WO2025034928A1

WO2025034928A1 - Articles comprising glass-ceramic substrates and methods for making the same

Info

Publication number: WO2025034928A1
Application number: PCT/US2024/041387
Authority: WO
Inventors: Yuhui Jin; Florence Christine Monique Verrier; David Lee Weidman; Lei Yuan
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2023-08-10
Filing date: 2024-08-08
Publication date: 2025-02-13
Anticipated expiration: 2026-02-10

Abstract

An article is described herein that includes a glass-ceramic substrate comprising a first surface and a second surface. The first surface is opposite the second surface. At least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material. The glass-ceramic substrate further comprises one or more glassy-phase regions on the first surface, wherein the one or more glassy-phase regions comprises an amorphous glass. The one or more glassy-phase regions have an Ag₂O concentration therein of at least 5 mol.% at a depth of 200 nm below a surface of the glassy-phase regions. A method of forming an article described herein includes converting at least a portion of a first surface of a glass-ceramic substrate to a glassy-phase material and ion-exchange processing the glassy-phase material to introduce silver into the glassy-phase material. At least 70 wt.% of the glass-ceramic substrate remains a glass-ceramic material.

Description

ARTICLES COMPRISING GLASS-CERAMIC SUBSTRATES AND METHODS FOR MAKING THE SAME

CLAIM OF PRIORITY

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application No. 63/531,916 filed August 10, 2023. The entire contents of this application are hereby incorporated herein by reference for all purposes.

FIELD

[0002] The present specification generally relates to articles and, more specifically, to articles that include glass-ceramic substrates.

BACKGROUND

[0003] Portable electronic devices, such as, smartphones, tablets, and wearable devices (such as, for example, watches and fitness trackers) utilize glass-based materials. For example, screens on such portable electronic devices may be made of glass-based materials. Optical properties associated with good viewing of the screen are generally sought. Coatings or other surface treatments may be used to enhance glass materials. However, current glass-based materials have optical limitations.

[0004] Accordingly, a need exists for glass-based materials with different optical characteristics, and methods of producing such materials. This need and other needs are addressed by the present disclosure.

SUMMARY

[0005] Various articles and a method which address the aforementioned need and other needs in the prior art are described in the independent claims. Advantageous embodiments of the various articles and method are further described in the dependent claims.

[0006] According to one or more embodiments, the present disclosure provides an article comprising: a glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite the second surface, and wherein at least 70 wt.% of the glassceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further comprising one or more glassy-phase regions on the first surface, wherein the one or more glassy -phase regions comprises an amorphous glass; and wherein the one or more glassy-phase regions have an Ag2O concentration therein of at least 5 mol.% at a depth of 200 nm below a surface of the glassy-phase regions. An advantage of the article is a refractive index of the glassy -phase regions may be tuned by modifying the Ag2O concentration therein, which may be useful in modifying optical properties of the article.

[0007] According to one or more embodiments, the present disclosure provides an article comprising: a glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite the second surface, and wherein at least 70 wt.% of the glassceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further comprising one or more glassy-phase regions on the first surface, wherein the one or more glassy-phase regions comprise an amorphous glass; and wherein the one or more glassy-phase regions have an Ag2O concentration therein of at least 5 mol.% at a depth of 200 nm below a surface of the glassy-phase regions; wherein the one or more glassy-phase regions on the first surface of the glass-ceramic substrate are textured; wherein a portion of the first surface that does not comprise the one or more glassy-phase regions comprises one or more glass-ceramic regions comprising the glass-ceramic material; and wherein the one or more glass-ceramic regions have an Ag2O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate. An advantage of the article is it may be utilized as transparent diffuser in a variety of applications, such as reducing sparkle on an antiglare product.

[0008] According to one or more embodiments, the present disclosure provides an article comprising a glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite the second surface, and wherein at least 70 wt.% of the glassceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further comprising one or more glassy-phase regions on the first surface, wherein the one or more glassy-phase regions comprise an amorphous glass; wherein a portion of the first surface that does not comprise the one or more glassy-phase regions comprises one or more glass-ceramic regions comprising the glass-ceramic material; wherein the first surface of the article exhibits a log kill greater than or equal to 2 according to the EPA Dry Test with Staph Aureus bacteria. An advantage of the article is it may exhibit improved antimicrobial properties over conventional articles.

[0009] According to one or more embodiments, the present disclosure provides a method of forming an article, the method comprising: converting at least a portion of a first surface of a glass-ceramic substrate to a glassy -phase material, wherein the glass-ceramic substrate comprises the first surface and a second surface opposite the first surface, and wherein at least 70% of the glass-ceramic substrate remains a glass-ceramic material; and ion-exchange processing the glassy-phase material to introduce silver into the glassy-phase material. An advantage of the method is a refractive index of the article formed therefrom may be tuned such that the article exhibits desired optical properties for applications as a transparent diffuser, the article formed therefrom may exhibit improved antimicrobial properties over conventional articles, or both.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] FIG. 1 schematically depicts a cross-sectional view of an article, according to one or more embodiments described herein;

[0011] FIG. 2 is a conceptual top down view of an article with an ordered pattern of glassyphase regions, according to one or more embodiments described herein;

[0012] FIG. 3 is a conceptual top down view of an article with a random pattern of glassyphase regions, according to one or more embodiments described herein;

[0013] FIG. 4 is a conceptual top down view of an article having a first region with glassyphase regions and a second region that does not include glassy-phase regions; according to one or more embodiments described herein;

[0014] FIG. 5 schematically depicts a cross-sectional view through a portion of an article, according to one or more embodiments described herein;

[0015] FIG. 6A schematically depicts a portion of an article that includes a glassy-phase region, according to one or more embodiments described herein;

[0016] FIG. 6B schematically depicts light passing through a portion of a comparative article that does not include glassy-phase regions.

[0017] FIG. 6C schematically depicts light passing through a portion of an article that includes glassy -phase regions, according to one or more embodiments described herein; [0018] FIG. 7A is a plan view of an exemplary electronic device incorporating an article, according to one or more embodiments described herein;

[0019] FIG. 7B is a perspective view of the exemplary electronic device of FIG. 7A, according to one or more embodiments described herein;

[0020] FIG. 8 is a flowchart of a method of forming an article, according to one or more embodiments described herein;

[0021] FIG. 9 is schematically depicts a method of forming an article, according to one or more embodiments described herein;

[0022] FIG. 10A is a scanning electron microscopy image of a cross-section view of the laser-treated glass-ceramic substrate; according to one or more embodiments described herein; [0023] FIG. 10B is a scanning electron microscopy image of an enhanced cross-section view of the laser-treated glass-ceramic substrate; according to one or more embodiments described herein;

[0024] FIG. 10C is a scanning electron microscopy image of a top view of the laser-treated glass-ceramic substrate; according to one or more embodiments described herein;

[0025] FIG. 11 A is a scanning electron microscopy image of a top view of the laser-treated glass-ceramic substrate; according to one or more embodiments described herein;

[0026] FIG. 1 IB is a scanning electron microscopy image of a top view of the laser-treated and chemically-etched glass-ceramic substrate; according to one or more embodiments described herein;

[0027] FIG. 11C is a scanning electron microscopy image of a top view of the laser-treated glass-ceramic substrate; according to one or more embodiments described herein;

[0028] FIG. 1 ID is a scanning electron microscopy image of a top view of the laser-treated and chemically-etched glass-ceramic substrate; according to one or more embodiments described herein;

[0029] FIG. 12A is a scanning electron image of an article, according to one or more embodiments described herein;

[0030] FIG. 12B is an elemental analysis plot of a glassy-phase region, as determined by scanning electron microscopy energy-dispersive X-ray spectroscopy, according to one or more embodiments described herein; and [0031] FIG. 12C is an elemental analysis plot of a glass-ceramic region, as determined by scanning electron microscopy energy-dispersive X-ray spectroscopy, according to one or more embodiments described herein.

DETAILED DESCRIPTION

[0032] Reference will now be made in detail to articles comprising glass-ceramic substrates according to various embodiments, as described herein. In particular, articles may comprise a glass-ceramic substrate including a first surface and a second surface, and one or more glassy-phase regions on the first surface of the glass-ceramic substrate. The glassyphase regions may include a concentration of Ag2O of greater than or equal to 5 mol%. In some embodiments, the incorporation of Ag2O in the glassy-phase regions may be utilized to achieve desired optical properties and/or anti-microbial efficacy, as described herein.

[0033] According to some embodiments, the articles may have relatively low sparkle, relatively low distinctness-of-image, relatively low haze, relatively high concentration of Ag2O, or combinations of these attributes. This combination of relatively low sparkle, relatively low distinctness-of-image, relatively low haze, and relatively high concentration of Ag2O may be desirable over conventional glass-based articles where distinctness-of-image and sparkle are usually inversely proportional to one another (meaning that a relatively low value of one property may be coupled to a relatively high value of the other property) or where conventional glass-based articles have a lower concentration of Ag2O, which may result in inferior anti -microbial properties.

[0034] In the following description, like reference characters designate like or corresponding parts throughout the several views shown in the figures. It is also understood that, unless otherwise specified, terms such as “top,” “bottom,” “outward,” “inward,” and the like are words of convenience and are not to be construed as limiting terms. Whenever a group is described as consisting of at least one of a group of elements or combinations thereof, it is understood that the group may consist of any number of those elements recited, either individually or in combination with each other. Unless otherwise specified, a range of values, when recited, includes both the upper and lower limits of the range as well as any ranges there between. As used herein, the indefinite articles “a,” “an,” and the corresponding definite article “the” mean “at least one” or “one or more,” unless otherwise specified. It alsois understood that the various features disclosed in the specification and the drawings can be used in any and all combinations.

[0035] Unless otherwise specified, all compositions of the glasses described herein are expressed in terms of mole percent (mol%), and the constituents are provided on an oxide basis. Unless otherwise specified, all temperatures are expressed in terms of degrees Celsius (°C). All ranges disclosed in this specification include any and all ranges and subranges encompassed by the broadly disclosed ranges whether or not explicitly stated before or after a range is disclosed.

[0036] It is noted that the terms "substantially" and "about" may be utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. These terms are also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue. As utilized herein, when the term “about” is used to modify a value, the exact value is also disclosed.

[0037] Referring now to FIG. 1, an article 100 is schematically depicted. The article 100 may include a glass-ceramic substrate 110. The glass-ceramic substrate 110 may have a first surface 104 and a second surface 102 opposite the first surface 104 and edges 106. In one or more embodiments, the first surface 104 and the second surface 102 may be generally planar and parallel as shown in FIG. 1. In other embodiments, the first surface 104 and the second surface 102 may be curved and/or not parallel (not depicted in FIG. 1). In one or more embodiments, at least a portion of the first surface 104 may be a region comprising glassyphase regions. In one or more embodiments, the region of the first surface 104 that includes glassy -phase regions can cover the entire first surface 104. In one or more embodiments, at least a portion of both the first surface 104 and the second surface 102 may be a region comprising glassy-phase regions. In some embodiments, the edges 106 may include a glassyphase region.

[0038] Now referring to FIGS. 2 and 3, in one or more embodiments, the portion of the first surface 104 that includes the region comprising the glassy-phase regions may comprises a first plurality of glassy-phase regions 400. FIGS. 2 and 3 are conceptual top down views of the portion of the first surface 104 that includes the glassy-phase regions 400. In one or more embodiments, the glassy-phase regions 400 may be arranged over the first surface 104 in an ordered pattern as shown in FIG. 2. In one or more embodiments, the glassy-phase regions 400 may be arranged over the first surface 104 in a random pattern as shown in FIG. 3.

[0039] Now referring to FIG. 4, in one or more embodiments, the glass ceramic substrate 110 may include a first region 405 comprising the glassy-phase regions 400 and a second region 410 that does not include the glassy-phase regions 400.

[0040] In one or more embodiments, the one or more glassy-phase regions may have a total surface area of from 50% to 100%, from 60% to 100%, from 70% to 100%, from 80% to 100%, from 90% to 100%, from 50% to 90%, from 60% to 90%, from 70% to 90%, from 80% to 90%, from 50% to 80%, from 60% to 80%, from 70% to 80%, from 50% to 70%, from 60% to 70%, or from 50% to 60% of the total surface area of the first surface 104 of the glass-ceramic substrate.

[0041] In one or more embodiments, at least 70 wt.%, at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, or at least 95 wt.% of the glass-ceramic substrate may comprise a glass-ceramic material. Conventional methods known in the art such as X-ray diffraction (XRD) may be used to measure the weight percent of the glass-ceramic material present in the glass-ceramic substrate.

[0042] FIG. 5 is a schematic cross-sectional view through a portion of the first surface 104 that includes glassy-phase regions, according to some embodiments, to illustrate a topography of the region comprising the glassy-phase regions 400 within the first surface 104. In embodiments, the glassy-phase regions may be concave. As shown in the cross-section of FIG. 5, the glassy-phase regions 400, when viewed from a cross-section, can have peaks 520 and valleys 540. The peaks 520 and valleys 540 occur at points along the cross-section where a curve drawn along the first surface 104 of the glass-ceramic substrate 110 would have a slope equal to zero when the thickness of the glass-ceramic substrate 110 is shown on the y axis.

[0043] In one or more embodiments, the peaks 520 and valleys 540 may define the glassyphase regions 400. The glassy-phase regions 400 may have an average well length size, where the well size is measured as the length I of a line drawn from the top of a first peak 520, to the top an adjacent second peak 520. The glassy-phase regions 400 may have a depth d, where the depth d is measured as the vertical distance from the top of the shortest peak 520 of the glassyphase region 400 to the bottom of the deepest valley 540 of the same glassy-phase region 400. In one or more embodiments, the glassy-phase region 400 of the first plurality of the glassyphase regions may have an average well length size of from 5 micrometers (pm) to 100 pm. In embodiments, the valley 520 of the glassy-phase material may positioned less than 10 pm below a surface of the first surface that is not converted to a glassy-phase material.

[0044] In one or more embodiments, the haze of the portion of the glass ceramic substrate 110 comprising the glassy-phase regions 400 is relatively low and may provide desirable optical properties and a pleasing aesthetic appearance. “Haze” (also referred to as “transmission haze”) is a surface light scatter characteristic and refers to the percentage of light scattered outside an angular cone of 4.0° in accordance with ASTM procedure D1003. For an optically smooth surface, transmission haze is generally close to zero. Low haze can be desirable for applications requiring high display contrast, while high haze can be useful for optical designs having scattering, such as edge illumination, or for aesthetic reasons, such as reducing the “black hole” appearance of the display in the off state. The general preference for low versus high haze (and the acceptance of performance trade-offs) can be motivated by customer or enduser preferences, and their final application and use mode. For example, the haze of the portion of the glass ceramic substrate 110 comprising the glassy-phase regions 400 may provide an antiglare capability that improves performance in high ambient light conditions, such as bright sunlight. In one or more embodiments, the haze of the portion of the glass ceramic substrate 110 comprising the glassy-phase regions 400 is from 5% to 40%, such as from 5% to 30%, from 5% to 20%, from 5% to 10%, from 10% to 40%, from 10% to 30%, from 10% to 20%, from 20% to 40%, from 20% to 30%, or from 30% to 40%. In one or more embodiments, the haze of the portion of the first surface 104 that includes the glassy -phase regions 400 is less than or equal to 40%, such as less than or equal to 30%, less than or equal to 25%, less than or equal to 20%, less than or equal to 15%, or less than or equal to 10%.

[0045] The portion of the glass ceramic substrate 110 comprising the glassy-phase regions 400 described herein may be further characterized by gloss. “Gloss,” “gloss level,” or like terms refer to, for example, surface luster, brightness, or shine, and more particularly to the measurement of specular reflectance calibrated to a standard (such as, for example, a certified black glass standard) in accordance with ASTM procedure D523, the contents of which are incorporated herein by reference in their entirety. Common gloss measurements are typically performed at incident light angles of 20°, 60°, and 85°, with the most commonly used gloss measurement being performed at 60°. 60° gloss,” or “gloss 60°” refers to gloss measurements in which the light is incident on the sample at 60° off the normal to the glassy-phase regions of the glass-ceramic substrate, as described in ASTM procedure D523. Unless otherwise noted, the amount of gloss is reported in this disclosure with either of the following interchangeable designations under ASTM D523: “standard gloss units (SGU)” (i.e., “a gloss from 30 SGU to 100 SGU”) or a unit-less number (i.e., a “gloss from 30 to 100”). In one or more embodiments, the portion of the glass ceramic substrate 110 comprising the glassy-phase regions 400 comprises a gloss 60° from 20 to 80, such as from 20 to 60, or from 20 to 40.

[0046] The portion of the glass ceramic substrate 110 comprising the glassy-phase regions 400 described herein may be further characterized by sparkle. “Sparkle,” “sparkle contrast,” “display sparkle,” “pixel power deviation,” “PPD”, or like terms refers to the visual phenomenon that occurs when a textured transparent surface is combined with a pixelated display. Generally speaking, quantitation of sparkle involves imaging a lit display or simulated display with the textured surface in the field of view. The calculation of sparkle for an area P is equal to o(P)/p(P), where o(P) is the standard deviation of the distribution of integrated intensity for each display pixel contained within area P divided by the mean intensity p(P). Following the guidance in: (1) J. Gollier, et al., “Apparatus and method for determining sparkle,” US9411180B2, United States Patent and Trademark Office, 20 July 2016; (2) A. Stillwell, et al., “Perception of Sparkle in Anti-Glare Display Screens,” JSID 22(2), 129-136 (2014); and (3) C. Cecala, et al., “Fourier Optics Modeling of Display Sparkle from Anti-Glare Cover Glass: Comparison to Experimental Data”, Optical Society of America Imaging and Applied Optics Congress, JW5B.8 (2020); one skilled in the art can build an imaging system to quantify sparkle. Alternatively, a commercially available system (e.g. the SMS- 1000, Display Messtechnik & Systeme GmbH & Co. KG, Germany) can also be used. As described herein, sparkle is measured with a 140 PPI display. A 140 PPI display (e.g. Z50, Eenovo Group Limited, Hong Kong) with only the green subpixels lit (R = 0, B = 0, G = 255), at full display brightness is imaged using a f = 50 mm lens/machine vision camera combination (e.g. C220503 1:2.8 50 mm 030.5, Tamron, Japan) and Stingray F-125 B, Allied Vision Technologies GmbH, Germany). The lens settings are aperture = 5.6, depth of field = 0.3, working distance = about 290 mm; with these settings, the ratio of display pixels to camera pixels is approximately 1 to 9. The field of view for analysis contains approximately 7500 display pixels. Camera settings have the gain and gamma correction turned off. Periodic intensity variations from, e.g. the display, and non-periodic intensity variations, e.g. dead pixels, are removed during analysis prior to the calculation of sparkle.

[0047] In one or more embodiments, the portion of the glass ceramic substrate 110 comprising the glassy-phase regions 400 may have a sparkle at 140 ppi of less than or equal to 5%. For example, in one or more embodiments, the region of the glass-ceramic substrate comprising the glassy-phase regions may have a sparkle at 140 ppi of less than or equal to 4.9%, less than or equal to 4.8%, less than or equal to 4.7%, less than or equal to 4.6%, less than or equal to 4.5%, less than or equal to 4.4%, less than or equal to 4.3%, less than or equal to 4.2%, less than or equal to 4.1%, less than or equal to 4%, less than or equal to 3.9%, less than or equal to 3.8%, less than or equal to 3.7%, less than or equal to 3.6%, less than or equal to 3.5%, less than or equal to 3.4%, less than or equal to 3.3%, less than or equal to 3.2%, less than or equal to 3.1%, less than or equal to 3%, less than or equal to 2.9%, less than or equal to 2.8%, less than or equal to 2.7%, less than or equal to 2.6%, less than or equal to 2.5%, less than or equal to 2.4%, less than or equal to 2.3%, less than or equal to 2.2%, less than or equal to 2.1%, less than or equal to 2%, less than or equal to 1.9%, less than or equal to 1.8%, less than or equal to 1.7%, less than or equal to 1.6%, less than or equal to 1.5%, less than or equal to 1.4%, less than or equal to 1.3%, less than or equal to 1.2%, less than or equal to 1.1%, or even less than or equal to 1.0%.

[0048] The portion of the glass ceramic substrate 110 comprising the glassy-phase regions 400 described herein may further be characterized by distinctness-of-image. “Distinctness-of- reflected image,” “distinctness-of-image,” “DOI” or like term is defined by method A of ASTM procedure D5767 (ASTM 5767), entitled “Standard Test Methods for Instrumental Measurements of Distinctness-of-image Gloss of Coating Surfaces.” In accordance with method A of ASTM 5767, glass reflectance factor measurements are made on the glassy-phase regions of the glass-ceramic substrate at the specular viewing angle and at an angle slightly off the specular viewing angle. The values obtained from these measurements are combined to provide a DOI value. In particular, DOI is calculated according to equation (1):

[0049] 100 (1)

[0050] Where Rs is the relative amplitude of reflectance in the specular direction and Ros is the relative amplitude of reflectance in an off-specular direction. As described herein, Ros, unless otherwise specified, is calculated by averaging the reflectance over an angular range from 0.2° to 0.4° away from the specular direction. Rs can be calculated by averaging the reflectance over an angular range of ±0.05° centered on the specular direction. Both Rs and Ros were measured using a goniophotometer (Rhopoint Instruments) that is calibrated to a certified black glass standard, as specified in ASTM procedures D523 and D5767. The goniophotometer uses a detector array in which the specular angle is centered about the highest value in the detector array. DOI is evaluated using the 1-side (black absorber coupled to rear of glass) method, where the result is referred to as the “coupled distinctness-of image”. DOI is also evaluated using the 2-side (reflections allowed from both glass surfaces, nothing coupled to glass) method, where the result is referred to as the “uncoupled distinctness-of-image.” The DOI measurement enables gloss, reflectance, and DOI to be determined for the glassy-phase regions of the glass-ceramic substrate as a whole. The Ro_S/Rs ratio can be calculated from the average values obtained for Rs and Ros as described above. “20° DOI,” or “DOI 20°” refers to DOI measurements in which the light is incident on the sample at 20° off the normal to the glass surface, as described in ASTM D5767. The measurement of either DOI or common gloss using the 1-side method or 2-side method can best be performed in a dark room or enclosure so that the measured value of these properties is zero when the sample is absent. The scale value obtained with the measuring procedures of ASTM D5767 range from 0 to 100 with a value of 100 representing perfect DOI (image clarity).

[0051] In one or more embodiments, portion of the glass ceramic substrate 110 comprising the glassy-phase regions 400 may have a coupled distinctness-of-image of less than 20%. For example, in one or more embodiments the glassy-phase regions of the glass-ceramic substrate may have a coupled distinctness-of-image of less than 15%, less than 10%, or even less than C JO //o.

[0052] In one or more embodiments, the portion of the glass ceramic substrate 110 comprising the glassy-phase regions 400 may exhibit a root mean square (RMS) roughness height (i.e., in the z-direction), “Rq”, of greater than 40 nanometers (nm), such as greater than 60 nm, greater than 80 nm, greater than 100 nm, greater than 150 nm, greater than 200 nm, greater than 300 nm, greater than 400 nm, greater than 500 nm, greater than 600 nm, or even greater than 700 nm. The Rq is measured using methods known in the art such as atomic force microscopy (AFM), stylus contact profilometry, and optical interference profilometry. The Rq as described herein is preferentially measured over a sample surface section having dimensions of at least about 0.5 mm by 0.5 mm to capture a representative average including a number of typical surface features in the range from about 10 to about 1000.

[0053] In one or more embodiments, the glassy-phase regions 400 may comprise Ag2O at a concentration of greater than or equal to 5 mol%, such as greater than or equal to 6 mol%, greater than or equal to 7 mol%, greater than or equal to 8 mol%, greater than or equal to 9 mol%, or greater than or equal to 10 mol%, at a depth of 200 nm below a surface of the glassyphase regions. The Ag2O concentration at a depth at a depth of 200 nm below a surface of the glassy -phase regions 400 may be 5 mol%, 15 mol%, 20 mol%, 25 mol% or 30 mol%, or any range having any two of these values as endpoints. In some embodiments, the Ag2O concentration at a depth of at a depth of 200 nm below a surface of the glassy -phase regions 400 is 5 mol% to 30 mol%, or 10 mol%to 25 mol%.

[0054] In one or more embodiments, the glassy-phase regions 400 may comprise Ag2O at a concentration of greater than or equal to 5 mol%, such as greater than or equal to 6 mol%, greater than or equal to 7 mol%, greater than or equal to 8 mol%, greater than or equal to 9 mol%, or greater than or equal to 10 mol%, at all depths therein of the glassy-phase regions 400 on the first surface 104. The Ag2O concentration at all depths therein of the glassy-phase regions 400 on the first surface 104 may be 5 mol%, 15 mol%, 20 mol%, 25 mol% or 30 mol%, or any range having any two of these values as endpoints. In some embodiments, the Ag2O concentration at all depths therein of the glassy-phase regions 400 on the first surface 104 is 5 mol% to 30 mol%, or 10 mol% to 25 mol%.

[0055] The concentration of Ag2O in the glassy-phase regions 400 can be determined using conventional elemental analysis methods known in the art, such as but not limited to scanning electron microscopy energy-dispersive X-ray spectroscopy (SEM/EDS), glow discharge optical emission spectrometry (GDOES), or secondary ion mass spectrometry (SIMS).

[0056] In embodiments, the glassy-phase regions 400 may comprise silver ion-exchanged (lOXed) amorphous glass material.

[0057] In embodiments, the glassy-phase regions 400 may be textured. In other embodiments, the glassy-phase regions 400 may not be textured. As used herein, the term “textured” refers to embodiments where the glassy -phase regions 400 have a depth of greater than or equal to 40 run, where the depth (d) is measured as the vertical distance from the top of the shortest peak 520 of the glassy-phase region 400 to the bottom of the deepest valley 540 of the same glassy-phase region 400 shown in FIG. 5.

[0058] In embodiments, a portion of the first surface 104 that does not comprise the glassyphase regions 400 may comprise one or more glass-ceramic regions. The glass-ceramic regions may comprise glass-ceramic material. In embodiments, the one or more glass-ceramic regions may have an Ag2O concentration of less than less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate. In embodiments, one or more glass-ceramic regions may have at all depths therein have an Ag2O concentration of less than 5 mol.%.

[0059] In embodiments, Ag2O may be introduced into article 100 by ion exchange, such that much of the Ag2O in article 100 is located in the glassy-phase regions 400, and the concentration of Ag2O in the glass-ceramic regions, that is the bulk material, may be significantly lower or zero (allowing for impurities) . In other words, it is preferred that the bulk composition has a low Ag2O concentration, for example equal to or less than 1 mol% or 0. 1 mol%. Without intending to be bound by any particular theory, it is believed that anti-microbial efficacy is a surface effect, and silver farther than 1 micron (1000 nm) away from a surface of the article is not expected to contribute significantly to antimicrobial efficacy. However, silver also has optical effects such as discoloration that may be considered undesirable, whether the Ag2O is in the bulk material or concentrated in the glassy-phase regions 400. Minimizing the amount of Ag2O in article 100 beyond that in glassy -phase regions 400 may minimize these undesirable optical effects without losing antimicrobial efficacy.

[0060] In some embodiments, delta E is equal to or less than 10, or equal to or less than 7. As used herein, “delta E” or “color delta E” refers to a difference in L*a*b* coordinates, and is a way to quantify color change. The relevant L*a*b* coordinates were measured on a PE X- RITE Color i7-860 using D65 Illuminant. The color change (Delta E) was determined by taking L*a*b* measurements on otherwise similar samples before and after silver ion exchange. Delta E is calculated by comparing the pre- and post- silver IOX using the equation:

where the “2” subscript indicates a post-IOX value, and the “1” subscript indicates a pre-IOX value. [0061] Lower delta E corresponds to a less noticeable color difference. In some embodiments, the surprising anti-microbial effectiveness of silver when combined with articles as described herein allows for exceptional antimicrobial effectiveness while not using so much silver that it changes the appearance of article too much.

[0062] In one or more embodiments, the glass-ceramic substrate 110 can be formed from a glass-ceramic material having both a glassy phase and a ceramic phase. Illustrative glassceramics include those materials where the glass phase is formed from a silicate, borosilicate, aluminosilicate, or boroaluminosilicate, and the ceramic phase is formed from [3-spodumene, P-quartz, nepheline, kalsilite, or carnegieite. “Glass-ceramics” include materials produced through controlled crystallization of glass. Examples of suitable glass-ceramics may include Li2O-A12O3-SiO2 system (z.e., LAS-System) glass-ceramics, MgO-AhCh-SiCh system (z.e., MAS-System) glass-ceramics, ZnO x AI2O3 ^x nSiCL (z.e., ZAS system), and/or glass-ceramics that include a predominant crystal phase including P-quartz solid solution, P-spodumene, cordierite, and lithium disilicate. In an exemplary embodiment, the glass-ceramic substrate 110 includes any one of the glass-ceramic compositions disclosed in U.S. Patent Application Publication No 2016/0102010 Al, filed on October 8, 2015, which is incorporated by reference in its entirety. The glass-ceramic substrates 110 may be strengthened using a chemical strengthening process.

[0063] In one or more embodiments, the glass-ceramic substrate 110 may include an alkali aluminosilicate glass, such as a lithium aluminosilicate glass. Exemplary lithium aluminosilicate glass materials are those described in U.S. Patent App. Pub. No. 2019/0300422 Al, titled “Glasses Having High Fracture Toughness,” published October 3, 2019, the contents of which are incorporated herein by reference in their entirety. In additional embodiments, alkaline earth aluminosilicate glass may be utilized.

[0064] Conventional articles including antiglare glass surfaces often display sparkle, which degrades the display performance. Antiglare surfaces may be coated and locally lOXed to modulate the surface refractive index, however these approaches are difficult to control and hard to use in manufacturing because of the complexity, limited control, and high cost. For example, the fast diffusion of silver ions in all vertical and lateral dimensions in glass may make local refractive index tuning challenging. Further, such modifications may compromise glass performance such as lower resistance to scratch. [0065] In embodiments, the articles described herein may be utilized as a transparent diffuser. In embodiments, the glassy-phase region 400 includes an increased concentration of Ag2O relative to a concentration of Ag2O in the bulk glass-ceramic region 420. The glassyphase region 400 may have an increased refractive index relative to the glass-ceramic material of the glass-ceramic substrate 110. In embodiments, the local refractive index of the glassyphase regions 400 may be tuned such that articles that include the glass ceramic substrate 110 having the glassy-phase regions 400 may be used as a transparent diffuser in a variety of applications, such as reducing sparkle on an antiglare product. Glass-ceramic substrates may be textured to provide antiglare properties. However, conventional substrates that include surface texture may increase sparkle and/or increase non-uniformity.

[0066] FIG. 6A schematically depicts a portion of the glass-ceramic substrate 110 that includes a glassy-phase region 400 and a bulk glass-ceramic region 420, where the glassyphase region 420 is concave and has an increased concentration of Ag2O. FIG. 6B schematically depicts a portion of a comparative glass-ceramic substrate used with a display that includes a bulk glass-ceramic region 420, concave glass-ceramic regions 620, and light emitted from pixel 640 and pixel 650 of the display. Light travelling from pixel 640 through the comparative glass-ceramic substrate may defocus 660, and light travelling from pixel 650 through the comparative glass-ceramic substrate may focus 670, which may respectively cause non-uniformity and sparkle. FIG. 6C schematically depicts a portion of a glass-ceramic substrate used with a display that includes a bulk glass-ceramic region 420, concave glassyphase regions 400, and light emitted from pixel 640 and pixel 650 of the display. Without intending to be bound by any particular theory, it is believed that by increasing a local refractive index of the glassy-phase regions relative to the bulk glass-ceramic region 420, the refractive index may be tuned such that light travelling from pixel 640 and from pixel 650 may pass through the glass-ceramic substrate without severe focusing or defocusing 680, thereby minimizing display non-uniformity and sparkle. Embodiments disclosed herein may be used as transparent diffusers in other applications such as on a window to provide an antiglare function while not causing the transmitted image to appear diffuse or fuzzy.

[0067] In embodiments, the articles described herein have enhanced anti-microbial efficacy, as described in U.S. Patent Application US20220169557A1, the contents of which are incorporated herein by reference in their entirety. [0068] ‘ ‘EPA Dry test” refers to a test published by the EPA as “Test Method for Efficacy of Copper Alloy Surfaces as a Sanitizer” that may be used to evaluate antimicrobial efficacy. To the extent there are differences between what is described in the EPA protocol and what is described herein, references to the “Dry Test’ refer to what is described herein. A sample of Staph Aureus bacteria is placed on a dry sample surface. The surface is held at room temperature (25°C) and room humidity (42% relative humidity) for 2 hours. The amount of bacteria surviving is then measured to determine the “log kill rate” due to exposure to the surface for two hours at room temperature and humidity. 10% surviving bacteria is a log kill rate of 1, 1% surviving bacteria is a log kill rate of 2, 0.1% surviving bacteria is a log kill rate of 3, and so on.

[0069] It is believed that a high silver concentration in the glassy-phase regions 400 may lead to a surprisingly high kill rate under the EPA Dry Test described herein. The articles may exhibit a log kill rate equal to or greater than 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1,

3.2, 3.3, 3.4, 3.5, 4, 4.5 or 5, according to the EPA dry test. The log kill rate may be 2, 2. 1, 2.2,

2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5, 5 or any range having any two of these values as endpoints, according to the EPA dry test. In some embodiments, the log kill rate is 2 to 5, according to the EPA dry test. It should be noted that it is much more difficult to achieve a high log kill rate under the EPA Dry Test than under wet tests often used to evaluate anti-microbial efficacy, because there is limited or no liquid water present under the test conditions of the EPA Dry Test to help antimicrobial ions diffuse out of an article . Accordingly, reports of kill rates under other tests for various samples is not dispositive of whether those samples can pass the EPA Dry Test, and kill rates under the EPA Dry Test are expected to be much lower than they would be under wet tests for many articles.

[0070] ‘ ‘JIS Z 2801 test” refers to a test published by Japanese Standards Association (JSA) that may be used evaluate the antimicrobial activity and efficacy of plastic material and other hard antimicrobial surfaces, the contents of which are incorporated herein by reference in their entirety. The articles may exhibit a log kill rate equal to or greater than 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5 or 5, according to the JIS Z 2801 test with Staph Aureus bacteria. The log kill rate may be 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5, 5, or any range having any two of these values as endpoints, according to the JIS Z 2801 test with Staph Aureus bacteria. In some embodiments, the log kill rate is 3 to 5, according to the JIS Z 2801 test with Staph Aureus bacteria. [0071] The articles 100 disclosed herein may be incorporated into another article such as an article with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, and the like), architectural articles, transportation articles (e.g., automobiles, trains, aircraft, sea craft, etc.), appliance articles, or any article that requires some transparency, scratch-resistance, abrasion resistance, anti-microbial efficacy, or a combination thereof. An exemplary article incorporating any of the articles 100 disclosed herein is shown in FIGS. 7A and 7B. Specifically, FIGS. 7A and 7B show a consumer electronic device 200 including a housing 202 having front 204, back 206, and side surfaces 208; electrical components (not shown) that are at least partially inside or entirely within the housing and including at least a controller, a memory, and a display 210 at or adjacent to the front surface of the housing; and a cover substrate 212 at or over the front surface of the housing such that it is over the display. In embodiments, at least a portion of at least one of the cover substrate 212 and/or the housing 202 may include any of the articles 100 disclosed herein. [0072] In embodiments, articles 100 disclosed herein may be incorporated into a structure, where the structure may comprise a transparent luminaire, transparent display, heads-up display, head-mounted display, transparent backlight, touch screen display, liquid-crystal display, aquarium, laser based reflective heads-up display, wearable display, window, vehicle dashboard, automotive window, waveguide, lightguide, or architectural window. In embodiments, the structure may comprise a microlens array, which may be used in applications such as optical and sensing systems. In embodiments, fabrication of microlens arrays with specific properties comprising articles 100 disclosed herein may be adjusted not only by the shape of the glassy-phase regions 400 but also by the local tuning of the refractive index. Further, articles 100 disclosed herein may be used for metalenses, such as when the wavelengths of interest are larger than the lateral feature sizes.

[0073] The articles 100 disclosed herein may be incorporated into a glass screen protector for a smart phone. The glass screen protector may comprise a cover glass and adhesive backing disposed on the cover glass. In embodiments, the adhesive backing is for attachment to the smart phone. In embodiments, at least one portion of the cover glass comprises any glassceramic substrate 110 disclosed herein, or any article 100 disclosed herein.

[0074] Referring now to FIG. 8, a method 800 of forming an article is depicted. The method 800 may comprise converting at least a portion of a first surface of a glass-ceramic substrate to a glassy-phase material, at step 810, and ion-exchange processing the glassy-phase material to introduce silver into the glassy-phase material, at step 820. The articles formed by method 800 may include any of the articles 100 or the glass ceramic substrates 110 disclosed herein.

[0075] As shown in the method 800 of FIG. 8, the method may comprise converting at least a portion of a first surface of a glass-ceramic substrate to a glassy-phase material, at step 810. In embodiments, the glass-ceramic substrate may comprise the first surface and a second surface opposite the first surface. In embodiments, at least 70 wt.%, at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, or at least 95 wt.% of the glass-ceramic substrate may remain a glass-ceramic material after the converting.

[0076] In one or more embodiments, the converting at least a portion of a first surface of a glass-ceramic substrate to a glassy-phase material may comprise directing radiation from a laser at the first surface of the glass ceramic substrate to form the glassy-phase material

[0077] In one or more embodiments, converting at least a portion of a first surface of a glassceramic substrate to a glassy-phase material may comprise laser etching the at least a portion of a first surface of a glass-ceramic substrate. In one or more embodiments, laser etching comprises heating to a target temperature. In one or more embodiments, the target temperature is at least 300 °C, at least 325 °C, at least 350 °C, at least 375 °C, at least 400 °C, at least 450 °C, at least 475 °C, at least 500 °C, or even at least 600 °C.

[0078] In one or more embodiments, laser etching may comprise directing pulsed radiation to the at least a portion of a first surface of a glass-ceramic substrate to form a plurality of glassy -phase regions. The glassy-phase regions may each have a feature size and a feature position, controlled by the pulsed radiation. The surface features may each have a surface feature shape and surface feature curvature controlled by the pulsed radiation. In one or more embodiments, the laser may be a CO2 laser. In embodiments, laser etching may cause a portion of the glass-ceramic substrate having surface crystal phases to melt, which may form glassyphase regions upon cooling.

[0079] In one or more embodiments, the pulsed radiation from the laser can cause a portion of material of the glass-ceramic substrate proximate to the first surface to have composition- and/or phase- related changes.

[0080] In one or more embodiments, configuring the laser to emit the pulsed radiation to form the glassy-phase regions comprises setting one or more parameters of the laser. The parameters can include a laser type, a center wavelength, a repetition rate, an average power, a pulse duration, a pulse energy, a beam shape, a focal length, a spot size, a scanning method, a scanning speed, a scanning pitch spacing, a seaming line spacing, a laser fluence, as well as other parameters. In embodiments, the laser may be an ultrafast laser, producing an ultrafast short pulse width (10‘¹² ~ 10'¹⁵ s) and a high peak intensity. When used for high precision fabrication, ultrafast lasers may have certain advantages, such as negligible cracks, minimum heat affected zones, low recast and high precision, compared with long pulse (i.e., nanosecond (10‘⁹ s). In embodiments, ultrafast lasers used for forming glassy-phase regions on the glass ceramic surface may have various operating wavelengths (i.e., 532 nm, 800 nm, 1030 nm, etc.) and the pulse width of the laser can also be varied from tens of fs to several ps (i.e., 10 ps). Both fiber-based and solid-state lasers may be used. In embodiments, the spot size after focusing may be controlled by changing the focal length of the F-theta lens. To improve the throughput, a single gaussian beam can be shaped to multi-foci beams on the glass ceramic substrate using special optics or a spatial light modulator (SLM) for parallel processing. In embodiments, a polygon scanner or other laser systems be used to form the glassy-phase regions. Details of the one or more parameters, including the settings thereof, are described in the Examples section of this disclosure.

[0081] In one or more embodiments, the method may further comprise wet etching the glassceramic substrate by contacting at least a portion of the glassy-phase material with an etchant. In one or more embodiments, the etchant may include hydrofluoric acid, ammonium bifluoride, sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, potassium hydroxide, or combinations of two or more thereof. In one or more embodiments, the etchant may include an aqueous hydroxide material such as NaOH, KOH, or combination thereof. The wet etching is configured to remove material from the first surface and the second surface of the substrate.

[0082] In one or more embodiments, the glass-ceramic substrate may be contacted with the etchant for a time period of from greater than or equal to 5 minutes to less than or equal to 200 minutes, such as from greater than or equal to 5 minutes to less than or equal to 150 minutes, from greater than or equal to 5 minutes to less than or equal to 100 minutes, from greater than or equal to 5 minutes to less than or equal to 50 minutes, from greater than or equal to 5 minutes to less than or equal to 25 minutes, from greater than or equal to 25 minutes to less than or equal to 200 minutes, from greater than or equal to 25 minutes to less than or equal to 150 minutes, from greater than or equal to 25 minutes to less than or equal to 100 minutes, from greater than or equal to 25 minutes to less than or equal to 50 minutes, from greater than or equal to 50 minutes to less than or equal to 200 minutes, from greater than or equal to 50 minutes to less than or equal to 150 minutes, from greater than or equal to 50 minutes to less than or equal to 100 minutes, from greater than or equal to 100 minutes to less than or equal to 200 minutes, from greater than or equal to 100 minutes to less than or equal to 150 minutes, from greater than or equal to 150 minutes to less than or equal to 200 minutes, or any combination of these ranges.

[0083] The etchant may be at an elevated temperature during the etching process. The elevated temperature may increase the etching rate. In one or more embodiments, the etchant is at a temperature of greater than or equal to 90 °C to less than or equal to 140 °C, such as greater than or equal to 90 °C to less than or equal to 132 °C, greater than or equal to 95 °C to less than or equal to 135 °C, greater than or equal to 100 °C to less than or equal to 130 °C, greater than or equal to 105 °C to less than or equal to 125 °C, greater than or equal to 110 °C to less than or equal to 120 °C, greater than or equal to 90 °C to less than or equal to 115 °C, and any and all sub-ranges formed from the foregoing endpoints. In one or more embodiments, the etchant may be at ambient temperature.

[0084] The etching rate and etching time may be selected to remove a desired amount of material from the surface of the glass-ceramic substrate 110. If the amount of material removed in the etching step is too low the desired surface properties, such as distinctness-of-image and sparkle, may not be achieved. Removing too much material from the abraded surface may increase cost and reduce manufacturing throughput.

[0085] In embodiments, the method may comprise wet etching prior to the ion-exchange processing. In other embodiments, the method does not comprise wet etching.

[0086] As shown in the method 800 of FIG. 8, the method may comprise ion-exchange processing the glassy-phase material to introduce silver into the glassy-phase material, at step 820.

[0087] Without intending to be bound by any particular theory, it is believed that by selectively converting a portion of the glass-ceramic substrate to a glassy-phase material, a surface of the glass-ceramic substrate may have tunable ion-exchange capability and capacity, which may provide more flexibility and control in developing articles having desired properties. For instance, the glassy-phase material may have a higher IOX rate and/or IOX capacity than the glass-ceramic material, thereby selectively exchanging more ions with the glassy -phase material. The increased concentration of silver in the glass-phase material may be used to tune the refractive index in applications such a transparent diffusers discussed herein, or may be used to increase antibacterial activity of articles comprising the glassy-phase material. Conventional articles (either glass or glass-ceramic) may comprise a uniform material with similar ion-exchange rate and capability throughout the entire surface of the article, thereby limiting the tunability of the ion-exchange rate of conventional articles. Further, conventional antimicrobial glass-based articles may only store a limited amount of silver ions restricted by the available exchangeable ions in the glass, thereby limiting their antimicrobial efficacy.

[0088] In embodiments, the ion-exchange processing may include contacting the glassyphase material with a molten salt solution comprising silver. In embodiments, the molten salt solution may comprise KNO3, NaNCh, and AgNCf.

[0089] In embodiments, the ion-exchange processing may comprise contacting the glassyphase material with the molten salt solution for a time period of less than or equal to 12 hours, such as less than or equal to 10 hours, less than or equal to 8 hours, less than or equal to 6 hours, or less than or equal to 4 hours. In embodiment, the ion-exchange processing may comprise contacting the glassy-phase material with the molten salt solution for a time period of greater than or equal to 5 minutes, greater than or equal to 30 minutes, greater than or equal to 1 hour, or greater than or equal to 2 hours.

[0090] The molten salt solution may be at an elevated temperature during the ion exchanging process. The elevated temperature may increase the ion exchanging rate. In one or more embodiments, the molten salt solution is at a temperature of greater than or equal to 250 °C to less than or equal to 500 °C, such as greater than or equal to 250 °C to less than or equal to 450 °C, greater than or equal to 250 °C to less than or equal to 450 °C, greater than or equal to 300 °C to less than or equal to 400 °C, greater than or equal to 250 °C to less than or equal to 350 °C, and any and all sub-ranges formed from the foregoing endpoints.

[0091] A schematic of a method of forming an article according to embodiments described herein is depicted in FIG. 9. In FIG. 9, a glass ceramic substrate 910 is subjected to conditions

glass ceramic substrate 910 is converted to glassy-phase material 940, and at least 70 wt.% of the glass ceramic substrate remains a glass-ceramic material 950. The intermediate substrate 930 is the ion-exchange processed under conditions 960 to form the article 970, such that silver is introduced into the glassy-phase material 940 to form glassy-phase material comprising silver 980.

EXAMPLES

[0092] Embodiments will be further clarified by the following examples. It should be understood that these examples are not limiting to the embodiments described above.

[0093] Example 1- Formation of laser-treated glass-ceramic substrate

[0094] In Example 1, a laser-treated glass-ceramic substrate is formed from an initial glassceramic substrate. The initial glass-ceramic substrate according to Table 1 was provided. The initial glass ceramic substrate of Example 1 includes a petalite crystalline phase (Li2O-AhO3- 8SiC>2) , a lithium disilicate crystalline phase (Li2O-2SiC>2, “LS2”), a lithium phosphate crystalline phase (LisCLP, “L3P”), and a glassy phase.

[0095] Table 1

[0096] The initial glass-ceramic substrate was then treated with an ultrafast laser system (Pharos, Light Conversion) to convert at least a portion of a surface of the glass ceramic substrate to a glassy-phase region, forming a laser-treated glass-ceramic substrate. Specifically, the central wavelength, pulse width, and repetition rate of a diode pumped solid state laser were set at 1030 nm, 300 fs, and 200 kHz, respectively. The output power (maximum) of the laser was 4 W and the actual power used for fabrication was approximately 10 pj per pulse. The laser beam was steered through a galvanometer scanner and focused on the initial glass-ceramic substrate through a conventional F-theta lens with a focal length of 80 mm. The spot size was approximately 17 pm in air at the focal point. The initial glass-ceramic substrate sample was rapidly scanned via cross-hatching method with a pitch of 25 pm. The scanning speed of the scanner was set at 500 mm/s, which resulted in the conversion of portions of the surface of the glass ceramic substrate to glassy-phase regions, forming the laser-treated glass-ceramic substrate. Because the laser treatment was focused on the glass-ceramic substrate surface, only the glass ceramic surface at the focal spots was transformed into glassy-phase regions while the rest of the bulk material remained a glass- ceramic. The laser-treated glass-ceramic substrate was then further characterized.

[0097] The laser-treated glass-ceramic substrate was characterized using scanning electron microscopy (SEM) imaging, as shown in FIG 10. FIG. 10A shows a cross-section view of the laser-treated glass-ceramic substrate (scale bar 10 pm), FIG. 10B shows an enhanced crosssection view of the laser-treated glass-ceramic substrate 710 (scale bar 1 pm), and FIG 10C shows a top view of the laser-treated glass-ceramic substrate (scale bar 10 pm). As shown in FIG. 10, the laser treatment of the initial glass-ceramic substrate resulted in a concave shape surface feature comprising the glassy-phase region 400 with a crescent shape cross section positioned on the glass-ceramic bulk 420. The thickness of the glassy -phase layer was approximately 3 pm.

[0098] The optical parameters and surface morphology of the laser-treated glass-ceramic substrate was characterized by measuring haze, transmittance (“Trans”), gloss (at 20° 60° and 85°), Ra, Rq, and Rsk. These measurements are summarized in Table 2.

[0099] Table 2.

[00100] Example 2- Modified laser conditions for the formation of laser-treated glass-ceramic substrates

[00101] In Example 2, two different laser-treated glass-ceramic substrates were formed from the initial glass-ceramic substrate of Example 1. The laser-treated glass-ceramic substrate of Example 2-1 was formed according to the laser treatment parameters of Example 1. The laser- treated glass-ceramic substrate of Example 2-2 was formed according to the laser treatment parameters of Example 1, except that in Example 2-2 the actual power used for fabrication was decreased to approximately 6 pj per pulse.

[00102] Example 3- Chemical etching of laser-treated glass-ceramic substrates

[00103] In Example 3, the laser-treated glass-ceramic substrates of Example 2-1 and Example 2-2 were treated with a chemical etchant to produce the laser-treated and chemically-etched glass-ceramic substrates of Examples 3-1 and 3-2, respectively. Specifically, Example 2-1 and Example 2-2 were treated with an etchant solution (50 wt.% NaOH) at 112 °C for 3 hours.

[00104] Example 4- Silver ion-exchange processing of laser-treated and laser-treated and chemically-etched glass-ceramic substrates

[00105] In Example 4, the laser-treated glass-ceramic substrates of Example 2-1 and Example 2-2 and the laser-treated and chemically-etched glass-ceramic substrates of Example 3-1 and Example 3-2 were ion exchanged with a molten salt solution comprising silver at 390 °C for 1 hour to produce silver-ion exchanged glass-ceramic substrates. Specifically, Examples 2-1, 2- 2, 3-1, and 3-2 were treated in a molten salt solution comprising 42.5 wt.% KNO3, 42.5 wt.% NaNO.v 5 wt.% AgNCh and 0.5 wt.% silicic acid. The concentration of silver in the glassyphase regions of the glass-ceramic substrates was determined according to glow discharge optical emission spectroscopy (GDOES). The silver concentration was quantified in the glassyphase regions of the glass-ceramic substrate at a depth of 200 nanometers within the glassyphase region and is summarized in Table 3.

[00106] Table 3

[00107] Example 5- Characterization of glass-ceramic substrates

[00108] In Example 5, Examples 2-1, 2-2, 3-1, and 3-2, and Example 4 were further characterized. The laser-treated glass-ceramic substrates of Example 2-1 and Example 2-2 and the laser-treated and chemically-etched glass-ceramic substrates of Example 3-1 and Example 3-2 before and after silver ion-exchange processing in Example 4 were characterized and summarized in Table 4.

[00109] Table 4

[00110] As shown in Table 4, the formation of glassy-phase regions in the glass-ceramic substrates, followed by ion-exchange processing silver in the glassy-phase regions provide low sparkle in the glassy-phase regions of glass-ceramic substrates. Further, chemical etching prior to silver ion-exchange processing resulted in reduced gloss and sparkle (Ex. 3-1 and Ex. 3-2) versus glass-ceramic substrates that were not chemically etched (Ex. 2-1 and Ex. 2-2). That is, the glass-ceramic substrates disclosed herein may be further treated to optimize desired haze, gloss, and sparkle.

[00111] The laser-treated glass-ceramic substrates of Example 2-1 and Example 2-2 and the laser-treated and chemically-etched glass-ceramic substrates of Example 3-1 and Example 3-2 were imaged using SEM imaging, as shown in FIG 11. FIG. 11 A shows a top view of the laser- treated glass-ceramic substrate of Example 2-1 (scale bar 50 pm). FIG. 1 IB shows a top view of the laser-treated and chemically-etched glass-ceramic substrate of Example 3-1 (scale bar 50 pm). FIG. 11C shows a top view of the laser-treated glass-ceramic substrate of Example 2- 2 (scale bar 50 pm). FIG. 11D shows a top view of the laser-treated and chemically-etched glass-ceramic substrate of Example 3-2 (scale bar 50 pm).

[00112] The laser-treated glass-ceramic substrate of Example 2-1 after ion-exchange processing according to Example 4 was further characterized using elemental analysis to quantify silver deposition in the glassy-phase regions of the glass-ceramic substrate and glassceramic region of the glass-ceramic substrate, as shown in FIG. 12. Specifically, scanning electron microscopy energy dispersive X-ray spectroscopy was performed at a first point 1210 within the glassy-phase region and a second point 1220 within the glass-ceramic portion of the glass-ceramic substrate, as shown in FIG. 12A. A plot of the elemental analysis of the first point 1210 within the glassy-phase region using EDS is shown in FIG. 12B. Peak 1230 in FIG. 12B is attributed to silver. A plot of the elemental analysis of the second point 1220 within the glass-ceramic region of the glass-ceramic substrate is shown in FIG. 12C. The EDS plots were analyzed using a standardless quantification routine, where the mole % by oxide of SiCE, AI2O3, ZrCf. P2O5, and Ag2O are normalized to 100%, and are reported in Table 5. As shown in FIG. 12B, Fig. 12C, and Table 5, the glassy-phase region of the glass-ceramic substrate has significantly greater silver compared to the glass-ceramic region of the glass-ceramic substrate. [00113] It is believed the compositional differences between the glass-ceramic region and the glassy-phase region play an important role in the observed ion exchange rates and resulting increased Ag2O concentration in the glassy-phase regions. Although the initial glass ceramic substrate includes ~ 22 mol.% Li2O, the amount of Li2O that may be ion-exchanged is much less due to ~I8 mol% of Li2O being within crystal phases that are inactive (not ionexchangeable). After forming the glassy-phase region at the surface of the glass-ceramic substrate, all Li2O at the glassy-phase region may be activated (ion-exchangeable) and can exchange with silver. Therefore, during the ion-exchange process, a significantly greater amount of Ag2O may be stored in the glassy-phase regions. Thus, the methods described herein to selectively form glassy-phase regions on the glass-ceramic substrate followed by ionexchange processing the entire substrate results in selective ion exchanging of silver in the glassy-phase regions.

[00114] Table 5

[00115] Example 6- Anti-microbial efficacy of glass-ceramic substrates

[00116] In Example 6, Examples 2-1 and 3-1 after ion-exchange processing according to Example 4 were evaluated for anti-microbial efficacy using a test method published by the EPA as “Test Method for Efficacy of Copper Alloy Surfaces as a Sanitizer”. Details are provided here as well, with steps numbered according to the EPA protocol:

1. Stock cultures: Initiate new stock cultures from lyophilized cultures from ATCC at least once every 18 months. Open ampule of freeze-dried organism per manufacturer’s instructions

2. Using a tube containing 5-6 mb of tryptic soy broth (TSB), aseptically withdraw 0.5 to 1.0 mb and rehydrate the lyophilized culture. Aseptically transfer the entire rehydrated pellet back into the original tube of broth. Mix thoroughly. Incubate broth culture at 36 ± 1°C for 24 ± 2 hours

3. After incubation, streak a loopful of the suspension on tryptic soy agar (TSA) to obtain isolated colonies. Incubate the plates for 18-24 h at 36 ± 1°C

4. Select 3-5 isolated colonies of the test organism and re-suspend in 1 mb of TSB. For S. aureus, select only golden yellow colonies. Spread plate 0. 1 mb of the suspension on each of the 6-10 TSA plates. Incubate the plates for 18-24 h at 36 ± 1°C

5. Following the incubation of the agar plates, place approximately 5 mb sterile cryoprotectant solution on the surface of each plate. Re-suspend the growth in the cryoprotectant solution using a sterile spreader without damaging the agar surface. Aspirate the suspension from the plate with a pipette and place it in a sterile vessel large enough to hold about 30 mb. Repeat the growth harvesting procedure with the remaining plates and continue adding the suspension to the vessel (more than 1 tube may be used is necessary). Mix the contents of the vessel(s) thoroughly; if more than 1 vessel is used, pool the vessels prior to aliquoting culture. Immediately after mixing, dispense 0.5-1 mb aliquots of the harvested suspension into cryovials; these represent the frozen stock cultures

6. Store the cryovials at -70 ± 5 °C for a maximum 18 months then reinitiate with a new lyophilized culture

7. Conduct Quality Control check of the pooled culture concurrently with freezing. For example, streak a loopfill on a blood agar plate, and selective media such as mannitol salt agar (MSA) and Cetrimide. Incubate all plates at 36±1°C for 24±2 hours. Record the colony morphology as observed on the blood agar plates and selective media plates (including the absence of growth). Perform a Gram stain from growth taken from the blood agar plates and observe the Gram reaction by using bright field microscopy at lOOOx magnification (oil immersion)

Test Cultures

8. For S. aureus, defrost a single stock culture cryo vial at room temperature and briefly vortex to mix. Each cryovial should be single use only. Add 20uL of the thawed stock to a tube containing 10 m of TSB and then vortex to mix. Incubate at 36 ± 1°C for 18-24 hours. Following incubation, use the broth culture to prepare a final test suspension. Briefly vortex the culture prior to use

9. Dilute in Phosphate Buffered Saline (PBS) or concentrate the culture appropriately to achieve the target carrier counts (4-5 logs/carrier). Centrifuge the 18-24 h broth cultures to achieve the desired level of viable cells on the dried carrier. Centrifuge at ~ 5000 gN for 20 ± 5 min and re-suspend the pellet in 6 m IX PBS. Note: Remove the supernatant without disrupting the pellet. For S. aureus, disrupt the pellet using vortexing or repetitive tapping/striking against a hard surface to disaggregate the pellet completely prior to resuspending it in 6 mb. If necessary, add Imb of PBS to the pellet to aid in disaggregation

10. Purity of the final test culture (with soil load) should be determined by streak isolation on TSA with 5% sheep’s blood, or other appropriate plating medium, incubate (36±°C for 48±4 hr), examine for purity

11. Titer of the final test culture (with soil load) will be determined for informational purposes. Plate dilutions on TSA plates or other appropriate medium and incubate (36 ± 1°C for 24- 48 hr) and enumerate. Count the number of colonies to determine the number of organisms per mb (i.e. CFU/mb) of the inoculum present at the start of the test

Soil Load

12. Add 0.25 ml aliquot of fetal bovine serum + 0.05 ml Triton X-100 to 4.70 ml bacteria suspension to yield a 5% fetal bovine serum and 0.01% Triton X-100 soil load. Following the addition of soil load, vortex the final test suspension for 10 seconds and immediately prior to use

Efficacy Test Procedure

13. Evaluate treated test carriers with untreated control carriers against the test organism Coated control carriers should be evaluated concurrently with the coated test carriers The exposure (contact time) of the inoculum to the carrier surface begins immediately upon inoculation; therefore, the contact time begins when final test suspension (with soil load) is deposited onto a carrier Record the initiation of the contact time and inoculate each carrier at staggered intervals with 20 pL of final test culture using a calibrated pipette (a positive displacement pipette is desirable) Spread the inoculum across the surface of the carrier moving back and forth to ensure full coverage of the surface, spreading as close to the edge of carrier as possible using a bent pipette tip. Use an appropriate interval (e.g. 30 sec to allow enough time for careful spreading of the inoculum) The contact time begins immediately following carrier inoculation. Record the lab temperature and relative humidity during the two-hour exposure period Allow carriers to remain in a horizontal position under ambient conditions on the Petri plate for 120 ± 5 min Following the exposure period, sequentially and aseptically transfer carriers to 20 m of Letheen broth (neutralizer solution)- this represents the 10° dilution a. For samples larger than l”x 1”, a plastic sticker (prepared using the Silhouette cutter system) with a l”xl” opening is add to the surface to achieve the correct testing area. These are added to Whirl Pak bags with the 20mL neutralizer for sonication (next step). After all the carriers have been transferred into the neutralizer, sonicate for 5 min ± 30 secs to suspend any survivors from the carriers, swirl to mix. Within 30 mins of sonication, prepare serial dilutions of the neutralized solution (10° dilution) out to 10'³ for the treated carriers. Transfer the coated control carriers to neutralizing subculture medium and plate the appropriate dilutions in duplicate to yield countable numbers (up to 300 colonies per plate). Incubate and enumerate with the treated carrier plates Plate 1.0 m aliquots of 10° dilution and 0.10 mL aliquots of the 10° -10'³ dilutions in duplicate using standard spread plating technique on TSA plates Incubate the plates at 36±1°C for 48±4 hr 25. Following incubation, count colonies and record results

26. Alternate incubation conditions may be needed for certain organisms. The incubation conditions may be modified to suit the test organisms if needed. If necessary, subculture plates can be stored for up to 3 days at 2-8°C prior to enumeration

[00117] The various features described in the specification may be combined in any and all combinations, for example, as listed in the following embodiments.

[00118] Embodiment 1. An article is provided that includes: a glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further comprising one or more glassy-phase regions on the first surface, wherein the one or more glassy-phase regions comprises an amorphous glass; and wherein the one or more glassy-phase regions have an Ag2O concentration therein of at least 5 mol.% at a depth of 200 nm below a surface of the glassy-phase regions.

[00119] Embodiment 2. The article of Embodiment 1 is provided, wherein the one or more glassy -phase regions on the first surface have at all depths therein an Ag2O concentration of at least 5 mol.%.

[00120] Embodiment 3. The article of Embodiment 1 or Embodiment 2 is provided, wherein the one or more glassy-phase regions on the first surface comprise silver ion-exchanged (lOXed) amorphous glass material.

[00121] Embodiment 4. The article of any one of Embodiments 1-3 is provided, wherein the one or more glassy-phase regions on the first surface of the glass-ceramic substrate are textured. [00122] Embodiment 5. The article of any one of Embodiments 1-3 is provided, wherein a portion of the first surface that does not comprise the one or more glassy-phase regions comprises one or more glass-ceramic regions comprising the glass-ceramic material.

[00123] Embodiment 6. The article of Embodiment 5 is provided, wherein the one or more glass-ceramic regions have an Ag2O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate.

[00124] Embodiment 7. The article of Embodiment 5 or Embodiment 6 is provided, wherein the one or more glass-ceramic regions have at all depths therein an Ag2O concentration of less than 5 mol.%. [00125] Embodiment 8. The article of any one of Embodiments 1-7 is provided, wherein at least a portion of the one or more glassy-phase regions are concave.

[00126] Embodiment 9. The article of any one of Embodiments 1-8 is provided, wherein the article has a color delta E equal to or less than 10 when compared to an otherwise equivalent article without Ag2O.

[00127] Embodiment 10. The article of any one of Embodiments 1-9 is provided, wherein the one or more glassy-phase regions have a total surface area of from 50% to 100% of a total surface area of the first surface.

[00128] Embodiment 11. The article of any one of Embodiments 1-10 is provided, wherein the article has a sparkle at 140 ppi of less than or equal to 3% in regions comprising the glassyphase regions.

[00129] Embodiment 12. The article of any one of Embodiments 1-11 is provided, wherein a portion of the glass ceramic substrate comprising the glassy-phase regions article has a haze of from greater than or equal to 5% to less than or equal to 40%.

[00130] Embodiment 13. The article of any one of Embodiments 1-12 is provided, wherein a portion of the glass ceramic substrate comprising the glassy-phase regions article has a coupled distinctness-of-image (DOI) of less than or equal to 20%.

[00131] Embodiment 14. The article of any one of Embodiments 1-13 is provided, wherein a portion of the glass ceramic substrate comprising the glassy-phase regions has a gloss 60° of greater than or equal to 20 and less than or equal to 80.

[00132] Embodiment 15. The article of any one of Embodiments 1-14 is provided, wherein a portion of the glass ceramic substrate comprising the glassy-phase regions article has a surface roughness Rqof greater than or equal to 40 nanometers.

[00133] Embodiment 16. The article of any one of Embodiments 1-15 is provided, wherein a portion of the glass ceramic substrate comprising the glassy-phase regions article has a sparkle at 140 ppi of less than or equal to 5% in regions comprising the glassy-phase regions.

[00134] Embodiment 17. The article of any one of Embodiments 1-16 is provided, wherein the first surface of the article exhibits a log kill greater than or equal to 2 according to an EPA Dry Test with Staph Aureus bacteria.

[00135] Embodiment 18. An article is provided that includes: a glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further comprising one or more glassy-phase regions on the first surface, wherein the one or more glassy-phase regions comprise an amorphous glass; and wherein the one or more glassy-phase regions have an Ag2O concentration therein of at least 5 mol.% at a depth of 200 nm below a surface of the glassy-phase regions; wherein the one or more glassy-phase regions on the first surface of the glass-ceramic substrate are textured;wherein a portion of the first surface that does not comprise the one or more glassyphase regions comprises one or more glass-ceramic regions comprising the glass-ceramic material; and wherein the one or more glass-ceramic regions have an Ag2O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate. [00136] Embodiment 19. The article ofEmbodiment 18 is provided, wherein: a portion ofthe glass ceramic substrate comprising the glassy-phase regions article has a sparkle at 140 ppi of less than or equal to 3%; a portion of the glass ceramic substrate comprising the glassy-phase regions has a haze of from greater than or equal to 5% to less than or equal to 40%; a portion of the glass ceramic substrate comprising the glassy-phase regions article has a coupled distinctness-of-image (DOI) of less than or equal to 20%; a portion of the glass ceramic substrate comprising the glassy-phase regions article has a gloss 60° of greater than or equal to 20 and less than or equal to 80; a portion of the glass ceramic substrate comprising the glassyphase regions article has asurface roughness Rq of greater than or equal to 40 nanometers; and the first surface of the article exhibits a log kill greater than or equal to 2 according to an EPA Dry Test with Staph Aureus bacteria.

[00137] Embodiment 20. The article of Embodiment 18 or Embodiment 19 is provided, wherein: the one or more glassy-phase regions have at all depths therein an Ag2O concentration of at least 5 mol.%; the one or more glassy-phase regions have a total surface area of from 50% to 100% of a total surface area of the first surface; the article has a color delta E equal to or less than 10 when compared to an otherwise equivalent article without Ag2O; and at least a portion of the one or more glassy-phase regions are concave.

[00138] Embodiment 21. An article is provided that includes: a glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further comprising one or more glassy-phase regions on the first surface, wherein the one or more glassy-phase regions comprise an amorphous glass; wherein a portion of the first surface that does not comprise the one or more glassyphase regions comprises one or more glass-ceramic regions comprising the glass-ceramic material; wherein the first surface of the article exhibits a log kill greater than or equal to 2 according to the EPA Dry Test with Staph Aureus bacteria.

[00139] Embodiment 22. The article of Embodiment 21 is provided, wherein: a portion of the glass ceramic substrate comprising the glassy-phase regions article has a sparkle at 140 ppi of less than or equal to 5%; a portion of the glass ceramic substrate comprising the glassy-phase regions article has a haze of from greater than or equal to 5% to less than or equal to 40%; a portion of the glass ceramic substrate comprising the glassy-phase regions article has an coupled distinctness-of-image (DOI) of less than or equal to 20%; and a portion of the glass ceramic substrate comprising the glassy-phase regions article has a gloss 60° of greater than or equal to 20 and less than or equal to 80.

[00140] Embodiment 23. The article of Embodiment 21 or Embodiment 22 is provided, wherein: the one or more glassy-phase regions have at all depths therein an Ag2O concentration of at least 5 mol.%; the one or more glassy-phase regions have a total surface area of from 50% to 100% of a total surface area of the first surface; the article has a color delta E equal to or less than 10 when compared to an otherwise equivalent article without Ag2O; the one or more glass-ceramic regions have an Ag2O concentration of less than less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate; and at least a portion of the one or more glassy-phase regions are concave.

[00141] Embodiment 24. A consumer electronic product is provided that includes: a housing comprising a front surface, a back surface and side surfaces; electronic components at least partially within the housing, the electronic components comprising at least one of a display and a sensor, the display at or adjacent to the front surface of the housing and the sensor at or adjacent to the front surface or the back surface of the housing; and at least one cover disposed over at least one of the display and the sensor, wherein at least one of at least a portion of the at least one of a cover, the back surface comprises the article of any one of Embodiments 1-23. [00142] Embodiment 25. A structure is provided that includes the article of any one of Embodiments 1-23, wherein the structure is a transparent luminaire, transparent display, headsup display, head-mounted display, transparent backlight, touch screen display, liquid-crystal display, aquarium, laser based reflective heads-up display, wearable display, window, vehicle dashboard, automotive window, waveguide, lightguide, or architectural window.

[00143] Embodiment 26. A structure is provided that includes the article of any one of Embodiments 1-23, wherein the structure is a microlens array.

[00144] Embodiment 27. A glass screen protector for a smart phone is provided that includes: a cover glass; and an adhesive backing disposed on the cover glass, wherein the adhesive backing is for attachment to the smart phone, and further wherein at least one portion of the cover glass comprises the article of any one of Embodiments 1 -23.

[00145] Embodiment 28. A method of forming an article is provided that includes: converting at least a portion of a first surface of a glass-ceramic substrate to a glassy-phase material, wherein the glass-ceramic substrate comprises the first surface and a second surface opposite the first surface, and wherein at least 70 wt.% of the glass-ceramic substrate remains a glassceramic material; and ion-exchange processing the glassy-phase material to introduce silver into the glassy-phase material.

[00146] Embodiment 29. The method of Embodiment 28 is provided, wherein the article comprises glassy-phase regions comprising the glassy-phase material, and wherein the glassyphase regions have an Ag2O concentration therein of at least 5 mol.% at a depth of 200 nm below a surface of the glassy-phase regions.

[00147] Embodiment 30. The method of Embodiment 28 or Embodiment 29 is provided, wherein the article comprises glassy-phase regions comprising the glassy-phase material, and wherein an entirety of the glassy-phase regions have an Ag2O concentration of at least 5 mol.%. [00148] Embodiment 31. The method of any one of Embodiments 28-30 is provided, wherein the converting of the at least a portion of the first surface of the glass-ceramic substrate to the glassy -phase material comprises directing radiation from a laser at the first surface of the glass ceramic substrate to form the glassy-phase material.

[00149] Embodiment 32. The method of any one of Embodiments 28-31 is provided, wherein the ion exchange processing comprises contacting the glassy -phase material with a molten salt solution comprising silver.

[00150] Embodiment 33. The method of Embodiment 32 is provided, wherein the molten salt solution comprises KNO3, NaNCE. and AgNCE. [00151] Embodiment 34. The method of claim 32 or claim 33 is provided, wherein the molten salt solution has a temperature of at least 250 °C.

[00152] Embodiment 35. The method of any one of Embodiments 32-34 is provided, wherein the ion-exchange processing is for a duration of less than 12 hours.

[00153] Embodiment 36. The method of any one of Embodiments 28-35 is provided, further comprising wet etching the glassy-phase material prior to the ion-exchange processing, wherein the wet etching comprises contacting at least a portion of the glassy-phase material with an etchant.

[00154] Embodiment 37. The method of Embodiment 36 is provided, wherein the etchant comprises hydrofluoric acid, ammonium bifluoride, sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, potassium hydroxide, or combinations of two or more thereof.

[00155] Embodiment 38. The method of any one of Embodiments 28-37 is provided, wherein a valley of a surface of the glassy-phase material is positioned less than 10 micrometers below a surface of the first surface that is not converted to a glassy-phase material.

Claims

CLAIMS What is claimed is:

1. An article comprising: a glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further comprising one or more glassy-phase regions on the first surface, wherein the one or more glassy-phase regions comprises an amorphous glass; and wherein the one or more glassy-phase regions have an Ag2O concentration therein of at least 5 mol.% at a depth of 200 nm below a surface of the glassy-phase regions.

2. The article of claim 1, wherein the one or more glassy-phase regions on the first surface have at all depths therein an Ag2O concentration of at least 5 mol.%.

3. The article of claim 1 or claim 2, wherein the one or more glassy-phase regions on the first surface comprise silver ion-exchanged (lOXed) amorphous glass material.

4. The article of any one of claims 1-3, wherein the one or more glassy-phase regions on the first surface of the glass-ceramic substrate are textured.

5. The article of any one of claims 1-4, wherein a portion of the first surface that does not comprise the one or more glassy-phase regions comprises one or more glass-ceramic regions comprising the glass-ceramic material.

6. The article of claim 5, wherein the one or more glass-ceramic regions have an Ag2O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glassceramic substrate.

7. The article of claim 5 or claim 6, wherein the one or more glass-ceramic regions have at all depths therein an Ag2O concentration of less than 5 mol.%.

8. The article of any one of claims 1 -7, wherein at least a portion of the one or more glassyphase regions are concave.

9. The article of any one of claims 1-8, wherein the article has a color delta E equal to or less than 10 when compared to an otherwise equivalent article without Ag2O.

10. The article of any one of claims 1 -9, wherein the one or more glassy-phase regions have a total surface area of from 50% to 100% of a total surface area of the first surface.

11. The article of any one of claims 1-10, wherein the article has a sparkle at 140 ppi of less than or equal to 3% in regions comprising the glassy -phase regions.

12. The article of any one of claims 1-11, wherein a portion of the glass ceramic substrate comprising the glassy-phase regions article has a haze of from greater than or equal to 5% to less than or equal to 40%.

13. The article of any one of claims 1-12, wherein a portion of the glass ceramic substrate comprising the glassy-phase regions article has a coupled distinctness-of-image (DOI) of less than or equal to 20%.

14. The article of any one of claims 1-13, wherein a portion of the glass ceramic substrate comprising the glassy-phase regions has a gloss 60° of greater than or equal to 20 and less than or equal to 80.

15. The article of any one of claims 1-14, wherein a portion of the glass ceramic substrate comprising the glassy-phase regions article has a surface roughness R_qof greater than or equal to 40 nanometers.

16. The article of any one of claims 1-15, wherein a portion of the glass ceramic substrate comprising the glassy-phase regions article has a sparkle at 140 ppi of less than or equal to 5% in regions comprising the glassy-phase regions.

17. The article of any one of claims 1-16, wherein the first surface of the article exhibits a log kill greater than or equal to 2 according to an EPA Dry Test with Staph Aureus bacteria.

18. An article comprising: a glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further comprising one or more glassy-phase regions on the first surface, wherein the one or more glassy-phase regions comprise an amorphous glass; and wherein the one or more glassy-phase regions have an Ag2O concentration therein of at least 5 mol.% at a depth of 200 nm below a surface of the glassy-phase regions; wherein the one or more glassy-phase regions on the first surface of the glass-ceramic substrate are textured; wherein a portion of the first surface that does not comprise the one or more glassyphase regions comprises one or more glass-ceramic regions comprising the glass-ceramic material; and wherein the one or more glass-ceramic regions have an Ag2O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate.

19. The article of claim 18, wherein: a portion of the glass ceramic substrate comprising the glassy-phase regions article has a sparkle at 140 ppi of less than or equal to 3%; a portion of the glass ceramic substrate comprising the glassy -phase regions has a haze of from greater than or equal to 5% to less than or equal to 40%; a portion of the glass ceramic substrate comprising the glassy-phase regions article has a coupled distinctness-of-image (DOI) of less than or equal to 20%; a portion of the glass ceramic substrate comprising the glassy-phase regions article has a gloss 60° of greater than or equal to 20 and less than or equal to 80; a portion of the glass ceramic substrate comprising the glassy-phase regions article has a surface roughness Rqof greater than or equal to 40 nanometers; and the first surface of the article exhibits a log kill greater than or equal to 2 according to an EPA Dry Test with Staph Aureus bacteria.

20. The article of claim 18 or claim 19, wherein. the one or more glassy-phase regions have at all depths therein an Ag2O concentration of at least 5 mol.%; the one or more glassy-phase regions have a total surface area of from 50% to 100% of a total surface area of the first surface; the article has a color delta E equal to or less than 10 when compared to an otherwise equivalent article without Ag2O; and at least a portion of the one or more glassy-phase regions are concave.

21. An article comprising: a glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further comprising one or more glassy-phase regions on the first surface, wherein the one or more glassy-phase regions comprise an amorphous glass; wherein a portion of the first surface that does not comprise the one or more glassyphase regions comprises one or more glass-ceramic regions comprising the glass-ceramic material; wherein the first surface of the article exhibits a log kill greater than or equal to 2 according to the EPA Dry Test with Staph Aureus bacteria.

22. The article of claim 21, wherein: a portion of the glass ceramic substrate comprising the glassy-phase regions article has a sparkle at 140 ppi of less than or equal to 5%; a portion of the glass ceramic substrate comprising the glassy-phase regions article has a haze of from greater than or equal to 5% to less than or equal to 40%; a portion of the glass ceramic substrate comprising the glassy-phase regions article has an coupled distinctness-of-image (DOI) of less than or equal to 20%; and a portion of the glass ceramic substrate comprising the glassy-phase regions article has a gloss 60° of greater than or equal to 20 and less than or equal to 80.

23. The article of claim 21 or claim 22, wherein: the one or more glassy-phase regions have at all depths therein an Ag2O concentration of at least 5 mol.%; the one or more glassy-phase regions have a total surface area of from 50% to 100% of a total surface area of the first surface; the article has a color delta E equal to or less than 10 when compared to an otherwise equivalent article without Ag2O; the one or more glass-ceramic regions have an Ag2O concentration of less than less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate; and at least a portion of the one or more glassy-phase regions are concave.

24. A consumer electronic product, comprising: a housing comprising a front surface, a back surface and side surfaces; electronic components at least partially within the housing, the electronic components comprising at least one of a display and a sensor, the display at or adjacent to the front surface of the housing and the sensor at or adjacent to the front surface or the back surface of the housing; and at least one cover disposed over at least one of the display and the sensor, wherein at least one of at least a portion of the at least one of a cover, the back surface comprises the article of any one of claims 1-23.

25. A structure comprising the article of any one of claims 1-23, wherein the structure is a transparent luminaire, transparent display, heads-up display, head-mounted display, transparent backlight, touch screen display, liquid-crystal display, aquarium, laser based reflective heads-up display, wearable display, window, vehicle dashboard, automotive window, waveguide, lightguide, or architectural window.

26. A structure comprising the article of any one of claims 1-23, wherein the structure is a microlens array.

27. A glass screen protector for a smart phone, comprising: a cover glass; and an adhesive backing disposed on the cover glass, wherein the adhesive backing is for attachment to the smart phone, and further wherein at least one portion of the cover glass comprises the article of any one of claims 1-23.

28. A method of forming an article, the method comprising: converting at least a portion of a first surface of a glass-ceramic substrate to a glassyphase material, wherein the glass-ceramic substrate comprises the first surface and a second surface opposite the first surface, and wherein at least 70 wt.% of the glass-ceramic substrate remains a glass-ceramic material; and ion-exchange processing the glassy-phase material to introduce silver into the glassyphase material.

29. The method of claim 28, wherein the article comprises glassy -phase regions comprising the glassy-phase material, and wherein the glassy-phase regions have an Ag2O concentration therein of at least 5 mol.% at a depth of 200 nm below a surface of the glassy-phase regions.

30 The method of claim 28 or claim 29, wherein the article comprises glassy-phase regions comprising the glassy-phase material, and wherein an entirety of the glassy-phase regions have an Ag2O concentration of at least 5 mol.%.

31. The method of any one of claims 28-30, wherein the converting of the at least a portion of the first surface of the glass-ceramic substrate to the glassy-phase material comprises directing radiation from a laser at the first surface of the glass ceramic substrate to form the glassy -phase material.

32. The method of any one of claims 28-31, wherein the ion exchange processing comprises contacting the glassy-phase material with a molten salt solution comprising silver.

33. The method of claim 32, wherein the molten salt solution comprises KNO3, NaNCh, and AgNC .

34. The method of claim 32 or claim 33, wherein the molten salt solution has a temperature of at least 250 °C.

35. The method of any one of claims 32-34, wherein the ion-exchange processing is for a duration of less than 12 hours.

36. The method of any one of claims 28-35, further comprising wet etching the glassyphase material prior to the ion-exchange processing, wherein the wet etching comprises contacting at least a portion of the glassy-phase material with an etchant.

37. The method of claim 36, wherein the etchant comprises hydrofluoric acid, ammonium bifluoride, sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, potassium hydroxide, or combinations of two or more thereof.

38. The method of any one of claims 28-37, wherein a valley of a surface of the glassyphase material is positioned less than 10 micrometers below a surface of the first surface that is not converted to a glassy-phase material.