CN117665979A

CN117665979A - Semitransparent anti-reflection assembly for air interface display applications

Info

Publication number: CN117665979A
Application number: CN202211086838.8A
Authority: CN
Inventors: 罗伯特·艾伦·贝尔曼; 陈海星; 高贵明; 欧阳煦; 孙亚伟
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2022-09-06
Filing date: 2022-09-06
Publication date: 2024-03-08
Also published as: WO2024054358A1; WO2024051164A1

Abstract

A cover article for a display panel, comprising: a substrate comprising a thickness of 50 μιη to 5000 μιη, an outer major surface, and an inner major surface, wherein the substrate comprises a glass, glass-ceramic, or ceramic material; an inner film disposed on the outer major surface of the substrate; and an outer film disposed on the inner film. One or both of the inner and outer films include one or more absorbent layers. The outer film includes a plurality of alternating high refractive index layers and low refractive index layers. Each absorbent layer exhibits at least 10 ⁵ Sheet resistance of Ohms/sq. Furthermore, the article exhibits a clear junction color shift (Δe) of less than 4.0 for an incident measurement angle of 0 ° to 90 °.

Description

Semitransparent anti-reflection assembly for air interface display applications

Technical Field

The present disclosure relates to a cover article for an air interface display, and more particularly to a vehicle interior system including an air interface cover article having translucent and anti-reflective properties.

Background

In various applications involving displays, it is desirable to have a display surface or functional surface that has an appearance of an empty junction. Generally, the air interface appearance is a way to hide a display or functional surface such that there is a seamless transition between a display area and a non-display area or between an air interface area and a non-air interface area or other surface of the article. For example, in a typical display having a glass or plastic cover surface, it is possible to see the edge of the display (or transition from a display area to a non-display area) even when the display is turned off. However, it is often desirable from an aesthetic or design perspective to have an empty junction appearance such that when the display is off, the display area and the non-display area appear indistinguishable from each other and the cover surface appears as a uniform appearance.

One application in which an empty interface appearance is desired is in automotive interiors, including in-vehicle displays or capacitive touch interfaces, and other applications in consumer mobile or home electronics, including mobile devices and home appliances. However, it is difficult to achieve a good air interface appearance and achieve a high quality display when the display is turned on.

Conventional methods of achieving an open junction appearance include depositing a non-conductive black ink on one major surface of a transparent substrate and depositing an anti-reflective (AR) coating on the opposite major surface of the substrate. Screen or inkjet printing processes and equipment may be used for the black ink layer and vacuum deposition processes and equipment may be used for the AR coating. Finally, conventional methods are expensive because they require at least two separate deposition processes using different deposition equipment.

Accordingly, there is a need for cover articles for use in air-interface displays, and more particularly for capacitive touch screen applications such as vehicle interior systems, including air-interface cover articles having translucent and antireflective properties that can be achieved with processes and equipment that result in low manufacturing costs.

Disclosure of Invention

According to an aspect of the present disclosure, there is provided a cover article for a display panel, the cover article including: a substrate comprising a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, wherein the outer major surface and the inner major surface are opposite to each other and the substrate comprises a glass, glass ceramic, or ceramic material; an inner film disposed on an outer major surface of the substrate; and an outer film disposed on the inner film. One or both of the inner and outer films include one or more absorbent layers. The outer 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 that of each of the low refractive index layers. Each absorbent layer exhibits at least 10 ⁵ Sheet resistance of Ohms/sq. Furthermore, the article exhibits a clear face color shift (ΔΣ) of less than 4.0 for an incident measurement angle of 0 ° to 90 °, as measured relative to a control article comprising a glass, glass-ceramic or ceramic material of a substrate and a standard black matrix disposed on the glass, glass-ceramic or ceramic material.

According to another aspect of the present disclosure, there is provided a cover article for a display panel, the cover article comprising: a substrate comprising a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, wherein the outer major surface and the inner major surface are opposite to each other and the substrate comprises a glass, glass ceramic, or ceramic material; an inner film disposed on an outer major surface of the substrate; and an outer film disposed on the inner film. The inner film includes a plurality of low refractive index layers and an absorber layer. The outer 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 that of each of the low refractive index layers. In addition, each absorber layer comprises a metal or metal alloy. Each absorption layer exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient greater than 0.05.

According to a further aspect of the disclosure, it is providedA cover article for a display panel, the cover article comprising: a substrate comprising a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, wherein the outer major surface and the inner major surface are opposite to each other and the substrate comprises a glass, glass ceramic, or ceramic material; an inner film disposed on an outer major surface of the substrate; and an outer film disposed on the inner film. One or both of the inner and outer films include one or more absorbent layers. The outer 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 that of each of the low refractive index layers. In addition, each absorber layer comprises a diamond-like carbon (DLC) material. Each absorption layer exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient of about 0.05 to about 0.4.

According to another aspect of the present disclosure, there is provided a cover article for a display panel, the cover article comprising: a substrate comprising a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, wherein the outer major surface and the inner major surface are opposite to each other and the substrate comprises a glass, glass ceramic, or ceramic material; an inner film disposed on an outer major surface of the substrate; and an inner layer film disposed on the inner layer film. The inner film includes a plurality of low refractive index layers and one or more absorber layers. The outer 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 that of each of the low refractive index layers. In addition, each absorber layer is a metallic silicon alloy comprising Si-Al, si-Sn, si-Zn, or a combination thereof. Each absorption layer exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient greater than 1.0.

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

It is to be understood that both the foregoing general description and the following detailed description are 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 in 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 operations of the various embodiments.

Drawings

FIG. 1A is a cross-sectional side view of a cover article according to one or more embodiments described herein;

FIG. 1B is a cross-sectional side view of a cover article according to one or more embodiments described herein;

FIG. 1C is a cross-sectional side view of a cover article according to one or more embodiments described herein;

FIG. 1D is a cross-sectional side view of a cover article according to one or more embodiments described herein;

FIG. 2A is a graph of sheet resistance versus reciprocal film thickness of various thicknesses of chromium films deposited at 23℃and 325℃in accordance with an embodiment of the present disclosure;

FIG. 2B is a graph of absorbance versus wavelength for various thicknesses of glass substrates and chromium films deposited on glass substrates at 23 ℃ in accordance with an embodiment of the disclosure;

FIGS. 2C and 2D are Scanning Electron Microscope (SEM) images of a chromium film having a thickness of 1.8nm deposited at 23℃and a thickness of 1.3nm deposited at 325℃respectively, in accordance with an embodiment of the present disclosure;

FIG. 3A is a graph of sheet resistance versus reciprocal film thickness of nickel films of various thicknesses deposited at 23℃and 325℃in accordance with an embodiment of the present disclosure;

FIG. 3B is a graph of absorbance versus wavelength for various thicknesses of nickel films deposited on a glass substrate at 23 ℃ in accordance with an embodiment of the disclosure;

FIGS. 4A-4C are graphs of transmittance versus wavelength for one layer of chromium, two layers of chromium, and three layers of chromium at three thickness levels, respectively, with a thin layer of silicon dioxide deposited between each chromium layer, in accordance with embodiments of the present disclosure;

FIG. 5 is a graph of reflectance, transmittance, and absorbance versus wavelength for an exemplary cover article of the present disclosure employing a chromium absorber layer;

FIG. 6 is a graph of reflectance, transmittance, and absorbance versus wavelength for an exemplary cover article of the disclosure employing a nickel absorber layer;

FIG. 7 is a graph of refractive index and extinction coefficient (n, k) of a diamond-like carbon (DLC) layer as deposited using a plasma enhanced chemical vapor deposition process, according to an embodiment of the disclosure;

FIG. 8A is a graph of reflectance, transmittance, and absorbance versus wavelength for an exemplary cap article of the present disclosure employing a single DLC layer;

FIG. 8B is a graph of reflectance, transmittance, and absorbance versus wavelength for an exemplary cap article of the present disclosure employing five DLC layers;

FIG. 8C is a graph of reflectance, transmittance, and absorbance versus wavelength for an exemplary cap article of the present disclosure employing three DLC layers;

FIG. 9A is a graph of reflectance and transmittance versus wavelength for an exemplary cap article of the present disclosure employing a single DLC layer, each having different thickness levels;

FIG. 9B is a graph of the color reflected by the first surface at normal incidence measurement angles for the D65 light source of the exemplary cap article of FIG. 9A and a comparative cap article having a black matrix material;

FIG. 10A is an optical image of a cap article having a half portion with the structure of FIG. 9A and another half portion with the black matrix material of FIG. 9B, in accordance with an embodiment of the present disclosure;

FIG. 10B is a bar graph of the blank face color shift (ΔE) of the cover article of FIGS. 9A and 9B as measured at incident angles of 0 °, 45 °, and 90 °, in accordance with an embodiment of the present disclosure;

FIG. 11A is a graph of the ratio of extinction coefficients (k) from 400nm to 550nm and 780nm to 440nm for Si-Al films as a function of Si volume fraction in accordance with embodiments of the disclosure;

FIGS. 11B-11D are corresponding graphs of reflectance, transmittance, and absorbance versus wavelength for three Si-Al film compositions at two film thicknesses according to embodiments of the present disclosure;

FIG. 12 is a graph of the ratio of extinction coefficients (k) for a 400nm to 550nm and 780nm to 440nm of Si-Zn film as a function of Si volume fraction according to an embodiment of the disclosure;

FIG. 13 is a graph of the ratio of extinction coefficients (k) from 400nm to 550nm and 780nm to 440nm for Si-Sn films as a function of Si volume fraction in accordance with embodiments of the present disclosure;

FIG. 14 is a graph comparing the ratio of extinction coefficients (k) for Si-Cu films from 400nm to 550nm and 780nm to 440nm as a function of Si volume fraction;

FIG. 15 is a graph comparing the ratio of extinction coefficients (k) for Si-Cr films from 400nm to 550nm and 780nm to 440nm as a function of Si volume fraction;

FIG. 16A is a graph of simulated reflectance, transmittance, and absorbance versus wavelength for an exemplary cap article of the present disclosure employing a Si-Al absorber layer; and is also provided with

Fig. 16B is a simulated color plot to the left of x and y in the 1931CIE chromaticity of the cover article of fig. 16A in accordance with an embodiment of the present disclosure.

Detailed Description

In the following detailed description, for purposes of explanation and not limitation, example embodiments disclosing specific details are set forth in order to provide a thorough understanding of the various principles of the present disclosure. However, it will be apparent to one having ordinary skill in the art having had the benefit of the present disclosure, that the present disclosure may be practiced in other embodiments that depart from the specific details disclosed herein. In addition, in other instances, descriptions of well-known devices, methods and materials may be omitted so as not to obscure the description of the various principles of the present disclosure. Finally, where applicable, like reference numerals refer to like elements.

Ranges may 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 the term "about" is used to express one or both endpoints of a range or any particular value, each such endpoint or value modified by the term "about" may vary within ±5% of the endpoint or value recited. Similarly, where values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will also be appreciated that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

Directional terms as used herein-e.g., upper, lower, left, right, front, rear, top, bottom, are made with reference only to the drawings as drawn and are not intended to imply absolute orientation.

Unless explicitly stated otherwise, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that the order be inferred, in any respect. This applies to any possible non-representation basis for interpretation, including: logic problems with respect to step or operational flow arrangements; explicit meaning obtained from grammatical organization or punctuation; the number or type of embodiments described in this specification.

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

As used herein, the term "disposing" includes coating, depositing, and/or forming a material onto a surface using any known or to be developed in the art. The disclosed materials may comprise layers, as defined herein. As used herein, the phrase "disposed on" includes forming a material onto a surface such that the material is in direct contact with the surface, and embodiments in which the material is formed on the surface with one or more intermediate materials disposed between the material and the surface. One or more intermediate materials may constitute a layer, as defined herein.

As used herein, the terms "low RI layer" and "high RI layer" refer to the relative values of the refractive index ("RI") of the layers of the optical film structure of the cap article according to the present disclosure (i.e., low RI layer < high RI layer). Thus, the refractive index value of the low RI layer is smaller than that of the high RI layer. Furthermore, as used herein, the "low RI layer" and "low index layer" are interchangeable with the same meaning. Also, "high RI layer" and "high index layer" are interchangeable with the same meaning.

As used herein, the term "reinforced substrate" refers to a substrate employed in the roofing articles of the present disclosure that has been reinforced in a manner that adds residual compressive stress. For example, the reinforced substrate may be formed by ion exchange of larger ions with smaller ions in the surface of the substrate. In addition, other strengthening methods known in the art, such as thermal tempering or utilizing a mismatch in thermal expansion coefficients between portions of the substrate to create compressive stress and a central tensile region, may be utilized to form the strengthened substrate.

As used herein, "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, substrate, outer film, or portion thereof). The term "reflectivity" 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, substrate, or outer film or portion thereof). Transmittance and reflectance were measured using specific line widths. As used herein, "average transmittance" refers to the average amount of incident optical power transmitted through a material over a defined wavelength band (region) (e.g., an "optical wavelength band," also defined herein as 400nm to 700 nm). A suitable interval for average transmittance measurement is 5nm unless otherwise indicated. As used herein, "average reflectivity" refers to the average amount of incident optical power reflected by a material.

As used herein, "photopic reflectivity" is throughThe response of the human eye is simulated by weighting the reflectivity or transmissivity and wavelength spectrum, respectively, according to the sensitivity of the human eye. The photopic reflectance is also defined as the brightness of reflected light or the tristimulus Y value according to known conventions such as CIE color space conventions. As used herein, "average photopic reflectance" (R) for a wavelength range of 380nm to 720nm _p ) Is defined in the following equation as spectral reflectance R (λ) times light source spectrum I (λ), and the CIE color matching function related to the spectral response of the eye given by equation (1)

In addition, the "average reflectivity" may be determined in the visible spectrum or in other wavelength ranges according to measurement principles understood by those skilled in the art of the present disclosure. Unless otherwise indicated, all reflectance values reported or otherwise referenced in this disclosure are associated with testing through the outer film of the cover article and away from the major surface of the substrate upon which the outer film is disposed, e.g., a "first surface" average photopic reflectance, a "first surface" average reflectance over a specified wavelength range, etc.

The usability of a given display may be related to the total amount of reflectivity in the display system. The photopic reflectance is particularly important for displays employed in vehicles. Reducing the reflectivity in the display system or in the cover product over the display may reduce the multiple bounce reflections in the display system that may generate 'ghost images'. Therefore, the reflectivity has an important relation to the image quality in the display system.

As used herein, "light transmittance" (T _p ) Is defined in the following equation as spectral transmittance T (λ) times light source spectrum I (λ), and the CIE color matching function related to the spectral response of the eye given by equation (2)

In addition, the "average transmittance" may be determined in the visible spectrum or other wavelength ranges according to measurement principles understood by those skilled in the art of the present disclosure. Unless otherwise indicated, all transmittance values reported or otherwise referenced in this disclosure are associated with testing through both major surfaces of the substrate and the outer layer film of the cover article, e.g., a "double-surface" average luminous transmittance, a "double-surface" average transmittance over a specified wavelength range, etc.

As noted above, the cover articles and materials of the present disclosure are described in terms of their reflectivity and transmissivity properties. The cover articles and materials of the present disclosure are also described in terms of their absorptivity properties, as calculated or expressed according to equation (3):

transmittance (T) =100% -reflectance (R) -absorptance (a) (3)

Thus, equation (3) may be employed to calculate the absorbance (a) value (interchangeably referred to as "absorbance" in this disclosure) using as measured transmittance (T) and reflectance (R) values.

Unless otherwise indicated, the thickness and refractive index (n) and extinction coefficient (k) of the materials and articles disclosed herein are determined using variable angle ellipsometry. The variable angle ellipsometry is based on maxwell's equations for polarized light and fresnel reflection or transmission equations, expressed in terms of Psi (ψ) and Delta (Δ) according to equation (4):

tan(Ψ)·e ^(iΔ) ＝ρ＝r _p /r _s (4)

wherein r is _p And r _s Is the complex fresnel reflection coefficient for samples of p-polarized light (in the plane of incidence) and s-polarized light (perpendicular to the plane of incidence), and where the complex ratio ρ is measured in terms of both wavelength and angle of incidence. Unless otherwise indicated, the present inventionThe refractive index (n) and extinction coefficient (k) values reported herein are determined for light having a wavelength of 550 nm. Additional information about variable angle ellipsometry can be found in 1999 in Critical Reviews of Optical Science and Technology, volume CR72, pages 3-28, "Overview of Variable Angle Spectroscopic Ellipsometry (VASE), part I: basic Theory and Typical Applications". The examples in this disclosure were analyzed using a W-200 spectroscopic ellipsometer from j.a. woollam. It should be appreciated that other instruments and methods, different working optical ranges, and/or different angles of incidence may also be employed to determine the thickness or optical characteristics of the materials disclosed herein in any necessary proportions.

As used herein, "transmissive color" and "reflective color" refer to colors that are transmitted or reflected by the cover articles of the present disclosure under D65 light sources with respect to color coordinates (L, a, and b) in the CIE L, a, b colorimetry systems. Further, "transmitted color" and "reflected color" may be given by CIE L, a, b color coordinates as measured at a given measured angle of incidence (e.g., at 0 degrees (°), 45 degrees, or 90 degrees) and/or over a measured range of angles of incidence (e.g., 0 degrees to 10 degrees, 0 degrees to 45 degrees, 0 degrees to 90 degrees, etc.).

To evaluate the void junction appearance, the cover articles of the present disclosure may be evaluated for their void junction color shift according to equation (5) below:

wherein is L _VA 、a* _VA And b is _VA CIE L, a, b, transmissive or reflective color coordinates, and L, that are part of a display panel having a cover article of the present disclosure _BM 、a* _BM And b is _BM CIE L, a, b, transmissive or reflective color coordinates of a portion of a display panel having a relatively black matrix ink material. Specifically, the comparative black matrix ink material is a polymer resin having the following color values: l=4.79, a=0.03 and b=0.18. In addition, as for the transmitted color value and the reflected color value, the clear junction color shift (ΔE) can be used Various measured angles of incidence and ranges (e.g., 0 °, 45 °, 90 °,0 ° to 45 °, etc.) are evaluated and reported. Thus, the smaller the clear junction color shift (ΔE) value, the better the clear junction appearance for a given roofing article sample.

The present disclosure relates generally to a cover article employing a cover article disposed on a glass substrate (e.g.,Gorilla/>product), a glass ceramic substrate, or an outer film and an inner film on a ceramic substrate. These cover articles may exhibit translucency (e.g., 40-80% transmittance) and anti-reflective properties (e.g., photopic reflectance)<4%) and also exhibits a void junction appearance (e.g., low Δe color shift, Δe<4.0). Additionally, the cover articles of the present disclosure may exhibit suitable sheet resistance values to afford their use in capacitive touch screen applications.

Further, the cover articles of the present disclosure can be manufactured in a manner wherein all layers are deposited on one major surface of a substrate in a single process sequence using the same deposition equipment (e.g., plasma enhanced chemical vapor deposition, vacuum metallization, vacuum sputtering, etc.) in a manner that reduces manufacturing costs relative to conventional air interface configurations and processes. The cover articles of the present disclosure may be used in a variety of display applications (e.g., mobile phone displays, dashboard displays in vehicles, appliance displays, etc.) that benefit from an empty junction appearance.

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

Referring again to fig. 1A, an outer layer film 130a (also referred to herein as an "anti-reflective layer film 130a" or "AR layer film 130 a") forms the outermost surface 122. Further, the outermost surface 122 of the outer layer film 130a may form an air interface and generally define the edges of the outer layer film 130a as well as the edges of the overall cover article 100 (e.g., when additional coatings such as the easy-to-clean coatings as described herein are not provided on the outer layer film 130 a). The substrate 110 may be substantially transparent, as described herein.

The outer film 130a includes at least one layer of at least one material. The term "layer" may include a single layer or may include one or more sublayers. Such sublayers may be in direct contact with each other. The sub-layers may be formed of the same material or two or more materials. In one or more alternative embodiments, such sub-layers may have intermediate layers of different materials disposed therebetween. In one or more embodiments, the layers may include one or more continuous and discontinuous layers and/or one or more discontinuous and interrupted layers (i.e., layers of different materials formed adjacent to one another). The layers or sublayers may be formed by any method known in the art, including discrete deposition or continuous deposition processes. In one or more embodiments, the layer may be formed using only a continuous deposition process or alternatively only a discrete deposition process.

The thickness of the outer layer film 130a may be about 0.25 μm or more. In one example, the thickness of the outer layer film 130a may be in the following range: 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 layer film 130a between these thickness values. For example, the thickness of the outer layer film 130a may be about 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 μm20 μm, and all thickness values between these thicknesses.

As also shown in fig. 1A, the outer layer film 130a includes a plurality of layers (130 a,130 b). In one or more embodiments, the outer film 130a may include a period including two or more layers. The outer film 130a may include one or more of such cycles. In one or more embodiments, two or more layers may be characterized as having refractive indices that are different from each other. Each layer in each cycle may have a different physical thickness than each other (i.e., the corresponding layers in successive cycles may 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 of the first low RI layer 130A and the second high RI layer 130N may be about 0.01 or greater, about 0.05 or greater, about 0.1 or greater, or even about 0.2 or greater.

As shown in fig. 1A, the cover article 100 may be configured according to some embodiments such that the outer layer film 130a may include multiple cycles. A single cycle may include a first low RI layer 130A and a second high RI layer 130B such that when multiple cycles are provided, the first low RI layer 130A (designated "L" for illustration) and the second high RI layer 130B (designated "H" for illustration) alternate in the following layer sequence: L/H/L/H or H/L/H/L such that the first low RI layer 130A and the second high RI layer 130B appear to alternate along the physical thickness of the outer film 130A. In the example of fig. 1A, the outer film 130A includes two (2) cycles and one additional low RI layer 130A in the stack according to the following sequence: L/H/L/H/L. In some embodiments, the outer film 130a may include up to twenty-five (25) cycles (also referred to herein as "N" cycles, where N is an integer). For example, the outer film 130a may include 2 to 20 cycles (i.e., n=2-20), 2 to 15 cycles, 2 to 12 cycles, 2 to 10 cycles, 2 to 12 cycles, 2 to 8 cycles, 2 to 6 cycles, or any other cycle within these ranges. For example, the outer film 130a may 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 cycles.

Optionally, and as shown in exemplary form in fig. 1A, an additional low RI layer 130A or high RI layer 130B may be disposed on top of the periodicity of the outer layer film 130A, and such that it is considered part of the outer layer film 130A stack (in such embodiments, the outer layer film 130A includes an odd number of layers, including a plurality of periodicity and additional layers, wherein the additional layer is one of the low RI layer 130A and the high RI layer 130B).

Various configurations for the outer layer film 130a are contemplated herein. For example, as described herein with respect to fig. 1B, the outer layer film 130a may include one or more absorber layers 150, the one or more absorber layers 150 being used in place of at least one of the high RI layers 130B depicted in fig. 1A. In another example, as described herein with respect to fig. 1C, one or more absorbent layers 150 may be incorporated into the outer layer film 130a. In such embodiments, one or more absorber layers 150 may be disposed between two of the low RI layers 130A (i.e., in place of one of the high RI layers 130B depicted in fig. 1A), between two of the high RI layers 130B (i.e., in place of one of the low RI layers 130A depicted in fig. 1A), or between the high RI layers 130B and the low RI layers 130A. The outer film 130A may incorporate one or more absorbent layers 150 at a variety of different locations and layers 150, and one or more layers 150 may 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 fig. 1D, the outer layer film 130a does not include any absorbent layer 150 (in contrast, in this embodiment, one or more absorbent layers 150 are included in the inner layer film 130 b).

As used herein, the terms "low RI" and "high RI" refer to the relative values of the refractive indices of the layers 130A and 130B with respect to each other (e.g., low RI < high RI). In one or more embodiments, the term "low RI" when 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" when used with high RI layer 130B includes a range of about 1.7 to about 2.6 (e.g., about 1.85 or greater).

Materials suitable for use in the low RI layer 130A and the high RI layer 130B of the outer film 130A include: siO (SiO) ₂ 、Al ₂ O ₃ 、GeO ₂ 、SiO、AlO _x N _y 、AlN、SiN _x 、SiO _x N _y 、Si _u Al _v O _x N _y 、Ta ₂ O ₅ 、Nb ₂ O ₅ 、TiO ₂ 、ZrO ₂ 、MgO、MgF ₂ 、BaF ₂ ,CaF ₂ 、SnO ₂ 、HfO ₂ 、Y ₂ O ₃ 、MoO ₃ 、DyF ₃ 、YbF ₃ 、YF ₃ 、CeF ₃ Polymers, fluoropolymers, plasma polymerized polymers, silicone polymers, silsesquioxanes, polyimides, fluorinated polyimides, polyetherimides, polyethersulfones, polyphenylsulfones, polycarbonates, polyethylene terephthalates, polyethylene naphthalates, acrylic polymers, urethane polymers, polymethyl methacrylates, other materials cited below as suitable for use in the anti-clutter coating, and other materials known in the art. Examples of suitable materials for use in the low RI layer 130A include SiO ₂ 、Al ₂ O ₃ 、GeO ₂ 、SiO、AlO _x N _y 、SiO _x N _y 、Si _u Al _v O _x N _y 、MgO、MgAl ₂ O ₄ 、MgF ₂ 、BaF ₂ 、CaF ₂ 、DyF ₃ 、YbF ₃ 、YF ₃ And CeF ₃ . Examples of suitable materials for use in the high RI layer 130B include SiAl _x O _y N _z 、Ta ₂ O ₅ 、Nb ₂ O ₅ 、AlN _x 、Si ₃ N ₄ 、AlO _x N _y 、SiO _x N _y 、SiN _x 、SiN _x :H _y 、HfO ₂ 、TiO ₂ 、ZrO ₂ 、Y ₂ O ₃ 、Al ₂ O ₃ 、MoO ₃ And diamond-like carbon (DLC). In some embodiments of the cap article 100, each low RI layer 130A comprises SiO or SiO ₂ And each high RI layer 130B comprises SiN _x 、Si3N ₄ Or Nb (Nb) ₂ O ₅ 。

Referring again to the cover article 100 depicted in exemplary form in fig. 1A-1D, an inner film 130b is disposed on the major surface 112 of the substrate 110. In an embodiment, the inner film 130b includes a plurality of low refractive index layers 130A and an absorption layer 150. These layers 130A and 150 may be arranged in various sequences, including in an alternating manner (as shown in fig. 1A) in the inner film 130 b. In some embodiments, the inner layer film 130B includes one absorbent layer 150 (see the cover article 100 depicted in fig. 1B-1D, described below) or multiple absorbent layers 150 (see the cover article 100 depicted in fig. 1A). In some embodiments, the inner layer film 130b includes 1 to 20, 2 to 15, or 2 to 10 absorbent layers 150; or the inner film 130b may contain any number of absorbent layers 150 in the aforementioned range.

The absorber layer 150 employed in one or both of the outer layer film 130a and the inner layer film 130b is generally configured to ensure that the cover article 100 (see fig. 1A-1D) exhibits translucency, may be employed in touch screen applications, and may promote anti-reflective properties. Further, the absorbent layer 150 is configured in the outer layer film 130a and the inner layer film 130b in embodiments of the cover article 100 such that these films follow manufacturing processes and equipment that can utilize the same equipment to form the outer layer film 130a and the inner layer film 130b in a single process sequence.

Regarding touch screen capability, the absorbent layer 150 of the cover article 100 (see fig. 1A-1D) should be electrically resistive, at least to some extent. In an embodiment, each of the absorbent layers 150 of the cover article 100 exhibits at least 10 ⁵ Ohms/sq、5×10 ⁵ Ohms/sq、10 ⁶ Ohms/sq or even 10 ⁷ Sheet resistance of Ohms/sq. For example, each of the absorbent layers 150 may exhibit 10 ⁵ Ohms/sq、5×10 ⁵ Ohms/sq、10 ⁶ Ohms/sq、5×10 ⁶ Ohms/sq、10 ⁷ Ohms/sq、5×10 ⁷ Sheet resistance of Ohms/sq and all sheet resistance values between these levels.

Regarding translucency of the cover article 100 (see fig. 1A-1D), embodiments may be configured such that each of the absorbing layers 150 exhibits a requisite degree of optical absorption. In some embodiments, each absorber layer 150 for a single absorber layer embodiment or the total number of absorber layers 150 for a multiple absorber layer embodiment exhibits an average absorbance of 1% to 60%, 2% to 60%, or 3% to 50%, and all absorbance values between the foregoing, as measured in the visible spectrum of 400nm to 700 nm. In an embodiment, each of the absorbing layers 150 exhibits an extinction coefficient (k) greater than 0.5, 0.75, 1.0, 1.5, 2.0, 3.0, or even 4.0 in the visible spectrum from 400nm to 700 nm. In some embodiments of the cover article 100, each of the absorbent layers 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 as measured in the visible spectrum of 400nm to 700 nm. For example, each of the absorbent layers 150 employed 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, 2.0, 3.0, 4.0, 5.0, 7.5, 10.0, and all extinction coefficient values between the foregoing values.

As depicted in exemplary form in fig. 1A-1D, each absorbent layer 150 employed in the cover article 100 of the present disclosure may comprise, for example, various materials as appropriate to exhibit the aforementioned properties. In a cover article 100 such as depicted in FIG. 1A, each of the absorber layers 150 can comprise 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 comprises Cr. In some embodiments, each absorbent layer 150 of the cover article 100 comprises Ni. In other embodiments of the cover article 100, for example as shown in fig. 1B and 1C, each of the absorber layers 150 may comprise a diamond-like carbon (DLC) material. Any of a variety of DLC materials known to those of skill in the art of the present disclosure may be employed in the absorber layer 150 of these caps 100. In further embodiments of the cap article 100, for example as shown in fig. 1D, each absorber layer 150 is a silicon metal alloy comprising Si and Al, sn, or Zn. In some of these embodiments, the absorber layer 150 does not contain any silicide. Further, according to some embodiments, the si—al containing absorber layer 150 has 69% or more Si (by volume); the absorption layer 150 including si—sn has 60% or more Si; and the absorption layer 150 containing Si-Zn has 80% or more Si.

Furthermore, according to some embodiments, the foregoing materials of the absorber layer 150 may be deposited using the same processes and equipment suitable for depositing the other layers of the outer layer 130A and the inner layer 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, and other deposition processes.

The thickness of the absorbent layer 150 employed in the cover article 100 (e.g., as depicted in fig. 1A of the present disclosure) can also be tailored to achieve targeted article-level properties and absorbent layer properties. In some embodiments, each of the absorber layers 150 of the inner layer film 130b of the cap article 100 (see fig. 1A) that includes Ni, cr, or a combination thereof has a thickness of less than 2nm, 1.8nm, 1.6nm, 1.4nm, 1.2nm, or 1.0nm. For the Cr-containing absorber layer 150, the thickness of each of these layers may be less than 2.0nm, according to some embodiments. For the Ni-containing absorber layer 150, the thickness of each of these layers may be less than 1.0nm, according to some embodiments. In essence, the metal-containing absorber layer 150 may be limited in thickness because such layers having a percolation thickness exceeding a threshold may exhibit coalescence of materials, which results in a reduction in sheet resistance levels, making such articles containing the materials unsuitable for capacitive touch screen applications. Thus, embodiments of the cover article 100 having such absorbent layers 150 may be configured such that each absorbent layer 150 maintains a thickness that is less than its percolation thickness depending on the metal from which it is made.

The thickness of the absorbent layer 150 employed in the cover article 100 (e.g., as depicted in fig. 1B and 1C of the present disclosure) can also be tailored to achieve targeted article-level properties and absorbent layer properties. In some embodiments, the thickness of each of the absorption layers 150 of the inner layer film 130B of the cap article 100 (see fig. 1B and 1C) that includes DLC material may be about 5nm to 500nm, 25nm to 500nm, or even 50nm to 500nm. For example, the thickness of each absorber layer 150 comprising DLC material may be about 5nm, 10nm, 15nm, 20nm, 25nm, 50nm, 75nm, 100nm, 125nm, 150nm, 175nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm, and all thickness values between these values. These absorber layers 150 comprising DLC material may advantageously be thicker than the absorber layers 150 comprising metal or metal alloy without sacrificing sheet resistance. However, the actual thickness of the absorber layer 150 comprising DLC material may be limited in terms of resistance to layer cracking (e.g., from thermal stress), and/or packaging considerations where thicker overall structures are not feasible in a given end-use application.

The thickness of the absorbent layer 150 employed in the cover article 100 (e.g., as depicted in fig. 1D of the present disclosure) can also be tailored to achieve targeted article-level properties and absorbent layer properties. In some embodiments, each of the absorber layers 150 of the inner layer film 130b of the cap article 100 (see fig. 1D) comprising Si-Al, si-Sn, si-Zn, or a combination thereof, has a thickness less than 150nm, 140nm, 130nm, 120nm, 110nm, 100nm, 80nm, 60nm, 50nm, 40nm, 30nm, 20nm, 15nm, or 10nm. For example, the thickness of each of the absorber layers 150 comprising silicon-aluminum, silicon-tin, or silicon-zinc alloy may be 145nm, 140nm, 135nm, 130nm, 125nm, 115nm, 105nm, 100nm, 90nm, 75nm, 50nm, 25nm, 10nm, 8nm, 6nm, 5nm, 2.5nm, and all thickness values less than 150 nm. Essentially, si-Al, si-Sn, and Si-Zn absorbing layers 150 may be limited in thickness because such layers having a percolation thickness exceeding a threshold may exhibit coalescence of materials, which results in a reduction in sheet resistance levels, making such articles containing the materials unsuitable for capacitive touch screen applications. Thus, embodiments of the cover article 100 having such absorbent layers 150 may be configured such that each absorbent layer 150 maintains a thickness that is less than its percolation thickness depending on the metal from which it is made.

In one or more embodiments, at least one of the one or more layers of the outer layer film 130A and the inner layer film 130B (e.g., the low RI layer 130A, the high RI layer 130B, and the absorber layer 150) may include a specific optical thickness range. As used herein, the term "optical thickness" is determined by the product of the physical thickness (d) and the refractive index (n) of the layer at a wavelength of 550 nm. In one or more embodiments, at least one of the layers of the outer layer film 130a may include an optical thickness in a range of about 2nm to about 200nm, about 10nm to about 100nm, about 15nm to about 100nm, or about 15nm to about 500 nm. In one or more embodiments, all layers in the outer layer film 130a may each have an optical thickness in the range of about 2nm to about 200nm, about 10nm to about 100nm, about 15nm to about 100nm, or about 15nm to about 500 nm. In some cases, one or more layers of the outer layer film 130a and the inner layer film 130b have an optical thickness of about 50nm or greater. In some cases, each of the low RI layers 130A has an optical thickness in a range of about 2nm to about 200nm, about 10nm to about 100nm, about 15nm to about 100nm, or about 15nm to about 500 nm. In other cases, each of the high RI layers 130B has an optical thickness in the range of about 2nm to about 200nm, about 10nm to about 100nm, or about 15nm to about 100 nm.

In some embodiments of the cover article 100 of the present disclosure, the outermost surface 122 of the outer film 130a may include a high RI layer 130B (not shown) that also exhibits high stiffness. In some embodiments, an additional coating (not shown) may be disposed on top of the exposed topmost air side high RI layer 130B, or an additional coating may be disposed on top of the topmost low RI layer 130A (as shown in fig. 1A-1D). Such additional coatings may include low friction coatings, oleophobic coatings, or coatings that are easy to clean, as will be appreciated by those of skill in the art of this disclosure.

In an embodiment, the cover article 100 includes one or more additional coatings (not shown in fig. 1A-1D) disposed on the outer film 130 a. In one or more embodiments, the additional coating may include an easy-to-clean coating. Examples of suitable easy-to-Clean Coatings are described in U.S. patent application Ser. No. 13/690,904, entitled "Process for Making of Glass Articles with Optical and Easy-to-Clean Coatings," filed on even 30, 11, 2012, and published as U.S. patent application publication Ser. No. 2014/01102083, 24, 2014, and the salient portions of this application are incorporated herein by reference in their entirety. The thickness of the easy-to-clean coating may be in the range of about 5nm to about 50nm and may include known materials such as fluorosilane. The easy-to-clean coating may alternatively or additionally comprise a low friction coating or a 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 may have a thickness in the range of: about 1nm to about 40nm, about 1nm to about 30nm, about 1nm to about 25nm, about 1nm to about 20nm, about 1nm to about 15nm, about 1nm to about 10nm, about 5nm to about 50nm, about 10nm to about 50nm, about 15nm to about 50nm, about 7nm to about 20nm, about 7nm to about 15nm, about 7nm to about 12nm, or about 7nm to about 10nm, and all ranges and subranges therebetween.

The additional coating employed in such a cover article 100 may also include one or more anti-tamper coatings, typically made of a material equivalent to the high RI layer 130B, as will be appreciated by those skilled in the art of the present disclosure. In some embodiments, the additional coating comprises a combination of an easy-to-clean material and a tamper-resistant material. In one example, the combination includes an easy-to-clean material and diamond-like carbon. The thickness of such additional coating layers may be in the range of about 5nm to about 20 nm. The components of the additional coating may be provided in separate layers. For example, diamond-like carbon may be provided as a first layer and the easily cleanable material may be provided as a second layer on the first layer of diamond-like carbon. The thicknesses of the first and second layers may be in the ranges provided above for the additional coating. For example, the thickness of the first layer of diamond-like carbon may be about 1nm to about 20nm or about 4nm to about 15nm (or more specifically about 10 nm), and the thickness of the second layer of easy-to-clean material may be about 1nm to about 10nm (or more specifically about 6 nm). The diamond-like carbon coating may include tetrahedral amorphous carbon (Ta-C), ta-C: H and/or a-C-H.

In one embodiment of the cover article 100 as depicted in fig. 1A, the cover article 100 comprises: a substrate 110, the substrate 110 comprising a thickness of about 50 μm to 5000 μm, an outer major surface 112 and an inner major surface 114, wherein the outer major surface 112 and the inner major surface 114 are opposite to each other, and the substrate 110 comprises a glass, glass ceramic or ceramic material. The cover article 100 further includes an inner film 130b disposed on the outer major surface 112 of the substrate 110, and an outer film 130a disposed on the inner film 130 b. The inner film 130b includes a plurality of low refractive index layers 130A and an absorption layer 150. The outer film 130a includes a plurality of alternating high refractive index layers 130B and Low refractive index layer 130A. The refractive index of each of the high refractive index layers 130B is greater than the refractive index of each of the low refractive index layers 130A. In addition, each absorber layer 150 comprises a metal or metal alloy. Furthermore, in such embodiments, each absorber layer 150 exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient greater than 0.5.

In some embodiments of the cover article 100, as depicted in exemplary form in fig. 1A, the outer layer film 130A includes two sets of alternating low RI layers 130A (e.g., siO ₂ ) And a high RI layer 130B (e.g., siN _x ) And an additional low RI layer 130A (SiO ₂ ). In addition, the inner film 130b includes five sets of alternating low RI layers 130A (SiO ₂ ) And an absorption layer 150 (Ni or Cr). Alternative embodiments may include more or fewer low RI layers 130A, high RI layers 130B, and/or absorber layers 150.

In embodiments such as those depicted in fig. 1B, 1C, and 1D, the cover article 100 includes an outer layer film 130a and an inner layer film 130B having an absorbent layer 150 of a different configuration than that described above with respect to the cover article 100 of fig. 1A. Fig. 1B depicts a cover article 100 in which the inner layer film 130B includes an absorbent layer 150 and the outer layer film 130A includes one or more absorbent layers 150 positioned adjacent to the low RI layer 130A (such that the absorbent layer 150 is not positioned adjacent to any of the other high RI layers 130B in the outer layer film 130A), while fig. 1C depicts an embodiment in which the inner layer film 130B includes an absorbent layer 150 and the outer layer film 130B includes one or more absorbent layers 150 that may be positioned 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. As described herein, in the embodiment of the cover article 100 depicted in fig. 1B and 1C, at least one of the absorbent layers 150 included in the cover article 100 is a DLC layer. In addition, fig. 1C depicts a cover article 100 in which the inner film 130B includes one absorbent layer 150 adjacent to the low RI layer 130A, and the outer film 130A includes a plurality of alternating low RI layers 130A and high RI layers 130B, with one high RI layer 130B in contact with the absorbent layer 150 of the inner film 130B. As described herein, in the embodiment of the cap article 100 depicted in fig. 1D, at least one absorber layer 150 included in the cap article 100 comprises Si-Al, si-Sn, or a Si-Zn alloy.

Referring generally to fig. 1B and 1C, the cover article 100 may comprise: a substrate 110, the substrate 110 comprising a thickness of about 50 μm to 5000 μm, an outer major surface 112 and an inner major surface 114, wherein the outer major surface 112 and the inner major surface 114 are opposite to each other, and the substrate 110 comprises a glass, glass ceramic or ceramic material. The cover article 100 further includes an inner film 130b disposed on the outer major surface 112 of the substrate 110, and an outer film 130a disposed on the inner film 130 b. One or both of the inner and outer films 130b, 130a include one or more absorbent layers 150. The outer film 130A includes a plurality of alternating high refractive index layers 130B and low refractive index layers 130A. The refractive index of each of the high refractive index layers 130B is greater than the refractive index of each of the low refractive index layers 130A. In addition, each absorber layer 150 includes a diamond-like carbon (DLC) material. Furthermore, in such embodiments, each absorber layer 150 exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient of about 0.05 to about 0.4.

In some embodiments of the cover article 100, as depicted in exemplary form in fig. 1B, the outer layer film 130A includes three sets of alternating layers, wherein each set includes a low RI layer 130A (e.g., siO ₂ ) Or a high RI layer 130B (e.g., nb ₂ O ₅ ) With an absorber layer 150 (DLC material) or a high RI layer 130B disposed thereon. The outer film 130A also includes an additional low RI layer 130A (SiO ₂ ). In addition, the inner layer film 130b includes an additional absorption layer 150 (DLC material).

In other embodiments of the cover article 100, as depicted in exemplary form in fig. 1C, the outer layer film 130A includes four sets of alternating low RI layers 130A (e.g., siO ₂ ) Or a high RI layer 130; and a high RI layer 130B (e.g., nb ₂ O ₅ ) And/or an absorber layer 150 (DLC material), an additional low RI layer 130A (SiO) disposed on the topmost RI layer 130B or absorber layer 150 ₂ ). In addition, the inner layer film 130b includes an additional absorption layer 150 (DLC material).

In generalReferring to fig. 1D, the cover article 100 may include: a substrate 110, the substrate 110 comprising a thickness of about 50 μm to 5000 μm, an outer major surface 112 and an inner major surface 114, wherein the outer major surface 112 and the inner major surface 114 are opposite to each other, and the substrate 110 comprises a glass, glass ceramic or ceramic material. The cover article 100 further includes an inner film 130b disposed on the outer major surface 112 of the substrate 110, and an outer film 130a disposed on the inner film 130 b. The inner film 130b may include one or more absorbent layers 150. The outer film 130A includes a plurality of alternating high refractive index layers 130B and low refractive index layers 130A. The refractive index of each of the high refractive index layers 130B is greater than the refractive index of each of the low refractive index layers 130A. In addition, each absorber layer 150 in the cover article 100 depicted in fig. 1D comprises a silicon metal alloy, such as Si-Al, si-Sn, si-Zn, or a combination thereof. Furthermore, in such embodiments, each absorber layer 150 exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient of about 0.05 to about 0.4.

In some embodiments of the cover article 100, as depicted in exemplary form in fig. 1D, the outer layer film 130A includes three sets of alternating layers, wherein each set includes a low RI layer 130A (e.g., siO ₂ ) And a high RI layer 130B (e.g., nb ₂ O ₅ ). As shown in exemplary form in fig. 1D, the outer film 130 may be configured such that it has an outermost low RI layer 130A defining the outermost surface 122 and an innermost high RI layer 130B in contact with the topmost layer of the inner film 130B. In addition, the inner layer film 130B includes an absorption layer 150 (e.g., si—al, si—sn, or si—zn alloy) as its topmost layer, and a series of low RI layers 130A and high RI layers 130B between the absorption layer 150 and the substrate 110. .

According to an embodiment of the cover article 100 of the present disclosure, as depicted in exemplary form in fig. 1A-1D, the cover article 100 exhibits a first surface average photopic reflectance of less than 4%, for example, at an orthogonal angle of incidence of 0 ° or a near-orthogonal angle of incidence of 8 °. In embodiments, the cover article 100 can 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 a first surface average light reflectance that is 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 foregoing ranges and subranges at orthogonal and near-orthogonal angles of incidence of 0 ° to 8 °.

1A-1D, the cover article 100 exhibits a dual surface average transmittance of 30% to 80%, 40% to 80%, 45% to 75%, or 50% to 70% in the visible spectrum of 400nm to 700nm, for example, at an orthogonal angle of incidence of 0 or a near-orthogonal angle of incidence of 8. For example, the cover article 100 may exhibit a dual surface transmittance of 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% and all transmittance values between the foregoing ranges and subranges in the visible spectrum from 400nm to 700nm, for example, at an normal incidence angle of 0 ° or a near normal incidence angle of 8 °.

According to an embodiment of the cover article 100 of the present disclosure, as depicted in exemplary form in fig. 1A-1D, the cover article 100 exhibits a first surface reflective or dual surface transmissive color (CIE coordinates under illumination from a D65 light source) for all angles of incidence from 0 ° to 90 °, where a is-20 to +50, and b is-50 to +10. In some embodiments of the cover article 100 of the present disclosure, the color reflected by the first surface or the color transmitted by the double surface for all angles of incidence from 0 ° to 90 ° is such that a is-20 to +50 or-10 to +40; and b is-50 to +10 or-45 to 0 or-40 to-10.

In an embodiment of the cover article 100 according to the present disclosure, as depicted in exemplary form in fig. 1A-1D, the cover article 100 exhibits a clear interface color shift (Δe) of less than 4.0, less than 3.5, or even less than 3.0 for an incident measurement angle of 0 ° to 90 ° as measured relative to a control article comprising a glass, glass-ceramic, or ceramic material of the substrate 110 and a standard black matrix material (as known to those in the vicinity of the present disclosure) disposed on the glass, glass-ceramic, or ceramic material of the control article (otherwise fabricated identically to the cover article 100). For example, the cover article 100 of the present disclosure may exhibit a clear face 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 clear face color shift values between the foregoing values, as measured at an angle of incidence of 0 ° to 90 °.

The substrate 110 may comprise an inorganic material and may include an amorphous substrate, a crystalline substrate, or a combination thereof. The substrate 110 may be formed of man-made materials and/or naturally occurring materials (e.g., quartz and polymers). For example, in some cases, the substrate 110 may be characterized as organic and may be specifically polymeric. Examples of suitable polymers include, but are not limited to: thermoplastics including Polystyrene (PS) (including styrene copolymers and blends), polycarbonate (PC) (including copolymers and blends), polyester fibers (including copolymers and blends, including polyethylene terephthalate and polyethylene terephthalate copolymers), polyolefin (PO) and cyclic polyolefin (cyclic-PO), polyvinyl chloride (PVC); acrylic polymers, including polymethyl methacrylate (PMMA), including copolymers and blends, thermoplastic Polyurethane (TPU), polyetherimide (PEI), and blends of these polymers with each other. Other exemplary polymers include epoxy resins, phenolic resins, melamine and silicone resins.

In some embodiments, the substrate 110 may specifically not include a polymer, plastic, and/or metallic material. The substrate 110 may be characterized as a base-containing substrate (i.e., the substrate includes one or more alkali metals). In one or more embodiments, the substrate 110 exhibits a refractive index in the range of about 1.45 to 1.55. In particular embodiments, the substrate 110 may exhibit damage at the surface located on one or more opposing major surfaces resulting from the following average strain: 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 as measured using the ball and socket test using at least 5, at least 10, at least 15, or at least 20 samples. In particular embodiments, the substrate 110 may exhibit damage at its surface on one or more opposing major surfaces caused by the following average strains: about 1.2%, about 1.4%, about 1.8%, about 2.2%, about 2.4%, about 2.6%, about 2.8%, or about 3% or more.

Suitable substrates 110 may exhibit an elastic modulus (or young's modulus) in the range of about 30GPa to about 120 GPa. In some cases, the elastic modulus of the substrate may be in the following range: about 30GPa to about 110GPa, about 30GPa to about 100GPa, about 30GPa to about 90GPa, about 30GPa to about 80GPa, about 30GPa to about 70GPa, about 40GPa to about 120GPa, about 50GPa to about 120GPa, about 60GPa to about 120GPa, about 70GPa to about 120GPa, and all ranges and subranges therebetween.

In one or more embodiments, the substrate 110 may include glass, which may be reinforced or unreinforced. Examples of suitable glasses include soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali borosilicate glass. In some variations, the glass may be free of lithium oxide. In one or more alternative embodiments, the substrate 110 may comprise a crystalline substrate, such as a ceramic glass substrate (which may be reinforced or unreinforced) or may comprise a single crystal structure such as sapphire. In one or more embodiments, the substrate 110 includes an amorphous base (e.g., glass) and a crystalline coating (e.g., a sapphire layer, a polycrystalline alumina layer, and/or spinel (MgAl) ₂ O ₄ ) A layer).

The substrate 110 may be substantially optically clear, transparent, and free of light scattering elements. In such embodiments, the substrate 110 may exhibit the following average light transmittance over the optical wavelength band for light orthogonally incident thereon: about 85% or greater, about 86% or greater, about 87% or greater, about 88% or greater, about 89% or greater, about 90% or greater, about 91% or greater, or about 92% or greater. In one or more alternative embodiments, the substrate 110 may be opaque or exhibit the following average light transmission over the optical wavelength band: 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 light reflectivity and transmittance values may be total reflectivity or total transmittance (taking into account reflectivity or transmittance on both major surfaces of the substrate) or may be observed on a single side of the substrate (i.e., only on the outermost surface 122 of the outer layer film 130a, without taking into account the opposing surface). Unless otherwise indicated, the individual average reflectivities or transmittances of substrate 110 are measured at an incident illumination angle of 0 degrees relative to substrate major surface 112 (however, such measurements may be provided at an incident illumination angle of 45 degrees or 60 degrees). The substrate 110 may optionally exhibit a color such as white, black, red, blue, green, yellow, orange, and the like.

Additionally or alternatively, the physical thickness of the substrate 110 may vary along one or more of its dimensions for aesthetic and/or functional reasons. For example, the edge of the substrate 110 may be thicker than more of the center region of the substrate 110. The length, width, and physical thickness of the substrate 110 may also vary depending on the application or use of the cover article 100.

The substrate 110 may be provided using a variety of processes. For example, where the substrate 110 comprises an amorphous substrate such as glass, various forming methods may include float glass processes and downdraw processes, such as fusion draw and slot draw.

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

In the case where the substrate 110 is chemically strengthened by an ion exchange process, ions in the surface layer of the substrate are replaced by or exchanged with larger ions having the same valence or oxidation state. Ion exchange processes are typically performed by immersing the substrate in a molten salt bath containing larger ions to be exchanged with smaller ions in the substrate. Those skilled in the art will appreciate that the parameters for the ion exchange process, including but not limited to bath composition and temperature, immersion time, immersion of the substrate in the salt bath(s), use of multiple salt baths, and additional steps such as annealing, washing, etc., are generally determined by the composition of the substrate and the desired Compressive Stress (CS) of the substrate due to the strengthening operation, depth of the compressive stress layer (or depth of layer DOL or depth of compression DOC). By way of example, the alkali-containing glass substrate may be achieved by immersion in at least one molten bath containing salts such as, but not limited to, nitrates, sulfates and chlorides of larger alkali ions. The temperature of the molten salt bath is typically in the range of about 380 ℃ to about 450 ℃ and the immersion time is in the range of about 15 minutes to about 40 hours. However, temperatures and immersion times other than those described above may also be used.

In addition, non-limiting examples of ion exchange processes in which glass substrates are immersed in multiple ion exchange baths with washing and/or annealing steps between the immersion are described in the following patents: U.S. patent application Ser. No. 12/500,650, entitled "Glass with Compressive Surface for Consumer Applications" by Douglas C.Allan et al, filed on 7.10 2009, and claiming priority from U.S. provisional patent application Ser. No. 61/079,995 filed on 11 2008, wherein glass substrates are strengthened by immersing in salt baths of different concentrations in a plurality of successive ion exchange treatments; and U.S. patent No. 8,312,739 issued 11/20 in 2012 belonging to Christopher m.lee et al and entitled "Dual Stage Ion Exchange for Chemical Strengthening of Glass" and claiming priority from U.S. provisional patent application No. 61/084,398 filed 29 in 2008, 7, wherein the glass substrate is strengthened by ion exchange in a first bath diluted with wastewater ions, followed by immersion in a second bath having a concentration of wastewater ions less than the first bath. The contents of U.S. patent application Ser. No. 12/500,650 and patent application Ser. No. 8,312,739 are incorporated by reference herein in their entirety.

The degree of chemical enhancement achieved by ion exchange can be quantified based on parameters of Center Tension (CT), surface CS, and depth of compression (DOC). Unless otherwise indicated, compressive stress (including surface CS) is measured by a surface stress meter (FSM) using commercially available instruments such as FSM-6000 manufactured by Orihara Industrial co., ltd (Japan). The surface stress measurement depends on an accurate measurement of the Stress Optical Coefficient (SOC) associated with the birefringence of the glass. SOC is then measured according to procedure C (glass disk method) described in ASTM Standard C770-16, entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," the contents of which are incorporated herein by reference in its entirety. The maximum CT value is measured using scattered light polariscope (SCALP) techniques known in the art. As used herein, DOC means the depth at which the stress in the chemically strengthened alkali aluminosilicate glass article described herein changes from compression to tension. Depending on the ion exchange treatment, DOC can be measured by FSM or SCALP. In the case of generating stress in a glass article by exchanging potassium ions into the glass article, FSM is used to measure DOC. In the case of stress generated by exchanging sodium ions into the glass article, the SCALP was used to measure DOC. In the case of generating stress in a glass article by exchanging both potassium and sodium ions into the glass, DOC is measured by SCALP, since it is believed that the depth of exchange of sodium indicates DOC and the depth of exchange of potassium ions indicates the change in magnitude of compressive stress (rather than the change in stress from compressive to tensile); the depth of potassium ion exchange in such glass articles was measured by FSM.

In one embodiment, the substrate 110 may have a surface CS of 250MPa or more, 300MPa or more, for example 400MPa or more, 450MPa or more, 500MPa or more, 550MPa or more, 600MPa or more, 650MPa or more, 700MPa or more, 750MPa or more, or 800MPa or more. The reinforced substrate may have a DOC (raw name DOL) of 10 μm or more, 15 μm or more, 20 μm or more (e.g., 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or more) and/or a CT of 10MPa or more, 20MPa or more, 30MPa or more, 40MPa or more (e.g., 42MPa, 45MPa or 50MPa or more) but less than 100MPa (e.g., 95MPa, 90MPa, 85MPa, 80MPa, 75MPa, 70MPa, 65MPa, 60MPa, 55MPa or less). In one or more embodiments, the reinforced substrate has one or more of the following: a surface CS of greater than 500MPa, a DOC (DOL under original name) of greater than 15 μm, and a CT of greater than 18 MPa.

Exemplary glasses that can be used in the substrate 110 can include alkali aluminosilicate glass compositions or alkali borosilicate glass compositions, although other glass compositions are contemplated. Such glass compositions can be chemically strengthened by ion exchange processes. An exemplary glass composition comprises SiO ₂ 、B ₂ O ₃ And Na (Na) ₂ O, where (SiO) ₂ +B ₂ O ₃ ) 66 mol% or more and Na ₂ O is more than or equal to 9 mol percent. In an embodiment, the glass composition comprises at least 6% by weight alumina. In further embodiments, the substrate comprises a glass composition having 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 comprise K ₂ O, mgO and CaO. In particular embodiments, the glass composition used in the substrate may comprise 61-75 mole% SiO2;7-15 mole% of Al ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the 0-12 mol% of B ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the 9-21 mol% Na ₂ O;0-4 mole% of K ₂ O;0-7 mole% MgO; and 0-3 mole% CaO.

Additional exemplary glass compositions suitable for substrate 110 include: 60-70 mol% SiO ₂ The method comprises the steps of carrying out a first treatment on the surface of the 6-14 mole% of Al ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the 0-15 mole% of B ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the 0-15 mole% of Li ₂ O;0-20 mole% of Na ₂ O;0-10 mole% of K ₂ O;0-8 mole% MgO;0-10 mole% CaO;0-5 mol% ZrO ₂ The method comprises the steps of carrying out a first treatment on the surface of the 0-1 mole% SnO ₂ The method comprises the steps of carrying out a first treatment on the surface of the 0-1 mole% CeO ₂ The method comprises the steps of carrying out a first treatment on the surface of the Less than 50ppm As ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the Less than 50ppm Sb ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the Wherein 12 mol% is less than or equal to (Li) ₂ O+Na ₂ O+K ₂ O is less than or equal to 20 mol percent and MgO+CaO is less than or equal to 0 mol percent and less than or equal to 10 mol percent.

Still other exemplary glass compositions suitable for substrate 110 comprise: 63.5 to 66.5 mol% SiO ₂ The method comprises the steps of carrying out a first treatment on the surface of the 8-12 mole% of Al ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the 0-3 mol% of B ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the 0-5 mol% of Li ₂ O;8-18 mol% Na ₂ O;0-5 mole% of K ₂ O;1-7 mole% MgO;0-2.5 mole% CaO;0-3 mol% ZrO ₂ The method comprises the steps of carrying out a first treatment on the surface of the 0.05 to 0.25 mol% SnO ₂ The method comprises the steps of carrying out a first treatment on the surface of the 0.05 to 0.5 mol% CeO ₂ The method comprises the steps of carrying out a first treatment on the surface of the Less than 50ppm As ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the Less than 50ppm Sb ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the Wherein 14 mol% is less than or equal to (Li) ₂ O+Na ₂ O+K ₂ O is less than or equal to 18 mol percent and 2 mol percent is less than or equal to (MgO+CaO) is less than or equal to 7 mol percent.

In particular embodiments, an alkali aluminosilicate glass composition suitable for substrate 110 comprises alumina, at least one alkali metal, and in some embodiments greater than 50 mole% SiO ₂ In other embodiments at least 58 mole% SiO ₂ In still other embodiments at least 60 mole% SiO ₂ Wherein the ratio (Al ₂ O ₃ +B ₂ O ₃ ) The/(Σ modifier (i.e., the sum of modifiers) is greater than 1, where the component is expressed in mol% and the modifier is an alkali metal oxide in the ratio. Such glass compositions, in particular embodiments, comprise: 58-72 mol% SiO ₂ The method comprises the steps of carrying out a first treatment on the surface of the 9-17 mole% Al ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the 2 to 12 mol% of B ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the 8-16 mol% of Na ₂ O; 0-4 mole% K ₂ O, wherein the ratio (Al ₂ O ₃ +B ₂ O ₃ ) The/(Σ modifier (i.e., the sum of the modifiers) is greater than 1.

In yet another embodiment, the substrate 110 may comprise an alkali aluminosilicate glass composition comprising: 64-68 mol% SiO ₂ The method comprises the steps of carrying out a first treatment on the surface of the 12-16 mole% Na ₂ O;8-12 mole% of Al ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the 0-3 mol% of B ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the 2-5 mole% of K ₂ O;4-6 mole% MgO; and 0-5 mole% CaO, wherein: 66 mol%SiO ₂ +B ₂ O ₃ +CaO/>69 mole%; na (Na) ₂ O+K ₂ O+B ₂ O ₃ +MgO+CaO+SrO>10 mol%; 5 mol% >>MgO+CaO+SrO/>8 mol%; (Na) ₂ O+B ₂ O ₃ )/>Al ₂ O ₃ />2 mole%; 2 mol% >>Na ₂ O/>Al ₂ O ₃ />6 mol%; 4 mol% >>(Na ₂ O+K ₂ O)/>Al ₂ O ₃ />10 mol%.

In alternative embodiments, the substrate 110 may comprise an alkali aluminosilicate glass composition comprising: 2 mol% or more of Al ₂ O ₃ And/or ZrO ₂ Or 4 mol% or more of Al ₂ O ₃ And/or ZrO ₂ 。

In the case where the substrate 110 comprises a crystalline substrate, the substrate may comprise a single crystal, which may comprise Al ₂ O ₃ . Such a single crystalline substrate is referred to as sapphire. Other suitable materials for the crystalline substrate include polycrystalline alumina and/or spinel (MgAl ₂ O ₄ )。

Optionally, the substrate 110 may be crystalline and include a glass-ceramic substrate, which may be reinforced or unreinforced. Examples of suitable glass ceramics may include Li ₂ O-Al ₂ O ₃ -SiO ₂ System (i.e., LAS system) glass ceramic, mgO-Al ₂ O ₃ -SiO ₂ The system (i.e., MAS system) glass-ceramic and/or glass-ceramic includes a dominant crystalline phase comprising β -quartz solid solution, β -spodumene, cordierite and/or lithium disilicate. The glass-ceramic substrate may be reinforced using the chemical reinforcement process disclosed herein. In one or more embodiments, the MAS-system glass-ceramic substrate may be a glass-ceramic substrate that is a glass-ceramic substrate ₂ SO ₄ Strengthening in molten salt, whereby 2Li can occur ⁺ For Mg ²⁺ Is a function of the exchange of (a).

The physical thickness of the substrate 110 in various portions of the substrate 110 according to one or more embodiments may be in the range of about 50 μm to about 5 mm. Exemplary substrate 110 physical thickness is in the range of about 50 μm to about 500 μm (e.g., 50 μm, 75 μm, 100 μm, 200 μm, 300 μm, 400 μm, or 500 μm). Additional exemplary substrate 110 physical thicknesses are in the range of about 50 μm to about 2000 μm (e.g., 50 μm, 75 μm, 100 μm, 250 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1000 μm, 1250 μm, 1500 μm, 1750 μm, or 2000 μm). The physical thickness of the substrate 110 may be greater than about 1mm (e.g., about 2mm, 3mm, 4mm, or 5 mm). In one or more embodiments, the physical thickness of the substrate 110 may be 2mm or less, or less than 1mm. The substrate 110 may be acid polished or otherwise treated to eliminate or reduce the effects of surface defects.

As depicted in an exemplary form in fig. 1A-1D and disclosed herein, the cover article 100 may be incorporated into another article, such as an article with a display (or display article) (e.g., consumer electronic devices including mobile phones, tablets, computers, navigation systems, etc.), architectural articles, transport articles (e.g., automobiles, trains, airplanes, marine vessels, etc.), electrical articles, or any article requiring certain translucent, antireflective properties, and/or touch screen capabilities.

Examples

Various embodiments of the present disclosure (e.g., any of the caps 100 depicted in fig. 1A-1D) will be further illustrated by the following examples. As explicitly noted, the optical properties (e.g., reflectivity and transmissivity) of the samples are measured or otherwise modeled using the stated methods and apparatus to model thin film performance, particularly transfer matrix modeling techniques, as will be appreciated by those skilled in the art of the present disclosure. From films (e.g. SiN _x Film properties (e.g., refractive index) obtained from previous thin film reactive sputtering, room test, and higher volume sputter fabrication are used in modeling.

Refractive indices and extinction coefficients (as a function of wavelength) of layers and substrates of molded cover article embodiments were measured in previous experiments using ellipsometry. In some embodiments focusing on layer properties, these properties, such as measurements, are reported. The refractive index measured is then used to calculate the reflectance spectrum of the embodiment. The embodiments use for convenience the individual refractive index values in their descriptive tables that correspond to points selected from the dispersion curve at about the midpoint of the visible spectrum at a wavelength of about 550 nm.

Example 1

In this example, a thin chromium (Cr) film was sputtered at room temperatureEagle/>And on the substrate. The electrical sheet resistance was measured by a 4-point probe (CD ResMap), and the optical properties were determined by collecting the R spectrum, T spectrum, and a spectrum with a film thickness measuring instrument F50xy, and the thickness and optical constants were determined by ellipsometry (Woollam M-2000).

Referring to fig. 2A, examples 1A and 1B provide graphs of sheet resistance versus reciprocal film thickness of chromium films of various thicknesses deposited at 23 ℃ and 325 ℃, respectively. Referring to fig. 2B, graphs of absorptance versus wavelength of various thicknesses of glass substrates (comparative example 1) and chromium films of examples 1C-1F deposited on glass substrates at 23 ℃ were provided with 7.1nm, 6.6nm, 4.4nm, and 2.7nm, respectively. As is apparent from fig. 2A, below-3 nm, the inverse of the sheet resistance of the chromium layer was found to deviate from the linear slope. Similarly, infrared absorption is seen in fig. 2B to irregularly decrease below the same thickness range, indicating that the percolation threshold is in this thickness range.

Referring now to fig. 2C and 2D, scanning Electron Microscope (SEM) images of a chromium film deposited at 23 ℃ (example 1A) and at 325 ℃ (example 1B) with a thickness of 1.8nm, respectively, are provided. The 'islands' or 'islands' structure of the chromium film is clearly visible. That is, the chromium films are physically discontinuous and the electrons have some difficulty in transferring from one 'island' to another, which reduces their conductivity. These results indicate that a thin chromium layer below-2 nm thick should be a suitable absorber layer with low conductivity not exceeding the percolation threshold of chromium.

Example 2

In this example, a thin nickel (Ni) film was sputtered to a thickness of 1mm at room temperature Glass 3 substrate (i.e., chemically strengthened Glass substrate). The electrical sheet resistance was measured by a 4-point probe (CD ResMap), and the optical properties were determined by collecting the R spectrum, T spectrum, and a spectrum with a film thickness measuring instrument F50xy, and the thickness and optical constants were determined by ellipsometry (Woollam M-2000).

Referring to fig. 3A, comparative examples 2A and 2B provide graphs of sheet resistance versus reciprocal of film thickness of nickel films of various thicknesses of 0.88nm to 42nm deposited at 23 ℃ and 325 ℃, respectively. Referring to fig. 3B, examples 2C, 2D and 2E provide graphs of absorbance versus wavelength of nickel films of various thicknesses of 0.62nm, 0.72nm and 0.84nm deposited on a glass substrate at 23 ℃, respectively. As is evident from fig. 3A and 3B, below-0.88 nm, sheet resistance is not measurable (< 500 kOhm/sq), while these layers produce optical absorption of more than 10% across the visible spectrum.

Example 3

Using the optical data from example 1, transmittance values were modeled for these chromium films. Specifically, the transmittance level of an absorber stack containing one to three Cr layers of 0.5nm, 1nm and 2nm thickness was simulated in this example. Referring to fig. 4A-4C, graphs of transmittance versus wavelength are provided for one, two, and three layers of chromium of examples 3A-3I at three thickness levels (i.e., 0.5nm, 1nm, and 2 nm), respectively, with a thin layer of silicon dioxide deposited between each chromium layer. As is apparent from fig. 4A-4C, these results indicate that the cover article construction of the present disclosure can be tuned for average transmittance levels of 20% to 80% (in the wavelength range of 350nm to 850 nm), including levels driven by a particular end use display application. This tuning can be achieved by variations in the composition, thickness and number of the absorbent layers.

Example 4

Table 1 shows the design (example 4) of an article with translucent and anti-reflective (AR) properties (see also fig. 1A) for the present disclosure. Specifically, the outer layer film (AR stack) is adoptedWith low refractive index material SiO ₂ And high refractive index material SiN _x Is a layer of the first layer. Furthermore, the inner layer film (absorber stack) employs a film having 10nm SiO ₂ A 0.16nm thick chromium absorber layer (low RI layer) of the dielectric spacer.

Referring to fig. 5, a plot of reflectance, transmittance, and absorbance versus wavelength for the example 4 cover article is provided. As is apparent from fig. 5, this design exhibits an average transmittance of about 80% and an average reflectance of about 0.6% across the visible spectrum of 400nm to 700 nm. In addition, example 4 hasThe cover product design of Glass 3 substrate is placed +.>On, and in->No change was observed in the touch screen performance of the device.

TABLE 1 example 4 cover article for an air interface display

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Example 5

Table 2 shows the design (example 5) of an article with translucent and anti-reflective (AR) properties (see also fig. 1A) for the present disclosure. In particular, the outer layer film (AR stack) employs a low refractive index material SiO ₂ And high refractive index material SiN _x Is a layer of the first layer. Furthermore, the inner layer film (absorber stack) employs a film having 10nm SiO ₂ A 0.6nm thick nickel absorber layer (low RI layer) of the dielectric spacer.

Referring to fig. 6, a plot of reflectance, transmittance, and absorbance versus wavelength for the example 5 cover article is provided. As is apparent from fig. 6, this design exhibits an average transmittance of about 63% and an average reflectance of about 0.8% reflection across the visible spectrum of 400nm to 700 nm.

TABLE 2 example 5 cover article for an air interface display

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Example 6

In this example, a thin diamond-like carbon (DLC) film was deposited to 1mm by PECVD at room temperatureGlass 3 substrate. The films of this example (example 6) were deposited using a PECVD process and measured across the visible spectrum using ellipsometry for refractive index and extinction coefficient. Referring to fig. 7, a graph of refractive index and extinction coefficient (n, k) of a diamond-like carbon (DLC) layer is provided. As is apparent from fig. 7, the DLC layer exhibits a refractive index (n) between 2.0 and 2.2 and a maximum extinction coefficient of about 0.27 across the visible spectrum of 400nm to 700 nm. In addition, these values indicate that the absorption rate of DLC layer is higher than other dielectric materials such as SiO ₂ And Nb2O ₅ Thereby making DLC layers particularly advantageous for use in the cover articles of the present disclosure.

Example 7A

Table 3A shows the design of an article with translucent and anti-reflective (AR) properties (see also fig. 1B) as constructed with one DLC absorber layer for the present disclosure (example 7A). In particular, the outer layer film (AR stack) employs a low refractive index material SiO ₂ And a high refractive index material Nb ₂ O ₅ Is a layer of the first layer. In addition, inner layer film (absorber stack) A single DLC absorber layer with a thickness of 50nm was used.

Referring to fig. 8A, a plot of reflectance, transmittance, and absorbance versus wavelength for the example 7A cover article is provided. As is apparent from fig. 8A, this design exhibits an average transmittance of about 83.2% and an average absorption of about 13.1% across the visible spectrum of 400nm to 700nm, and an average photopic reflectance of about 0.28%.

Table 3A-example 7A, cover article for an air interface display

Example 7B

Table 3B shows the design of an article with semitransparent and anti-reflective (AR) properties (see also fig. 1C) as constructed with a total of five (5) DLC absorber layers for the present disclosure (example 7B). Specifically, the outer layer film (AR stack) employs a low refractive index layer (SiO ₂ ) Or a high refractive index layer (Nb) ₂ O ₅ ) Is a layer of the first layer. Furthermore, the inner layer film (absorber stack) employs a single DLC absorber layer with a thickness of 127.2 nm.

Referring to fig. 8B, a plot of reflectance, transmittance, and absorbance versus wavelength for the example 7B cover article is provided. As is apparent from fig. 8B, this design exhibits an average transmittance of about 62.8% and an average absorption of about 36.8% across the visible spectrum of 400nm to 700nm, and an average photopic reflectance of about 0.25%.

Table 3B-example 7B, cover article for an air interface display

Example 7C

Table 3C shows the design of an article with translucent and anti-reflective (AR) properties (see also fig. 1B) as constructed with a total of three (3) DLC absorber layers for the present disclosure (example 7C). In particularThe outer film (AR stack) employs a low refractive index layer (SiO ₂ ) And a high refractive index layer (Nb ₂ O ₅ ) Is a layer of the first layer. Furthermore, the inner layer film (absorber stack) employs a single DLC absorber layer with a thickness of 200 nm.

Referring to fig. 8C, a plot of reflectance, transmittance, and absorbance versus wavelength for the example 7C cover article is provided. As is apparent from fig. 8C, this design exhibits an average transmittance of about 42.3% and an average absorption of about 53.5% across the visible spectrum of 400nm to 700nm, and an average photopic reflectance of about 0.44%.

Table 3C-example 7C, cover product for an air interface display

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Example 8

In this example, a cap article of the present disclosure having translucent and anti-reflective (AR) properties, such as one DLC absorber layer configured with the design according to table 3A and having different thickness levels, was fabricated. Specifically, DLC absorbing layers with thicknesses of 55nm, 81nm and 180nm were employed in the samples of this example, designated as examples 8A-8C, respectively.

Referring to fig. 9A, a plot of reflectance and transmittance versus wavelength for the cover articles of this example (examples 8A-8C) is provided. The measured spectra demonstrate that the average transmittance (T) of these samples in the visible spectrum from 400nm to 700nm is in the range of 30% to 75% as a function of DLC layer thickness from 55nm to 180 nm. Furthermore, the reflectivity (R) level of these samples varied from 0.34% to 2.2% as a function of DLC layer thickness from 55nm to 180 nm. More specifically, the average transmittance and photopic reflectance values of the samples with the 55nm DLC layer (example 8A) were 74.1% and 0.34%, respectively; the average transmittance and photopic reflectance values for the samples with 81nm DLC layer (example 8B) were 67.2% and 0.58%, respectively; and the average transmittance and photopic reflectance values of the samples with 180nm DLC layer (example 8C) were 31.5% and 2.5%, respectively.

Referring now to fig. 9B, a graph of the color reflected by the first surface at normal incidence measurement angles for the D65 light source of the exemplary cap product of this example (examples 8A-8C) and the comparative cap product with respect to black matrix materials (comparative examples 8A-8C) having the same thickness for the corresponding inventive cap products (i.e., 55nm, 81nm, and 180 nm) is provided. The CIE L, a, and b values for each of the samples of this example are: 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 reflective color coordinates of the samples of this example (examples 8A-8C) are very similar to the reflective color coordinates of the comparative black matrix material samples of this example (comparative examples 8A-8C). This demonstrates that the cap product of this example with various DLC layer thickness levels can achieve color levels comparable to conventional black matrix coatings.

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 fig. 10A. As shown in the optical image of fig. 10A, these samples were designated as examples 9A-9C, where each sample had a single DLC absorber layer with thicknesses of 81nm, 180nm and 55nm, and corresponding portions of black matrix material with the same thickness.

The clear junction color shift value (ΔE) was then calculated for each of the samples (examples 9A-9C) at incidence measurement angles of 0 °, 45 °, and 90 °, using a-and b-color coordinate measurements of the samples by a CM-700d (Konica-Minolta) spectrophotometer. Referring now to fig. 10B, a bar graph of the clear junction color shift (Δe) calculated for each of these caps is provided. The data in fig. 10B clearly show that a translucent cover article with AR properties with DLC absorber layer thickness of 180nm exhibits very good void junction effect with respect to all incident measurement angles, and Δe is 2.3 at 90 ° and less than 1.5 for both 0 ° and 45 °. In contrast, the Δe value between the conventional black matrix and the viewable area of the LCD module (found by the conventional black matrix) is >5 at a 45 ° incident measurement angle. These results indicate that the layered films described herein improve air interface performance relative to existing displays.

Example 10

In this example, examples 11 and 12 and comparative examples 13 and 14, thin metal alloy absorber layers were formed by DC sputtering in an AJA Orion sputter deposition system at room temperature in confocal geometry<150nm thick) co-sputtered on Si and 1mm thickBoth on Glass 3 substrates (i.e., chemically reinforced boali substrates). Sputtering was performed in an argon atmosphere using a 3 "target at 2 mTorr. All composition determinations were made by measuring the deposition rate of each gun independently of the quartz crystal monitor. The resulting films were characterized by a four-point probe (CD ResMap), optical transmittance and reflectance (film thickness gauge F50 xy) and ellipsometry for refractive index determination (Woollam CompleteEase). By placing each coated sample at +.>SE top and use +.>Is used to pay attention to the effect of the sample on touch screen performance for touch screen compatibility assessment.

In this example, thin absorbing films of si—al alloys were deposited with various compositions, as indicated below in table 4 and shown in fig. 11A. Table 4 also lists the reciprocal of sheet resistance ("1/Rs"), optical density ("OD"), transmittance at 550nm ("T550 nm"), film thickness ("Th (nm)") and touch screen capability ("touch"). Referring to fig. 11A, a graph of the ratio of extinction coefficients (k) as a function of Si volume fraction for the Si-Al films of this example from 400nm to 550nm and 780nm to 440nm is provided. As is apparent from table 4 and fig. 11A, acceptable touch screen performance was not observed in films having greater than or equal to 69% silicon (by volume) (i.e., examples 10A-10J) and si—al alloy films having 67% Si exhibited unacceptable touch screen performance (i.e., comparative example 10).

Referring to fig. 11B to 11D, the respective graphs of reflectance, transmittance, and absorptance with respect to wavelength at two film thicknesses of the three si—al film compositions (65 to 71% Si) of this example and comparative example (i.e., example 10A, example 10B, and comparative example 10) are provided. In particular, these figures show the optical properties of thin (< 10 nm) thick si—al films according to this embodiment. The transmittance is higher in red than in blue, but the performance is better than the DLC absorbing layer. From these measurements, it is seen that the translucent AR coating can be formed with a si—al film thickness <50nm for transmission as low as 10%. The relative red and blue absorptivity of the film was quantified by plotting k at 400nm normalized to k at 550nm and k at 780nm normalized to 550 nm. The ideal material would exhibit k 400/k550=k780/k550=1. For Si-Al alloy absorber films, the best optical performance is achieved at nearly 70% Si (by volume), with a k400/k550 of about 2 and a k780/k550 of about 0.5.

TABLE 4 Properties of Si-Al alloy absorber films as a function of Si volume fraction

Example 11

In this example, thin absorbing films of Si-Zn alloy were deposited with various compositions, as shown in FIG. 12. Referring to FIG. 12, a graph of the ratio of the extinction coefficients (k) of 400nm to 550nm and 780nm to 440nm as a function of Si volume fraction for the Si-Zn films of this example is provided, each Si-Zn film having a thickness of 105.53nm. As is apparent from fig. 12, acceptable touch screen performance was not observed in films having greater than or equal to 80% silicon (by volume) (i.e., examples 11A-11D) and si—zn alloy films having less than 80% Si (by volume) exhibited unacceptable touch screen performance (i.e., comparative examples 11A-E). Furthermore, the best optical performance was observed in a Si-Zn film with about 80% Si (by volume) (example 11A), where k400/k550 was 2 and k780/k550 was 0.31, as shown in FIG. 12.

Example 12

In this example, thin absorber films of Si-Sn alloys are deposited with various compositions, as shown in FIG. 13. Referring to fig. 13, a graph of the ratio of the extinction coefficients (k) of 400nm to 550nm and 780nm to 440nm as a function of Si volume fraction for the Si-Sn films of this example is provided, each Si-Sn film having a thickness of 105.92nm. As is apparent from fig. 13, acceptable touch screen performance was not observed in films having greater than or equal to 60% silicon (by volume) (i.e., examples 12A-12H) and si—sn alloy films having less than 60% Si (by volume) exhibited unacceptable touch screen performance (i.e., comparative example 12). Furthermore, the best optical performance was observed in a Si-Zn film with about 60% Si (by volume) (example 12A), where k400/k550 was 2 and k780/k550 was 0.37, as shown in FIG. 13.

Comparative example 13

In this comparative example, thin absorbing films of si—cu alloy were deposited with various compositions as shown in fig. 14 (all designated as "comparative example 13"). Referring to fig. 14, a graph of the ratio of extinction coefficients (k) of 400nm to 550nm and 780nm to 440nm for the Si-Cu films of this example as a function of Si volume fraction is provided, each Si-Cu film having a thickness of 51.50nm. As is apparent from fig. 14, only acceptable touch screen performance was observed in films with greater than or equal to 95% silicon (by volume). However, all samples were considered unacceptable because all si—cu alloys formed silicide and the range of acceptable touch screen performance combinations was narrow. Furthermore, the Si-Cu film of this example exhibits a k400/k550 of 2.0 and a k780/k550 of 0.37, as depicted in FIG. 14.

Comparative example 14

In this comparative example, thin absorbing films of si—cr alloy were deposited with various compositions as shown in fig. 15 (all designated as "comparative example 14"). Referring to FIG. 15, a plot of the ratio of extinction coefficients (k) for the 400nm to 550nm and 780nm to 440nm of the Si-Cr film of this example as a function of Si volume fraction is provided. As is apparent from fig. 15, acceptable touch screen performance was not observed in the films of this example, including films having greater than or equal to 95% silicon (by volume). Furthermore, all samples were considered unacceptable because all si—cr alloys formed silicides.

Example 15

In this example, a cap article of the present disclosure having translucent and anti-reflective (AR) properties, such as one constructed with an absorber layer comprising an si—al alloy comparable to example 10A (see table 4 in example 10 above) in composition and structure, was fabricated according to the design of table 5 below (designated "example 15"). Specifically, the Si-Al alloy absorption layer is located in the inner layer film, higher than SiO ₂ 、Nb ₂ O ₅ And SiO ₂ The layers were alternately impedance matched stacked and had a thickness of 9.64 nm. The impedance matching stack is intended to minimize reflection from the substrate, which is Glass 3 substrate. Further, in this cover article design, the outer layer film has a plurality of Nb configured to provide an anti-reflection (AR) function ₂ O ₅ And SiO ₂ Layers, six total layers.

Referring to fig. 16A, a graph of simulated reflectance, transmittance, and absorbance (%) versus wavelength for an exemplary cap article employing a si—al absorber layer of this example (example 15) is provided. As is apparent from fig. 16A, the sample of this example exhibited an average photopic reflectance of 2.8% and an average transmittance of 53%.

Referring now to fig. 16B, a simulated color plot of x and y coordinates in 1931CIE chromaticity with normal incidence (0 °) for the cover article of this example (example 15) is provided. As is apparent from fig. 16B, the analog color of this embodiment is a white or pink hue.

TABLE 5 example 15 cover article for an air interface display with Si-Al absorber layer

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The various features described in the specification may be combined in any and all combinations, for example as set forth in the following embodiments.

Embodiment 1 provides a cover product for a display panel, the cover product comprising: a substrate comprising a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, wherein the outer major surface and the inner major surface are opposite to each other and the substrate comprises a glass, glass-ceramic, or ceramic material; an inner film disposed on the outer major surface of the substrate; and an outer film disposed on the inner film. One or both of the inner and outer films include one or more absorbent layers. The outer 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 that of each of the low refractive index layers. Each absorbent layer exhibits at least 10 ⁵ Sheet resistance of Ohms/sq. Furthermore, the article exhibits a clear junction color shift (ΔΣ) of less than 4.0 for an incident measurement angle of 0 ° to 90 °, as measured relative to a control article comprising a glass, glass-ceramic or ceramic material of the substrate and a standard black matrix disposed on the glass, glass-ceramic or ceramic material.

Embodiment 2. The cap article of embodiment 1 is provided, wherein the cap article exhibits an average double surface transmittance of 40% to 80% in the visible spectrum of 400nm to 700 nm.

Embodiment 3. Providing the cap article of embodiment 1 or embodiment 2, wherein the cap article exhibits an average first surface photopic reflectance of less than 4%.

Embodiment 4. Providing the cover article of any of embodiments 1-3, wherein each of the high refractive index layers in the outer film comprises Si ₃ N ₄ 、SiN _x 、SiO _x N _y 、AlN _x 、AlO _x N _y 、SiAl _x O _y N _z 、TiO ₂ 、HfO ₂ 、ZrO ₂ 、Nb ₂ O ₅ Or Ta ₂ O ₅ And wherein each of the low refractive index layers in the outer layer film comprises a silicon-containing oxide.

Embodiment 5. Providing the roofing article of any of embodiments 1-4, wherein the inner layer film comprises the one or more absorbent layers.

Embodiment 6. Providing the cover article of any of embodiments 1-5, wherein each absorbing layer exhibits an average reflectance of 1% to 60% in the visible spectrum of 400nm to 700 nm.

Embodiment 7 provides a cover product for a display panel, the cover product comprising: a substrate comprising a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, wherein the outer major surface and the inner major surface are opposite to each other and the substrate comprises a glass, glass-ceramic, or ceramic material; an inner film disposed on the outer major surface of the substrate; and an outer film disposed on the inner film. The inner film includes a plurality of low refractive index layers and an absorbing layer. The outer 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 that of each of the low refractive index layers. In addition, each absorber layer comprises a metal or metal alloy. Each absorption layer exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient greater than 0.5.

Embodiment 8. Providing the cap article of embodiment 7, wherein each absorber layer comprises Ni, cr, a Ni-containing alloy, a Cr-containing alloy, or a Ni/Cr alloy.

Embodiment 9. The cap article of embodiment 8, wherein each absorbing layer comprises Cr and has a thickness of less than 2 nm.

Embodiment 10. Providing the cap article of embodiment 8, wherein each absorber layer comprises Ni and has a thickness of less than 1 nm.

Embodiment 11. Providing the roofing article of any of embodiments 7-10, wherein the inner layer film comprises two (2) to twenty (20) absorbent layers.

Embodiment 12. Providing the cap article of any one of embodiments 7-11, wherein each of the high refractive index layers in the outer film comprises Si ₃ N ₄ 、SiN _x、 SiO _x N _y 、AlN _x 、AlO _x N _y 、SiAl _x O _y N _z 、TiO ₂ 、HfO ₂ 、ZrO ₂ 、Nb ₂ O ₅ Or Ta ₂ O ₅ And wherein each of the low refractive index layers in the outer layer film and the inner layer film contains a silicon-containing oxide.

Embodiment 13. The cap article of any one of embodiments 7-12, wherein the cap article exhibits an average dual surface transmittance of 40% to 80% and an average first surface photopic reflectance of less than 4% in the visible spectrum of 400nm to 700 nm.

Embodiment 14 provides a cover article for a display panel, the cover article comprising: a substrate comprising a thickness of 50 μm to 5000 μm, an outer major surface, and an inner major surface, wherein the outer major surface and the inner major surface are opposite to each other and the substrate comprises a glass, glass-ceramic, or ceramic material; an inner film disposed on the outer major surface of the substrate; and an outer film disposed on the inner film. One or both of the inner and outer films include one or more absorbent layers. The outer layer film bagComprising 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 that of each of the low refractive index layers. In addition, each absorber layer comprises a diamond-like carbon (DLC) material. Each absorption layer exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient of about 0.05 to about 0.4.

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

Embodiment 16. Providing the cover article of embodiment 14 or embodiment 15, wherein one or both of the inner layer film and the outer layer film comprises one (1) to ten (10) absorbent layers.

Embodiment 17. The cap article of any one of embodiments 14-16, wherein the total thickness of the absorbing layer is about 25nm to 500nm.

Embodiment 18. Providing the cap article of any one of embodiments 14-17, wherein each of the high refractive index layers in the outer film comprises Si ₃ N ₄ 、SiN _x 、SiO _x N _y 、AlN _x 、AlO _x N _y 、SiAl _x O _y N _z 、TiO ₂ 、HfO ₂ 、ZrO ₂ 、Nb ₂ O ₅ Or Ta ₂ O ₅ And wherein each of the low refractive index layers in the outer layer film and the inner layer film contains a silicon-containing oxide.

Embodiment 19. The cap article of any one of embodiments 14-18, wherein the cap article exhibits an average dual surface transmittance of 40% to 80% and an average first surface photopic reflectance of less than 4% in the visible spectrum of 400nm to 700 nm.

Embodiment 20. Providing the cap article of any one of embodiments 14-19, wherein the article exhibits a clear junction color shift (ΔΣ) of less than 4.0 for an incident measurement angle of 0 ° to 90 °, as measured relative to a control article comprising a glass, glass-ceramic or ceramic material of the substrate and a standard black matrix disposed on the glass, glass-ceramic or ceramic material.

Embodiment 21. A cover product for a display panel includes: a substrate comprising a thickness of 50 μm to 5000 μm; an outer major surface and an inner major surface, wherein the outer major surface and the inner major surface are opposite to each other and the substrate comprises a glass, glass ceramic or ceramic material; an inner film disposed on the outer major surface of the substrate; and an outer film disposed on the inner film. The inner film includes a plurality of low refractive index layers and one or more absorber layers, the outer 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 each of the low refractive index layers, and each absorber layer is a silicon metal alloy comprising Si-Al, si-Sn, si-Zn, or a combination thereof. Furthermore, each absorption layer exhibits at least 10 in the visible spectrum of 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient greater than 1.0.

Embodiment 22. Providing the cap article of embodiment 21, wherein the silicon metal alloy does not contain any silicide.

Embodiment 23. The cap article of embodiment 21 or embodiment 22 is provided wherein each of the absorbing layers has a thickness of less than 100 nm.

Embodiment 24. Providing the cap article of any one of embodiments 21-23, wherein the silicon metal alloy is Si-Al with at least 69% silicon (by volume).

Embodiment 25. Providing the cap article of any one of embodiments 21-23, wherein the silicon metal alloy is Si-Sn with at least 60% silicon (by volume).

Embodiment 26. The cap article of any of embodiments 21-23, wherein the silicon metal alloy is Si-Zn with at least 80% silicon (by volume).

Claims

1. A cover article for a display panel, comprising:

a substrate comprising a thickness of about 50 μm to 5000 μm; an outer major surface and an inner major surface, wherein the outer major surface and the inner major surface are opposite to each other and the substrate 110 comprises glass, glass-ceramic, or ceramic material;

an inner film disposed on the outer major surface of the substrate; and

An outer layer film disposed on the inner layer film; and is also provided with

Wherein one or both of the inner and outer films comprises one or more absorbent layers,

wherein the outer film comprises a plurality of alternating high refractive index layers and low refractive index layers,

wherein each of the high refractive index layers has a refractive index greater than that of each of the low refractive index layers, an

Wherein each absorbent layer exhibits at least 10 ⁵ Sheet resistance of Ohms/sq, and

further wherein the article exhibits a clear junction color shift (ΔΣ) of less than 4.0 for an incident measurement angle of 0 ° to 90 °, as measured relative to a control article comprising a glass, glass-ceramic or ceramic material of the substrate and a standard black matrix disposed on the glass, glass-ceramic or ceramic material.

2. The cap article of claim 1, wherein the cap article exhibits an average dual surface transmittance of 40% to 80% in the visible spectrum of 400nm to 700 nm.

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. The cover article of claim 1 or claim 2, wherein each of the high refractive index layers in the outer film comprises Si ₃ N ₄ 、SiN _x 、SiO _x N _y 、AlN _x 、AlO _x N _y 、SiAl _x O _y N _z 、TiO ₂ 、HfO ₂ 、ZrO ₂ 、Nb ₂ O ₅ Or Ta ₂ O ₅ And wherein each of the low refractive index layers in the outer layer film comprises a silicon-containing oxide.

5. The cover article of claim 1 or claim 2, wherein the inner layer film comprises the one or more absorbent layers.

6. The cover article of claim 1 or claim 2, wherein each absorbing layer exhibits an average reflectance of 1% to 60% in the visible spectrum of 400nm to 700 nm.

7. A cover article for a display panel, comprising:

an inner film disposed on the outer major surface of the substrate; and

an outer layer film disposed on the inner layer film; and is also provided with

Wherein the inner film comprises a plurality of low refractive index layers and an absorbing layer,

Wherein the refractive index of each of the high refractive index layers is greater than the refractive index of each of the low refractive index layers,

wherein each absorber layer comprises a metal or metal alloy, and

further wherein each absorption layer exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient greater than 0.5.

8. The cover article of claim 7, wherein each absorber layer comprises Ni, cr, a Ni-containing alloy, a Cr-containing alloy, or a Ni/Cr alloy.

9. The cover article of claim 8, wherein each absorbing layer comprises Cr and has a thickness of less than 2 nm.

10. The cover article of claim 8, wherein each absorber layer comprises Ni and has a thickness of less than 1 nm.

11. The cover article of any of claims 7-10, wherein the inner layer film comprises from two (2) to twenty (20) absorbent layers.

12. The cover article of any of claims 7-10, wherein each of the high refractive index layers in the outer film comprises Si ₃ N ₄ 、SiN _x 、SiO _x N _y 、AlN _x 、AlO _x N _y 、SiAl _x O _y N _z 、TiO ₂ 、HfO ₂ 、ZrO ₂ 、Nb ₂ O ₅ Or Ta ₂ O ₅ And wherein each of the low refractive index layers in the outer layer film and the inner layer film contains a silicon-containing oxide.

13. The cap article of any one of claims 7-10, wherein the cap article exhibits an average dual surface transmittance of 40% to 80% and an average first surface photopic reflectance of less than 4% in the visible spectrum of 400nm to 700 nm.

14. A cover article for a display panel, comprising:

an inner film disposed on the outer major surface of the substrate; and

an outer layer film disposed on the inner layer film; and is also provided with

wherein each absorption layer comprises a diamond-like carbon (DLC) material, and

further wherein each absorption layer exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient of about 0.05 to about 0.4.

15. The cover article of claim 14, wherein each absorbent layer comprises a thickness of about 5nm to about 500nm.

16. The cover article of claim 14 or claim 15, wherein one or both of the inner layer film and the outer layer film comprises one (1) to ten (10) absorbent layers.

17. The cover article of any of claims 14 or 15, wherein the total thickness of the absorbent layer is from about 25nm to 500nm.

18. The cover article of claim 14 or claim 15, wherein each of the high refractive index layers in the outer film comprises Si ₃ N ₄ 、SiN _x 、SiO _x N _y 、AlN _x 、AlO _x N _y 、SiAl _x O _y N _z 、TiO ₂ 、HfO ₂ 、ZrO ₂ 、Nb ₂ O ₅ Or Ta ₂ O ₅ And wherein each of the low refractive index layers in the outer layer film and the inner layer film contains a silicon-containing oxide.

19. The cap article of claim 14 or claim 15, wherein the cap article exhibits an average double-surface transmittance of 40% to 80% and an average first surface photopic reflectance of less than 4% in the visible spectrum of 400nm to 700 nm.

20. The cover article of claim 14 or claim 15, wherein the article exhibits a clear-joint-face color shift (ΔΣ) of less than 4.0 for an incident measurement angle of 0 ° to 90 °, as measured relative to a control article comprising a glass, glass-ceramic or ceramic material of the substrate and a standard black matrix disposed on the glass, glass-ceramic or ceramic material.

21. A cover article for a display panel, comprising:

an inner film disposed on the outer major surface of the substrate; and

an outer layer film disposed on the inner layer film; and is also provided with

Wherein the inner film comprises a plurality of low refractive index layers and one or more absorber layers,

wherein each absorber layer is a metallic silicon alloy comprising Si-Al, si-Sn, si-Zn, or a combination thereof, and

further wherein each absorption layer exhibits at least 10 in the visible spectrum from 400nm to 700nm ⁵ Sheet resistance of Ohms/sq and an extinction coefficient greater than 1.0.

22. The cap article of claim 21, wherein the silicon metal alloy is free of any silicide.

23. The cover article of claim 21 or claim 22, wherein each absorbent layer has a thickness of less than 150 nm.

24. The cap article of claim 21 or claim 22, wherein the silicon metal alloy is Si-Al with at least 69% silicon (by volume).

25. The cap article of claim 21 or claim 22, wherein the silicon metal alloy is Si-Sn with at least 60% silicon (by volume).

26. The cap article of claim 21 or claim 22, wherein the silicon metal alloy is Si-Zn with at least 80% silicon (by volume).