Fingerprint-resistant glass substrates

FINGERPRINT-RESISTANT GLASS SUBSTRATES

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of U.S. Patent Application No.

12/625,020, filed November 24, 2009, which claims the benefit of U.S. Provisional Patent Application No. 61/175,909, filed May 6, 2009.

BACKGROUND

[0002] Surfaces for touch screen applications are increasingly in demand.

From both aesthetic and technological standpoints, touch screen surfaces which are resistant to the transfer or smudging of fingerprints are desired. For applications related to hand-held electronic devices, the general requirements for the user- interactive surface include high transmission, low haze, resistance to fingerprint transfer, robustness to repeated use, and non-toxicity. A fingerprint-resistant surface must be resistant to both water and oil transfer when touched by a finger of a user. The wetting characteristics of such a surface are such that the surface is both hydrophobic and oleophobic.

SUMMARY

[0003] A glass substrate having at least one surface with engineered properties that include, but are not limited to, hydrophobicity (i.e., contact angle of water > 90°), oleophobicity (i.e., contact angle of oil > 90°), anti-stick or adherence of particulate or liquid matter found in fingerprints, durability, and transparency (i.e., haze < 10%) is provided. The glass substrate has at least one set of topological features that provides hydrophobic and oleophobic properties.

[0004] Accordingly, one aspect of the disclosure is to provide a glass substrate that is optically transparent and has at least one surface that is finger-print resistant. The glass substrate is resistant to mechanical and chemical abrasion.

[0005] A second aspect of the disclosure is to provide a glass substrate having at least one surface that is hydrophobic and oleophobic. The at least one surface comprises at least one set of topological features an average dimension, wherein the topological features together have a re-entrant geometry that prevents a decrease in contact angle of drops comprising at least one of water and sebaceous oils.

[0006] A third of the disclosure is to provide a method of making a glass substrate having at least one surface that is hydrophobic and oleophobic. The method comprises the steps of: providing a glass substrate; and forming at least one set of topological features on at least one surface of the glass substrate. The at least one set of topological features has topological features of an average dimension, wherein the topological features together have a re-entrant geometry that prevents a decrease in contact angle of drops comprising at least one of water and sebaceous oils.

[0007] These and other aspects, advantages, and salient features will become apparent from the following detailed description, the accompanying drawings, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIGURE Ia is a schematic representation of the Wenzel model of wetting behavior of a fluid droplet on a roughened solid surface;

[0009] FIGURE Ib is a schematic representation of the Cassie-Baxter model of wetting behavior of a fluid droplet on a roughened solid surface;

[0010] FIGURE 2 is a schematic representation of a glass substrate having multiple levels of topography;

[0011] FIGURE 3 is an atomic force microscope image of surface topographic features having dimensions greater than 1 μm;

[0012] FIGURE 4a is a cross-sectional view of the columnar structure of a sputtered SnO₂ film before etching;

[0013] FIGURE 4b is a top view of the columnar structure of a sputtered SnO₂ film before etching; [0014] FIGURE 4c is a top view of the columnar structure of a sputtered

SnO₂ film after etching with concentrated HCl for 5 minutes;

[0015] FIGURE 5a is a top view of the columnar structure of a sputtered ZnO film before etching;

[0016] FIGURE 5b is a top view of the columnar structure of a sputtered ZnO film after etching with 0.1 M HCl for 15 seconds;

[0017] FIGURE 5c is a top view of the columnar structure of a sputtered ZnO film after etching with 0.1M HCl for 45 seconds;

[0018] FIGURE 6a is a schematic representation of second topography voids that act as sites for pinning of fingerprints;

[0019] FIGURE 6b is a schematic representation of Teflon cusps formed to minimize pinning of fingerprints in second topography voids shown in FIG. 6a; and

[0020] FIGURE 7 is plot of projected solid-liquid area fraction as a function of roughness factor.

DETAILED DESCRIPTION

[0021] 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. In addition, whenever a group is described as comprising at least one of a group of elements and combinations thereof, it is understood that the group may comprise, consist essentially of, or consist of any number of those elements recited, either individually or in combination with each other. Similarly, 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.

[0022] Referring to the drawings in general, it will be understood that the illustrations are for the purpose of describing particular embodiments and are not intended to limit the disclosure or appended claims thereto. The drawings are not necessarily to scale, and certain features and views of the drawings may be exaggerated in scale or in schematic in the interest of clarity and conciseness.

[0023] The primary characteristic of an article that resists or repels fingerprints is that the surface of the article must be non-wetting (i.e., the contact angle (CA) between a liquid drop and the surface is greater than 90°) with respect to the liquids that comprise such fingerprints. As used herein, the terms "anti- fingerprint," "anti-fingerprinting," and "fingerprint resistant" refer to the resistance of a surface to the transfer of fluids and other materials found in human fingerprints; the non-wetting properties of a surface with respect to such fluids and materials; the minimization, hiding, or obscuring of human fingerprints on a surface, and combinations thereof. Fingerprints comprise both sebaceous oils (e.g. secreted skin oils, fats, and waxes), debris of dead fat-producing cells, and aqueous components. Combinations and/or mixtures of such materials are also referred to herein as "fingerprint materials." An anti-fingerprinting surface must therefore be resistant to both water and oil transfer when touched by a finger of a user. In one embodiment, the amount of fingerprint materials transferred from a human finger to the fingerprint resistant surfaces of the glass substrates described herein is less than 0.02 mg per touch of a human finger. In another embodiment, less than 0.01 mg per touch of such materials is transferred. In yet another embodiment, less than 0.005 mg per touch of such materials is transferred. The area of the fingerprint resistant surface covered by the droplets transferred per touch is less than 20% and, in one embodiment, less than 10% of the total area of the surface of the glass substrate contacted by a human finger. The wetting characteristics of such a surface are such that that the surface is both hydrophobic (i.e., the contact angle (CA) between water and the glass substrate is greater than 90°) and oleophobic (i.e., the contact angle (CA) between oils and the glass substrate is greater than 90°). [0024] The presence of surface roughness (e.g., protrusions, depressions, grooves, pore, pits, voids, and the like) can alter the contact angle between a given fluid and a flat substrate, and is frequently referred to as the "lotus leaf or "lotus" effect. As described by Quere (Ann. Rev. Mater. Res. 2008, vol. 38, pp. 71-99), the wetting behavior of liquids on a roughened solid surface can be described by either the Wenzel (low contact angle) model or the Cassie-Baxter (high contact angle) model. In the Wenzel model, schematically shown in FIG. Ia, a fluid droplet 120 on a roughened solid surface 110 penetrates free space 114, which can include, but is not necessarily limited to, pits, holes, grooves, pores, voids and the like, on the roughened solid surface 110 and, in some instances, is "pinned" on roughened surface 112. The Wenzel model takes the increase in interface area of roughened solid surface 110 relative to a smooth surface (not shown) into account and predicts that when smooth surfaces are hydrophobic, roughening such surfaces will further increase their hydrophobicity. Conversely, when smooth surfaces are hydrophilic, the Wenzel model predicts that roughening such surfaces will further increase their hydrophilic behavior. In contrast to the Wenzel model, the Cassie-Baxter model (schematically shown in FIG. Ib) predicts that surface roughening always increases the contact angle θy of fluid droplet 120 regardless of whether the smooth solid surface is hydrophilic or hydrophobic. The Cassie-Baxter model describes the case in which gas pockets 130 are formed in free space 114 of roughened solid surface 110 and trapped beneath fluid droplet 120 on a roughened solid surface 130, thus preventing a decrease in contact angle θy and pinning of fluid droplet 120 on roughened solid surface 110. In addition to preventing pinning of fluid droplet 120, the presence of gas pockets 130 also increases contact angle θy of fluid droplet 120. Pressure, such as that applied by a human finger, applied to fluid droplet 120 can cause fluid droplet 120 to penetrate free space 114 and become pinned on roughened solid surface - i.e., fluid droplet 120 transitions from the Cassie-Baxter state (FIG. Ib) to the Wenzel state (FIG. Ia). An anti- fingerprinting surface should, when in contact with a given fluid, provide a lotus leaf effect and maintain droplets in the Cassie-Baxter state, in which gas pockets are trapped beneath fluid droplets on a roughened solid surface and pinning of the fluid droplets is avoided and, to some degree, prevent or retard a decrease in contact angle 9γ and transition to the Wenzel state when pressure is applied to the fluid droplets. [0025] The hyrodphobicity and oleophobicity of surfaces are also related to the surface energy γsv of the solid substrate. The contact angle θy of a surface with a fluid droplet is defined by the equation

COSΘ_Ύ = ^{ΥSV ~ ΥSL}

ΪLV

where By is the contact angle for a flat surface (also known as Young's contact angle), γsv is the surface energy of the solid, γsL is the interface energy between the liquid and solid, and Y_LV is the liquid surface tension. In order for θy > 90°, the term cos θy must be negative, thereby constraining the surface energy γ_Sv to values less than γ_SL- The interface energy between the liquid and solid γsL is typically not known and the contact angle θy is usually increased to greater than 90° (i.e., cos θy <0) in order to minimize the surface energy γsv of the solid and achieve hydrophobicity and/or oleophobicity. For example, traditional non-wetting unroughened or smooth surfaces, including fluorinated materials such as Teflon™ (polytetrafluoro ethane), have surface energies as low as 18 dynes/cm. A Teflon surface is not oleophobic, as routinely studied oils such as oleic acid (Y_LV ~32 dyne/cm) exhibit contact angles on Teflon of about 80°.

[0026] Anti- fingerprinting surfaces that are hydrophobic and oleophobic can be achieved by creating rough surfaces having low surface energy. Accordingly, an optically transparent glass article or substrate (unless otherwise specified, the terms "glass article" and "glass substrate" are equivalent terms and are used interchangeably herein) that has a finger-print resistant surface, and is resistant to mechanical and chemical abrasion is provided. The glass substrate, in various embodiments, has at least one surface with engineered properties that include, but are not limited to, hydrophobicity and oleophobicity. Other properties, including anti-fingerprinting, anti-stick or anti-adherence of particulate matter, mechanical and chemical durability, transparency (e.g., haze < 10%), and the like are also provided in various embodiments. These attributes are achieved by providing at least one surface of the substrate with at least one set of topological features that together have a reentrant geometry that prevents a decrease in contact angle of drops comprising least one of water, sebaceous oils, and fingerprint materials. In some embodiments, the at least one set of topological features has an average dimension in a range from about 50 nm up to about 1 μm. In some embodiments, the attributes listed above are achieved by providing the surface of the glass substrate with a plurality of different sets or levels of topological features that include, but are not limited to, bumps, protrusions, depressions, pits, voids, and the like. The topological features in one set or level of topological features has an average dimension that differs from the average dimensions of the topological features in the other sets or levels. The sets of topological features together form a re-entrant geometry that prevents a decrease in contact angle θy and pinning of drops comprising at least one of water and sebaceous oils.

[0027] A cross sectional view of an example of a glass substrate surface having multiple sets of topographies is schematically shown in FIG. 2. The surface structure shown in FIG. 2 resists material a decrease in contact angle θy and penetration or "pinning" of liquid drops in surface voids, thus providing hydrophobic, oleophobic, anti-adhesive, and anti- fingerprinting properties. Furthermore, the surface structure shown in FIG. 2 serves as a non-limiting example of the type of surface that is capable of providing some measure of the lotus leaf effect. Hydrophobic/oleophobic surface 200 includes a first topography 210, a second topography 220, and a third topography 230.

[0028] First topography 210 comprises a plurality of protrusions 212 and depressions 214. First topography 210 has the largest length scale of the topographies shown in FIG. 2, in which the topological features (here, protrusions 212 and depressions 214) have a first average dimension which, in some embodiments, is less than or equal to 2 μm. In one embodiment, the average dimension of the topological features of first topography 210 is in a range from about 50 nm up to about 300 nm. In other embodiments, the average dimension of the topological features of first topography 210 is in a range from about 1 μm up to about 50 μm. In another embodiment, the average dimension of the topological features of first topography 210 is in a range from about 1 μm up to about 10 μm. First topography 210, in one embodiment, can comprise any etchable inorganic oxide such as, but not limited to, SnO₂, ZnO, ceria, alumina, zirconia, or the like.

[0029] A second or intermediate length scale topography 220 is superimposed on first topography 210. Second topography 220 provides a reentrant geometry that prevents or slows the transition of fluid droplets 120 on a roughened surface from a Cassie-Baxter state (FIG. Ib) to a Wenzel state (FIG. Ia). In a Cassie-Baxter state, fluid drop 120 rests atop protrusions 212 that comprise first topography 210. Features of second topography 220 protrude from first topography 210 at an angle a (also referred to as the "reentrant angle") from the plane of glass substrate 200 and at least partially block entry of fluid drop 120 into free space, formed by depressions 214, between protrusions 212 and thus prevent or slow the transition of the surface of glass substrate 200 to the Wenzel state (FIG. Ia).

[0030] As seen in FIG. 2, second topography 220 can comprise protrusions on the surfaces on the larger protrusions of first topography 210. The average dimension of topological features in second topography 220 is less than the average dimension of first topography 210 and, in some embodiments, is in a range from about 1 nm up to about 1 μm. In other embodiments, the average dimension of second topography 220 is in a range from 1 nm up to about 50 nm. In one embodiment, second topography 220 comprises metals or any etchable inorganic oxide such as, but not limited to, SnO₂, ZnO, ceria, alumina, zirconia, or the like.

[0031] A third or smallest length scale topography 230 has topological features on the scale of a chemical bond (in a range from about 0.7 Angstrom up to about 3 Angstroms (70 - 300 pm). The third topography 230 is wax-like and has a low surface energy derivatization. In some embodiments, third topography 230 is a coating that covers at least a portion of the surface of first and second topography 210, 220 and comprises a low surface energy polymer or an oligomer, such as, but not limited to, Teflon™ or other commercially available fluoropolymers or fluorosilanes such as, but are not limited to Dow Corning 2604, 2624, 2634, DK Optool DSX, Shintesu OPTRON, heptadecafluoro silane (Gelest), FluoroSyl (Cytonix), and the like. To prevent pinning of droplet 120 in voids within second topography 210 upon application of pressure (e.g. pressure applied by a finger), third topography 230 is tailored to form cusps 230 at re-entrant voids or trench walls to minimize pinning, thus providing an additional effective re-entry impeding geometry.

[0032] The topographical features of the first and second length scales can be ordered, disordered, "self-affined" or fractal, or any combination thereof. Irrespective of the actual topological and/or micro-structural nature of the topological textures, certain mean geometric conditions need to be fulfilled for the article surface to be fingerprint resistant, oleophobic, and/or super-oleophobic.

[0033] For oleophobicity, the following requirement must be met between the surface roughness fraction (r/) and the solid-liquid fractional area (J) of the substrate according to the equation:

/ ≤ - '

0.26 r_f

(1)

For super-oleophobicity (contact angle > 150°), therefore, the following requirement must be met between the surface roughness fraction (r/) and the solid-liquid fractional area (J) of the substrate:

0.13

1 + 0.26 r_f

For an intermediate level of oleophobicity - e.g., contact angle greater than 125° - the following requirement between the surface roughness fraction (r_f) and the solid-liquid fractional area (f) of the substrate must be satisfied:

/ ≤ °-⁴³ (3)

1 + r_f cosθ_γ

The relationship between the solid-liquid area fraction / and the roughness factor r/ that is needed to achieve a fingerprint resistant surface is plotted in FIG. 7. For the article to have minimal fingerprint resistance, the texture should be such that the coordinate (f, Xf) falls under the CA=90° curve in FIG. 7. For the surface to exhibit super-oleophobic behavior and/or extremely high fingerprint resistance, the textures on the surface of the substrate need to be such that the /versus r/ co-ordinate falls in the area underneath the CA = 150° curve shown in FIG. 7. The fingerprint resistant surface of the glass substrate described herein has a texture that is defined by the relationship expressed in equation(l), In another embodiment, the texture is defined by the relationship expressed in equation (2) and, in a third embodiment, the texture is defined by the relationship expressed in equation (3).

[0034] For the purpose of optical transparency, the length-scales of the textures should be constrained within a selected range. The length scale constraint also arises due to the fact that fingerprint droplets have a finite size distribution with mean diameter of the order of 2-5 μm. In the anti- fingerprint surface and substrate described herein, the textures have a root mean square (RMS) amplitude of between 1 nm and 2 μm. In one embodiment the RMS amplitude of the textures is between lnm and 500nm and, in another embodiment, between lnm and 300nm. The textures have auto-correlation length scales of between 1 nm and IOnm. In some embodiments, the autocorrelation is between lnm and 1 μm and, in another embodiment, is between 1 nm and 500 nm.

[0035] In order to create negative Laplace pressure that would stop the penetration of the liquid meniscus, especially the oil meniscus, into the space between adjacent asperities, at least 10% of the texture of the second topography has an orientation angle (angle a in FIG. 2) of less than 90° and, in one embodiment, less than less than 75°.

[0036] In some embodiments, the glass substrate is a planar or three dimensional sheet having two major surfaces. At least one major surface of the glass substrate has a plurality of different sets or levels of topological features as described herein. In some embodiments both major surfaces of the substrate have a plurality of levels of topographical features. In other embodiments, a single major surface of the glass substrate has such features. [0037] A method of making a glass substrate having a surface that is hydrophobic and oleophobic is also provided. The method comprises the steps of providing a glass substrate having a surface; and forming at least one set of topological features having topological features of an average dimension on at least one surface of the glass substrate. The topological features together have a re-entrant geometry that prevents a decrease in contact angle of drops comprising at least one of water and sebaceous oils. In one embodiment, a plurality of sets of topological features is formed on the surface of the substrate. Each of the sets has topological features of an average dimension that differs from average dimensions of topological features in the other sets. Together the sets of topological features have a re-entrant geometry that prevents a decrease in contact angle θy and pinning of drops comprising at least one of water and sebaceous oils.

[0038] In various embodiments, the plurality of sets of topological features comprises at least one of first topography 210, second topography 220, and third topography 230, previously described hereinabove.

[0039] In one embodiment, first topography 210 can be formed by sandblasting the surface of the glass substrate 200. In one non-limiting example, the surface of the glass substrate 200 is sandblasted with 50 μm alumina grit for differing amounts of time to achieve desired roughness parameters. The sandblasted surface is then coated with inorganic oxide via deposition methods described herein to achieve first topography 210.

[0040] In another embodiment, first topography 210 is formed by depositing a thin oxide film through a shadow mask onto the surface of glass substrate 200 using physical or chemical vapor deposition methods known in the art. In one embodiment, a shadow mask is placed on a surface of the glass substrate. ZnO is then sputtered onto the glass substrate through a mask, resulting in a first topography 210 that mimics the mask features. FIG. 3, which is an atomic force microscope (AFM) image of the sputtered ZnO surface, shows features of first topography 210. Such features include 25 μm-diameter "bumps" 212 having a height a of approximately 50 nm and a pitch or spacing b of about 55 μm. [0041] Second topography 220 can be formed using those physical (e.g., sputtering, evaporation, laser ablation, or the like) or chemical vapor deposition methods (e.g., CVD, plasma assisted or enhanced CVD, or the like) known in the art. In one embodiment, second topography 220 is achieved by etching a sputtered metal oxide thin film or by anodizing an evaporated metal film. Sputtering parameters (e.g., sputtering pressure and substrate temperature) can be correlated with etching behavior to produce a desired topography. The modified Thornton model of O. Kluth, et al. ("Modified Thornton Model for Magnetron Sputtered Zinc Oxide: Film Structure and Etching Behavior," Thin Solid Films, 2003, vol. 442, pp. 80-85), the contents of which are incorporated by reference herein in their entirety, describes the correlation between sputter parameters (sputter pressure and glass substrate temperature), structural film properties, and etching behavior of RF sputtered films on glass substrates. Appropriate adjustment of sputtering conditions is used to select and form a sputtered columnar or granular morphology that is subsequently etched.

[0042] FIGS. 4a-c and 5a-c are scanning electron microscopy (SEM) images showing two examples of how 10 - 100 nm surface features of second topography 220 are formed by etching. The individual surface features shown in FIGS. 4 and 5 have dimensions of between about 10 and 500 nm. FIGS. 4a-c show the effect of strong etching using concentrated HCl for 5 minutes on a sputtered SnO₂ film having a columnar structure. FIG. 4 includes SEM images of side or cross-sectional (FIG. 4a) and top (FIG. 4b) views of the columnar structure 410 of the SnO₂ film before etching. A microscopic image of a top view of the SnO₂ film after etching to achieve the desired level of roughness and produce second topography 420 is shown in FIG. 4c.

[0043] FIGS. 5a-c show the effect of mild etching upon sputtered ZnO films having a columnar structure similar to that shown for SnO₂ in FIG. 4a. FIG. 5a is a top view of the columnar structure 510 of the ZnO film before etching and FIGS. 5b and 5c are top views of the columnar structure of the sputtered ZnO film after etching for 15 seconds and 45 seconds, respectively, with 0.1 M HCl to produce second topography 520. The roughness of the ZnO films increased with increasing etch time. [0044] The third topography comprises a low surface energy polymer or an oligomer, such as, but not limited to, fluoropolymers or fluorosilanes previously described herein. The third topography is formed following formation of the first and second topography layers. The oligomers or polymer comprising the third topography are deposited onto the surface of the glass substrate 200 by sputtering, spray coating, spin-coating, dip-coating, or the like.

[0045] Teflon adheres well to alkali aluminosilicate glass surfaces, whether or not those surfaces are ion exchanged, and is easy to sputter. Teflon deposition rates are as high as about 7 nm/minute for argon sputtering (50 W, 1 - 5 millitorr conditions). Sputtered Teflon exhibits little change in hydrophobicity when treated with O₂ plasma (5 - 15 min, 200 W); the contact angle for water did not exceed about 100° contact angle. However, O₂ plasma-treatment of sputtered Teflon increases the oleophobicity threefold from 20° to 60°.

[0046] A non-limiting example of a third topography comprising a low surface energy surface of sputtered Teflon is schematically shown in FIGS. 6a and b. FIGS. 6a-b also schematically shows how the re-entrant impeding geometry and pinning of the fingerprint components are mitigated. To prevent adsorbed components of fingerprints from dispersing into and being pinned in voids 610 in the second topography (FIG. 6a) upon application of finger pressure, deposition conditions for sputtering Teflon are tailored to form cusps 620 (FIG. 6b) at re-entrant void (trench) walls 710 to minimize pinning in the voids or trench walls, thus providing an inexpensive effective re-entry impeding geometry. This is achieved by using sputtering conditions known in the art under which the mean free path during deposition is small. In addition, the surface of the glass substrate is cooled to reduce surface migration.

[0047] In one embodiment, the glass substrates described herein are transparent, having a transmittance through that substrate and anti-fingerprint surface of greater than 70%. In some embodiments, the transmittance through the glass substrate and anti-glare surface is greater than 80% and, in other embodiments, greater than 90%. [0048] As used herein, the terms "haze" and "transmission haze" refer to the percentage of transmitted light scattered outside an angular cone of ±4.0° in accordance with ASTM procedure D 1003, the contents of which are incorporated herein by reference in their entirety. For an optically smooth surface, transmission haze is generally close to zero. The anti- fingerprint surface of the glass substrate describe has a haze of less than about 80%. In a second embodiment, the anti-glare surface has a haze of less than 50% and, in a third embodiment, the transmission haze of the anti- fingerprint surface is less than 10%.

[0049] As used herein, the term "gloss" refers 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. The anti- fingerprint surface of the glass substrates described herein has a gloss (i.e.; the amount of light that is specularly reflected from sample relative to a standard at 60) of greater than 60%.

[0050] The combination of different surface topographies as described herein provides, in one embodiment, the surface of the glass substrate with enhanced durability when rubbed with a fabric or other instrument such as, for example, a human finger, or when exposed to chemical abrasion such as attack by acids or bases. Coating durability (also referred to as Crock Resistance) refers to the ability of the coated glass sample to withstand repeated rubbing with a cloth. The Crock Resistance test is meant to mimic the physical contact between garments or fabrics with a touch screen device and to determine the durability of the coating after such treatment.

[0051] A Crockmeter is a standard instrument that is used to determine the

Crock resistance of a surface subjected to such rubbing. The Crockmeter subjects a glass slide to direct contact with a rubbing tip or finger mounted on the end of a weighted arm. The standard finger supplied with the Crockmeter is a 15 mm diameter solid acrylic rod. A clean piece of standard crocking cloth is mounted to this acrylic finger. The finger then rests on the sample with a pressure of 900 g and the arm is moved repeatedly back and forth across the sample in an attempt to observe a change in the durability/crock resistance. The Crockmeter used in the tests described herein is a motorized model that provides a uniform stroke rate of 60 revolutions per minute. The Crockmeter test is described in ASTM test procedure Fl 319-94, entitled "Standard Test Method for Determination of Abrasion and Smudge Resistance of Images Produced from Business Copy Products."

[0052] Crock Resistance or durability of the coatings and surfaces described herein is determined by optical (e.g., haze or transmittance) or chemical (e.g., water and/or oil contact angle) measurements after a specified number of wipes as defined by ASTM test procedure F1319-94, where a wipe is defined as two strokes or one cycle, of the rubbing tip or finger. In one embodiment, the contact angle of oil on the fingerprint resistant surfaces described herein of the substrate is within 20% of its initial value after 50 wipes. In some embodiments, the contact angle of oil on the fingerprint resistant surfaces is within 20% of its initial value after 1000 wipes and, in some embodiments, the contact angle of oil on the fingerprint resistant surfaces is within 20% of its initial value after 5000 wipes. Similarly, the contact angle of water on the surface of the substrate remains within 20% of its initial value after 50 wipes. In other embodiments, the contact angle of water on the surface of the substrate remains within 20% of its initial value 1000 wipes and, in other embodiments, remains within 20% of its initial value after 5000 wipes. The anti- fingerprint surfaces described herein also retains a low level of haze after such repeated wiping. In one embodiment, the glass substrate has a haze of less than 10% after at least 100 wipes as defined by ASTM test procedure F1319-94.

[0053] The contact angle (θy), previously described herein, is frequently used as a metric for assessing anti-fingerprinting oleophobic and hydrophobic properties. As previously discussed, the contact angle is a measure of the degree of wetting between hydrophilic and/or oleophilic fingerprint components and the engineered surface of the glass substrate. The less wetting (i.e., the higher the contact angle), the less adhesion to the surface. For anti-fingerprinting and anti-adhesive properties, the contact angle, in one embodiment, is greater than 90⁰C for both oleophilic and hydrophilic materials. [0054] In one non- limiting example, water (hydrophilic) and oleic acid

(oleophilic) contact angles were measured on alkali alumino silicate glass samples having surfaces with the topographies described herein. Each glass surface was prepared for ZnO sputtering by first subjecting each glass surface to plasma treatment with O₂ plasma at 200 Watts for 5 minutes. ZnO was then deposited on the glass surface by sputtering ZnO targets for 60 minutes using 50 Watts RF power in a 1 millitorr argon chamber. The samples were etched for either 15, 30, 45, or 90 seconds in 0.05 M HCl, and the contact angles for water and oleic acid were then measured. The samples were then dip-coated in a fluorosilane solution comprising EZ-Clean™ (Dow Corning DC2604), followed by another contact angle measurement. Water and oleic contact angles for each sample are listed in Table 1. As seen in Table 1, hydrophilic contact angles measured before coating the textured samples with EZ- clean ("Without EZ-clean" in Table 1) are low, ranging from about 15° (sample D) to slightly less than 30° (sample 1). Following dip coating in EZ clean ("With EZ- clean" in Table 1), the hydrophilic contact angle for each sample was substantially increased to values that are greater than the 90° threshold for hydrophobicity, and in a range from about 131° up to 139°. Similarly, the contact angle for oleic acid measured for each sample exceeded the threshold for oleophobic behavior, and ranged from about 93° up to about 96. The glass surfaces that had been provided with the surfaces having multiple topographies (including the third topography provided by EZ-clean) as described herein exhibit both hydrophobic and oleophobic behavior, as evidenced by the results of the contact angle measurements presented in Table 1.

Table 1. Contact angles of water and oleic acid, expressed in degrees, on alkali alumino silicate glass surfaces sputtered with ZnO.

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[0055] In one embodiment, the glass article comprises, consists essentially of, or consists of a soda lime glass. In another embodiment, the glass article comprises, consists essentially of, or consists of any glass that can be down-drawn, such as, but not limited to, an alkali alumino silicate glass. In one embodiment, the alkali alumino silicate glass comprises, consists essentially of, or consists of: 60-72 mol% SiO₂; 9-16 mol% Al₂O₃; 5-12 mol% B₂O₃; 8-16 mol% Na₂O; and 0-4 mol % K₂O,

, . ₊, ₊. Al₂O₃ (mo/%) + B₂O₃ (mo/%) . . ₊, „ ,. ₊ , wherein the ratio =i — - — — — — — &gt; 1 , where the alkali metal

2_, alkali metal modifiers (mol %) modifiers are alkali metal oxides. In another embodiment, the alkali alumino silicate glass comprises, consists essentially of, or consists of: 61-75 mol% SiO₂; 7-15 mol% Al₂O₃; 0-12 mol% B₂O₃; 9-21 mol% Na₂O; 0-4 mol% K₂O; 0-7 mol% MgO; and 0-3 mol% CaO. In yet another embodiment, the alkali alumino silicate glass comprises, consists essentially of, or consists of: 60-70 mol% SiO₂; 6-14 mol% Al₂O₃; 0-15 mol% B₂O₃; 0-15 mol% Li₂O; 0-20 mol% Na₂O; 0-10 mol% K₂O; 0-8 mol% MgO; 0- 10 mol% CaO; 0-5 mol% ZrO₂; 0-1 mol% SnO₂; 0-1 mol% CeO₂; less than 50 ppm As₂O₃; and less than 50 ppm Sb₂O₃; wherein 12 mol% ≤ Li₂O + Na₂O + K₂O ≤ 20 mol% and 0 mol% ≤ MgO + CaO ≤ 10 mol%. In still another embodiment, the alkali alumino silicate glass comprises, consists essentially of, or consists of: 64-68 mol% SiO₂; 12-16 mol% Na₂O; 8-12 mol% Al₂O₃; 0-3 mol% B₂O₃; 2-5 mol% K₂O; 4-6 mol% MgO; and 0-5 mol% CaO, wherein: 66 mol% ≤ SiO₂ + B₂O₃ + CaO ≤ 69 mol%; Na₂O + K₂O + B₂O₃ + MgO + CaO + SrO &gt; 10 mol%; 5 mol% ≤ MgO + CaO + SrO ≤ 8 mol%; (Na₂O + B₂O₃) - Al₂O₃ ≤ 2 mol%; 2 mol% ≤ Na₂O - Al₂O₃ ≤ 6 mol%; and 4 mol% ≤ (Na₂O + K₂O) - Al₂O₃ ≤ 10 mol%. In a third embodiment, the alkali alumino silicate glass comprises, consists essentially of, or consists of: 50-80 wt% SiO₂; 2-20 wt% Al₂O₃; 0-15 wt% B₂O₃; 1-20 wt% Na₂O; 0-10 wt% Li₂O; 0-10 wt% K₂O; and 0-5 wt% (MgO + CaO + SrO + BaO); 0-3 wt% (SrO + BaO); and 0-5 wt% (ZrO₂ + TiO₂), wherein 0 ≤ (Li₂O + K₂0)/Na₂0 &lt;0.5.

[0056] In one particular embodiment, the alkali alumino silicate glass has the composition: 66.7 mol% SiO₂; 10.5 mol% Al₂O₃; 0.64 mol% B₂O₃; 13.8 mol% Na₂O; 2.06 mol% K₂O; 5.50 mol% MgO; 0.46 mol% CaO; 0.01 mol% ZrO₂; 0.34 mol% As₂O₃; and 0.007 mol% Fe₂O₃. In another particular embodiment, the alkali alumino silicate glass has the composition: 66.4 mol% SiO₂; 10.3 mol% Al₂O₃; 0.60 mol% B₂O₃; 4.0 mol% Na₂O; 2.10 mol% K₂O; 5.76 mol% MgO; 0.58 mol% CaO; 0.01 mol% ZrO₂; 0.21 mol% SnO₂; and 0.007 mol% Fe₂O₃.

[0057] The alkali aluminosilicate glass is, in some embodiments, substantially free of lithium, whereas in other embodiments, the alkali aluminosilicate glass is substantially free of at least one of arsenic, antimony, and barium. In some embodiments, the glass article is down-drawn, using those methods known in the art such as, but not limited to fusion-drawing, slot-drawing, re-drawing, and the like.

[0058] Non-limiting examples of such alkali aluminosilicate glasses are described in U.S. Patent Application No. 11/888,213, by Adam J. Ellison et al, entitled "Down-Drawable, Chemically Strengthened Glass for Cover Plate," filed on July 31, 2007, which claims priority from U.S. Provisional Patent Application 60/930,808, filed on May 22, 2007, and having the same title; U.S. Patent Application No. 12/277,573, by Matthew J. Dejneka et al., entitled "Glasses Having Improved Toughness and Scratch Resistance," filed on November 25, 2008, which claims priority from U.S. Provisional Patent Application 61/004,677, filed on November 29, 2007, and having the same title; U.S. Patent Application No. 12/392,577, by Matthew J. Dejneka et al., entitled "Fining Agents for Silicate Glasses," filed February 25, 2009, which claims priority from U.S. Provisional Patent Application No. 61/067,130, filed February 26, 2008, and having the same title; U.S. Patent Application No. 12/393,241 by Matthew J. Dejneka et al, entitled "Ion-Exchanged, Fast Cooled Glasses," filed February 26, 2009, which claims priority from U.S. Provisional Patent Application No. 61/067,732, filed February 29, 2008. and having the same title; U.S. Patent Application No. 12/537,393, by Kristen L. Barefoot et al., entitled "Strengthened Glass Articles and Methods of Making," filed August 7, 2009, which claims priority from U.S. Provisional Patent Application No. 61/087,324, entitled "Chemically Tempered Cover Glass," filed August 8, 2008; U.S. Provisional Patent Application No. 61/235,767, by Kristen L. Barefoot et al., entitled "Crack and Scratch Resistant Glass and Enclosures Made Therefrom," filed August 21, 2009; and U.S. Provisional Patent Application No. 61/235,762, by Matthew J. Dejneka et al., entitled "Zircon Compatible Glasses for Down Draw," filed August 21, 2009; the contents of which are incorporated herein by reference in their entirety.

[0059] The glass article or substrate is chemically or thermally strengthened before forming the roughened glass substrate surface described herein. In one embodiment, the glass article is strengthened either before or after being cut or separated from a "mother sheet" of glass. The strengthened glass article has strengthened surface layers extending from a first surface and a second surface to a depth of layer below each surface. The strengthened surface layers are under compressive stress, whereas a central region of the glass article is under tension, or tensile stress, so as to balance forces within the glass. In thermal strengthening (also referred to herein as "thermal tempering"), the glass article is heated up to a temperature that is greater than the strain point of the glass but below the softening point of the glass and rapidly cooled to a temperature below the strain point to create strengthened layers at the surfaces of the glass. In another embodiment, the glass article can be strengthened chemically by a process known as ion exchange. In this process, ions in the surface layer of the glass are replaced by - or exchanged with - larger ions having the same valence or oxidation state. In those embodiments in which the glass article comprises, consists essentially of, or consists of an alkali alumino silicate glass, ions in the surface layer of the glass and the larger ions are monovalent alkali metal cations, such as Li⁺ (when present in the glass), Na⁺, K⁺, Rb⁺, and Cs⁺. Alternatively, monovalent cations in the surface layer may be replaced with monovalent cations other than alkali metal cations, such as Ag⁺ or the like.

[0060] Ion exchange processes typically comprise immersing a glass article in a molten salt bath containing the larger ions to be exchanged with the smaller ions in the glass. It will be appreciated by those skilled in the art that parameters for the ion exchange process including, but not limited to, bath composition and temperature, immersion time, the number of immersions of the glass in a salt bath (or baths), use of multiple salt baths, additional steps such as annealing, washing, and the like, are generally determined by the composition of the glass and the desired depth of layer and compressive stress of the glass to be achieved by the strengthening operation. By way of example, ion exchange of alkali metal-containing glasses may be achieved by immersion in at least one molten salt bath containing a salt such as, but not limited to, nitrates, sulfates, and chlorides of the larger alkali metal ion. The temperature of the molten salt bath typically is in a range from about 38O⁰C up to about 45O⁰C, while immersion times range from about 15 minutes up to about 16 hours. However, temperatures and immersion times different from those described above may also be used. Such ion exchange treatments typically result in strengthened alkali alumino silicate glasses having depths of layer ranging from about 10 μm up to at least 50 μm with a compressive stress ranging from about 200 MPa up to about 800 MPa, and a central tension of less than about 100 MPa.

[0061] Non-limiting examples of ion exchange processes are provided in the

U.S. patent applications and provisional patent applications that have been previously referenced hereinabove. Additional non- limiting examples of ion exchange processes in which glass is immersed in multiple ion exchange baths, with washing and/or annealing steps between immersions, are described in U.S. Patent Application No. 12/500,650, by Douglas C. Allan et al, entitled "Glass with Compressive Surface for Consumer Applications," filed July 10, 2009, which claims priority from U.S. Provisional Patent Application No. 61/079,995, filed July 11, 2008, and having the same title, in which glass is strengthened by immersion in multiple, successive, ion exchange treatments in salt baths of different concentrations; and U.S. Patent Application No. 12/510,599, by Christopher M. Lee et al., entitled "Dual Stage Ion Exchange for Chemical Strengthening of Glass," filed July 28, 2009, which claims priority from U.S. Provisional Patent Application No. 61/084,398fϊled July 29, 2008, and having the same title, in which glass is strengthened by ion exchange in a first bath is diluted with an effluent ion, followed by immersion in a second bath having a smaller effluent ion concentration than the first bath. The contents of U.S. Patent Application Nos. 12/500,650 and 12/510,599 are incorporated herein by reference in their entirety.

[0062] The glass substrate described herein can be used as a protective cover for display and touch applications, such as, but not limited to, portable communication and entertainment devices such as telephones, music players, video players, or the like; and as display screens for information-related terminals (IT) (e.g., portable or laptop computers) devices; as well as in other applications.

[0063] While typical embodiments have been set forth for the purpose of illustration, the foregoing description should not be deemed to be a limitation on the scope of the disclosure or appended claims. Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present disclosure or appended claims.