styrene, phenolic, melamine, and silicone resins.

[0084] In some particular embodiments, substrate 110 may specifically exclude polymer, plastic, and / or metal materials. Substrate 110 may be characterized as an alkali-containing substrate (i.e., the substrate includes one or more alkalis). In one or more embodiments, substrate 110 exhibits a refractive index ranging from about 1.45 to about 1.55. In particular embodiments, substrate 110 may exhibit an average strain to failure of 0.5% or greater, 0.6% or greater, 0.7% or greater, 0.8% or greater, 0.9% or greater, 1% or greater, 1.1% or greater, 1.2% or greater, 1.3% or greater, 1.4% or greater, 1.5% or greater, or even 2% or greater on one or more opposing major surfaces, as measured using a ball-on-ring test with at least 5, at least 10, at least 15, or at least 20 samples. In certain embodiments, the substrate 110 may exhibit an average surface failure strain on one or more opposing major surfaces of about 1.2%, about 1.4%, about 1.6%, about 1.8%, about 2.2%, about 2.4%, about 2.6%, about 2.8%, or about 3% or greater.

[0085] Suitable substrates 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 may be 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 therebetween.

[0086] In one or more embodiments, the substrate 110 can comprise glass, which can be tempered or untempered. 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 lithia-free. In one or more alternative embodiments, the substrate 110 can comprise a crystalline substrate, such as a glass-ceramic substrate (which may be tempered or untempered), or can comprise a single crystalline structure, such as sapphire. In one or more particular embodiments, the substrate 110 comprises an amorphous base (e.g., glass) and a crystalline cladding (e.g., a sapphire layer, a polycrystalline alumina layer, and / or a spinel (MgAlO) layer).

[0087] Substrate 110 can be a substantially optically clear, transparent, and non-light-scattering element. In such embodiments, substrate 110 can exhibit an average light transmittance for normally incident light across the optical wavelength range 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, substrate 110 can be opaque or exhibit an average light transmittance across the optical wavelength range 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 0.5%. In some embodiments, these optical reflectance and transmittance values ​​may be total reflectance or transmittance (considering the reflectance or transmittance of both major surfaces of the substrate) or may be observed on a single surface of the substrate (i.e., only the outermost surface 122 of the outer layered film 130a, without considering the opposite surface). Unless otherwise specified, the average reflectance or transmittance of the substrate 110 alone is measured at an incident illumination angle of 0 degrees relative to the outer major surface 112 (however, such measurements may also be provided at incident illumination angles of 45 degrees or 60 degrees). The substrate 110 may optionally exhibit colors such as white, black, red, blue, green, yellow, orange, etc.

[0088] Additionally or alternatively, the physical thickness of substrate 110 may vary along one or more of its dimensions for aesthetic and / or functional reasons. For example, the edges of substrate 110 may be thicker compared to more central regions of substrate 110. The length, width, and physical thickness dimensions of substrate 110 may also vary depending on the application or use of cover article 100.

[0089] The substrate 110 can be provided using a variety of different processes. For example, if the substrate 110 comprises an amorphous substrate such as glass, various forming methods can include float glass processes and downdraw processes such as fusion draw and slot draw.

[0090] After forming, the substrate 110 can be strengthened to form a strengthened substrate. As used herein, the term "strengthened substrate" can refer to a substrate that has been chemically strengthened, for example, through ion exchange of larger ions for smaller ions at the surface of the substrate. However, other strengthening methods known in the art can be used to form a strengthened substrate, such as thermal tempering or using a mismatch in thermal expansion coefficients between portions of the substrate to create compressive stress regions and central tension regions.

[0091] When the substrate 110 is chemically strengthened by an ion exchange process, ions in the surface layer of the substrate are replaced or exchanged with 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 the larger ions to be exchanged for the smaller ions in the substrate. Those skilled in the art will recognize that the parameters for the ion exchange process, including but not limited to the bath composition and temperature, immersion time, number of times the substrate is immersed in one or more salt baths, use of multiple salt baths, and additional steps such as annealing and washing, are generally determined by the composition of the substrate, as well as the desired compressive stress (CS) of the substrate and the depth of the compressive stress layer (or depth of layer DOL or depth of compression DOC) resulting from the strengthening operation. By way of example, ion exchange of an alkali metal-containing glass substrate can be achieved by immersion in at least one molten bath containing salts of larger alkali metal ions, such as, but not limited to, nitrates, sulfates, and chlorides. The temperature of the molten salt bath typically ranges from about 380° C. up to about 450° C., while the soaking time ranges from about 15 minutes up to about 40 hours, although temperatures and soaking times other than those stated above can also be used.

[0092] Additionally, non-limiting examples of ion exchange processes in which a glass substrate is immersed in multiple ion exchange baths with washing and / or annealing steps between immersions include U.S. Patent Application No. 12 / 500,650, filed July 10, 2009, by Douglas C. Allan et al., entitled "Glass with Compressive Surface for Consumer Applications," which claims priority to U.S. Provisional Patent Application No. 61 / 079,995, filed July 11, 2008, in which a glass substrate is strengthened by immersion in multiple successive ion exchange treatments in salt baths of different concentrations; and "Dual Stage Ion Exchange for Chemical Strengthening of Glass," published November 20, 2012, by Christopher M. Lee et al., in which a glass substrate is strengthened by ion exchange in a first bath, diluted with effluent ions, and then immersed in a second bath having a lower concentration of effluent ions than the first bath. No. 8,312,739, entitled "A New Glass for a Semiconductor Device," which claims priority to U.S. Provisional Patent Application No. 61 / 084,398, filed July 29, 2008. The contents of U.S. Patent Application No. 12 / 500,650 and U.S. Patent No. 8,312,739 are incorporated herein by reference in their entireties.

[0093] The degree of chemical strengthening achieved by ion exchange can be quantified based on the parameters of central tension (CT), surface stress (CS), and depth of compression (DOC). Compressive stress (including surface stress) is measured by a surface stress meter (FSM) using commercially available equipment such as the FSM-6000 manufactured by Orihara Seisakusho, Japan. Surface stress measurement relies on accurate measurement of the stress-optical coefficient (SOC), which is related to the birefringence of the glass. SOC is measured in accordance with Procedure C (glass disk method) described in ASTM Standard C770-16, entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," the entire contents of which are incorporated herein by reference. Maximum CT value is measured using the scattered light polarizer (SCALP) technique, known in the art. As used herein, DOC refers to the depth at which the stress of the chemically strengthened alkali aluminosilicate glass article described herein changes from compressive to tensile. DOC can be measured by FSM or SCALP, depending on the ion exchange process. If the stress in the glass article is generated by exchanging potassium ions into it, the DOC is measured using FSM. If the stress in the glass article is generated by exchanging sodium ions into it, the DOC is measured using SCALP. If the stress in the glass article is generated by exchanging both potassium and sodium ions into it, the DOC is measured by SCALP because the exchange depth of the sodium ions is indicative of the DOC, and the exchange depth of the potassium ions is believed to indicate a change in the magnitude of the compressive stress (but not a change in stress from compressive to tensile); the exchange depth of the potassium ions in such glass articles is measured by FSM.

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

[0095] Exemplary glasses that can be used for the substrate 110 can include alkali aluminosilicate or alkali aluminoborosilicate glass compositions, although other glass compositions are contemplated. Such glass compositions can be chemically strengthened by an ion-exchange process. An exemplary glass composition includes SiO, BO, and NaO, where (SiO + BO) > 66 mol% and NaO > 9 mol%. In one embodiment, the glass composition includes at least 6 wt% aluminum oxide. In a further embodiment, the substrate includes a glass composition including one or more alkaline earth oxides, such that the alkaline earth oxide content is at least 5 wt%. In some embodiments, suitable glass compositions further include at least one of KO, MgO, and CaO. In certain embodiments, the glass composition used in the substrate can include 61-75 mol% SiO2; 7-15 mol% Al2O3; 0-12 mol% B2O3; 9-21 mol% Na2O; 0-4 mol% K2O; 0-7 mol% MgO; and 0-3 mol% CaO.

[0096] Further exemplary glass compositions suitable for substrate 110 include 60-70 mol% SiO2; 6-14 mol% Al2O3; 0-15 mol% B2O3; 0-15 mol% Li2O; 0-20 mol% Na2O; 0-10 mol% K2O; 0-8 mol% MgO; 0-10 mol% CaO; 0-5 mol% ZrO2; 0-1 mol% SnO2; 0-1 mol% CeO2; less than 50 ppm As2O3; and less than 50 ppm Sb2O3, where 12 mol%≦(Li2O+Na2O+K2O)≦20 mol% and 0 mol%≦(MgO+CaO)≦10 mol%.

[0097] Further exemplary glass compositions suitable for substrate 110 include 63.5-66.5 mol% SiO2; 8-12 mol% Al2O3; 0-3 mol% B2O3; 0-5 mol% Li2O; 8-18 mol% Na2O; 0-5 mol% K2O; 1-7 mol% MgO; 0-2.5 mol% CaO; 0-3 mol% ZrO2; 0.05-0.25 mol% SnO2; 0.05-0.5 mol% CeO2; less than 50 ppm As2O3; and less than 50 ppm Sb2O3, where 14 mol%≦(Li2O+Na2O+K2O)≦18 mol% and 2 mol%≦(MgO+CaO)≦7 mol%.

[0098] In certain embodiments, alkali aluminosilicate glass compositions suitable for substrate 110 include alumina, at least one alkali metal, and in some embodiments greater than 50 mol% SiO, in other embodiments at least 58 mol% SiO, and in still other embodiments at least 60 mol% SiO, where the ratio (Al2O3 + B2O3) / Σmodifiers (i.e., the sum of modifiers) is greater than 1, where the components are expressed in mol% and the modifiers are alkali metal oxides. In certain embodiments, the glass composition includes 58-72 mol% SiO; 9-17 mol% Al2O3; 2-12 mol% B2O3; 8-16 mol% Na2O; and 0-4 mol% KO, where the ratio (Al2O3 + B2O3) / Σmodifiers (i.e., the sum of modifiers) is greater than 1.

[0099] In yet another embodiment, the substrate 110 can comprise an alkali aluminosilicate glass composition including 64-68 mol% SiO; 12-16 mol% NaO; 8-12 mol% AlO; 0-3 mol% BO; 2-5 mol% KO; 4-6 mol% MgO; and 0-5 mol% CaO, where 66 mol%≦SiO+BO+CaO≦69 mol%; NaO+KO+BO 3+ MgO+CaO+SrO>10 mol%; 5 mol%≦MgO+CaO+SrO≦8 mol%; (Na2O+B2O3)-Al2O3≦2 mol%; 2 mol%≦Na2O-Al2O3≦6 mol%; and 4 mol%≦(Na2O+K2O)-Al2O3≦10 mol%.

[0100] In alternative embodiments, the substrate 110 may include an alkali aluminosilicate glass composition including 2 mol % or more of Al2O3 and / or ZrO2, or 4 mol % or more of Al2O3 and / or ZrO2.

[0101] If the substrate 110 comprises a crystalline substrate, the substrate may comprise a single crystal that may include Al2O3. Such single crystal substrates are called sapphire. Other suitable materials for the crystalline substrate include polycrystalline alumina and / or spinel (MgAl2O4).

[0102] Optionally, the substrate 110 may be crystalline and may include a glass-ceramic substrate, which may be tempered or untoughened. Examples of suitable glass-ceramics may include LiO-AlO-SiO-based (i.e., LAS-based) glass-ceramics, MgO-AlO-SiO-based (i.e., MAS-based) glass-ceramics, and / or glass-ceramics containing predominant crystalline phases including β-quartz solid solution, β-spodumene ss, cordierite, and lithium disilicate. Glass-ceramic substrates may be tempered using the chemical tempering processes disclosed herein. In one or more embodiments, MAS-based glass-ceramic substrates may be tempered in a LiSO molten salt, thereby strengthening the 2Li + to Mg 2+There may be an exchange for

[0103] The substrate 110, according to one or more embodiments, can have a physical thickness ranging from about 50 μm to about 5 mm at various portions of the substrate 110. Exemplary physical thicknesses of the substrate 110 range from about 50 μm to about 500 μm (e.g., 50, 75, 100, 200, 300, 400, or 500 μm). Further exemplary physical thicknesses of the substrate 110 range from about 50 μm to about 2000 μm (e.g., 50, 75, 100, 250, 500, 600, 700, 800, 900, 1000, 1250, 1500, 1750, or 2000 μm). The substrate 110 can 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 can have a physical thickness of 2 mm or less, or less than 1 mm. The substrate 110 may be acid polished or otherwise treated to remove or reduce the effect of surface scratches.

[0104] The cover article 100 illustratively shown in FIGS. 1A-1D and disclosed herein can be incorporated into another article, such as an article with a display (or display article) (e.g., consumer electronics including cell phones, tablets, computers, navigation systems, etc.), a building product, a transportation product (e.g., automobiles, trains, aircraft, ships, etc.), a home appliance product, or any article requiring translucency, anti-reflective properties, and / or touchscreen capabilities. [Example]

[0105] Various embodiments of the present disclosure (e.g., any of the cover articles 100 shown in FIGS. 1A-1D) will be further clarified by the following examples. As specifically described, the optical properties (e.g., reflectance and transmittance) of the examples were measured using the methods and apparatus described or computational techniques, particularly transfer matrix modeling techniques for modeling thin film performance, as understood by those skilled in the art of the present disclosure. xThin film properties (e.g., refractive index values) obtained from previous thin film reactive sputtering of high RI layers, laboratory experiments, and bulk sputter fabrication were used in the modeling.

[0106] The refractive indices and extinction coefficients (as a function of wavelength) of the layers and substrate of the modeled cover article examples were measured using spectroscopic ellipsometry in previous experiments. In some examples focusing on layer properties, these measured properties are reported. The refractive indices measured in this way were used to calculate the reflectance spectra of the examples. For convenience, the examples use a single refractive index value in the descriptive tables, which corresponds to a point selected from the dispersion curve at a wavelength of about 550 nm, approximately the midpoint of the visible spectrum.

[0107] Example 1 In this example, thin chromium (Cr) films were sputtered onto Corning Eagle XG® substrates at room temperature. Electrical sheet resistance was measured with a four-point probe (CD ResMap), optical properties were determined by collecting R, T, and A spectra with a Filmetrics F50xy, and thickness and optical constants were determined with spectroscopic ellipsometry (Woollam M-2000).

[0108] Referring to FIG. 2A, a plot of the reciprocal of sheet resistance versus film thickness is provided for chromium films of various thicknesses deposited at 23° C. and 325° C. in Examples 1A and 1B, respectively. Referring to FIG. 2B, a plot of the absorptance versus wavelength is provided for glass substrates (Comparative Example 1) and chromium films of various thicknesses, 7.1 nm, 6.6 nm, 4.4 nm, and 2.7 nm, deposited on glass substrates at 23° C. in Examples 1C-1F, respectively. As can be seen from FIG. 2A, below about 3 nm, the reciprocal of the sheet resistance of the chromium layer deviates from a linear slope. Similarly, FIG. 2B shows an anomalous decrease in infrared absorption below the same thickness range, suggesting a percolation threshold in this thickness range.

[0109] 2C and 2D, scanning electron microscope (SEM) images of chromium films deposited at 23° C. and 325° C., respectively, are provided. The "island" or "island-like" structure of the chromium film is clearly visible. That is, the chromium film is physically discontinuous, and electrons have some difficulty moving from one "island" to another, resulting in reduced electrical conductivity. These results suggest that a thin chromium layer, less than about 2 nm thick, would be a suitable absorber layer with low electrical conductivity that does not exceed the percolation threshold of chromium.

[0110] Example 2 In this example, thin nickel (Ni) films were sputtered at room temperature onto 1 mm thick Corning Gorilla® Glass 3 substrates (i.e., chemically strengthened glass substrates). Electrical sheet resistance was measured with a four-point probe (CD ResMap), optical properties were determined by collecting R, T, and A spectra with a Filmetrics F50xy, and thickness and optical constants were determined with spectroscopic ellipsometry (Woollam M-2000).

[0111] Referring to Figure 3A, a plot of reciprocal sheet resistance versus film thickness is provided for nickel films of various thicknesses, from 0.88 nm to 42 nm, deposited at 23°C and 325°C in Examples 2A and 2B, respectively. Referring to Figure 3B, a plot of absorbance versus wavelength is provided for nickel films of various thicknesses, from 0.62 nm, 0.72 nm, and 0.84 nm, deposited on glass substrates at 23°C in Examples 2C, 2D, and 2E, respectively. As is evident from Figures 3A and 3B, below about 0.88 nm, the sheet resistance is immeasurable (<500 kOhm / sq), yet these layers produce optical absorbance greater than 10% across the visible spectrum.

[0112] Example 3 The optical data from Example 1 was used to model transmittance values ​​for these chrome films. Specifically, in this example, transmittance levels were simulated for absorber stacks containing one to three chromium layers at thicknesses of 0.5, 1, and 2 nm. Referring to Figures 4A-4C, plots of transmittance versus wavelength are provided for one, two, and three chromium layers at three thickness levels (i.e., 0.5, 1, and 2 nm) in Examples 3A-3I, respectively, with a thin silica layer deposited between each chromium layer. As is evident from Figures 4A-4C, these results demonstrate that the cover article configurations of the present disclosure can be tailored to achieve transmittance levels from 20% to 80% (over a wavelength range of 350 nm to 850 nm), including levels dictated by the specific end-use display application. This tailoring can be achieved by varying the composition, thickness, and number of absorber layers.

[0113] Example 4 Table 1 shows the design (Example 4) of a cover article (see also FIG. 1A) of the present disclosure that is semi-transparent and has anti-reflective (AR) properties. In particular, the outer layered film (AR stack) is made of low and high refractive index materials, SiO and SiN. x Furthermore, the inner layered film (absorber stack) employs a 0.16 nm thick chromium absorber layer (low RI layer) with a 10 nm SiO2 dielectric spacer.

[0114] Referring to Figure 5, a plot of reflectance, transmittance, and absorbance versus wavelength for the cover article of Example 4 is provided. As can be seen from Figure 5, this design exhibits an average transmittance of about 80% and an average reflectance of about 0.6% across the visible spectrum from 400 to 700 nm. In addition, the cover article design of Example 4 using a Corning Gorilla Glass 3 substrate was placed on an Apple® iPad®, and no change in the touchscreen performance of the iPad device was observed.

[0115] [Table 1]

[0116] Example 5 Table 2 shows the design (Example 5) of a cover article (see also FIG. 1A) of the present disclosure that is semi-transparent and has anti-reflective (AR) properties. In particular, the outer layered film (AR stack) is made of low and high refractive index materials, SiO and SiN. x Furthermore, the inner layered film (absorber stack) employs a 0.6 nm thick nickel absorber layer (low RI layer) with a 10 nm SiO2 dielectric spacer.

[0117] Referring to Figure 6, a plot of reflectance, transmittance, and absorbance versus wavelength is provided for the cover article of Example 5. As can be seen from Figure 6, this design exhibits an average transmittance of about 63% and an average reflectance of about 0.8% reflectance across the visible spectrum from 400 to 700 nm.

[0118] [Table 2]

[0119] Example 6 In this example, a thin diamond-like carbon (DLC) film was deposited at room temperature by PECVD on a 1 mm Corning Gorilla Glass 3 substrate. The film in this example (Example 6) was deposited using a PECVD process, and the refractive index and extinction coefficient across the visible spectrum were measured using spectroscopic ellipsometry. Referring to Figure 7, a plot of the refractive index and extinction coefficient (n, k) of the diamond-like carbon (DLC) layer is provided. As can be seen from Figure 7, the DLC layer exhibits a refractive index (n) of 2.0 to 2.2 across the visible spectrum from 400 nm to 700 nm, and a maximum extinction coefficient of approximately 0.27. Additionally, these values ​​suggest that the absorption of the DLC layer is higher than that of other dielectric materials, such as SiO2 and Nb2O5, making it particularly advantageous for use in the cover articles of the present disclosure.

[0120] Example 7A Table 3A shows the design (Example 7A) of a semi-transparent, anti-reflective (AR) cover article (see also FIG. 1B) of the present disclosure, constructed with a single DLC absorber layer. In particular, the outer layered film (AR stack) employs seven alternating layers of low and high refractive index materials, SiO and NbO. Furthermore, the inner layered film (absorber stack) employs a single DLC absorber layer having a thickness of 50 nm.

[0121] Referring to Figure 8A, a plot of reflectance, transmittance, and absorbance versus wavelength is provided for the cover article of Example 7. As can be seen from Figure 8A, this design exhibits an average transmittance of about 83.2% and an average absorbance of about 13.1% across the visible spectrum from 400 to 700 nm, and an average photopic reflectance of about 0.28%.

[0122] [Table 3A]

[0123] Example 7B Table 3B shows a design (Example 7B) of a semi-transparent, anti-reflective (AR) cover article (see also FIG. 1C) of the present disclosure, constructed with a total of five DLC absorber layers. In particular, the outer layered film (AR stack) employs nine alternating layers of low refractive index (SiO) or high refractive index (NbO) and absorber layers (DLC). Furthermore, the inner layered film (absorber stack) employs a single DLC absorber layer having a thickness of 127.2 nm.

[0124] Referring to Figure 8B, a plot of reflectance, transmittance, and absorbance versus wavelength is provided for the cover article of Example 7B. As can be seen from Figure 8B, this design exhibits an average transmittance of about 62.8%, an average absorbance of about 36.8%, and an average photopic reflectance of about 0.25% across the visible spectrum from 400 to 700 nm.

[0125] [Table 3B]

[0126] Example 7C Table 3C shows a design (Example 7C) of a semi-transparent, anti-reflective (AR) cover article (see also FIG. 1B) of the present disclosure, constructed with a total of three DLC absorber layers. In particular, the outer layered film (AR stack) employs seven alternating layers of low refractive index (SiO) and high refractive index (NbO) or absorber layers (DLC). Furthermore, the inner layered film (absorber stack) employs a single DLC absorber layer having a thickness of 200 nm.

[0127] Referring to Figure 8C, a plot of reflectance, transmittance, and absorbance versus wavelength is provided for the cover article of Example 7C. As can be seen from Figure 8C, this design exhibits an average transmittance of about 42.3% and an average absorbance of about 53.5% across the visible spectrum from 400 to 700 nm, as well as an average photopic reflectance of about 0.44%.

[0128] [Table 3C]

[0129] Example 8 In this example, semi-transparent, anti-reflective (AR) cover articles of the present disclosure were fabricated with a single DLC absorber layer having various thickness levels according to the design in Table 3A. Specifically, the samples in this example employed DLC absorber layers having thicknesses of 55 nm, 81 nm, and 180 nm, designated Examples 8A-8C, respectively.

[0130] Referring to Figure 9A, plots of reflectance and transmittance versus wavelength are provided for the cover articles of this example (Examples 8A-8C). The measured spectra show that the average transmittance (T) of these samples in the visible spectrum from 400 nm to 700 nm ranges from 30% to 75% as a function of DLC layer thickness from 55 nm to 180 nm. Furthermore, the reflectance (R) levels of these samples vary from 0.34% to 2.2% as a function of DLC layer thickness from 55 nm to 180 nm. More specifically, the average transmittance and photopic reflectance values ​​for the sample with a 55 nm DLC layer (Example 8A) are 74.1% and 0.34%, respectively; the average transmittance and photopic reflectance values ​​for the sample with an 81 nm DLC layer (Example 8B) are 67.2% and 0.58%, respectively; and the average transmittance and photopic reflectance values ​​for the sample with a 180 nm DLC layer (Example 8C) are 31.5% and 2.5%, respectively.

[0131] 9B, a plot of the reflected color of the first surface of the exemplary cover articles of this example (Examples 8A-8C) and comparative cover articles (Comparative Examples 8A-8C) utilizing black matrix material at the same thicknesses (i.e., 55 nm, 81 nm, and 180 nm) as the corresponding cover articles of the present disclosure, measured at normal incidence angles with a D65 illuminant, is provided. * , a * , and b * The values ​​are as follows: 3.1, 35.7, and -40.4, respectively (Example 8A); 5.3, 16.4, and -24.8, respectively (Example 8B); and 17.8, -4.5, and -12.9, respectively (Example 8C). Notably, the reflection color coordinates of the samples of this example (Examples 8A-8C) are very similar to the reflection color coordinates of the comparative black matrix samples of this example (Comparative Examples 8A-8C). This indicates that the cover articles of this example, employing various DLC layer thickness levels, can achieve color levels equivalent to those of conventional black matrix coatings.

[0132] Example 9 In this example, the cover article of Example 8 and the comparative article of Example 8 were fabricated on respective portions of a glass substrate, as shown in Figure 10A. As shown in the optical image in Figure 10A, these samples were designated Examples 9A-9C and each had a single DLC absorber layer having thicknesses of 81 nm, 180 nm, and 55 nm, and a corresponding portion with black matrix material having the same thickness.

[0133] Next, using the a* and b* color coordinate measurements performed on the samples on a CM-700d (Konica Minolta, Inc.) spectrophotometer, the dead-front color shift (ΔE) values ​​for each sample (Examples 9A-9C) were calculated at incident measurement angles of 0°, 45°, and 90°. Referring now to FIG. 10B, a bar graph of the calculated dead-front color shift (ΔE) values ​​for each of these cover articles is provided. The data in FIG. 10B clearly demonstrates that the translucent cover article with AR properties and a DLC absorber layer thickness of 180 nm exhibits very good dead-front performance across all incident measurement angles, with ΔE values ​​of 2.3 at 90° and less than 1.5 at both 0° and 45°. In comparison, the ΔE value between the conventional black matrix and the viewing area of ​​the LCD module (the area not covered by the conventional black matrix) is greater than 5 at an incident measurement angle of 45°. These results demonstrate that the layered films described herein improve dead-front performance over existing displays.

[0134] Example 10 In this example, Examples 11 and 12, and Comparative Examples 13 and 14, thin metal alloy absorber layer films (<150 nm thick) were co-sputtered on Si substrates and 1 mm thick Corning Gorilla Glass 3 substrates (i.e., chemically strengthened glass substrates) in a confocal configuration by DC sputtering with an AJA Orion sputtering deposition system at room temperature. Sputtering was performed under an argon atmosphere at 2 mTorr (approximately 267 mPa) using a 3-inch target. All composition determinations were made by measuring the deposition rate of each gun individually with a quartz crystal monitor. The resulting films were characterized by a four-point probe (CD ResMap), optical transmittance and reflectance (Filmetrics F50xy), and spectroscopic ellipsometry (Woollam CompleteEase) for refractive index determination. Touchscreen compatibility was assessed by placing each coated sample on an iPhone® SE and recording the sample's effect on touchscreen performance using the iPhone's calculator application.

[0135] In this example, thin absorbing films of Si—Al alloys were deposited with various compositions, as listed in Table 4 below and shown in FIG. 11A. Table 4 also lists the inverse sheet resistance ("1 / Rs"), optical density ("OD"), transmittance at 550 nm ("T550nm"), film thickness ("Th(nm)"), and touchscreen performance ("Touch"). Referring to FIG. 11A, a plot of the ratio of extinction coefficients (k) at 400 nm / 550 nm and 780 nm / 440 nm for the Si—Al films of this example as a function of Si volume fraction is provided. As is evident from Table 4 and FIG. 11A, acceptable touchscreen performance was observed for films containing 69% or more silicon (by volume) (i.e., Examples 10A-10J), while a Si—Al alloy film containing 67% Si exhibited unacceptable touchscreen performance (i.e., Comparative Example 10).

[0136] Referring to Figures 11B-11D, plots of reflectance, transmittance, and absorbance versus wavelength are provided for three Si-Al film compositions (65-71% Si) at two film thicknesses for this example and the comparative examples (i.e., Example 10A, Example 10B, and Comparative Example 10), respectively. In particular, these figures demonstrate the optical performance of thin (<10 nm) Si-Al films according to this example. While transmittance is higher for the red than for the blue, performance is better than that of a DLC absorber layer. These measurements demonstrate that semitransparent AR coatings can be formed at Si-Al film thicknesses less than 50 nm, with transmittance down to 10%. The relative red and blue absorption of the films is quantified by plotting k at 400 nm normalized to k at 550 nm and k at 780 nm normalized to 550 nm. An ideal material would exhibit k400 / k550 = k780 / k550 = 1. For Si-Al alloy absorbing films, the best optical performance is achieved with about 70% Si (by volume), where k400 / k550 is about 2 and k780 / k550 is about 0.5.

[0137] [Table 4]

[0138] Example 11 In this example, thin absorbing films of Si-Zn alloys were deposited with various compositions, as shown in FIG. 12. Referring to FIG. 12, a plot of the ratio of extinction coefficients (k) at 400 nm / 550 nm and 780 nm / 440 nm for the Si-Zn films of this example, each having a thickness of 105.53 nm, as a function of Si volume fraction is provided. As can be seen from FIG. 12, acceptable touchscreen performance was observed for films containing 80% or more silicon (by volume) (i.e., Examples 11A-11D), while unacceptable touchscreen performance was observed for Si-Zn alloy films containing less than 80% Si (by volume) (i.e., Comparative Examples 11A-E). Furthermore, as shown in FIG. 12, the best optical performance was observed for the Si-Zn film containing approximately 80% Si (by volume) (Example 11A), with k400 / k550 of 2 and k780 / k550 of 0.31.

[0139] Example 12 In this example, thin absorbing films of Si—Sn alloys were deposited with various compositions, as shown in FIG. 13. Referring to FIG. 13, a plot of the ratio of the extinction coefficients (k) at 400 nm / 550 nm and 780 nm / 440 nm of the Si—Sn films of this example, each having a thickness of 105.92 nm, as a function of Si volume fraction is provided. As can be seen from FIG. 13, acceptable touchscreen performance was observed for films containing 60% or more silicon (by volume) (i.e., Examples 12A-12H), while unacceptable touchscreen performance was observed for Si—Sn alloy films containing less than 60% Si (by volume) (i.e., Comparative Example 12). Furthermore, as shown in FIG. 13, the best optical performance was observed for the Si—Zn film containing approximately 60% Si (by volume) (Example 12A), with a k400 / k550 of 2 and a k780 / k550 of 0.37.

[0140] Comparative Example 13 In this comparative example, thin absorbing films of Si—Cu alloys were deposited with various compositions, as shown in FIG. 14 (all designated “Comparative Example 13”). Referring to FIG. 14, a plot of the ratio of extinction coefficients (k) at 400 nm / 550 nm and 780 nm / 440 nm for the Si—Cu films of this example, each having a thickness of 51.50 nm, as a function of Si volume fraction is provided. As is evident from FIG. 14, acceptable touchscreen performance was observed only for films containing 95% or more silicon (by volume). Nevertheless, all samples are considered unacceptable because all Si—Cu alloys form silicides, and the compositional range for acceptable touchscreen performance is narrow. Furthermore, the Si—Cu films of this example exhibit k400 / k550 of 2.0 and k780 / k550 of 0.37, as shown in FIG. 14.

[0141] Comparative Example 14 In this comparative example, thin absorbing films of Si—Cr alloys were deposited at various compositions, as shown in FIG. 15 (all designated “Comparative Example 14”). Referring to FIG. 15, a plot of the ratio of extinction coefficients (k) at 400 nm / 550 nm and 780 nm / 440 nm for the Si—Cr films of this example as a function of Si volume fraction is provided. As is evident from FIG. 15, acceptable touchscreen performance was not observed for the films of this example, including films containing 95% or more silicon (by volume). Furthermore, because all Si—Cr alloys form silicides, all samples are considered unacceptable.

[0142] Example 15 In this example, a semi-transparent, anti-reflective (AR) cover article of the present disclosure was fabricated according to the design in Table 5 below (designated "Example 15"), comprising a single absorbing layer including a Si-Al alloy of composition and structure equivalent to that of Example 10A (see Table 4 in Example 10 above). Specifically, the Si-Al alloy absorbing layer was located within an inner layered film above an impedance matching stack of alternating SiO, NbO, and SiO layers, and had a thickness of 9.64 nm. This impedance matching stack was intended to minimize reflections from the substrate (a Corning Gorilla Glass 3 substrate). Furthermore, in this cover article design, the outer layered film included multiple NbO and SiO layers configured to provide anti-reflective (AR) functionality, for a total of six layers.

[0143] Referring to Figure 16A, a plot of simulated reflectance, transmittance, and absorptance (%) versus wavelength is provided for an exemplary cover article of this example (Example 15) employing a Si-Al absorbing layer. As can be seen from Figure 16A, the sample of this example exhibits an average photopic reflectance of 2.8% and an average transmittance of 53%.

[0144] Referring now to Figure 16B, a simulated color plot of x and y coordinates on the 1931 CIE scale at normal incidence (0°) for the cover article of this example (Example 15) employing a Si-Al absorber layer is provided. As can be seen from Figure 16B, the simulated color of this example is a white or pinkish hue.

[0145] [Table 5]

[0146] Example 16 Table 6 shows the design (Example 16) of a cover article (see also FIG. 1A) of the present disclosure that is translucent and has anti-reflective (AR) properties. Specifically, the outer layered film (AR stack) employs four alternating layers of low and high refractive index materials, SiO and NbO, with SiO forming the outermost layer (the layer farthest from the substrate). Furthermore, the inner layered film (absorber stack) employs a first low-RI layer (SiO) and six Nb layers separated from each other by low-RI (SiO) layers. The inner layered film employs a stack of six periods, each period including Nb and SiO layers with the same thickness.

[0147] [Table 6]

[0148] Referring to Figure 18, there is provided a plot of simulated reflectance, transmittance, and absorptance versus wavelength for the cover article of Example 16. As can be seen from Figure 18, this design exhibits an average transmittance of about 86% across the visible spectrum from 400 to 700 nm, and a photopic reflectance of about 0.3%.

[0149] Example 17 Table 7 shows the design (Example 17) of a cover article (see also FIG. 1A) of the present disclosure that is translucent and has anti-reflective (AR) properties. In particular, the outer layered film (AR stack) employs four alternating layers of low and high refractive index materials, SiO and NbO. Furthermore, the inner layered film (absorption stack) employs a first low RI layer (SiO) and 18 Nb layers separated from each other by low RI (SiO) layers. The inner layered film employs a stack of 18 periods, each period including Nb and SiO layers with the same thickness.

[0150] [Table 7-1]

[0151] [Table 7-2]

[0152] Referring to Figure 19, the measured reflectance and transmittance plots for the cover article of Example 17 are provided against wavelength. As can be seen from Figure 19, this design exhibits an average transmittance of about 29% across the visible spectrum from 400 to 700 nm, and a photopic reflectance of about 0.42%. Under the D65 light source, the article of Example 17 exhibits a reflected color of a*=-4.582, b*=-2.21 (when not laminated to a display). The cover article of Example 17 is also laminated to a commercially available display panel, and color is measured to determine the ΔE value. The results are provided in Table 8 below.

[0153] [Table 8]

[0154] The ΔE measurements shown in Table 8 were measured at a 45° viewing angle. The "BM" value in Table 8 represents the area of ​​a display incorporating both the black matrix ink material and the coating stack (including the inner and outer layered films) disposed on both sides of the glass (e.g., around the periphery extending inward from the edge of the glass substrate). Such low values ​​indicate that the film stack of the present disclosure can provide an effective dead-front effect in which the display areas of the article that transmit images generated by the display panel through the cover article (areas that do not overlap with the black matrix material associated with the attached display panel or black matrix material disposed on the article) blend in appearance with the non-display areas that do not transmit images when the display panel is in an inactive state (e.g., the non-display areas may be covered by or overlapped with a black matrix material such as a high optical density ink). Indeed, the cover article according to Example 17 allowed images generated by the display panel to be transmitted without any visible degradation in image quality while providing a blended appearance with the black matrix material when powered off.

[0155] In embodiments, the cover article described herein exhibits a maximum ΔE value between viewing areas not covered with black matrix material and non-viewing areas covered with black matrix material that is less than 0.2 (e.g., 0.19 or less, 0.18 or less, 0.17 or less, 0.16 or less, 0.15 or less, 0.15) at a viewing angle of 45° when the cover article is illuminated with a D65 light source.

[0156] The various features described herein may be combined in any combination, for example, as listed in the following embodiments.

[0157] Embodiment 1. A cover article for a display panel is provided, comprising: a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other, the substrate comprising a glass, glass ceramic, or ceramic material; an inner layer film disposed on the outer major surface of the substrate; and an outer layer film disposed on the inner layer film. One or both of the inner layer film and the outer layer film comprises one or more absorbing layers. The outer layer film comprises a plurality of alternating high and low refractive index layers. Each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers. Each absorbing layer has at least 10 5 The article exhibits a sheet resistance of Ω / sq. Furthermore, the article exhibits a dead-front color shift (ΔE) of less than 4.0 at incident measurement angles of 0° to 90° as measured relative to a control article comprising a substrate glass, glass-ceramic, or ceramic material and a standard black matrix disposed on the glass, glass-ceramic, or ceramic material.

[0158] Embodiment 2. The cover article of embodiment 1 is provided, wherein the cover article exhibits an average two-sided transmittance of 40% to 80% in the visible spectrum from 400 nm to 700 nm.

[0159] Embodiment 3. The cover article of embodiment 1 or embodiment 2 is provided, wherein the cover article exhibits an average first surface photopic reflectance of less than 4%.

[0160] Embodiment 4. Each of the high refractive index layers in the outer layered film is Si3N4, SiN x , SiO x N y , AlN x , AlO x N y , SiAl x O y N z , TiO2, HfO2, ZrO2, Nb2O5, or Ta2O5, and each of the low refractive index layers in the outer layered film comprises a silicon-containing oxide.

[0161] Embodiment 5. A cover article according to any one of embodiments 1 to 4, wherein the inner layered membrane comprises one or more absorbent layers.

[0162] Embodiment 6. The cover article of any one of embodiments 1 to 5, wherein each absorbing layer exhibits an average absorbance of 1% to 60% in the visible spectrum from 400 nm to 700 nm.

[0163] Embodiment 7. A cover article for a display panel is provided, comprising: a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other, the substrate comprising a glass, glass ceramic, or ceramic material; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. The inner layered film comprises a plurality of low refractive index layers and an absorbing layer. The outer layered film comprises a plurality of alternating high refractive index layers and low refractive index layers. Each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers. Additionally, each absorbing layer comprises a metal or metal alloy. Each absorbing layer comprises at least 10 5 They exhibit sheet resistances of Ω / sq and extinction coefficients greater than 0.5 in the visible spectrum from 400 nm to 700 nm.

[0164] Embodiment 8. The cover article of embodiment 7 is provided, wherein each absorbent layer comprises Ni, Cr, a Ni-containing alloy, a Cr-containing alloy, or a Ni / Cr alloy.

[0165] Embodiment 9. The cover article of embodiment 8 is provided, wherein each absorbing layer comprises Cr and has a thickness of less than 2 nm.

[0166] Embodiment 10. The cover article of embodiment 8 is provided, wherein each absorbing layer comprises Ni and has a thickness of less than 1 nm.

[0167] Embodiment 11. The cover article of any of embodiments 7 to 10 is provided, wherein the inner layered membrane comprises 2 to 20 absorbent layers.

[0168] Embodiment 12. Each of the high refractive index layers of the outer layered film is Si3N4, SiN x , SiO x N y , AlN x , AlO x N y , SiAl x O y N z , TiO2, HfO2, ZrO2, Nb2O5, or Ta2O5, and each of the low refractive index layers of the outer layered film and the inner layered film comprises a silicon-containing oxide.

[0169] Embodiment 13. The cover article of any of embodiments 7 to 12 is provided, wherein the cover article exhibits an average two-side transmission of 40% to 80% in the visible spectrum from 400 nm to 700 nm, and an average first-surface photopic reflectance of less than 4%.

[0170] Embodiment 14. A cover article for a display panel is provided, comprising: a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other, the substrate comprising a glass, glass ceramic, or ceramic material; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. One or both of the inner layered film and the outer layered film comprise one or more absorbing layers. The outer layered film comprises a plurality of alternating high and low refractive index layers. Each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers. Additionally, each absorbing layer comprises a diamond-like carbon (DLC) material. Each absorbing layer comprises at least 10 5 They exhibit sheet resistances of Ω / sq and extinction coefficients of about 0.05 to about 0.4 in the visible spectrum from 400 nm to 700 nm.

[0171] Embodiment 15. The cover article of embodiment 14 is provided, wherein each absorbing layer comprises a thickness of about 5 nm to about 500 nm.

[0172] Embodiment 16. A cover article according to embodiment 14 or embodiment 15 is provided, wherein one or both of the inner layered membrane and the outer layered membrane comprises 1 to 10 absorbent layers.

[0173] Embodiment 17. The cover article of any one of embodiments 14 to 16, wherein the total thickness of the absorbing layer is 25 nm to 500 nm.

[0174] Embodiment 18. Each of the high refractive index layers of the outer layered film is Si3N4, SiN x , SiO x N y , AlN x , AlO x N y , SiAl x O y N z, TiO2, HfO2, ZrO2, Nb2O5, or Ta2O5, and each of the low refractive index layers of the outer layered film and the inner layered film comprises a silicon-containing oxide.

[0175] Embodiment 19. The cover article of any of embodiments 14 to 18 is provided, wherein the cover article exhibits an average two-side transmission of 40% to 80% in the visible spectrum from 400 nm to 700 nm, and an average first-surface photopic reflectance of less than 4%.

[0176] Embodiment 20. The cover article of any of embodiments 14 to 19, wherein the article exhibits a dead-front color shift (ΔE) of less than 4.0 at incident measurement angles of 0° to 90°, as measured compared to a control article comprising a substrate glass, glass ceramic, or ceramic material and a standard black matrix disposed on the glass, glass ceramic, or ceramic material.

[0177] Embodiment 21. A cover article for a display panel includes a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other, the substrate comprising a glass, glass ceramic, or ceramic material; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. The inner layered film includes a plurality of low refractive index and one or more absorbing layers, the outer layered film including a plurality of alternating high refractive index and low refractive index layers, each high refractive index layer having a refractive index greater than the refractive index of each low refractive index layer, and each absorbing layer is a silicon-metal alloy including Si—Al, Si—Sn, Si—Zn, or a combination thereof. Further, each absorbing layer has at least 10 5 They exhibit sheet resistances of Ω / sq and extinction coefficients greater than 1.0 in the visible spectrum from 400 nm to 700 nm.

[0178] Embodiment 22. The cover article of embodiment 21 is provided, wherein the silicon-metal alloy does not include any silicides.

[0179] Embodiment 23. The cover article of embodiment 21 or embodiment 22 is provided, wherein each absorbing layer has a thickness of less than 100 nm.

[0180] Embodiment 24. The cover article of any of embodiments 21 to 23, wherein the silicon metal alloy is Si—Al containing at least 69% silicon by volume.

[0181] Embodiment 25. The cover article of any of embodiments 21 to 23 is provided, wherein the silicon metal alloy is Si—Sn containing at least 60% silicon by volume.

[0182] Embodiment 26. The cover article of any one of embodiments 21 to 23 is provided, wherein the silicon metal alloy is Si-Zn containing at least 80% silicon by volume.

[0183] Embodiment 27. A cover article for a display panel includes a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. The outer layered film includes a plurality of alternating high refractive index layers and low refractive index layers. Each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers. The high refractive index layer of the outer layered film includes a metal oxide. The inner layered film includes one or more absorbing layers having an average extinction coefficient of 1.3 or greater from 400 nm to 700 nm. The one or more absorbing layers are formed from a metal of the metal oxide included in the outer layered film, rather than an oxide. The article exhibits a dead-front color shift (ΔE) of less than 7.0 at incident measurement angles of 0° to 90°, measured relative to a black matrix material disposed on the substrate.

[0184] Embodiment 28. The cover article of embodiment 27 is provided, wherein the cover article exhibits an average two-sided transmittance of 20% to 90% in the visible spectrum from 400 nm to 700 nm.

[0185] Embodiment 29. The cover article of embodiment 27 or embodiment 28 is provided, wherein the cover article exhibits an average first surface photopic reflectance of less than 4%.

[0186] Embodiment 30. Each absorbent layer has at least 10 5 30. The cover article of any of embodiments 27 to 29, wherein the cover article exhibits a sheet resistance of Ω / sq.

[0187] Embodiment 31. The cover article of any of embodiments 27 to 30 is provided, wherein each of the one or more absorbent layers comprises Nb and the metal oxide comprises Nb2O5.

[0188] Embodiment 32. A cover article according to any one of embodiments 27 to 31 is provided, wherein the inner layered film comprises alternating low refractive index layers and absorbing layers, each absorbing layer having a refractive index greater than the refractive index of an adjacent one of the low refractive index layers over a wavelength range of 400 nm to 700 nm.

[0189] Embodiment 33. A cover article as described in embodiment 32 is provided, wherein the alternating low refractive index layers and absorbing layers of the inner layered film include: a first low refractive index layer positioned closest to the substrate; and a plurality of alternating periods, each period including an absorbing layer having a first thickness and a low refractive index layer having a second thickness, and the first low refractive index layer having a thickness greater than the second thickness.

[0190] Embodiment 34. The cover article of embodiment 33 is provided, wherein each of the one or more absorbing layers comprises Nb, and the total thickness of the absorbing layers in the plurality of alternating periods ranges from 10 nm to 24 nm.

[0191] Embodiment 35. The cover article of embodiment 34 is provided, wherein the plurality of alternating periods includes at least three periods.

[0192] Embodiment 36. The cover article of embodiment 34 or 35 is provided, wherein each of the absorbing layers comprises a thickness of 0.7 nm or less.

[0193] Embodiment 37. The cover article of any of embodiments 34 to 35 is provided, wherein each of the absorbing layers comprises a thickness of 0.8 nm or more and 2.0 nm or less.

[0194] Embodiment 38. A cover article according to any one of embodiments 27 to 36 is provided, wherein the cover article exhibits a maximum ΔE value between a viewing area not covered with black matrix material and a non-viewing area covered with black matrix material that is less than 0.2 at a viewing angle of 45° when the cover article is illuminated with a D65 light source.

[0195] Embodiment 39. A cover article for a display panel is provided, comprising: a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. The outer layered film comprises a plurality of alternating high and low refractive index layers. Each of the high refractive index layers has a refractive index greater than that of each of the low refractive index layers. The high refractive index layer of the outer layered film comprises Nb2O5. The inner layered film comprises one or more absorbing layers comprising Nb not in the form of an oxide. The article exhibits a dead-front color shift (ΔE) of less than 7.0 at incident measurement angles of 0° to 90°, as measured relative to a black matrix material disposed on the substrate.

[0196] Embodiment 40. The cover article of embodiment 39 is provided, wherein the cover article exhibits an average two-sided transmittance of 20% to 90% in the visible spectrum from 400 nm to 700 nm.

[0197] Embodiment 41. The cover article of embodiment 39 or embodiment 40 is provided, wherein the cover article exhibits an average first surface photopic reflectance of less than 4%.

[0198] Embodiment 42. A cover article according to any one of embodiments 39 to 41, wherein the inner layered film comprises alternating low refractive index layers and absorbing layers.

[0199] Embodiment 43. A cover article as described in embodiment 42 is provided, wherein the alternating low refractive index layers and absorbing layers of the inner layered film include: a first low refractive index layer positioned closest to the substrate; and a plurality of alternating periods, each period including an absorbing layer having a first thickness and a low refractive index layer having a second thickness, and the first low refractive index layer having a thickness greater than the second thickness.

[0200] Embodiment 44. The cover article of embodiment 43 is provided, wherein the total thickness of the absorbing layer in the plurality of alternating periods ranges from 10 nm to 24 nm.

[0201] Embodiment 45. The cover article of embodiment 43 or 44 is provided, wherein the plurality of alternating periods includes at least three periods.

[0202] Embodiment 46. The cover article of any of embodiments 43 to 45 is provided, wherein each of the absorbing layers comprises a thickness of 0.7 nm or less.

[0203] Embodiment 47. The cover article of any of embodiments 43 to 45 is provided, wherein each of the absorbing layers comprises a thickness of 0.8 nm or more and 2.0 nm or less.

[0204] Embodiment 48. A cover article according to any one of embodiments 39 to 47 is provided, wherein the cover article exhibits a maximum ΔE value between a viewing area not covered with black matrix material and a non-viewing area covered with black matrix material of less than 0.2 at a viewing angle of 45° when the cover article is illuminated with a D65 light source.

[0205] Embodiment 49. A cover article for a display panel is provided, comprising: a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other; an inner layered film disposed on the outer major surface of the substrate; and an outer layered film disposed on the inner layered film. The outer layered film comprises a plurality of alternating high and low refractive index layers. Each of the high refractive index layers has a refractive index greater than that of each of the low refractive index layers. The high refractive index layer of the outer layered film comprises Nb2O5. The inner layered film comprises an inner low refractive index layer disposed closest to the substrate; and a plurality of alternating periods, each period comprising a Nb layer having a first thickness and a low refractive index layer having a second thickness. Each of the low refractive index layers in the inner layered film has a refractive index at 550 nm that is less than that of the Nb layer. The plurality of alternating periods comprises at least three periods.

[0206] Embodiment 50. The cover article of embodiment 49 is provided, wherein the cover article exhibits an average two-sided transmittance of 20% to 90% in the visible spectrum from 400 nm to 700 nm.

[0207] Embodiment 51. The cover article of embodiment 49 or embodiment 50 is provided, wherein the cover article exhibits an average first surface photopic reflectance of less than 4%.

[0208] Embodiment 52. A cover article according to any of embodiments 49 to 51 is provided, wherein the article exhibits a dead-front color shift (ΔE) of less than 7.0 at incident measurement angles of 0° to 90°, as measured relative to a black matrix material disposed on a substrate.

[0209] Embodiment 53. The cover article of any of embodiments 49 to 52 is provided, wherein each of the absorbing layers comprises a thickness of 0.7 nm or less.

[0210] Embodiment 54. The cover article of any of embodiments 49 to 52 is provided, wherein each of the absorbing layers comprises a thickness of 0.8 nm or more and 2.0 nm or less.

[0211] Preferred embodiments of the present invention will be described below in detail.

[0212] Embodiment 1 In a cover article for a display panel, a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other; an inner layered film disposed on the outer major surface of the substrate; and an outer layer membrane disposed on the inner layer membrane; It is equipped with the outer layered film includes a plurality of alternating high and low refractive index layers; each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers; the high refractive index layer of the outer layered film comprises a metal oxide; the inner layered film comprises one or more absorbing layers having an average extinction coefficient of 1.3 or greater from 400 nm to 700 nm; the one or more absorbing layers are not oxides but are formed from the metal of the metal oxide contained in the outer layered film; and the article exhibits a dead-front color shift (ΔE) of less than 7.0 at incident measurement angles of 0° to 90°, as measured relative to a black matrix material disposed on the substrate; Cover article for display panel.

[0213] Embodiment 2 10. The cover article of embodiment 1, wherein the cover article exhibits an average two-sided transmission of 20% to 90% in the visible spectrum from 400 nm to 700 nm.

[0214] Embodiment 3 3. The cover article of embodiment 1 or embodiment 2, wherein the cover article exhibits an average first surface photopic reflectance of less than 4%.

[0215] Embodiment 4 Each absorbent layer is at least 10 54. The cover article of any of embodiments 1 to 3, exhibiting a sheet resistance of Ω / sq.

[0216] Embodiment 5 5. The cover article of any one of the preceding claims, wherein each of the one or more absorbent layers comprises Nb and the metal oxide comprises Nb2O5.

[0217] Embodiment 6 6. The cover article of any one of claims 1 to 5, wherein the inner layered film comprises alternating low refractive index layers and absorbing layers, each absorbing layer having a refractive index greater than the refractive index of an adjacent one of the low refractive index layers over a wavelength range of 400 nm to 700 nm.

[0218] Embodiment 7 The alternating low refractive index layers and absorbing layers of the inner layered film are a first low refractive index layer disposed closest to the substrate; and a plurality of alternating periods, each period comprising an absorbing layer having a first thickness and a low refractive index layer having a second thickness, the first low refractive index layer comprising a thickness greater than the second thickness; 7. The cover article of embodiment 6, comprising:

[0219] Embodiment 8 8. The cover article of embodiment 7, wherein each of the one or more absorbing layers comprises Nb, and the total thickness of the absorbing layers in the plurality of alternating periods ranges from 10 nm to 24 nm.

[0220] Embodiment 9 9. The cover article of embodiment 8, wherein the plurality of alternating periods comprises at least three periods.

[0221] Embodiment 10 10. The cover article of embodiment 8 or 9, wherein each of the absorbing layers comprises a thickness of 0.7 nm or less.

[0222] Embodiment 11 10. The cover article of embodiment 8 or 9, wherein each of the absorbing layers comprises a thickness of 0.8 nm or more and 2.0 nm or less.

[0223] Embodiment 12 12. The cover article of any one of claims 1 to 11, wherein the cover article exhibits a maximum ΔE value between a viewing area not covered with the black matrix material and a non-viewing area covered with the black matrix material at a viewing angle of 45°, when the cover article is illuminated with a D65 light source, of less than 0.2.

[0224] Embodiment 13 In a cover article for a display panel, a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other; an inner layered film disposed on the outer major surface of the substrate; and an outer layer membrane disposed on the inner layer membrane; It is equipped with the outer layered film includes a plurality of alternating high and low refractive index layers; each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers; the high refractive index layer of the outer layered film comprises Nb2O5, the inner layered film comprises one or more absorbing layers containing Nb not in the form of an oxide; and the article exhibits a dead-front color shift (ΔE) of less than 7.0 at incident measurement angles of 0° to 90°, as measured relative to a black matrix material disposed on the substrate; Cover article for display panel.

[0225] Embodiment 14 14. The cover article of embodiment 13, wherein the cover article exhibits an average two-sided transmission of 20% to 90% in the visible spectrum from 400 nm to 700 nm.

[0226] Embodiment 15 15. The cover article of embodiment 13 or embodiment 14, wherein the cover article exhibits an average first surface photopic reflectance of less than 4%.

[0227] Embodiment 16 16. The cover article of any of embodiments 13 to 15, wherein the inner layered film comprises alternating low refractive index layers and absorbing layers.

[0228] Embodiment 17 The alternating low refractive index layers and absorbing layers of the inner layered film are a first low refractive index layer disposed closest to the substrate; and a plurality of alternating periods, each period comprising an absorbing layer having a first thickness and a low refractive index layer having a second thickness, the first low refractive index layer comprising a thickness greater than the second thickness; 17. The cover article of embodiment 16, comprising:

[0229] Embodiment 18 18. The cover article of embodiment 17, wherein the total thickness of the absorbing layer in the plurality of alternating periods ranges from 10 nm to 24 nm.

[0230] Embodiment 19 19. The cover article of claim 17 or claim 18, wherein the plurality of alternating periods includes at least three periods.

[0231] Embodiment 20 20. The cover article of any of embodiments 17-19, wherein each of the absorbing layers comprises a thickness of 0.7 nm or less.

[0232] Embodiment 21 20. The cover article of any one of embodiments 17-19, wherein each of the absorbing layers comprises a thickness of 0.8 nm or more and 2.0 nm or less.

[0233] Embodiment 22 22. The cover article of any one of claims 13 to 21, wherein the cover article exhibits a maximum ΔE value between a viewing area not covered with the black matrix material and a non-viewing area covered with the black matrix material at a viewing angle of 45° that is less than 0.2 when the cover article is illuminated with a D65 light source.

[0234] Embodiment 23 In a cover article for a display panel, a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other; an inner layered film disposed on the outer major surface of the substrate; and an outer layer membrane disposed on the inner layer membrane; It is equipped with the outer layered film includes a plurality of alternating high and low refractive index layers; each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers; the high refractive index layer of the outer layered film comprises Nb2O5, The inner layered membrane is an inner low refractive index layer disposed proximate the substrate; and a plurality of alternating periods, each period including a Nb layer having a first thickness and a low refractive index layer having a second thickness; Including, each of the low refractive index layers in the inner layered film has a refractive index at 550 nm that is less than the refractive index of the Nb layer; and the plurality of alternating periods includes at least three periods; Cover article for display panel Embodiment 24 24. The cover article of embodiment 23, wherein the cover article exhibits an average two-sided transmission of 20% to 90% in the visible spectrum from 400 nm to 700 nm.

[0235] Embodiment 25 25. The cover article of embodiment 23 or embodiment 24, wherein the cover article exhibits an average first surface photopic reflectance of less than 4%.

[0236] Embodiment 26 26. The cover article of any one of claims 23 to 25, wherein the article exhibits a dead-front color shift (ΔE) of less than 7.0 at incident measurement angles of 0° to 90°, as measured relative to a black matrix material disposed on the substrate.

[0237] Embodiment 27 27. The cover article of any of embodiments 23-26, wherein each of the absorbing layers comprises a thickness of 0.7 nm or less.

[0238] Embodiment 28 27. The cover article of any of embodiments 23 to 26, wherein each of the absorbing layers comprises a thickness of 0.8 nm or more and 2.0 nm or less. [Explanation of symbols]

[0239] 100 Covered items 110 Substrate 112 Outer main surface 114 Inner main surface 122 Outermost surface 130A Low refractive index layer / low RI layer 130a Outer layer film / Anti-reflection layer film / AR layer film 130B High refractive index layer / High RI layer 130b inner lamellar membrane 150 Absorbing Layer

Claims

1. In a cover article for a display panel, a substrate having a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, the outer major surface and the inner major surface facing each other; an inner layered film disposed on the outer major surface of the substrate; and an outer layer membrane disposed on the inner layer membrane; where: the outer layered film includes a plurality of alternating high and low refractive index layers; each of the high refractive index layers has a refractive index greater than the refractive index of each of the low refractive index layers; the high refractive index layer of the outer layered film comprises a metal oxide; the inner layered film comprises one or more absorbing layers having an average extinction coefficient of 1.3 or greater from 400 nm to 700 nm; the one or more absorbing layers are formed from a metal of the metal oxide contained in the outer layered film rather than an oxide; the article exhibits a dead-front color shift (ΔE) of less than 7.0 at incident measurement angles of 0° to 90°, as measured relative to a black matrix material disposed on the substrate; Cover article for display panel.

2. 10. The cover article of claim 1, wherein the cover article exhibits an average two-sided transmission of 20% to 90% in the visible spectrum from 400 nm to 700 nm.

3. 3. The cover article of claim 1 or claim 2, wherein the cover article exhibits an average first surface photopic reflectance of less than 4%.

4. Each absorbent layer has at least 10 ５ 3. The cover article of claim 1 or claim 2, exhibiting a sheet resistance of Ω / sq.

5. each of the one or more absorbing layers comprises Nb, and the metal oxide is Nb ２ O ５ The cover article of claim 1 or claim 2, comprising:

6. 3. The cover article of claim 1 or claim 2, wherein the inner layered film comprises alternating low refractive index layers and absorbing layers, each absorbing layer having a refractive index greater than the refractive index of an adjacent one of the low refractive index layers over a wavelength range of 400 nm to 700 nm.

7. The alternating low refractive index layers and absorbing layers of the inner layered film are a first low refractive index layer disposed closest to the substrate; and a plurality of alternating periods, each period comprising an absorbing layer having a first thickness and a low refractive index layer having a second thickness, the first low refractive index layer comprising a thickness greater than the second thickness; The cover article of claim 6, comprising:

8. 8. The cover article of claim 7, wherein each of the one or more absorbent layers comprises Nb, and the total thickness of the absorbent layers in the plurality of alternating periods ranges from 10 nm to 24 nm.

9. The cover article of claim 8 , wherein the plurality of alternating periods includes at least three periods.

10. 3. The cover article of claim 1 or claim 2, wherein the cover article exhibits a maximum ΔE value between a viewing area not covered with the black matrix material and a non-viewing area covered with the black matrix material at a viewing angle of 45° that is less than 0.2 when the cover article is illuminated with a D65 light source.

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