Optical coating for non-planar substrates and method for producing the same

文档序号：1056427 发布日期：2020-10-13 浏览：15次中文

阅读说明：本技术 非平面基材的光学涂层及其生产方法 (Optical coating for non-planar substrates and method for producing the same ) 是由 S·D·哈特 K·W·科奇三世 C·A·K·威廉姆斯 L·林 T·A·T·恩古延 C·A· 于 2020-03-27 设计创作，主要内容包括：提供了非平面基材的光学涂层及其生产方法。一种经涂覆的制品,其具有：具有主表面的基材,所述基材包括第一部分和弯曲或带刻面的第二部分；和在主表面上并且形成抗反射表面的光学涂层。第一方向垂直于第一部分并且不同于与第二部分垂直的多个第二方向,第一方向与每个第二方向之间的角为约10度至60度。经涂覆的制品在第一和第二部分处还展现出在约100nm或更大的压痕深度处的约8GPa或更大的硬度。经涂覆的制品在第一和第二部分处还展现出约3％或更小的单侧最大反射率,其中,所述反射率在约425nm至约950nm的范围内测量。(Optical coatings for non-planar substrates and methods for producing the same are provided. A coated article having: a substrate having a major surface, the substrate comprising a first portion and a curved or faceted second portion; and an optical coating on the major surface and forming an antireflective surface. The first direction is perpendicular to the first portion and different from a plurality of second directions perpendicular to the second portion, and an angle between the first direction and each of the second directions is about 10 to 60 degrees. The coated article also exhibits a hardness at the first and second portions of about 8GPa or greater at an indentation depth of about 100nm or greater. The coated article also exhibits a single-sided maximum reflectance of about 3% or less at the first and second portions, wherein the reflectance is measured in the range of about 425nm to about 950 nm.)

1. A coated article, comprising:

a substrate having a major surface comprising a first portion and a second portion, wherein the second portion is curved or faceted, and further wherein a first direction perpendicular to the first portion of the major surface is different from a plurality of second directions perpendicular to the second portion of the major surface, and an angle between the first direction and each of the second directions is in a range from about 10 degrees to about 60 degrees; and

an optical coating disposed on at least a first portion and a second portion of the major surface, the optical coating forming an antireflective surface, wherein:

(a) at the first portion of the substrate and at the second portion of the substrate, the coated article exhibits a hardness of about 8GPa or greater at an indentation depth of about 100nm or greater, the hardness measured on the antireflective surface by a berkovich indenter hardness test; and is

(b) The coated article exhibits a single-sided maximum light reflectance of about 3% or less as measured at the antireflective surface at a first portion and a second portion of the substrate, wherein the single-sided maximum light reflectance of the first portion is measured at a first incident illumination angle relative to the first direction, wherein the first incident illumination angle comprises an angle from about 0 degrees to about 45 degrees from the first direction, wherein the single-sided maximum light reflectance of the second portion is measured at two or more second incident illumination angles, each second incident illumination angle being an angle relative to a respective second direction of the plurality of second directions, wherein each second incident illumination angle comprises an angle from about 0 degrees to about 45 degrees from the respective second direction,

and further wherein the one-sided maximum light reflectance at the first portion is measured within an optical wavelength region of about 425nm to about 950 nm.

2. The coated article of claim 1, wherein an angle between the first direction and one of the second directions is in a range of about 10 degrees to about 20 degrees, and an angle between the first direction and the other of the second directions is in a range of about 20 degrees to about 60 degrees.

3. The coated article of claim 1, wherein an angle between the first direction and one of the second directions is in a range of about 10 degrees to about 20 degrees, and an angle between the first direction and the other of the second directions is in a range of about 40 degrees to about 60 degrees.

4. The coated article of any of claims 1-3, wherein the optical coating comprises a first antireflective coating, a scratch resistant layer over the first antireflective coating, and a second antireflective coating over the scratch resistant layer, the second antireflective coating defining an antireflective surface, wherein the first antireflective coating comprises at least a low RI layer and a high RI layer, and the second antireflective coating comprises at least a low RI layer and a high RI layer.

5. The coated article of claim 4, wherein at least the low RI layer in each of the first and second antireflective coatings comprises silicon oxide, wherein at least the high RI layer in the first antireflective coating comprises silicon oxynitride, wherein at least the high RI layer in the second antireflective coating comprises silicon nitride, and further wherein the scratch resistant layer comprises silicon oxynitride.

6. The coated article of claim 4, wherein the optical coating comprises a cap layer over the second antireflective coating, the cap layer comprising a low RI material.

7. The coated article of claim 4, wherein each adjacent low RI layer and high RI layer, respectively, in each of the first anti-reflective coating and the second anti-reflective coating defines a period N, and further wherein N is 2 to 12.

8. The coated article of claim 4, wherein the total thickness of the optical coating is from about 2 μm to about 4 μm and the combined total thickness of the first and second antireflective coatings is from about 500nm to about 1000 nm.

9. A coated article according to claim 4 wherein the scratch resistant layer has a thickness of from about 200nm to about 3000 nm.

10. A coated article, comprising:

an optical coating disposed on at least a first portion and a second portion of the major surface, the optical coating forming an antireflective surface, wherein:

(b) The coated article has a first surface reflected color at the first and second portions of the major surface of b < about 5 as measured by reflected color coordinates in an (L, a, b) color system under a commission internationale de L' eclairage D65 light source, wherein the reflected color at the first portion is measured at a first angle of incident illumination relative to the first direction, wherein the first angle of incident illumination comprises an angle of about 0 degrees to about 90 degrees from the first direction, wherein the reflected color at the second portion is measured at two or more second angles of incident illumination, each second angle of incident illumination being an angle relative to a respective second direction of the plurality of second directions, wherein each second angle of incident illumination comprises an angle of about 0 degrees to about 90 degrees from the respective second direction, and each second angle of incident illumination differs from each other by at least 10 degrees.

11. The coated article of claim 10, wherein an angle between the first direction and one of the second directions is in a range of about 10 degrees to about 20 degrees, and an angle between the first direction and the other of the second directions is in a range of about 20 degrees to about 60 degrees.

12. The coated article of claim 10, wherein an angle between the first direction and one of the second directions is in a range of about 10 degrees to about 20 degrees, and an angle between the first direction and the other of the second directions is in a range of about 40 degrees to about 60 degrees.

13. The coated article of claim 10, wherein the coated article has a reflected color at the first and second portions of the major surface of b < about 3 as measured by reflected color coordinates in the (L, a, b) color system under the commission international lighting system D65 light source.

14. The coated article of claim 10, wherein the coated article has a reflected color at the first and second portions of the major surface of (a + b) < about 10 as measured by reflected color coordinates in the (L, a, b) color system under the commission international commission on illumination D65 light source.

15. The coated article of any of claims 10-14, wherein the optical coating comprises a first antireflective coating, a scratch resistant layer over the first antireflective coating, and a second antireflective coating over the scratch resistant layer, the second antireflective coating defining an antireflective surface, wherein the first antireflective coating comprises at least a low RI layer and a high RI layer, and the second antireflective coating comprises at least a low RI layer and a high RI layer.

16. The coated article of claim 15, wherein at least the low RI layer in each of the first and second antireflective coatings comprises silicon oxide, wherein at least the high RI layer in the first antireflective coating comprises silicon oxynitride, wherein at least the high RI layer in the second antireflective coating comprises silicon nitride, and further wherein the scratch resistant layer comprises silicon oxynitride.

17. The coated article of claim 15, wherein the coated article exhibits a hardness of about 11GPa or greater at an indentation depth of about 100nm or greater, as measured on the antireflective surface by the berkovich indenter hardness test, at the first portion of the substrate and at the second portion of the substrate.

18. The coated article of any one of claims 10-12, wherein the reflected color of the coated article is b x < about 5 at the first portion and the second portion of the major surface, wherein the reflected color at the first portion is measured at a plurality of first incident illumination angles relative to the first direction, the plurality of first incident illumination angles comprising an illumination angle of 0 to 20 degrees and an illumination angle of 55 to 85 degrees, and further wherein the reflected color at the second portion is measured at a plurality of second incident illumination angles relative to the second direction, the plurality of second incident illumination angles comprising an illumination angle of 0 to 20 degrees and an illumination angle of 55 to 85 degrees.

19. The coated article of claim 15, wherein the total thickness of the optical coating is from about 2 μ ι η to about 4 μ ι η, and the combined total thickness of the first and second antireflective coatings is from about 500nm to about 1000 nm.

20. A coated article according to claim 15 wherein the scratch resistant layer has a thickness of from about 200nm to about 3000 nm.

21. A coated article, comprising:

an optical coating disposed on at least a first portion and a second portion of the major surface, the optical coating forming an antireflective surface, wherein:

(b) the coated article exhibits an average photopic reflectance of about 2% or less, measured at the antireflective surface at the first portion and the second portion of the substrate, wherein the one-sided maximum light reflectance of the first portion is measured at a first incident illumination angle relative to the first direction, wherein the first incident illumination angle comprises an angle of about 0 degrees to about 45 degrees from the first direction, wherein the one-sided maximum light reflectance of the second portion is measured at two or more second incident illumination angles, each second incident illumination angle being an angle relative to a respective second direction of the plurality of second directions, wherein each second angle of incident illumination comprises an angle of about 0 degrees to about 45 degrees from the corresponding second direction, and further, wherein the average photopic reflectance at the first portion and the second portion is measured over a light wavelength region of about 425nm to about 950 nm;

(c) a first surface of the coated article at the first and second portions of the major surface has a reflected color b < about 5, this is measured by the reflected color coordinates in the (L, a, b) color system under the light source D65 of the international commission on illumination, wherein the reflected color at the first portion is measured at a first incident illumination angle relative to the first direction, wherein the first incident illumination angle comprises an angle of about 0 degrees to about 90 degrees from the first direction, and wherein, the reflected color at the second portion is measured at two or more second incident illumination angles, each second incident illumination angle being an angle relative to a respective second direction of the plurality of second directions, wherein each second angle of incident illumination comprises an angle of about 0 degrees to about 90 degrees from the corresponding second direction, and the second angles of incident illumination differ from each other by at least 10 degrees.

22. The coated article of claim 21, wherein an angle between the first direction and one of the second directions is in a range of about 10 degrees to about 20 degrees, and an angle between the first direction and the other of the second directions is in a range of about 20 degrees to about 60 degrees.

23. The coated article of claim 22, wherein an angle between the first direction and one of the second directions is in a range of about 10 degrees to about 20 degrees, and an angle between the first direction and the other of the second directions is in a range of about 40 degrees to about 60 degrees.

24. The coated article of any of claims 21-23, wherein the optical coating comprises a first antireflective coating, a scratch resistant layer over the first antireflective coating, and a second antireflective coating over the scratch resistant layer, the second antireflective coating defining an antireflective surface, wherein the first antireflective coating comprises at least a low RI layer and a high RI layer, and the second antireflective coating comprises at least a low RI layer and a high RI layer.

25. The coated article of claim 24, wherein at least the low RI layer in each of the first and second antireflective coatings comprises silicon oxide, wherein at least the high RI layer in the first antireflective coating comprises silicon oxynitride, wherein at least the high RI layer in the second antireflective coating comprises silicon nitride, and further wherein the scratch resistant layer comprises silicon oxynitride.

26. The coated article of claim 24, wherein the optical coating comprises a cap layer over the second antireflective coating, the cap layer comprising a low RI material.

27. The coated article of claim 24, wherein each adjacent low RI layer and high RI layer in each of the first and second antireflective coatings, respectively, defines a period N, and further wherein N is from 2 to 12.

28. The coated article of claim 24, wherein the total thickness of the optical coating is from about 2 μ ι η to about 4 μ ι η, and the combined total thickness of the first and second antireflective coatings is from about 500nm to about 1000 nm.

29. A coated article according to claim 24, wherein the scratch resistant layer has a thickness of about 200nm to about 3000 nm.

30. A consumer electronic product, comprising:

a housing having a front surface, a rear surface, and side surfaces;

electrical components at least partially within the housing, the electrical components including at least a controller, a memory, and a display, the display being located at or near a front surface of the housing; and

a cover substrate disposed over the display,

wherein at least one of the cover substrate or a portion of the housing comprises the coated article of any one of claims 1, 10, or 21.

31. The coated article of claim 4, wherein there is a first anti-reflective coating and a second anti-reflective coating, respectivelyEach adjacent low RI layer and high RI layer of each antireflective coating of the second antireflective coating defines a period N, and further wherein N is from 6 to 12, wherein the thickness of the scratch resistant layer is from about 1000nm to 3000nm, wherein the optical coating further comprises SiO-containing over the second antireflective coating₂And SiO-containing layer between the substrate and the first anti-reflective coating₂The low RI layer of (a).

32. The coated article of claim 15, wherein each adjacent low RI layer and high RI layer in each antireflective coating of the first antireflective coating and the second antireflective coating, respectively, defines a period N, and further wherein N is 6 to 12, wherein the scratch resistant layer has a thickness of about 1000nm to 3000nm, wherein the optical coating further comprises a SiO-containing layer over the second antireflective coating₂And SiO-containing layer between the substrate and the first anti-reflective coating₂The low RI layer of (a).

33. The coated article of claim 24, wherein each adjacent low RI layer and high RI layer in each antireflective coating of the first antireflective coating and the second antireflective coating, respectively, defines a period N, and further wherein N is 6 to 12, wherein the scratch resistant layer has a thickness of about 1000nm to 3000nm, wherein the optical coating further comprises a SiO-containing layer over the second antireflective coating₂And SiO-containing layer between the substrate and the first anti-reflective coating₂The low RI layer of (a).

Technical Field

The present disclosure relates to durable and/or scratch resistant articles and methods of making the same, and more particularly to durable and/or scratch resistant optical coatings on non-planar substrates.

Background

Cover articles are often used to protect critical components within electronic products, to provide a user interface for input and/or display, and/or to provide many other functions. These products include mobile devices such as smart phones, mp3 players, and tablet computers. Cover sheet articles also include building articles, transportation articles (e.g., articles for automotive applications, trains, aircraft, ships, etc.), appliance articles, or any article that requires some transparency, scratch resistance, abrasion resistance, or a combination of the above properties. These applications often require scratch resistance and high optical performance characteristics-in terms of maximum light transmission and minimum reflectance. In addition, some cover applications require that the color displayed or seen in reflection and/or transmission not change significantly with changing viewing angle. This is because, in display applications, if the color in reflection or transmission changes to an appreciable extent with a change in viewing angle, the user of the product will perceive a change in the color or brightness of the display, which will reduce the perceived quality of the display. In other applications, the change in color can negatively impact aesthetic or other functional requirements.

The optical properties of the cover sheet article can be improved by the use of various antireflective coatings; known antireflective coatings are susceptible to wear, abrasion and/or scratch damage. Such wear, abrasion and scratch damage can diminish any optical property improvement achieved by the antireflective coating. For example, optical filters are often made from multilayer coatings having different refractive indices, as well as from optically transparent dielectric materials (e.g., oxides, nitrides, and fluorides). Most typical oxides for such optical filters are wide bandgap materials that do not have the mechanical properties, such as hardness, necessary for use in mobile devices, building articles, transportation articles, or electrical articles. Nitride and diamond-like coatings can exhibit high hardness values, but these materials typically do not exhibit the transmittance required for these applications.

Some electronic devices include non-planar cover sheet articles. For example, some smartphone touchscreens may be non-planar, with at least a portion of the coverlay article being curved over its surface. Similarly, some smart watches may be non-planar, wherein at least a portion of the cover article is curved over its surface. The optical properties of the coating on the cover article may change due to the inclusion of the non-planar article. For example, if the substrate includes one or more curved, faceted, or otherwise shaped non-planar surfaces in addition to planar surface portions, the coating will be viewed at two different angles on different portions of the substrate.

Accordingly, there is a need for non-planar cover sheet articles and methods of making the same that are resistant to abrasion, scratch, and/or have improved optical properties. There is also a need for optical coating configurations having these properties suitable for non-planar cover sheet articles and various line-of-sight methods for forming these coatings.

Disclosure of Invention

According to one aspect of the present disclosure, there is provided a coated article comprising: a substrate having a major surface comprising a first portion and a second portion, wherein the second portion is curved or faceted, and wherein a first direction perpendicular to the first portion of the major surface is different from a plurality of second directions perpendicular to the second portion of the major surface, and an angle between the first direction and each of the second directions is in a range from about 10 degrees to about 50 degrees; and an optical coating disposed on at least the first and second portions of the major surface. The optical coating forms an antireflective surface, wherein (a) the coated article exhibits a hardness of about 8GPa or greater at an indentation depth of about 100nm or greater at the first portion of the substrate and at the second portion of the substrate, as measured on the antireflective surface by a berkovich indenter hardness test; and (b) the coated article exhibits an average photopic reflectance of about 2% or less, as measured at the antireflective surface at the first portion and the second portion of the substrate; and (c) the first surface of the coated article has a reflected color, b < about 5, at the first and second portions of the major surface, as measured by the reflected color coordinates in the (L, a, b) color system under the commission international lighting system D65 light source. The one-sided maximum light reflectance of the first portion is measured at a first incident illumination angle relative to the first direction, wherein the first incident illumination angle comprises an angle of about 0 degrees to about 45 degrees from the first direction. The one-sided maximum light reflectance of the second portion is measured at two or more second incident illumination angles, each second incident illumination angle being an angle relative to a respective second direction of the plurality of second directions, wherein each second incident illumination angle comprises an angle of about 0 degrees to about 45 degrees from the respective second direction. Further, the average photopic reflectance at the first portion and at the second portion is measured over an optical wavelength region of about 425nm to about 950 nm. Additionally, the reflected color at the first portion is measured at a first incident illumination angle relative to the first direction, wherein the first incident illumination angle comprises an angle of about 0 degrees to about 90 degrees from the first direction. Further, the reflected color at the second portion is measured at two or more second incident illumination angles, each second incident illumination angle being an angle relative to a respective second direction of the plurality of second directions, wherein each second incident illumination angle comprises an angle of about 0 degrees to about 90 degrees from the respective second direction, and the second illumination angles differ from each other by at least 10 degrees.

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

FIG. 2 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

FIG. 3 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

FIG. 4 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

FIG. 5 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

FIG. 6 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

FIG. 7 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

FIG. 8 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

FIG. 9 is a graph of optical coating thickness scaling factor versus partial surface curvature for a deposition process according to one or more embodiments described herein;

FIG. 10A is a plot of photopic reflectance versus wavelength for a first surface at near-normal light incidence angles (8 degrees) for comparative optical coatings at four optical coating thickness scale factor values;

FIG. 10B is a plot of average first surface photopic reflectance versus incident light (viewing) angle for the comparative optical coating of FIG. 10A at seven optical coating thickness scale factor values;

FIG. 10C is a plot of the first surface reflected color with a D65 light source for all viewing angles from 0 to 90 degrees for the comparative optical coating of FIG. 10A at seven optical coating thickness scale factor values;

FIG. 11A is a plot of first surface photopic reflectance versus wavelength at near-normal light incidence angles (8 degrees) for exemplary optical coatings of the present disclosure at four optical coating thickness scale factor values;

FIG. 11B is a plot of average first surface photopic reflectance versus incident light (viewing) angle for the exemplary optical coating of FIG. 11A at seven optical coating thickness scale factor values;

FIG. 11C is a plot of first surface reflected color with a D65 light source for all viewing angles from 0 to 90 degrees for the exemplary optical coating of FIG. 11A at seven optical coating thickness scale factor values;

FIG. 12A is a plot of first surface photopic reflectance versus wavelength at near-normal light incidence angles (8 degrees) for exemplary optical coatings of the present disclosure at four optical coating thickness scale factor values;

FIG. 12B is a plot of average first surface photopic reflectance versus incident light (viewing) angle for the exemplary optical coating of FIG. 12A at seven optical coating thickness scale factor values;

FIG. 12C is a graph of first surface reflected color with a D65 light source for all viewing angles from 0 to 90 degrees for the exemplary optical coating of FIG. 12A at seven optical coating thickness scale factor values;

FIG. 13A is a plot of first surface photopic reflectance versus wavelength at near-normal light incidence angles (8 degrees) for exemplary optical coatings of the present disclosure at four optical coating thickness scale factor values;

FIG. 13B is a plot of average first surface photopic reflectance versus incident light (viewing) angle for the exemplary optical coating of FIG. 13A at seven optical coating thickness scale factor values;

FIG. 13C is a graph of first surface reflected color with a D65 light source for all viewing angles from 0 to 90 degrees for the exemplary optical coating of FIG. 13A at seven optical coating thickness scale factor values;

FIG. 14A is a plot of first surface photopic reflectance versus wavelength at near-normal light incidence angles (8 degrees) for exemplary optical coatings of the present disclosure at four optical coating thickness scale factor values;

FIG. 14B is a plot of average first surface photopic reflectance versus incident light (viewing) angle for the exemplary optical coating of FIG. 14A at seven optical coating thickness scale factor values;

FIG. 14C is a plot of first surface reflected color with a D65 light source for all viewing angles from 0 to 90 degrees for the exemplary optical coating of FIG. 14A at seven optical coating thickness scale factor values;

FIG. 15 is a graph of hardness (GPa) versus indentation depth (nm) for three (3) variations of the exemplary optical coating shown in FIGS. 14A-14C;

FIG. 16A is a plot of first surface photopic reflectance versus wavelength at near-normal light incidence angles (8 degrees) for exemplary optical coatings of the present disclosure at four optical coating thickness scale factor values;

FIG. 16B is a plot of average first surface photopic reflectance versus incident light (viewing) angle for the exemplary optical coating of FIG. 16A at 9 optical coating thickness scale factor values;

FIG. 16C is a plot of first surface reflected color with a D65 light source for all viewing angles from 0 to 90 degrees for the exemplary optical coating of FIG. 16A at nine optical coating thickness scale factor values;

FIGS. 17A and 17B are graphs of first surface reflected color with a D65 light source for all viewing angles from 0 to 90 degrees for the exemplary optical coatings of the present disclosure shown in FIGS. 14C and 16C at nine optical coating thickness scale factor values, respectively;

fig. 18A is a plan view of an exemplary electronic device comprising any one of the coated articles disclosed herein; and

fig. 18B is a perspective view of the exemplary electronic device of fig. 18A.

Detailed Description

Reference will now be made in detail to various embodiments of coated articles, examples of which are illustrated in the accompanying drawings. Referring to fig. 1, a coated article 100 may include a non-planar substrate 110 and an optical coating 120 disposed on the substrate, according to one or more embodiments disclosed herein. The non-planar substrate 110 may include opposing major surfaces 112, 114 and opposing minor surfaces 116, 118. Optical coating 120 is shown in FIG. 1 as being disposed on first opposing major surface 112; however, in addition to or instead of being disposed on the first opposing major surface 112, the optical coating 120 may also be disposed on the second opposing major surface 114 and/or one or both of the opposing minor surfaces. The optical coating 120 forms an antireflective surface 122. The antireflective surface 122 forms an air interface and generally defines the edges of the optical coating 120 as well as the edges of the entire coated article 100. As described herein, the substrate 110 can be substantially transparent.

According to some embodiments described herein, the substrate 110 is non-planar. As used herein, a non-planar substrate refers to a substrate in which at least one of the major surfaces 112, 114 of the substrate 110 is not geometrically flat in shape. For example, as shown in fig. 1, a portion of the major surface 112 may include a curved geometry. The degree of curvature of the major surface 112 may vary. For example, embodiments may have a curvature measured by an approximate radius that is about 1mm to several meters (i.e., a near-plane), such as about 3mm to about 30mm, or about 5mm to about 10 mm. In embodiments, the non-planar substrate may include a planar portion, as shown in fig. 1. For example, a touch screen of a portable electronic device may include a substantially planar surface at or near its center and curved (i.e., non-planar) portions around its edges. Examples of such substrates include cover glasses from Apple (Apple) iPhone 6 smartphones or Samsung Galaxy S6 Edge smartphones. While some embodiments of the non-planar substrate are shown, it is understood that the non-planar substrate may take on various shapes, such as curved sheets, faceted sheets, sheets with angled surfaces, or even tubular sheets.

The non-planar substrate 110 includes a major surface 112 that includes at least two portions, a first portion 113 and a second portion 115, that are non-planar with respect to one another (i.e., the portions 113, 115 are not in the same plane or are not parallel to one another). According to some embodiments, the shape of the second portion 115 is curved or faceted. Direction n₁Perpendicular to the first portion 113 of the main surface 112, and in the direction n₂Perpendicular to second portion 115 at location 115A of major surface 112. In addition, the direction n₃Perpendicular to the second portion 115 at portion 115B of the major surface 112. A direction n perpendicular to the first portion 113₁And a direction n perpendicular to the second portion 115 at positions 115A and 115B, respectively₂And n₃Are not identical. It will be appreciated that depending on the curvature of the portion 115, the respective directions n₂、n₃And a plurality of other directions n_x(wherein x>2) Etc. may be perpendicular to the second portion 115 and to the direction n₁In the different direction n₁I.e. perpendicular to the direction of the first portion 113. In an embodiment, n₁And n₂(and/or n)₃) The angle therebetween can be at least about 5 degrees, at least about 10 degrees, at least about 15 degrees, at least about 20 degrees, at least about 25 degrees, at least about 30 degrees, at least about 35 degrees, at least about 40 degrees, at least about 45 degrees, at least about 50 degrees, at least about 55 degrees, at least about 60 degrees, at least about 70 degrees, at least about 80 degrees, at least about 90 degrees, at least about 120 degrees, at least about 150 degrees, or even at least about 180 degrees (e.g., for a tubular substrate, n is at least about 5 degrees, at least about 10 degrees, at least about 15 degrees, at least about 20 degrees, at least about 25 degrees₁And n₂The angle therebetween may be 180 degrees). E.g. n₁And n₂(and/or n)₃) The angle therebetween may be in the following range: about 10 degrees to about 30 degrees, about 10 degrees to about 45 degrees, about 10 degrees to about 60 degrees, about 10 degrees to about 75 degrees, about 10 degrees to about 90 degrees, about 10 degrees to about 120 degrees, about 10 degrees to about 150 degrees, or about 10 degrees to about 180 degrees. In further embodiments, n₁And n₂(and/or n)₃) The angle therebetween may be in the following range: about 10 degrees to about 80 degrees, about 20 degrees to about 80 degrees, about 30 degrees to about 80 degrees, about 40 degrees to about 80 degrees, about 50 degrees to about 80 degrees, about 60 degrees to about 80 degrees, about 70 degrees to about 80 degrees, about 20 degrees to about 180 degrees, about 30 degrees to about 180 degrees, about 40 degrees to about 180 degrees, about 50 degrees to about 180 degrees, about 60 degrees to about 180 degrees, about 70 degrees to about 150 degrees, or about 80 degrees to about 180 degrees.

Light transmitted through or reflected by the coated article 100 can be in the viewing direction v (i.e., for n)₁Is v is₁For n₂Is v is₂For n₃Is v is₃Etc.) the viewing direction v may not be perpendicular to the major surface 112 of the substrate 110, as shown in fig. 1. The viewing direction may be referred to as the incident illumination angle, which is measured from the normal direction of each surface. For example, as will be explained herein, the reflected color, the transmitted color, the average light reflectance, the average light transmittance, the photopic reflectance, and the photopic transmittance. The viewing direction v defines an incident illumination angle θ, which is the angle between the direction n normal to the substrate surface and the viewing direction v (i.e., θ!)₁Is the normal direction n₁And a viewing direction v₁Angle of incidence between, theta₂Is the normal direction n₂And a viewing direction v₂Angle of incident illumination in between, and θ₃Is the normal direction n₃And a viewing direction v₃Angle of incident illumination in between, etc.). It should be understood that while FIG. 1 depicts an incident illumination angle that is not equal to 0 degrees, in some embodiments, the incident illumination angle may be approximately equal to 0 degrees such that v is equal to n. When changing the incident illumination angle θ, the optical properties of a portion of the coated article 100 may differ.

Still referring to fig. 1, in some embodiments, the thickness of the optical coating 120, measured in a direction perpendicular to the major surface 112 of the substrate, may be different between portions of the optical coating 120 disposed over the first and second portions 113 and 115 of the substrate 110. For example, the optical coating 120 can be deposited onto the non-planar substrate 110 by vacuum deposition techniques such as chemical vapor deposition (e.g., Plasma Enhanced Chemical Vapor Deposition (PECVD), low pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, and plasma enhanced atmospheric pressure chemical vapor deposition), Physical Vapor Deposition (PVD) (e.g., reactive or non-reactive sputtering or laser ablation), thermal or electron beam evaporation, and/or atomic layer deposition. Liquid-based methods such as spray coating, dip coating, spin coating or slot coating (e.g., using sol-gel materials) can also be used. In some embodiments, PVD techniques relying on reactive sputtering in a "metal mode" may be employed, where a thin layer of metal is deposited in one portion of the deposition chamber and the film is reacted with a gas (e.g., oxygen or nitrogen) in a different portion of the deposition chamber. In some embodiments, PVD techniques that rely on "in-line" reactive sputtering may be employed, wherein material deposition and reaction occur in the same portion of the deposition chamber. In general, vapor deposition techniques can include various vacuum deposition methods for producing thin films. For example, physical vapor deposition uses a physical process (e.g., heating or sputtering) to generate a vapor of a material that is subsequently deposited on the object being coated. These deposition processes (especially PVD methods) may have a "line of sight" feature, wherein the deposited material moves onto the substrate in a uniform direction during deposition, regardless of the angle between the deposition direction and the angle perpendicular to the substrate surface.

Referring to fig. 1, arrow d shows the line-of-sight deposition direction. The deposition direction d in fig. 1 is perpendicular to the major surface 114 of the substrate 110, for example, the deposition direction d in fig. 1 may be common in systems where the substrate is placed against the major surface 114 during deposition of the optical coating 120. The arrow of line d points in the direction of line-of-sight deposition. Line t shows a direction perpendicular to the major surface 112 of the substrate 110. The normal thickness of the optical coating 120 is measured in a direction perpendicular to the major surface 112, which is represented by the length of line t. Deposition angleDefined as the angle between the deposition direction d and the direction perpendicular to the main surface 112, i.e. the line t. If optical coating 120 is deposited with line-of-sight deposition characteristics, for some vapor deposition processes, it has been observed that the thickness of a portion of optical coating 120 generally followsThe square root of the cosine of (see fig. 9 and corresponding description). Thus, withIncreasing the thickness of the optical coating 120 decreases. Although the actual thickness of the optical coating 120 deposited by vapor deposition may be determined by cosineThe thickness determined by a scalar of the square root of (a), but it provides a useful estimate for modeling optical coating designs that can have good performance when applied to a non-planar substrate 110. Furthermore, although n is shown in FIG. 1₁And d are in the same direction, but in all embodiments they need not be in the same direction. Without being bound by theory, it has been observed that the physical vapor deposition processes of the present disclosure do not always follow a complete line-of-sight feature, as the sputtered atoms and molecules may interact with each other as they travel from the sputtering target to the glass substrate 110 during deposition with the sputtering plasma. However, the physical vapor deposition process can be adjusted to achieve

The square root of the cosine of (see fig. 9 and corresponding description), which in turn can be advantageously used to construct the structure of the optical coating 120 to have desired optical and mechanical properties at both the first portion 113 and the second portion 115.

It should be understood that in the present disclosure, the thickness of the optical coating 120 is measured in the normal direction n unless otherwise specified.

According to some embodiments, various portions (e.g., first portion 113 and second portion 115) of coated article 100 may have optical characteristics that look similar to one another, such as light reflectance, light transmittance, reflected color, and/or transmitted color, as described herein. For example, when in a direction generally perpendicular to the substrate 110 (i.e., θ) at the respective portions 113, 115₁Approximately equal to 0 degrees and theta₂Approximately equal to 0 degrees), the optical characteristics at the first portion 113 may be similar to the optical characteristics at the second portion 115. In other embodiments, the illumination angle (e.g., θ) when incident at the respective portions 113, 115 is within a particular range from the normal direction₁Is about 0 degrees to about 60 degrees, θ₂Is about 0 degrees to about 60 degrees and theta₃About 0 degrees to about 60 degrees) can be similar to the optical characteristics at the second portion 115 at the first portion 113The optical characteristics of (1). In other embodiments, when in substantially the same direction (e.g., v)₁And v₂Angle between approximately 0 degrees), the optical characteristics at the first portion 113 may be similar to the optical characteristics at the second portion 115.

The optical coating 120 includes at least one layer of at least one material. The term "layer" may include a single layer or may include one or more sub-layers. These sublayers may be in direct contact with each other. These sublayers may be formed of the same material or two or more different materials. In one or more alternative embodiments, an intervening layer of a different material may be provided between the sublayers. In one or more embodiments, a layer may include one or more contiguous and uninterrupted layers and/or one or more discontinuous and interrupted layers (i.e., layers of different materials formed adjacent to each other). The layers or sub-layers may be formed by any method known in the art, including discrete deposition (discrete deposition) or continuous deposition. In one or more embodiments, the layers may be formed using only a continuous deposition process, or alternatively, only a discrete deposition process.

The optical coating 120 can have a thickness in the deposition direction of about 1 μm or more while still being able to provide an article exhibiting the optical properties described herein. In some examples, the optical coating thickness in the deposition direction may be in the following range: about 1 μm to about 20 μm, about 1 μm to about 10 μm, about 1 μm to about 5 μm, about 2 μm to about 10 μm, about 2 μm to about 5 μm, about 2 μm to about 4 μm, or all thickness values of the optical coating 120 in between these thickness values. For example, the thickness of the optical coating 120 can be about 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, and all thickness values in between these thicknesses.

As used herein, the term "disposing" includes coating, depositing, and/or forming a material onto a surface using any method known in the art. The disposed material may constitute a layer as defined herein. The phrase "disposed at … …" includes the following situations: forming a material onto a surface such that the material directly contacts the surface, further comprising: a material is formed on the surface with one or more intervening materials between the disposed material and the surface. The intervening material may constitute a layer as defined herein. In addition, it should be understood that while fig. 2-8 schematically illustrate a planar substrate, fig. 2-8 should be considered to have a non-planar substrate, such as that shown in fig. 1, with fig. 2-8 being shown in plan view in order to simplify the conceptual teaching of the respective figures.

As shown in fig. 2, the optical coating 120 can include an anti-reflective coating 130, and the anti-reflective coating 130 can include multiple layers (130A, 130B). In one or more embodiments, the anti-reflective coating 130 can include: a period 132 comprising two or more layers. In one or more embodiments, the two or more layers may be characterized as having different indices of refraction from one another. In one embodiment, the period 132 includes a first low RI layer 130A and a second high RI layer 130B. The difference in refractive index between the first low RI layer and the second high RI layer 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. 2, the anti-reflective coating 130 may comprise a plurality of periods 132. The single period 132 may include a first low RI layer 130A and a second high RI layer 130B such that when multiple periods 132 are provided, the first low RI layer 130A (labeled "L" for illustration) and the second high RI layer 130B (labeled "H" for illustration) alternate in the following sequence of layers: L/H/L/H or H/L/H/L such that the first low RI layer 130A and the second high RI layer 130B exhibit an alternation in physical thickness along the optical coating 120. In the example of fig. 2, the anti-reflective coating 130 includes three (3) periods 132. In some embodiments, the antireflective coating 130 can include up to twenty-five (25) periods 132 (also referred to herein as "N" periods, where N is an integer). For example, the anti-reflective coating 130 can include about 2 to about 20 cycles 132, about 2 to about 15 cycles 132, about 2 to about 12 cycles 132, about 2 to about 10 cycles 132, about 2 to about 12 cycles 132, about 3 to about 8 cycles 132, about 3 to about 6 cycles 132, or any other cycles 132 within these ranges. For example, the anti-reflective coating 130 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 periods 132.

In the embodiment shown in fig. 3, the anti-reflective coating 130 may include an additional capping layer 131, which may include a material having a lower refractive index than the second high RI layer 130B. In some embodiments, the period 132 may include one or more third layers 130C, as shown in fig. 3. The third layer 130C may have a low RI, a high RI, or a medium RI. In some embodiments, the third layer 130C may have the same RI as that of the first low RI layer 130A or the second high RI layer 130B. In other embodiments, the third layer 130C may have a medium RI between the RI of the first low RI layer 130A and the RI of the second high RI layer 130B. Alternatively, the third layer 130C may have a larger refractive index than the second high RI layer 130B. The third layer 130C may be provided in the optical coating 120 according to the following exemplary configuration: l is_{Third layer}/H/L/H/L；H_{Third layer}/L/H/L/H；L/H/L/H/L_{Third layer}；H/L/H/L/H_{Third layer}；L_{Third layer}/H/L/H/L/H_{Third layer}；H_{Third layer}/L/H/L/H/L_{Third layer}；L_{Third layer}/L/H/L/H；H_{Third layer}/H/L/H/L；H/L/H/L/L_{Third layer}；L/H/L/H/H_{Third layer}；L_{Third layer}/L/H/L/H/H_{Third layer}；H_{Third layer}//H/L/H/L/L_{Third layer}；L/M_{Third layer}H/L/M/H; H/M/L/H/M/L; M/L/H/L/M; and other combinations. In these configurations, "L" without any subscript represents the first low RI layer and "H" without any subscript represents the second high RI layer. Mentioned as "L_{Third layer}"refers to a third layer with a low RI," H_{Third sub-layer}"refers to a third layer having a high RI, and" M "refers to a third layer having a medium RI, all relative to the first and second layers.

As used herein, the terms "low RI," "high RI," and "medium RI" are in terms of relative values between RIs (e.g., low RI < medium RI < high RI). In one or more embodiments, the term "low RI" when used with respect to the first low RI layer or the third layer 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 respect to a second high RI layer or a third layer includes a range of about 1.7 to about 2.6 (e.g., about 1.85 or greater). In some embodiments, the term "intermediate RI" when used for the third layer includes a range of about 1.55 to about 1.8. In some cases, the ranges of low RI, high RI, and medium RI may overlap; in most cases, however, the various layers of the anti-reflective coating 130 have the following general relationship with respect to RI: low RI < medium RI < high RI.

One or more third layers 130C may be provided as a layer independent of period 132, and may be disposed between one or more periods 132 and cap layer 131, as shown in fig. 4. One or more third layers 130C may also be provided as a layer separate from the periods 132, and may be disposed between the substrate 110 and the plurality of periods 132, as shown in fig. 5. As shown in fig. 6, one or more third layers 130C may be used in addition to the additional coating 140 instead of the cap layer 131, or in addition to the cap layer 131. In some embodiments, in the configuration shown in fig. 7 and 8, one or more third layers 130C (not shown) are disposed adjacent to the scratch-resistant layer 150 or the substrate 110.

Suitable materials for the anti-reflective coating 130 include: SiO2₂、Al₂O₃、GeO₂、SiO、AlOxNy、AlN、SiNx、SiO_xN_y、Si_uAl_vO_xN_y、Ta₂O₅、Nb₂O₅、TiO₂、ZrO₂、TiN、MgO、MgF₂、BaF₂、CaF₂、SnO₂、HfO₂、Y₂O₃、MoO₃、DyF₃、YbF₃、YF₃、CeF₃Polymers, fluoropolymers, plasma polymerized polymers, siloxane 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 a scratch resistant layerAnd other materials known in the art. Some examples of suitable materials for the first low RI layer include SiO₂、Al₂O₃、GeO₂、SiO、AlO_xN_y、SiO_xN_y、Si_uAl_vO_xN_y、MgO、MgAl₂O₄、MgF₂、BaF₂、CaF₂、DyF₃、YbF₃、YF₃And CeF₃. The nitrogen content of the material used for the first low RI layer may be minimized (e.g., in a material such as Al)₂O₃And MgAl₂O₄Such as a material). Some examples of suitable materials for the second high RI layer include Si_uAl_vO_xN_y、Ta₂O₅、Nb₂O₅、AlN、Si₃N₄、AlO_xN_y、SiO_xN_y、SiN_x、SiN_x:H_y、HfO₂、TiO₂、ZrO₂、Y₂O₃、Al₂O₃、MoO₃And diamond-like carbon. In an example, the high RI layer can also be a high hardness layer or a scratch resistant layer, and the high RI materials listed above can also include high hardness or scratch resistance. The oxygen content of the material of the second high RI layer and/or the scratch resistant layer can be minimized, especially in SiN_xOr AlN_xIn the material. AlO (aluminum oxide)_xN_yThe material may be considered oxygen-doped AlN_xThat is, they may have AlN_xA crystalline structure (e.g., a wurtzite-type structure) and need not have an AlON crystalline structure. Exemplary AlO_xN_yThe high RI material may contain from about 0 atomic% to about 20 atomic% oxygen, or from about 5 atomic% to about 15 atomic% oxygen, while including from 30 atomic% to about 50 atomic% nitrogen. Exemplary Si_uAl_vO_xN_yThe high RI material may comprise from about 10 atomic% to about 30 atomic%, or from about 15 atomic% to about 25 atomic% silicon, from about 20 atomic% to about 40 atomic%, or from about 25 atomic% to about 35 atomic% aluminum, from about 0 atomic% to about 20 atomic%, or from about 1 atomic% to about 20 atomic% aluminum% oxygen, and from about 30 atomic% to about 50 atomic% nitrogen. The above materials may be hydrogenated to no more than about 30 weight percent. In some embodiments, Si_uAl_vO_xN_yThe high RI material includes 45 atomic% to 50 atomic% silicon, 45 atomic% to 50 atomic% nitrogen, and 3 atomic% to 10 atomic% oxygen. In another embodiment, Si_uAl_vO_xN_yThe high RI material includes 45 atomic% to 50 atomic% silicon, 35 atomic% to 50 atomic% nitrogen, and 3 atomic% to 20 atomic% oxygen. Some embodiments may use AlN and/or SiO if a material with a moderate refractive index is desired_xN_y. The hardness of the second high RI layer and/or the scratch resistant layer may be particularly characterized. In some embodiments, the maximum hardness of the second high RI layer 130B and/or the scratch resistant layer 150 (see fig. 7 and 8, and their corresponding description below) as measured by the berkovich indenter hardness test at an indentation depth of about 100nm or greater can be about 8GPa or greater, about 10GPa or greater, about 12GPa or greater, about 15GPa or greater, about 18GPa or greater, or about 20GPa or greater. In some cases, the second high RI layer 130B material can be deposited as a single layer and can be characterized as a scratch resistant layer (e.g., scratch resistant layer 150 shown in fig. 7 and 8 and described further below), and the single layer can have a thickness of about 200nm to 5000nm for repeatable hardness determination. In other embodiments where the second high RI layer 130B is deposited as a monolayer in the form of a scratch resistant layer (e.g., the scratch resistant layer 150 as shown in fig. 7 and 8), the layer can have a thickness of about 200nm to about 5000nm, about 200nm to about 3000nm, about 500nm to about 5000nm, about 1000nm to about 4000nm, about 1500nm to about 3000nm, and all thickness values in between.

In one or more embodiments, at least one of the various layers of the anti-reflective coating 130 can include a particular optical thickness range. The term "optical thickness" as used herein is determined by the sum of the physical thickness and the refractive index of the layer. In one or more embodiments, at least one layer of the anti-reflective coating 130 can comprise an optical thickness in the range of: from about 2nm to about 200nm, from about 10nm to about 100nm, from about 15 to about 500nm, or from about 15 to about 5000 nm. In some embodiments, all of the layers in the anti-reflective coating 130 can each have an optical thickness within the following range: from about 2nm to about 200nm, from about 10nm to about 100nm, from about 15nm to about 500nm, or from about 15nm to about 5000 nm. In some cases, at least one layer of the anti-reflective coating 130 has an optical thickness of about 50nm or greater. In some cases, each of the first low RI layers has an optical thickness in the range of: from about 2nm to about 200nm, from about 10nm to about 100nm, from about 15nm to about 500nm, or from about 15nm to about 5000 nm. In other cases, each of the second high RI layers has an optical thickness in the range of: from about 2nm to about 200nm, from about 10nm to about 100nm, from about 15nm to about 500nm, or from about 15nm to about 5000 nm. In other cases, each of the third layers has an optical thickness in the range of: from about 2nm to about 200nm, from about 10nm to about 100nm, from about 15nm to about 500nm, or from about 15nm to about 5000 nm.

In some embodiments, the topmost air-side layer may include a high RI layer 130B (see fig. 2), which also exhibits high stiffness. In some embodiments, an additional coating 140 (see fig. 6 and corresponding description below) may be disposed on top of the high RI layer on the topmost air side (e.g., the additional coating may include a low friction coating, an oleophobic coating, or an easy-to-clean coating). When added to the topmost air-side layer comprising the high RI layer, the addition of a low RI layer having a very low thickness (e.g., about 10nm or less, about 5nm or less, or about 2nm or less) has minimal impact on optical performance. The low RI layer with very low thickness may comprise SiO₂Oleophobic or low friction layer, or SiO₂And oleophobic materials. Exemplary low friction layers may include diamond-like carbon, and these materials (or one or more layers of the optical coating) may exhibit a coefficient of friction of less than 0.4, less than 0.3, less than 0.2, or even less than 0.1.

In one or more embodiments, the physical thickness of the anti-reflective coating 130 can be about 800nm or less. The physical thickness of the anti-reflective coating 130 may be in the following range: from about 10nm to about 800nm, from about 50nm to about 800nm, from about 100nm to about 800nm, from about 150nm to about 800nm, from about 200nm to about 800nm, from about 300nm to about 800nm, from about 400nm to about 800nm, from about 10nm to about 750nm, from about 10nm to about 700nm, from about 10nm to about 650nm, from about 10nm to about 600nm, from about 10nm to about 550nm, from about 10nm to about 500nm, from about 10nm to about 450nm, from about 10nm to about 400nm, from about 10nm to about 350nm, from about 10nm to about 300nm, from about 50nm to about 300nm, and all ranges and subranges therebetween. In some embodiments, the physical thickness of the anti-reflective coating 130 may be in the following range: from about 250nm to about 1000nm, from about 500nm to about 1000nm, and all ranges and subranges therebetween. For example, the physical thickness of the anti-reflective coating 130 can be about 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1000nm, and all thicknesses between these thickness values.

In one or more embodiments, the combined physical thickness of the second high RI layer may be characterized. For example, in some embodiments, the combined thickness of the second high RI layer may be about 100nm or greater, about 150nm or greater, about 200nm or greater, about 250nm or greater, about 300nm or greater, about 350nm or greater, about 400nm or greater, about 450nm or greater, about 500nm or greater, about 550nm or greater, about 600nm or greater, about 650nm or greater, about 700nm or greater, about 750nm or greater, about 800nm or greater, about 850nm or greater, about 900nm or greater, about 950nm or greater, or even about 1000nm or greater. The combined thickness is the calculated combined thickness of each of the high RI layers in the anti-reflective coating 130, even if there are intervening low RI layers or other layers. In some embodiments, the combined physical thickness of the second high RI layer, which may also include a high hardness material (e.g., a nitride or oxynitride material), may be greater than 30% of the total physical thickness of the anti-reflective coating. For example, the combined physical thickness of the second high RI layer may be about 40% or greater, about 50% or greater, about 60% or greater, about 70% or greater, about 75% or greater, or even about 80% or greater of the total physical thickness of the anti-reflective coating 130 or the total physical thickness of the optical coating 120. Alternatively or additionally, the amount of high refractive index material (which may also be a high hardness material) included in the optical coating may be characterized as a percentage of the physical thickness of the article or the uppermost portion (i.e., the user side or the side of the optical coating opposite the substrate) of the optical coating 120 of 500 nm. Expressed as a percentage of the uppermost 500nm of the article or optical coating, the combined physical thickness of the second high RI layer (or the thickness of the high refractive index material) may comprise about 50% or more, about 60% or more, about 70% or more, about 80% or more, or even about 90% or more of the uppermost 500 nm. In some embodiments, as further described elsewhere herein, a higher proportion of hard and high index of refraction materials in the antireflective coating may also be simultaneously made such that it also exhibits low reflectivity, low color, and high abrasion resistance. In one or more embodiments, the second, high RI layer may comprise a material having a refractive index greater than about 1.85, and the first, low RI layer may comprise a material having a refractive index less than about 1.75. In some embodiments, the second high RI layer may comprise a nitride or oxynitride material. In some cases, the combined thickness of all first low RI layers in the optical coating (or in layers disposed on the thickest second high RI layer of the optical coating) can be about 200nm or less (e.g., about 150nm or less, about 100nm or less, about 75nm or less, or about 50nm or less).

As shown in fig. 6, the coated article 100 may include one or more additional coatings 140 disposed on the anti-reflective coating. In one or more embodiments, the additional coating may comprise an easy-clean coating. An example of a suitable Easy-Clean coating is described in U.S. patent application No. 13/690,904 entitled "Process for manufacturing Glass articles with Optical and Easy-to-Clean Coatings," filed on 11/30/2012, and U.S. patent application publication No. 2014/0113083, published on 24/4/2014, the salient portions of which are incorporated herein by reference in their entirety. The easy-clean coating may have a thickness in the range of about 5nm to about 50nm and may comprise known materials, such as fluorinated silanes. The easy-clean coating may alternatively or additionally comprise a low-friction coating or surface treatment. Exemplary low friction coating materials may include diamond-like carbon, silanes (e.g., fluorosilanes), phosphonates, alkenes, and alkynes. In some embodiments, the thickness of the easy-clean coating can be in the following range: from about 1nm to about 40nm, from about 1nm to about 30nm, from about 1nm to about 25nm, from about 1nm to about 20nm, from about 1nm to about 15nm, from about 1nm to about 10nm, from about 5nm to about 50nm, from about 10nm to about 50nm, from about 15nm to about 50nm, from about 7nm to about 20nm, from about 7nm to about 15nm, from about 7nm to about 12nm, or from about 7nm to about 10nm, and all ranges and subranges therebetween.

The additional coating 140 may comprise one or more scratch resistant layers. In some embodiments, the additional coating 140 includes a combination of an easy-to-clean material and a scratch resistant material. In one example, the combination comprises an easy-to-clean material and diamond-like carbon. These additional coatings 140 may have a thickness in the range of about 5nm to about 20 nm. The composition of the additional coating 140 may be provided in a separate layer. For example, diamond-like carbon may be provided as a first layer and the easy-to-clean material may be provided as a second layer on the diamond-like carbon first layer. The thickness of the first and second layers may be within the thickness range of the additional coating provided above. For example, the diamond-like carbon first layer may have a thickness of about 1nm to about 20nm or about 4nm to about 15nm (or more specifically about 10nm), while the easy-to-clean material second layer may have a thickness of about 1nm to about 10nm (or more specifically about 6 nm). The diamond-like coating may comprise tetrahedral amorphous carbon (Ta-C), Ta-C: H, and/or a-C-H.

As described herein, the optical coating 120 can include a scratch resistant layer 150, which can be disposed between the antireflective coating 130 and the substrate 110. In some embodiments, the scratch resistant layer 150 is disposed between layers of the anti-reflective coating 130 (e.g., the scratch resistant layer 150 shown in fig. 7 and 8). The two portions of the anti-reflective coating 130 (i.e., the first portion disposed between the scratch resistant layer 150 and the substrate 110 and the second portion disposed on the scratch resistant layer) may have different thicknesses from each other, or may have substantially the same thickness as each other. The layers in the two portions of the anti-reflective coating 130 may have the same composition, order, thickness, and/or arrangement as each other or different from each other. Furthermore, each of the two portions of the anti-reflective coating 130 may contain the same number (N) of periods 132 or the number of periods 132 in each of the portions may be different from each other (see fig. 2-6 and periods 132 described above). Further, one or more optional layers 130C (not shown) can be disposed in either or both portions (e.g., directly on the substrate 110, in contact with the scratch resistant layer 150 at the top of the first anti-reflective coating 130 portion, in contact with the scratch resistant layer 150 at the bottom of the second anti-reflective coating 130 portion, and/or in contact with the substrate 110 at the bottom of the second anti-reflective coating).

Exemplary materials for the scratch resistant layer 150 (or scratch resistant layer for use as the additional coating 140) may include inorganic carbides, nitrides, oxides, diamond-like materials, or combinations of these materials. Examples of suitable materials for the scratch resistant layer 150 include metal oxides, metal nitrides, metal oxynitrides, metal carbides, metal oxycarbides, and/or combinations thereof. Exemplary metals include B, Al, Si, Ti, V, Cr, Y, Zr, Nb, Mo, Sn, Hf, Ta, and W. Specific examples of materials that may be used for the scratch resistant layer 150 or coating layer may include Al₂O₃、AlN、AlO_xN_y、Si₃N₄、SiO_xN_y、Si_uAl_vO_xN_yDiamond, diamond-like carbon, Si_xC_y、Si_xO_yC_z、ZrO₂、TiO_xN_yAnd combinations thereof. The scratch resistant layer 150 may also comprise a nanocomposite or material with a controlled microstructure to improve hardness, toughness, or abrasion/wear resistance. For example, the scratch resistant layer 150 may comprise nanocrystals having a size of about 5nm to about 30 nm. In embodiments, the scratch resistant layer 150 may comprise phase change toughened zirconia, partially stabilized zirconia, or zirconia toughened alumina. In an embodiment, the scratch resistant layer 150 exhibits a fracture toughness value greater than about 1MPa v m and simultaneously exhibits a hardness value greater than about 8 GPa.

The scratch resistant layer 150 may comprise a single layer (as shown in fig. 7 and 8), or multiple sublayers exhibiting a refractive index gradient or a single plurality of sublayersAnd (3) a layer. If multiple layers are used, these layers form a scratch resistant coating. For example, the scratch resistant layer 150 may comprise Si_uAl_vO_xN_yWherein the concentration of any one or more of Si, Al, O and N is varied to increase or decrease the refractive index. The refractive index gradient may also be formed using voids. Such gradients are more fully described in U.S. patent application No. 14/262,224 entitled "Scratch-Resistant Articles with a Gradient Layer," filed on 28.4.2014, which is now entitled U.S. patent No. 9,703,011 on 11.7.7.2017, the salient portions of each of which are incorporated herein by reference in their entirety.

According to some embodiments, the scratch resistant layer 150 may have a thickness of about 200nm to about 5000 nm. In some embodiments, the scratch resistant layer 150 has a thickness of about 200nm to about 5000nm, about 200nm to about 3000nm, about 500nm to about 5000nm, about 500nm to 3000nm, about 500nm to about 2500nm, about 1000nm to about 4000nm, about 1500nm to about 3000nm, and all thickness values in between. For example, the thickness of the scratch resistant layer 150 can be 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1100nm, 1200nm, 1300nm, 1400nm, 1500nm, 1600nm, 1700nm, 1800nm, 1900nm, 2000nm, 2100nm, 2200nm, 2300nm, 2400nm, 2500nm, 2600nm, 2700nm, 2800nm, 2900nm, 3000nm, 3500nm, 4000nm, 4500nm, 5000nm, and all thickness subranges and thickness values therebetween.

In one embodiment, as shown in fig. 8, the optical coating 120 can comprise a scratch resistant layer 150 integrated as a high RI layer, and one or more low RI layers 130A and high RI layers 130B can be positioned over the scratch resistant layer 150, and an optional cap layer 131 is positioned over the low RI layer 130A and high RI layer 130B, wherein the cap layer 131 comprises a low RI material. Scratch resistant layer 150 can alternatively be defined as the thickest hard layer or thickest high RI layer throughout optical coating 120 or throughout coated article 100. Without being bound by theory, it is believed that the coated article 100 may exhibit an increase in hardness at the indentation depth when a relatively small amount of material is deposited over the scratch resistant layer 150. However, the inclusion of low and high RI layers over scratch resistant layer 150 may enhance the optical properties of coated article 100. In some embodiments, relatively few layers (e.g., only 1, 2, 3, 4, or 5 layers) may be placed over the scratch-resistant layer 150, and each of these layers may be relatively thin (e.g., less than 100nm, less than 75nm, less than 50nm, or even less than 25 nm). In other embodiments, a greater number of layers (e.g., 3 to 15 layers) can be placed over the scratch-resistant layer 150, and each of these layers can also be relatively thin (e.g., less than 200nm, less than 175nm, less than 150nm, less than 125nm, less than 100nm, less than 75nm, less than 50nm, and even less than 25 nm). In one embodiment of the embodiment shown in fig. 8, the anti-reflective coating 130 can comprise a period 132, a layer 130C (not shown) disposed adjacent to the scratch resistant layer 150 or the substrate 110, and a capping layer 131 (as shown in fig. 8), the period 132 comprising four periods 132 above the scratch resistant layer 150 and four periods 132 below the scratch resistant layer (i.e., N-8). In another embodiment of the embodiment shown in fig. 8, the anti-reflective coating 130 can comprise a period 132, a layer 130C (not shown) disposed adjacent to the scratch resistant layer 150 or the substrate 110, and a capping layer 131 (as shown in fig. 8), the period 132 comprising five periods 132 above the scratch resistant layer 150 and five periods 132 below the scratch resistant layer (i.e., N-10).

In embodiments, the total thickness (i.e., the combined thickness) of the layers disposed above the scratch-resistant layer 150 (i.e., on the air side of the scratch-resistant layer 150) is less than or equal to about 1000nm, less than or equal to about 500nm, less than or equal to about 450nm, less than or equal to about 400nm, less than or equal to about 350nm, less than or equal to about 300nm, less than or equal to about 250nm, less than or equal to about 225nm, less than or equal to about 200nm, less than or equal to about 175nm, less than or equal to about 150nm, less than or equal to about 125nm, less than or equal to about 100nm, less than or equal to about 90nm, less than or equal to about 80nm, less than or equal to about 70nm, less than or equal to about 60nm, or even less than or equal to about 50 nm.

In embodiments (e.g., the coated article 100 shown in fig. 7 and 8), the total thickness of the low RI layer (i.e., the sum of the thicknesses of all low RI layers 130A, even though they are not in contact) disposed over the scratch-resistant layer 150 (i.e., on the air-side of the scratch-resistant layer 150) can be less than or equal to about 500nm, less than or equal to about 450nm, less than or equal to about 400nm, less than or equal to about 350nm, less than or equal to about 300nm, less than or equal to about 250nm, less than or equal to about 225nm, less than or equal to about 200nm, less than or equal to about 175nm, less than or equal to about 150nm, less than or equal to about 125nm, less than or equal to about 100nm, less than or equal to about 90nm, less than or equal to about 80nm, less than or equal to about 70nm, less than or equal to about 60nm, less than or equal to about 50nm, less than or equal to about 40nm, less than or equal to about 30nm, less than or equal to about 20, Or even less than or equal to about 10 nm.

The hardness of the optical coating 120 and/or the coated article 100 can be described as measured by the berkovich indenter hardness test. As used herein, the "Berkovich Indenter Hardness Test" (Berkovich index Hardness Test) involves the use of a diamond Berkovich Indenter to indent the surface, thereby measuring the Hardness of the material on the surface of the material. The berkovich indenter hardness test involves embossing the surface of any one or more of the anti-reflective surface 122 or the optical coating 120 of the coated article 100 (see fig. 1-8) with a diamond berkovich indenter to form an indentation with an indentation depth in the range of about 50nm to about 1000nm (or the entire thickness of the optical coating 120 or the thickness of the layers of the optical coating 120, whichever is less), and measuring the maximum hardness from the indentation along the entire indentation depth range or a segment of the indentation depth (e.g., in the range of about 100nm to about 600nm, e.g., at an indentation depth of 100nm or greater, etc.), typically using methods in the following references: oliver, w.c.; "An improved technique for determining hardness and modulus of elasticity using load and displacement sensing indentation experiments" by Pharr, G.M., J.Mater.Res., Vol.7, No. 6, 1992, 1564-1583; and Oliver, w.c.; pharr, G.M. "Measurement of Hardness and Elastic Module by Instrument indexing: Advances in Understanding and improvements in methods" ("improvements in Hardness and Modulus of elasticity using Instrument Indentation"), J.Mater.Res., Vol.19, No. 1, 2004, 3-20, the highlights of which are incorporated by reference in their entirety in this disclosure. As used herein, "hardness" refers to the maximum hardness and not to the average hardness.

Typically, in nanoindentation measurement methods (e.g., by using a Berkovich indenter) performed on harder coatings than the underlying substrate, the measured hardness may initially show an increase as a result of the formation of a plastic zone at shallower indentation depths, and then increase and reach a maximum or plateau at deeper indentation depths. Subsequently, the hardness starts to decrease at deeper indentation depths due to the influence of the underlying substrate. The same effect can be seen in the case of substrates having an increased hardness relative to the coating used; however, the hardness increases at deeper indentation depths due to the influence of the underlying substrate.

The range of indentation depths and hardness values over a range of indentation depths can be selected to determine the specific hardness response of an optical film structure and its layers as described herein, independent of the underlying substrate. When the hardness of the optical film structure (when disposed on a substrate) is measured using a berkovich indenter, the area of permanent deformation (plastic zone) of the material correlates with the hardness of the material. During embossing, the extent of the elastic stress field extends well beyond this permanent deformation region. As the indentation depth increases, the apparent hardness and modulus are affected by the interaction of the stress field with the underlying substrate. The effect of the substrate on hardness occurs at deeper indentation depths (i.e., typically at depths greater than about 10% of the optical film structure or layer thickness). In addition, another complication is that the hardness response requires some minimum load to develop full plasticity during embossing. The stiffness shows a generally increasing trend before this determined minimum load is reached.

At small indentation depths (which may also be characterized as small loads) (e.g., no more than about 50nm), a sharp increase in the apparent hardness of the material relative to the indentation depth occurs. This smaller indentation depth area does not represent a true measure of hardness, but rather reflects the formation of a plastic zone as described above, which is related to the finite radius of curvature of the indenter. At intermediate indentation depths, the apparent hardness approaches a maximum level. At deeper indentation depths, the effect of the substrate becomes more pronounced as the indentation depth increases. Once the indentation depth exceeds about 30% of the optical coating 120 thickness or layer thickness, the hardness begins to decrease dramatically.

In some embodiments, the coated article 100 (e.g., as shown in fig. 1-8) may exhibit the following hardness when measured on the antireflective surface 122: about 8GPa or greater, about 10GPa or greater, or about 12GPa or greater (e.g., about 14GPa or greater, about 16GPa or greater, about 18GPa or greater, or about 20GPa or greater). The hardness of the coated article 100 may even be as high as about 20GPa or 30 GPa. The measured hardness values may be exhibited by the optical coating 120 and/or the coated article 100 along an indentation depth of about 50nm or greater, or about 100nm or greater (e.g., about 50nm to about 300nm, about 50nm to about 400nm, about 50nm to about 500nm, about 50nm to about 600nm, about 100nm to about 300nm, about 100nm to about 400nm, about 100nm to about 500nm, about 100nm to about 600nm, about 200nm to about 300nm, about 200nm to about 400nm, about 200nm to about 500nm, or about 200nm to about 600 nm). In one or more embodiments, the coated article 100 exhibits a hardness that is greater than the hardness of the substrate 110 (the hardness of the substrate 110 can be measured on the surface opposite the antireflective surface).

Depending on the embodiment, hardness may be measured at different portions of the coated article 100. For example, at the antireflective surface 122 at the first portion 113 and at the second portion 115, the coated article may exhibit a hardness of at least 8GPa or greater at an indentation depth of at least about 100nm or greater. For example, the hardness at the first portion 113 and at the second portion 115 may be about 8GPa or greater, about 10GPa or greater, or about 12GPa or greater (e.g., about 14GPa or greater, about 16GPa or greater, about 18GPa or greater, or about 20GPa or greater).

According to embodiments, the coated articles described herein may have desirable optical properties (e.g., low reflectivity and neutral color) at various portions of the coated article 100, such as at the first portion 113 and the second portion 115. For example, when viewing the respective portions at an incident illumination angle that is approximately perpendicular to the respective first and second portions 113 and 115, the light reflectance may be relatively low (and the transmittance may be relatively high) at the first portion 113 and at the second portion 115. In another embodiment, the color difference between the two portions may be insignificant to the naked eye when each portion is viewed at an angle of illumination near normal incidence. In another embodiment, the color may be insignificant to the naked eye when the portions are viewed at incident illumination angles that are in the same direction, and may have a relatively low reflectivity in each portion (i.e., because the portions are at an angle to each other, the incident illumination angles are not the same relative to the surface of each portion, but the illumination directions are the same). The optical properties may include average light transmittance, average light reflectance, photopic reflectance, maximum photopic reflectance, photopic transmittance, reflected color (i.e., in laxa b color coordinates), and transmitted color (i.e., in laxa b color coordinates).

As used herein, the term "transmittance" is defined as the percentage of incident optical power in a given wavelength range that is transmitted through a material (e.g., an article, substrate, or optical film or portion thereof). Similarly, the term "reflectivity" is defined as the percentage of incident optical power within a given wavelength range that is reflected from a material (e.g., an article, substrate, or optical film or portion thereof). When measured only at the antireflective surface 122 [ e.g., when reflection is removed from the uncoated back surface of the article (e.g., 114 in fig. 1), such as by using an index matching oil on the back surface that is connected to the absorber, or using other known methods ], the reflectance can be measured as a single-sided reflectance (also referred to herein as "first surface reflectance"). In one or more embodiments, the spectral resolution characterizing the transmittance and reflectance is less than 5nm or 0.02 eV. The color may be more pronounced in reflection. Since the spectral reflection oscillation shifts with the incident illumination angle, the character color in reflection also shifts with the viewing angle. The character color in transmission also shifts with viewing angle due to the same shift in spectral transmission oscillation with incident illumination angle. Observed color and character color shifts with incident illumination angle often cause aversion or dislike to device users, particularly under illumination with sharp spectral features, such as fluorescent illumination and some LED illumination. The shift in the role in transmission can also be a factor in the shift in color in reflection and vice versa. Factors for cast in transmission and/or reflection also include cast due to viewing angle or cast away from a white point that may be caused by material absorption (somewhat angle independent), as defined by a particular light source or test system.

The average light reflectance and average light transmittance can be measured over a wavelength region of from about 400nm to about 800nm, from about 400nm to about 1000nm, or any wavelength region or sub-region between the endpoints of these wavelength ranges. In further embodiments, the optical wavelength region may include a range of wavelengths, for example, from about 450nm to about 650nm, from about 420nm to about 680nm, from about 420nm to about 700nm, from about 420nm to about 740nm, from about 420nm to about 850nm, from about 420nm to about 950nm, or from about 425nm to about 950 nm.

The coated article 100 can also be characterized by photopic transmittance and photopic reflectance at various portions. As used herein, photopic reflectance simulates the response of the human eye by reflectance weighting of the wavelength spectrum according to the sensitivity of the human eye. Photopic reflectance may also be defined as the brightness or tristimulus value Y of reflected light according to known conventions, such as the CIE color space convention. The average photopic reflectance is defined in the following equation as the spectral reflectance R (λ) multiplied by the illumination spectrum I (λ) and the CIE color matching functionWhich is related to the spectral response of the eye, the equation is as follows:

average photopic transmittanceRefractive index is defined in the following equation as the spectral transmittance T (λ) multiplied by the illumination spectrum I (λ) and the CIE color matching functionWhich is related to the spectral response of the eye, the equation is as follows:

it is also understood that photopic transmittance and/or photopic reflectance may be reported as the maximum photopic transmittance and/or maximum photopic reflectance within a given spectral range (e.g., 425nm to 950 nm).

According to one embodiment, the coated article 100 may exhibit a single-sided average, average photopic, or maximum light reflectance of about 8% or less, about 7% or less, about 6% or less, about 5% or less, about 4% or less, about 3% or less, about 2% or less, about 1.5% or less, about 1.2% or less, or about 1% or less, as measured at the antireflective surface 122 at the first portion 113 of the substrate 110, wherein the single-sided average light reflectance of the first portion 113 is relative to n₁First incident illumination angle theta₁Lower measurement, and wherein the first incident illumination angle θ₁Containing and n₁An angle of about 0 degrees to about 60 degrees. In further embodiments, the first incident illumination angle θ₁May contain n₁An angle of about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees. In further embodiments, for and n₁All incident illumination angles θ in the range of about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees₁The coated article 100 may exhibit the following single-sided average light reflectance when measured at the antireflective surface 122 at the first portion 113 of the substrate 110: about 8% or less, about 7% or less, about 6% or less, about 5% or less, about 4% or less, about 3% or less,About 2% or less, about 1.5% or less, about 1.2% or less, or about 1% or less. In further embodiments, in view of any of the described incident illumination angles θ₁A range of (a), a single-sided average or maximum light reflectance measured at the antireflective surface 122 of the first portion 113 of the substrate 110 can be about 10% or less, about 9% or less, about 8% or less, about 7% or less, about 6% or less, about 5% or less, about 4% or less, about 3% or less, about 2% or less, about 1% or less, or about 0.8% or less over the optical wavelength region. For example, the single-sided average or maximum light reflectance may be in the following range: about 0.4% to about 9%, about 0.4% to about 8%, about 0.4% to about 7%, about 0.4% to about 6%, or about 0.4% to about 5%, and all ranges therebetween.

According to one embodiment, the coated article 100 may exhibit a single-sided average or maximum light reflectance of about 8% or less, about 7% or less, about 6% or less, about 5% or less, about 4% or less, about 3% or less, about 2% or less, or about 1% or less, as measured at the antireflective surface 122 at the second portion 115 of the substrate 110, wherein the single-sided average light reflectance of the second portion 115 is (a) relative to n₂Angle of incident illumination theta₂Lower measurement, and wherein the incident illumination angle θ₂Containing and n₂An angle of about 0 degrees to about 60 degrees, and/or (b) with respect to n₃Angle of incident illumination theta₃Lower measurement, and wherein the incident illumination angle θ₃Containing and n₃An angle of about 0 degrees to about 60 degrees. In other embodiments, the incident illumination angle θ₂And theta₃May each comprise n₂And n₃An angle of about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 45 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees. In further embodiments, for and n₂And/or n₃About 0 degrees to about 60 degrees, about 0 degrees to about 45 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees, respectivelyIncident illumination angle theta₂And/or theta₃The coated article 100 may exhibit a single-sided average or maximum light reflectance of about 8% or less, as measured at the antireflective surface 122 at the second portion 115 of the substrate 110. In further embodiments, in view of any of the described incident illumination angles θ₂And theta₃Ranges, respectively, the single-sided average or maximum light reflectance measured at the antireflective surface 122 of the second portion 115 of the substrate 110 can be about 10% or less, about 9% or less, about 8% or less, about 7% or less, about 6% or less, about 5% or less, about 4% or less, about 3% or less, about 2% or less, about 1% or less, or about 0.8% or less over the optical wavelength region. For example, the single-sided average or maximum light reflectance may be in the following range: about 0.4% to about 9%, about 0.4% to about 8%, about 0.4% to about 7%, about 0.4% to about 6%, or about 0.4% to about 5%, and all ranges therebetween.

In another embodiment, the difference between the single-sided average or maximum light reflectance within any of the disclosed angular ranges measured at the antireflective surface 122 of the first portion 113 of the substrate 110 and the single-sided average light reflectance within any of the disclosed angular ranges measured at the antireflective surface 122 of the second portion 115 of the substrate 110 is 5% or less, 4% or less, 3% or less, 2% or less, or even 1% or less.

In another embodiment, the photopic reflectance at the first portion 113 and/or the second portion 115 is within the disclosed ranges with respect to a single-sided average or maximum light reflectance within the disclosed angular ranges.

According to one embodiment, the coated article 100 may exhibit an average light transmission of about 90% or greater as measured at the antireflective surface 122 of the first portion 113 of the substrate 110, wherein the average light transmission of the first portion 113 is relative to n₁Angle of incident illumination theta₁Lower measurement, and wherein the incident illumination angle θ₁Containing and n₁An angle of about 0 degrees to about 60 degrees. In other embodiments, the incident illumination angle θ₁May contain n₁An angle of about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees. In further embodiments, for and n₁All incident illumination angles θ in the range of about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees₁The coated article 100 may exhibit an average light transmission of about 90% or greater, as measured at the antireflective surface 122 of the first portion 113 of the substrate 110. In further embodiments, in view of any of the described incident illumination angles θ₁The average light transmission measured at the antireflective surface 122 of the first portion 113 of the substrate 110 can be about 90% or greater, 91% or greater, 92% or greater, 93% or greater, 94% or greater, 95% or greater, 96% or greater, 97% or greater, or 98% or greater in the optical wavelength region. For example, the average light transmission may be in the following range: about 90% to about 95.5%, about 91% to about 95.5%, about 92% to about 95.5%, about 93% to about 95.5%, about 94% to about 95.5%, about 95% to about 95.5%, about 96% to about 96.5%, and all ranges therebetween.

According to one embodiment, the coated article 100 may exhibit an average light transmission of 90% or greater as measured at the antireflective surface 122 of the second portion 115 of the substrate 110, wherein the average light transmission of the second portion 115 is at (a) relative to n₂Angle of incident illumination theta₂Lower measurement, and wherein the incident illumination angle θ₂Containing and n₂An angle of about 0 degrees to about 60 degrees, and/or (b) with respect to n₃Angle of incident illumination theta₃Lower measurement, and wherein the incident illumination angle θ₃Containing and n₃An angle of about 0 degrees to about 60 degrees. In other embodiments, the incident illumination angle θ₂And theta₃May each comprise n₂And n₃An angle of about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees. In another embodiment, forAnd n₂And n₃All incident illumination angles θ ranging from about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees, respectively₂And/or theta₃The coated article 100 may exhibit an average light transmission of about 90% or greater, as measured at the antireflective surface 122 of the second portion 115 of the substrate 110. In further embodiments, in view of any of the described incident illumination angles θ₂And theta₃Can be about 90% or greater, 91% or greater, 92% or greater, 93% or greater, 94% or greater, 95% or greater, 96% or greater, 97% or greater, or 98% or greater in the optical wavelength region. For example, the average light transmission may be in the following range: about 90% to about 95.5%, about 91% to about 95.5%, about 92% to about 95.5%, about 93% to about 95.5%, about 94% to about 95.5%, about 95% to about 95.5%, about 96% to about 95.5%, and all ranges therebetween.

In another embodiment, the difference between the average light transmission over any of the disclosed angular ranges measured at the antireflective surface 122 of the first portion 113 of the substrate 110 and the average light transmission over any of the disclosed angular ranges measured at the antireflective surface 122 of the second portion 115 of the substrate 110 is 5% or less, 4% or less, 3% or less, 2% or less, or even 1% or less.

In another embodiment, the photopic transmittance at the first portion 113 and/or the second portion 115 is within the disclosed ranges with respect to the average light transmittance within the disclosed angular ranges.

According to another embodiment, one or more of a one-sided average or maximum light reflectance, an average light transmittance, a photopic reflectance, a photopic transmittance, a reflected color, and a transmitted color may be measured at the first portion 113 and the second portion 115, wherein the incident illumination angle θ₁Including with n₁A given optical value (e.g., transmission, degree of optical distortion, degree,Reflectance, etc.) at an incident illumination angle θ₂And/or theta₃Measured below, wherein the incident illumination angle θ₂And theta₃At an angle theta to the incident illumination₁V direction of₁In the same direction such that the optical properties at the first portion 113 and the second portion 115 are measured in the same viewing direction (i.e., v |)₁Is equal to v₂(and v)₃As applicable), but θ₁Is not equal to theta₂(and/or θ)₃) Since n is₁Is not equal to n₂(and n)₃As applicable).

Optical interference between reflected waves from the optical coating 120/air interface and reflected waves from the optical coating 120/substrate 110 interface can cause spectral reflectance and/or transmittance oscillations, thereby producing an apparent color in the coated article 100. In one or more embodiments, when illuminated at an incident illumination angle θ₁At normal n₁To the viewing direction v₁The coated article 100 may exhibit a color shift in reflection and/or transmission at the first portion 113 of about 10 or less, or about 5 or less, when measured therebetween. Additionally, in one or more embodiments, the illumination angle θ is measured as the angle of incidence₂At normal n₂To the viewing direction v₂Measured at an incident illumination angle theta, and/or₃At normal n₃To the viewing direction v₃The coated article 100 can exhibit a color shift in reflection and/or transmission at the second portion 115 of about 10 or less, or about 5 or less, when measured in between.

According to one or more embodiments, the reference point color at the first portion 113 and the second portion 115 can be less than about 10 (e.g., about 9 or less, about 8 or less, about 7 or less, about 6 or less, about 5 or less, about 4 or less, about 3 or less, or even about 2 or less). As used herein, the phrase "reference point color" refers to a and b in reflection and/or transmission with respect to a reference color under the CIE L, a, b chromaticity system. The reference color may be (a, b) ═ 0, (-2, -2), (-4, -4), or the color coordinates of the substrate 110. The reference point color may be at different incident illumination angles theta₁And theta₂And (4) measuring. At the (0, 0) reference, the reference point color is defined as √ ((a √ b)_{Article of manufacture})²+(b*_{Article of manufacture})²) (ii) a At the (-2, -2) reference, the reference point color is defined as √ ((a) } v_{Article of manufacture}+2)²+(b*_{Article of manufacture}+2)²) (ii) a At the (-4, -4) reference, the reference point color is defined as √ (a @)_{Article of manufacture}+4)²+(b*_{Article of manufacture}+4)²) (ii) a When the color of the substrate 110 is a reference, the reference point color is defined as √ ((a) }_{Article of manufacture}-a*_{Base material})²+(b*_{Article of manufacture}-b*_{Base material})²). In an embodiment, the reference point color may be measured over a range of angles such that the incident illumination angle θ₁And theta₂And/or theta₃To include with n₁、n₂And/or n₃An angle of about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 45 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees. In another embodiment, a may be about 5 or less and b may be about 5 or less, or they may each be about 4 or less, 3 or less, 2 or less, or even 1 or less, at the first portion 113, the second portion 115, or both the first portion 113 and the second portion 115, for any of the disclosed incident illumination angle ranges.

As used herein, the term "angular color shift" refers to a shift in both a and b in reflection and/or transmission with a shift in the angle of incident illumination under the CIE L, a, b chromaticity system. It should be understood that unless otherwise noted, the L-coordinate of the articles described herein is the same at any angle or reference point and does not affect color shift. For example, the following equation may be used to determine the angular color shift at a particular location of the coated substrate 100, as follows:

√((a*_v-a*_n)²+(b*_v-b*_n)²)

wherein a_vAnd b_vDenotes the a and b coordinates of the article when viewed at an angle of incident illumination, a_nAnd b_nWhen at or near normalA and b coordinates of the article when viewed.

In one or more embodiments, the character bias at the first portion 113 can be about 10 or less, about 9 or less, about 8 or less, about 7 or less, about 6 or less, about 5 or less, about 4 or less, about 3 or less, or even about 2 or less. Likewise, the character bias at the second portion 115 can be about 10 or less, about 9 or less, about 8 or less, about 7 or less, about 6 or less, about 5 or less, about 4 or less, about 3 or less, or even about 2 or less. Corresponding incident illumination angle theta₁And theta₂(and/or θ)₃And any other angle of incident illumination) may include n₁And n₂(and/or n)₃As applicable) an angle of about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees. In further embodiments, for and n₁And n₂(and/or n)₃As applicable) all incident illumination angles θ ranging from about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees₁And theta₂(and/or θ)₃And any other angle of incident illumination), the coated article 100 can be characterized by a reflected or transmitted color shift of about 10 or less at the first portion 113 and at the second portion 115 of the substrate 110. In some embodiments, the role offset may be about 0.

The light sources may include standard light sources determined by CIE, including a light source (representing a tungsten filament luminaire), B light source (a daylight analog light source), C light source (a daylight analog light source), D series light source (representing natural daylight), and F series light source (representing various types of fluorescent luminaires).

In another embodiment, the coated article 100 has a difference in reflected color between the first portion 113 of the substrate 110 and the second portion 115 of the substrate 110 of less than or equal to about 10, such as about 9 or less, about 8 or less, about 7 or less, about 6 or less, about 5 or less, about 4 or less, about 3 or less, about 2 or less, or even about 1 or less, wherein the difference in reflected color is defined as:

√((a*_{the first part}-a*_{The second part})²+(b*_{The first part}-b*_{The second part})²)，

And wherein the reflected color at the first portion 113 is with respect to n₁Angle of incident illumination theta₁Lower measurement, and the reflected color at the second portion 115 is relative to n₂Angle of incident illumination theta₂And/or with respect to n₃Angle of incident illumination theta₃(and any other illumination angles applicable to second portion 115). Corresponding incident illumination angle theta₁And theta₂(and/or θ)₃And any other angle of incident illumination) may include n₁And n₂(and/or n)₃As applicable) an angle of about 0 degrees to about 60 degrees, about 0 degrees to about 50 degrees, about 0 degrees to about 40 degrees, about 0 degrees to about 30 degrees, about 0 degrees to about 20 degrees, or about 0 degrees to about 10 degrees. In another embodiment, a measurement can be made of √ ((a √ x)_{The first part}-a*_{The second part})²+(b*_{The first part}-b*_{The second part})²) Difference in reflected color defined such that incident illumination angle θ₂And the direction of the first incident illumination angle v₁Same to measure the optical properties (i.e., v) at the first portion 113 and at the second portion 115 in the same viewing direction₁Is equal to v₂But theta₁Is not equal to theta₂Since n is₁Is not equal to n₂)。

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

In some particular embodiments, the substrate 110 may specifically exclude polymeric, plastic, and/or metallic materials. Substrate 110 can be characterized as an alkali-containing substrate (i.e., the substrate comprises 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 about 1.55. In particular embodiments, the substrate 110 may exhibit an average strain-to-failure at a surface on one or more opposing major surfaces of 0.5% or greater, 0.6% or greater, 0.7% or greater, 0.8% or greater, 0.9% or greater, 1% or greater, 1.1% or greater, 1.2% or greater, 1.3% or greater, 1.4% or greater, 1.5% or greater, or even 2% or greater, as measured using a ball-on-ring testing (ball-on-ring testing) using at least 5, at least 10, at least 15, or at least 20 samples. In particular embodiments, the substrate 110 may exhibit an average strain-to-failure at a surface on one or more opposing major surfaces of about 1.2%, about 1.4%, about 1.6%, about 1.8%, about 2.2%, about 2.4%, about 2.6%, about 2.8%, or about 3% or greater.

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

In one or more embodiments, the amorphous substrate may comprise glass, which may or may not be strengthened. Of suitable glassesExamples include soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass, and alkali aluminoborosilicate 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 glass-ceramic substrate (which may or may not be strengthened), or may comprise a single crystal structure, such as sapphire. In one or more particular embodiments, the substrate 110 includes an amorphous substrate (e.g., glass) and a crystalline cladding (e.g., a sapphire layer, a polycrystalline aluminum oxide layer, and/or a spinel (MgAl)₂O₄) Layers).

The substrate 110 of one or more embodiments may have a hardness that is less than the hardness of the entire coated article 100 (as measured by the berkovich indenter hardness test described herein). The hardness of the substrate 110 may be measured using methods known in the art, including but not limited to the berkovich indenter hardness test or the vickers hardness test.

The substrate 110 may be substantially optically clear, transparent, and free of light scattering elements. In these embodiments, the substrate may exhibit an average light transmission of about 85% or greater, about 86% or greater, about 87% or greater, about 88% or greater, about 89% or greater, about 90% or greater, about 91% or greater, or about 92% or greater in the optical wavelength region. In one or more alternative embodiments, the substrate 110 may be opaque or exhibit an average light transmission in the optical wavelength region of less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, or less than about 0.5%. In some embodiments, these light reflectance and transmittance values may be total reflectance or total transmittance (taking into account reflectance or transmittance on both major surfaces of the substrate), or may be observed on a single side of the substrate (i.e., only on the antireflective surface 122 and not the opposing surface). Unless otherwise specified, the average reflectance or transmittance of the substrate alone is measured at an incident illumination angle of 0 degrees relative to the major surface 112 of the substrate (however, these measurements may also be provided at incident illumination angles 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 dimensions thereof for aesthetic and/or functional reasons. For example, the edges of the substrate 110 may be thicker than more central regions of the substrate 110. The length, width, and physical thickness dimensions of the substrate 110 may also vary depending on the application or use of the coated article 100.

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

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

In the case of chemical strengthening of the substrate 110 by an ion exchange process, ions in the surface layer of the substrate are replaced or exchanged by larger ions having the same valence or oxidation state. Ion exchange processes are typically carried out as follows: the substrate is immersed in a molten salt bath containing larger ions that will be exchanged with smaller ions in the substrate. It will be understood by those skilled in the art that parameters of the ion exchange process including, but not limited to, bath composition and temperature, immersion time, number of times the substrate is immersed in one or more salt baths, use of multiple salt baths, other steps such as annealing, washing, etc., are generally determined based on the following factors: the composition of the substrate and the desired Compressive Stress (CS), depth of layer of compressive stress (or depth of layer DOL, or depth of compression DOC) of the substrate obtained by the strengthening operation. For example, ion exchange of 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 the larger alkali ions. The temperature of the molten salt bath is typically in the range of about 380 ℃ up to about 450 ℃, while the immersion time is in the range of about 15 minutes up to about 40 hours. However, temperatures and immersion times other than those described above may also be employed.

In addition, the following references describe non-limiting examples of ion exchange processes in which a glass substrate is immersed in multiple ion exchange baths and a washing and/or annealing step is performed between immersions: us patent application No. 12/500,650 entitled "Glass with Compressive Surface for Glass with Compressive Surface Applications" by Douglas c.alan et al, filed on 10.7.2009, claiming priority from us provisional patent application No. 61/079,995, filed on 11.7.2008, wherein a Glass substrate is strengthened by immersion in salt baths of different concentrations in a plurality of successive ion exchange treatments; and Christopher m.lee et al entitled "Dual Stage Ion Exchange for chemical strength of Glass" (two-step Ion Exchange for Glass chemical strengthening) "granted on 11/20/2012, which claims priority to U.S. provisional patent application No. 61/084,398, filed on 29/7/2008, wherein the Glass substrate is strengthened by: ion exchange is first carried out in a first bath diluted with effluent ions and then immersed in a second bath having a concentration of effluent ions less than that of the first bath. The contents of U.S. patent application No. 12/500,650 and U.S. patent No. 8,312,739 are incorporated herein by reference in their entirety.

The degree of chemical strengthening obtained by ion exchange can be quantified based on the Central Tension (CT), surface CS, and depth of compression (DOC) parameters. Compressive stress (including surface CS) was measured by a surface stress meter (FSM) using a commercially available instrument, such as FSM-6000 manufactured by Orihara Industrial co. Surface stress measurements rely on the accurate measurement of the Stress Optical Coefficient (SOC), which is related to the birefringence of the glass. The SOC was then measured according to protocol C (glass disk Method) entitled "Standard Test Method for measuring glass stress-Optical Coefficient" described in ASTM Standard C770-16, the contents of which are incorporated herein by reference in their entirety. The maximum CT value is measured using the scattered light polarising mirror (scapp) technique known in the art. As used herein, DOC means the depth at which the stress in a chemically strengthened alkali aluminosilicate glass article described herein changes from compressive to tensile stress. Depending on the ion exchange treatment regime, DOC can be measured by FSM or SCALP. If the stress in the glass article is generated by exchanging potassium ions into the glass article, the DOC is measured using FSM. If the stress is generated by exchanging sodium ions into the glass article, the DOC is measured using SCALP. If the stress in the glass article is generated by exchanging both potassium and sodium ions into the glass, the DOC is measured by SCALP, since the exchange depth of sodium is considered to represent the DOC, while the exchange depth of potassium represents the magnitude of the change in compressive stress (but not the change in stress from compressive to tensile); the exchange depth of potassium ions in this glass article was measured by FSM.

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

Exemplary glasses that may be used for the substrate 110 may comprise alkali aluminosilicate glass compositions or alkali aluminoborosilicate glass compositions, although other glass compositions are also contemplated. These glass compositions can be chemically strengthened by ion exchange processes. An exemplary glass composition comprises SiO₂、B₂O₃And Na₂O, wherein (SiO)₂+B₂O₃) Not less than 66 mol% and Na₂O is more than or equal to 9 mol percent. In one embodiment, the glass composition comprises at least 6 wt.% alumina. In another embodiment, the substrate comprises a glass composition having one or more alkaline earth metal oxides such that the alkaline earth metal oxides are present in an amount of at least 5 wt.%. In some embodiments, suitable glass compositions further comprise K₂O, MgO and CaO. In a particular embodiment, the glass composition for the substrate may comprise 61-75 mol% SiO 2; 7-15 mol% Al₂O₃(ii) a 0-12 mol% B₂O₃(ii) a 9-21 mol% Na₂O; 0-4 mol% K₂O; 0-7 mol% MgO; and 0-3 mol% CaO.

Another exemplary glass composition suitable for substrate 110 comprises: 60-70 mol% SiO₂(ii) a 6-14 mol% Al₂O₃(ii) a 0-15 mol% B₂O₃(ii) a 0-15 mol% Li₂O; 0-20 mol% Na₂O; 0-10 mol% K₂O; 0-8 mol% MgO; 0-10 mol% CaO; 0-5 mol% ZrO₂(ii) a 0-1 mol% SnO₂(ii) a 0-1 mol% CeO₂(ii) a Less than 50ppm As₂O₃(ii) a And less than 50ppm Sb₂O₃(ii) a Wherein, 12 mol percent is less than or equal to (Li)₂O+Na₂O+K₂O) is less than or equal to 20 mol percent, and 0 mol percent is less than or equal to (MgO + CaO) is less than or equal to 10 mol percent.

Another exemplary glass composition suitable for substrate 110 comprises: 63.5-66.5 mol% SiO₂(ii) a 8-12 mol% Al₂O₃(ii) a 0-3 mol% B₂O₃(ii) a 0-5 mol% Li₂O; 8-18 mol% Na₂O; 0-5 mol% K₂O; 1-7 mol% MgO; 0-2.5 mol% CaO; 0-3 mol% ZrO₂(ii) a 0.05-0.25 mol% SnO₂(ii) a 0.05-0.5 mol% CeO₂(ii) a Less than 50ppmAs₂O₃(ii) a And less than 50ppm Sb₂O₃(ii) a Wherein, 14 mol percent is less than or equal to (Li)₂O+Na₂O+K₂O) 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 one particular embodiment, an alkali aluminosilicate glass composition suitable for use in substrate 110 comprises alumina, at least one alkali metal, and in some embodiments greater than 50 mole% SiO₂And in other embodiments at least 58 mole% SiO₂And in other embodiments at least 60 mole% SiO₂Wherein (Al)₂O₃+B₂O₃) The ratio of/∑ modifiers (i.e., the total amount of modifiers) is greater than 1, in which ratio the components are in mole percent and the modifiers are alkali metal oxides₂(ii) a 9-17 mol% Al₂O₃(ii) a 2-12 mol% B₂O₃(ii) a 8-16 mol% Na₂O; and 0-4 mol% K₂O, wherein (Al)₂O₃+B₂O₃) The ratio of/∑ modifier (i.e. total amount of modifier) is greater than 1.

In another embodiment, the substrate 110 may comprise: an alkali aluminosilicate glass composition comprising: 64-68 mol% SiO₂(ii) a 12-16 mol% Na₂O; 8-12 mol% Al₂O₃(ii) a 0-3 mol% B₂O₃(ii) a 2-5 mol% K₂O; 4-6 mol% MgO; and 0-5 mol% CaO, wherein: SiO is not more than 66 mol percent₂+B₂O₃CaO is less than or equal to 69 mol%; na (Na)₂O+K₂O+B₂O₃+MgO+CaO+SrO>10 mol%; MgO, CaO and SrO are more than or equal to 5 mol% and less than or equal to 8 mol%; (Na)₂O+B₂O₃)-Al₂O₃Less than or equal to 2 mol percent; na is not more than 2 mol percent₂O-Al₂O₃Less than or equal to 6 mol percent; and 4 mol% is less than or equal to (Na)₂O+K₂O)-Al₂O₃Less than or equal to 10 mol percent.

In an alternative embodiment, the substrate 110 may comprise: an alkali aluminosilicate glass composition comprising: 2 mol% or more of Al₂O₃And/or ZrO₂Or 4 mol% or more of Al₂O₃And/or ZrO₂。

Where the substrate 110 comprises a crystalline substrate, the substrate may comprise a single crystal, which may comprise Al₂O₃. Such single crystal substrates are called sapphire. Other materials suitable for the crystalline substrate include a polycrystalline alumina layer and/or spinel (MgAl)₂O₄)。

Optionally, the substrate 110 may be crystalline and include a glass-ceramic substrate, which may or may not be strengthened. Examples of suitable glass-ceramics may include Li₂O-Al₂O₃-SiO₂Glass-ceramic of system (i.e., LAS system), MgO-Al₂O₃-SiO₂The glass-ceramic of the system (i.e., the MAS system), and/or the glass-ceramic comprising a primary crystalline phase comprising β -quartz solid solution, β -spodumene solid solution, cordierite, and lithium disilicate₂SO₄Strengthening in molten salts, whereby 2Li can occur⁺For Mg²⁺The exchange of (2).

The substrate 110 of one or more embodiments may have a physical thickness of about 100 μm to about 5mm in each portion of the substrate 110. Exemplary substrates 110 have a physical thickness in the range of about 100 μm to about 500 μm (e.g., 100, 200, 300, 400, or 500 μm). Another exemplary substrate 110 has a physical thickness in a range from about 500 μm to about 1000 μm (e.g., 500, 600, 700, 800, 900, or 1000 μm). The substrate 110 may have a physical thickness greater than about 1mm (e.g., about 2, 3, 4, or 5 mm). In one or more particular embodiments, the physical thickness of the substrate 110 may be 2mm or less than 1 mm. The substrate 110 may be acid polished or otherwise treated to eliminate or reduce the effects of surface imperfections.

As previously mentioned, embodiments of the coated article 100 of the present disclosure (see fig. 1-8) include an optical coating 120 having low reflectivity and controlled color. The optical coating 120 in these articles 100 can be optimized to give a desired combination of hardness, reflectivity, color, and color shift over a range of viewing angles. These desired combinations are maintained when the coating 120 is at its original design thickness, and when all layers in the coating are thinned by a scaling factor corresponding to the thinning of the coating that may occur during various vacuum deposition techniques, such as reactive sputtering, thermal evaporation, CVD, PECVD, etc., due to line-of-sight effects in the coating process.

Embodiments of the present disclosure also include coated articles 100 (see fig. 1-8) having a range of partial surface angles (partial surface curvatures) in combination with optical coatings 120, where the coatings 120 are designed to be robust to thinning of the coating that occurs during various coating deposition processes. The net result is that a coated article 100 having a range of partial surface curvature angles and optical coating 120 has controlled hardness, reflectivity, color, and color shift at viewing angles over the entire surface of the article 100, including some or all of the curved region (e.g., at second portion 115). In addition to meeting the absolute levels of hardness, reflectivity, and color of certain targets, the coated article 100 may also exhibit small variations in these values, particularly in visible reflectance and color, when the thickness of the coating 120 is reduced by a scaling factor that corresponds to the actual reduction in coating thickness that occurs when an industrially scalable sputtering process is performed on a manufactured part having a surface angle of curvature of 0 to 60 degrees.

An important understanding that a coated article 100 (see fig. 1-8) having surface curvature produces an optimal coating design is the knowledge of the specific coating process used to form the layers of the optical coating 120, as well as the level of line-of-sight coating effects that occur in that process. Some coating deposition processes do not have line-of-sight properties at all, such as atomic layer deposition, in which a monolayer of molecules or atoms is deposited one at a time. However, this process can be slow (at least limited by existing processing techniques) and is often too expensive for applications involving large substrates or cost-sensitive industries (e.g., consumer electronics and automotive industries). The cheaper process for forming the optical coating 120, reactive sputtering, can be easily extended to large areas and the cost can be relatively low. However, the nature of industrial reactive sputtering processes generally includes deposition, which has at least some line-of-sight characteristics, meaning that the surface of the article directly facing the sputter target will receive more deposited material (resulting in a thicker coating), while the surface of the article that is tilted at an angle relative to the sputter target (e.g., its curved surface) will generally receive less material, resulting in a thinner coating.

Accordingly, embodiments of the present disclosure include a coated article 100 (see fig. 1-8) in which the optical coating 120 has been optimized in terms of the trade-offs between hardness, reflectivity, color, and number of coatings. The addition of any number of layers to an optical coating to achieve an optical goal (e.g., without regard to hardness or other mechanical properties) tends to reduce the hardness of the coating to a level lower than the range required for the application of the target scratch resistant chemically strengthened glass in consumer electronics, automotive, and touch screen applications (e.g., to a hardness < <8GPa as measured by the berkovich indenter hardness test at indentation depths of about 100nm or greater). In the case of a coated article 100 having a curved surface (e.g., at the second portion 115 of the major surface 112), it may be important to assess how the partial surface curvature relates to the amount, or scale factor, by which the layers of the optical coating 120 will be reduced or thinned from their target design thicknesses. The target design thickness (or thickness at 100% scale factor or 1.0 scale factor) is generally the thickness coated on "flat" areas of the article 100 (e.g., at the first portion 113 of the major surface 112), those portions of the article 100 closest to facing the sputter target, or those portions of the article 100 that receive the most material from the sputter target. Any portion of the article 100 that is away from the bend from its direction of maximum thickness deposition will generally receive less material, resulting in a thinner coating on these bend regions when the various layers of the coating 120 are formed. For optimal optical coating design of the optical coating 120 of an embodiment of the coated article 100 (see fig. 1-8), it may be advantageous to understand the design window for the curvature of the targeted portion, and how the curvature of the portion corresponds to coating thinning during deposition. This may enable the optical design of the coating 120 such that, for example, reflectivity and color are optimized over a targeted range of part angle and coating thickness variations without unduly sacrificing coating hardness, number of layers in the coating, or other criteria. In other words, without understanding the relevant window of part angle and coating thickness scaling factor, the coating may be over-engineered to include too many layers in order to achieve the desired combination of optical properties, thereby sacrificing hardness and scratch resistance.

Referring now to FIG. 9, a graph of optical coating thickness scaling factor versus partial surface curvature for one deposition process is provided. In particular, fig. 9 illustrates the experimentally measured correspondence between the partial surface angle (i.e., at the second portion 115 of the major surface 112) and the coating thickness scaling factor (i.e., for the optical coating 120) for the reflective sputtering process employed on the coated article 100 (see fig. 1-8 and corresponding description above), according to an embodiment of the present disclosure. Fig. 9 can be used to establish a target process window to optimize the deposition process for forming the optical coatings of the disclosed articles. As shown in FIG. 9, the coating thickness scaling factor followsDependence of square root of (1), wherein

Is the partial surface angle. The data shown in fig. 9 were obtained from measurements of sputtered films using a known optical interferometric calculation method that utilized a sample holder that allowed the curved part to rotate and measure the reflectance spectrum along normal angles at each point along the part curvature. As shown in fig. 9, a partial surface angle of 30 degreesCorresponding to a coating thickness scaling factor of about 0.95, a part surface angle of 40 degrees corresponds to a coating thickness scaling factor of about 0.85, a part surface angle of 50 degrees corresponds to a coating thickness scaling factor of about 0.8, and a part surface angle of 60 degrees corresponds to a coating thickness scaling factor of about 0.7. For example, having a non-planar second portion 115 and having an angle of 30 degrees with respect to its first portion 113

The layers in the optical coating 120 on the second portion 115 of the coated article 100 may undergo thinning, and thinning by a scale factor of 0.85. That is, the thickness of each layer of the coating 120 on the first portion 113 and on the second portion 115 may vary based on a thickness scaling factor, as shown in fig. 9.

Referring again to fig. 9, the inventive design of the coated article 100 of the present disclosure can be particularly optimized such that the optical coating 120 is characterized by an advantageous combination of low reflectivity, controlled color, and controlled color shift with viewing angle (incident light angle) at 100% thickness (1.0 scale factor) and at thickness scale factors in the range of 0.7 (70%) to 0.85 (85%), which correspond to 0 degrees of article surface angle (for 100% thickness), 40 degrees of article surface angle (for 85% thickness), and 60 degrees of article surface angle (for 70% thickness), respectively, with all surface angles and thickness scale factors in between. Referring also to fig. 9, the inventive design of the coated article 100 of the present disclosure can be particularly optimized such that the optical coating 120 is characterized by an advantageous combination of low reflectivity, controlled color, and controlled color shift with viewing angle (incident light angle) at 100% thickness (1.0 scale factor) and at thickness scale factors in the range of 0.6 (60%) to 0.85 (85%), which correspond to an article surface angle of 0 degrees (for 100% thickness), an article surface angle of 40 degrees (for 85% thickness), and an article surface angle of 70 degrees (for 60% thickness), respectively, with all surface angles and thickness scale factors in between. To calculate the optical performance for each thickness scale factor, all layers of a 100% thickness layer design were scaled in phaseThe optical results are recalculated using a transfer matrix technique, in accordance with principles understood by those of ordinary skill in the art of the present disclosure. According to principles understood by those of ordinary skill in the art of this disclosure, for SiO₂、SiO_xN_yAnd SiN_xThe sputter-deposited film (or other material used in the layers of the optical coating 120) measures the optical refractive index dispersion curve and inputs these refractive index dispersion values into the optical model.

The coated articles disclosed herein can be incorporated into another article, such as an article having a display (or display article) (e.g., consumer electronics devices including cell phones, tablets, computers, navigation systems, etc.); a building product; a transportation article (e.g., an automobile, train, aircraft, ship, etc.), an appliance article, or any article that requires a degree of transparency, scratch resistance, abrasion resistance, or a combination of the above properties. Fig. 18A and 18B illustrate an exemplary article comprising any of the coated articles disclosed herein. In particular, fig. 18A and 18B illustrate a consumer electronic device 200 comprising a housing 202, the housing 202 having a front surface 204, a rear surface 206, and side surfaces 208; electrical components (not shown) located at least partially or entirely within the housing and including at least a controller, memory and display 210 at or adjacent the front surface of the housing; and a cover substrate 212 at or over the front surface of the housing such that the cover substrate 212 is over the display. In some embodiments, at least one of the cover substrate 212 or a portion of the housing 202 can comprise any of the coated articles disclosed herein.

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