WO2021154620A1

WO2021154620A1 - Laser texturing of glass

Info

Publication number: WO2021154620A1
Application number: PCT/US2021/014833
Authority: WO
Inventors: David August Sniezek Loeber; Barada Kanta Nayak; Michael Yoshiya Nishimoto
Original assignee: Corning Incorporated
Priority date: 2020-01-27
Filing date: 2021-01-25
Publication date: 2021-08-05
Also published as: JP2023511605A; TW202138330A; KR20220134593A; CN115175879A

Abstract

Methods for making and treating glass articles include directing a beam of at least one laser source onto at least a major surface of a glass article such that the beam imparts a plurality of texturing features on the major surface, the plurality of texturing features having a peak-to-valley height H ranging from about 5 nanometers to about 40 nanometers.

Description

LASER TEXTURING OF GLASS

Field

[0001] This application claims the benefit of priority of U.S. Provisional Application Serial No. 62/966,324 filed on January 27, 2020 the contents of which are relied upon and incorporated herein by reference in their entirety as if fully set forth below.

[0002] The present disclosure relates generally to texturing of glass substrates and more particularly to laser texturing of glass substrates.

Background

[0003] Thin glass substrates are commonly utilized in flat panel display (FPD) devices such as liquid crystal display (LCD) and organic light emitting diode (OLED) displays. Substrates used in FPD devices generally have a functional A-side surface on which the thin- film transistors are fabricated and a non-functional backside or B-side surface which opposes the A-side surface. During manufacture of the FPD device, the B-side surface of the glass substrate may come into contact with conveyance and handling equipment of various materials, such as metals, ceramics, polymeric materials and the like. The interaction between the substrate and these materials often results in charging through the triboelectric effect or contact electrification. As a result, charge is transferred to the glass surface and can be accumulated on the substrate. As charge accumulates on the surface of the glass substrate, the surface voltage of the glass substrate also changes.

[0004] Electrostatic charging (ESC) of B-side surfaces of glass substrates used in FPD devices may degrade the performance of the glass substrate and/or damage the glass substrate. For example, electrostatic charging of the B-side surface may cause gate damage to thin film transistor (TFT) devices deposited on the A-side surface of the glass substrate through dielectric breakdown or electric field induced charging. Moreover, charging of the B-side surface of the glass substrate may attract particles, such as dust or other particulate debris, which may damage the glass substrate or degrade the surface quality of the glass substrate. In either circumstance, electrostatic charging of the glass substrate may decrease FPD device manufacturing yields thereby increasing the overall cost of the manufacturing process. [0005] Further, frictional contact between the glass substrate and handling and/or conveyance equipment may cause such equipment to wear, thereby reducing the service life of the equipment. Repair or replacement of worn equipment results in process down-time, decreasing manufacturing yields and increasing the overall costs of the FPD device manufacturing process.

[0006] One method of addressing these issues involves applying a wet etch chemistry to at least the B-side of the glass substrate. An exemplary wet etch chemistry is an aqueous solution comprising NaF and H3PO4. In a typical process, wet etch chemistry solutions are circulated for treatment of multiple glass sheets during which process such solutions ultimately experience degradation and require replacement. In addition, such processes typically involve additional processing steps, substantially large processing footprints, as well as significant investment in safety equipment for handling hazardous byproducts, such as HF. Moreover, wet etch processes are less amenable to adjustments for different glass types or desired surface characteristics without process down-time and/or substantial retrofitting of processing materials or equipment.

[0007] Accordingly, a need exists for glass substrate processing methods that address one or more of these issues.

SUMMARY

[0008] Embodiments disclosed herein include a method of making a glass article. The method includes melting raw materials into molten glass. The method also includes forming the glass article from the molten glass. The glass article includes a first major surface and a second major surface on an opposite side of the glass article as the first major surface. In addition, the method includes directing a beam of at least one laser source onto at least the second major surface of the glass article such that the beam imparts a plurality of texturing features on the second major surface. The plurality of texturing features have a peak-to- valley height H ranging from about 5 nanometers to about 40 nanometers.

[0009] Embodiments disclosed herein also include a method of treating a glass article. The method includes directing a beam of at least one laser source onto at least a major surface of the glass article such that the beam imparts a plurality of texturing features on the major surface. The plurality of texturing features have a peak-to-valley height H ranging from about 5 nanometers to about 40 nanometers.

[0010] Additional features and advantages of the embodiments disclosed herein will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the disclosed embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.

[0011] It is to be understood that both the foregoing general description and the following detailed description present embodiments intended to provide an overview or framework for understanding the nature and character of the claimed embodiments. The accompanying drawings are included to provide further understanding, and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments of the disclosure, and together with the description serve to explain the principles and operations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] FIG. l is a schematic view of an example fusion down draw glass making apparatus and process;

[0013] FIG. 2 is a perspective view of a glass sheet;

[0014] FIG. 3 is a schematic side view of an example laser texturing of fusion drawn glass; [0015] FIG. 4 is a schematic cross-section view of a portion of an example glass sheet that includes a plurality of texturing features; and

[0016] FIG. 5 is a schematic top view of a portion an example glass sheet that includes a plurality of texturing features.

DETAILED DESCRIPTION

[0017] Reference will now be made in detail to the present preferred embodiments of the present disclosure, examples of which are illustrated in the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to refer to the same or like parts. However, this disclosure may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[0018] Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, for example by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0019] Directional terms as used herein - for example up, down, right, left, front, back, top, bottom - are made only with reference to the figures as drawn and are not intended to imply absolute orientation.

[0020] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order, nor that with any apparatus specific orientations be required. Accordingly, where a method claim does not actually recite an order to be followed by its steps, or that any apparatus claim does not actually recite an order or orientation to individual components, or it is not otherwise specifically stated in the claims or description that the steps are to be limited to a specific order, or that a specific order or orientation to components of an apparatus is not recited, it is in no way intended that an order or orientation be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps, operational flow, order of components, or orientation of components; plain meaning derived from grammatical organization or punctuation, and; the number or type of embodiments described in the specification.

[0021] As used herein, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a” component includes aspects having two or more such components, unless the context clearly indicates otherwise.

[0022] As used herein, the term “glass article” refers to an amount of glass, which can be in various processing states, such as a glass ribbon, or portion thereof, and/or a glass sheet, or portion thereof. Embodiments disclosed herein include those in which the glass article comprises a first major surface and an opposing second major surface. In some embodiments, the first major surface can be substantially parallel with the second major surface.

[0023] Shown in FIG. 1 is an exemplary glass manufacturing apparatus 10. In some examples, the glass manufacturing apparatus 10 can comprise a glass melting furnace 12 that can include a melting vessel 14. In addition to melting vessel 14, glass melting furnace 12 can optionally include one or more additional components such as heating elements (e.g., combustion burners or electrodes) that heat raw materials and convert the raw materials into molten glass. In further examples, glass melting furnace 12 may include thermal management devices (e.g., insulation components) that reduce heat lost from a vicinity of the melting vessel. In still further examples, glass melting furnace 12 may include electronic devices and/or electromechanical devices that facilitate melting of the raw materials into a glass melt. Still further, glass melting furnace 12 may include support structures (e.g., support chassis, support member, etc.) or other components.

[0024] Glass melting vessel 14 is typically comprised of refractory material, such as a refractory ceramic material, for example a refractory ceramic material comprising alumina or zirconia. In some examples glass melting vessel 14 may be constructed from refractory ceramic bricks. Specific embodiments of glass melting vessel 14 will be described in more detail below.

[0025] In some examples, the glass melting furnace may be incorporated as a component of a glass manufacturing apparatus to fabricate a glass sheet, for example a glass ribbon of a continuous length. In some examples, the glass melting furnace of the disclosure may be incorporated as a component of a glass manufacturing apparatus comprising a slot draw apparatus, a float bath apparatus, a down-draw apparatus such as a fusion process, an up- draw apparatus, a press-rolling apparatus, a tube drawing apparatus or any other glass manufacturing apparatus that would benefit from the aspects disclosed herein. By way of example, FIG. 1 schematically illustrates glass melting furnace 12 as a component of a fusion down-draw glass manufacturing apparatus 10 for fusion drawing a glass ribbon for subsequent processing into individual glass sheets.

[0026] The glass manufacturing apparatus 10 (e.g., fusion down-draw apparatus 10) can optionally include an upstream glass manufacturing apparatus 16 that is positioned upstream relative to glass melting vessel 14. In some examples, a portion of, or the entire upstream glass manufacturing apparatus 16, may be incorporated as part of the glass melting furnace 12

[0027] As shown in the illustrated example, the upstream glass manufacturing apparatus 16 can include a storage bin 18, a raw material delivery device 20 and a motor 22 connected to the raw material delivery device. Storage bin 18 may be configured to store a quantity of raw materials 24 that can be fed into melting vessel 14 of glass melting furnace 12, as indicated by arrow 26. Raw materials 24 typically comprise one or more glass forming metal oxides and one or more modifying agents. In some examples, raw material delivery device 20 can be powered by motor 22 such that raw material delivery device 20 delivers a predetermined amount of raw materials 24 from the storage bin 18 to melting vessel 14. In further examples, motor 22 can power raw material delivery device 20 to introduce raw materials 24 at a controlled rate based on a level of molten glass sensed downstream from melting vessel 14. Raw materials 24 within melting vessel 14 can thereafter be heated to form molten glass 28.

[0028] Glass manufacturing apparatus 10 can also optionally include a downstream glass manufacturing apparatus 30 positioned downstream relative to glass melting furnace 12. In some examples, a portion of downstream glass manufacturing apparatus 30 may be incorporated as part of glass melting furnace 12. In some instances, first connecting conduit 32 discussed below, or other portions of the downstream glass manufacturing apparatus 30, may be incorporated as part of glass melting furnace 12. Elements of the downstream glass manufacturing apparatus, including first connecting conduit 32, may be formed from a precious metal. Suitable precious metals include platinum group metals selected from the group of metals consisting of platinum, iridium, rhodium, osmium, ruthenium and palladium, or alloys thereof. For example, downstream components of the glass manufacturing apparatus may be formed from a platinum-rhodium alloy including from about 70 to about 90% by weight platinum and about 10% to about 30% by weight rhodium. However, other suitable metals can include molybdenum, palladium, rhenium, tantalum, titanium, tungsten and alloys thereof.

[0029] Downstream glass manufacturing apparatus 30 can include a first conditioning (i.e., processing) vessel, such as fining vessel 34, located downstream from melting vessel 14 and coupled to melting vessel 14 by way of the above-referenced first conecting conduit 32. In some examples, molten glass 28 may be gravity fed from melting vessel 14 to fining vessel 34 by way of first connecting conduit 32. For instance, gravity may cause molten glass 28 to pass through an interior pathway of first connecting conduit 32 from melting vessel 14 to fining vessel 34. It should be understood, however, that other conditioning vessels may be positioned downstream of melting vessel 14, for example between melting vessel 14 and fining vessel 34. In some embodiments, a conditioning vessel may be employed between the melting vessel and the fining vessel wherein molten glass from a primary melting vessel is further heated to continue the melting process, or cooled to a temperature lower than the temperature of the molten glass in the melting vessel before entering the fining vessel.

[0030] Bubbles may be removed from molten glass 28 within fining vessel 34 by various techniques. For example, raw materials 24 may include multivalent compounds (i.e. fining agents) such as tin oxide that, when heated, undergo a chemical reduction reaction and release oxygen. Other suitable fining agents include without limitation arsenic, antimony, iron and cerium. Fining vessel 34 is heated to a temperature greater than the melting vessel temperature, thereby heating the molten glass and the fining agent. Oxygen bubbles produced by the temperature-induced chemical reduction of the fining agent(s) rise through the molten glass within the fining vessel, wherein gases in the molten glass produced in the melting furnace can diffuse or coalesce into the oxygen bubbles produced by the fining agent. The enlarged gas bubbles can then rise to a free surface of the molten glass in the fining vessel and thereafter be vented out of the fining vessel. The oxygen bubbles can further induce mechanical mixing of the molten glass in the fining vessel.

[0031] Downstream glass manufacturing apparatus 30 can further include another conditioning vessel such as a mixing vessel 36 for mixing the molten glass. Mixing vessel 36 may be located downstream from the fining vessel 34. Mixing vessel 36 can be used to provide a homogenous glass melt composition, thereby reducing cords of chemical or thermal inhomogeneity that may otherwise exist within the fined molten glass exiting the fining vessel. As shown, fining vessel 34 may be coupled to mixing vessel 36 by way of a second connecting conduit 38. In some examples, molten glass 28 may be gravity fed from the fining vessel 34 to mixing vessel 36 by way of second connecting conduit 38. For instance, gravity may cause molten glass 28 to pass through an interior pathway of second connecting conduit 38 from fining vessel 34 to mixing vessel 36. It should be noted that while mixing vessel 36 is shown downstream of fining vessel 34, mixing vessel 36 may be positioned upstream from fining vessel 34. In some embodiments, downstream glass manufacturing apparatus 30 may include multiple mixing vessels, for example a mixing vessel upstream from fining vessel 34 and a mixing vessel downstream from fining vessel 34. These multiple mixing vessels may be of the same design, or they may be of different designs.

[0032] Downstream glass manufacturing apparatus 30 can further include another conditioning vessel such as delivery vessel 40 that may be located downstream from mixing vessel 36. Delivery vessel 40 may condition molten glass 28 to be fed into a downstream forming device. For instance, delivery vessel 40 can act as an accumulator and/or flow controller to adjust and/or provide a consistent flow of molten glass 28 to forming body 42 by way of exit conduit 44. As shown, mixing vessel 36 may be coupled to delivery vessel 40 by way of third connecting conduit 46. In some examples, molten glass 28 may be gravity fed from mixing vessel 36 to delivery vessel 40 by way of third connecting conduit 46. For instance, gravity may drive molten glass 28 through an interior pathway of third connecting conduit 46 from mixing vessel 36 to delivery vessel 40.

[0033] Downstream glass manufacturing apparatus 30 can further include forming apparatus 48 comprising the above-referenced forming body 42 and inlet conduit 50. Exit conduit 44 can be positioned to deliver molten glass 28 from delivery vessel 40 to inlet conduit 50 of forming apparatus 48. For example, exit conduit 44 may be nested within and spaced apart from an inner surface of inlet conduit 50, thereby providing a free surface of molten glass positioned between the outer surface of exit conduit 44 and the inner surface of inlet conduit 50. Forming body 42 in a fusion down draw glass making apparatus can comprise a trough 52 positioned in an upper surface of the forming body and converging forming surfaces 54 that converge in a draw direction along a bottom edge 56 of the forming body. Molten glass delivered to the forming body trough via delivery vessel 40, exit conduit 44 and inlet conduit 50 overflows side walls of the trough and descends along the converging forming surfaces 54 as separate flows of molten glass. The separate flows of molten glass join below and along bottom edge 56 to produce a single ribbon of glass 58 that is drawn in a draw or flow direction 60 from bottom edge 56 by applying tension to the glass ribbon, such as by gravity, edge rolls 72 and pulling rolls 82, to control the dimensions of the glass ribbon as the glass cools and a viscosity of the glass increases. Accordingly, glass ribbon 58 goes through a visco-elastic transition and acquires mechanical properties that give the glass ribbon 58 stable dimensional characteristics. Glass ribbon 58 may, in some embodiments, be separated into individual glass sheets 62 by a glass separation apparatus 100 in an elastic region of the glass ribbon. A robot 64 may then transfer the individual glass sheets 62 to a conveyor system using gripping tool 65, whereupon the individual glass sheets may be further processed. [0034] FIG. 2 shows a perspective view of a glass sheet 62 having a first major surface 162, a second major surface 164 extending in a generally parallel direction to the first major surface 162 (on the opposite side of the glass sheet 62 as the first major surface) and an edge surface 166 extending between the first major surface 162 and the second major surface 164 and extending in a generally perpendicular direction to the first and second major surfaces 162, 164.

[0035] FIG. 3 shows a schematic side view of an exemplary embodiment of laser texturing of fusion drawn glass. As shown in FIG. 3, separate flows of molten glass descend along converging forming surfaces 54 as separate flows of molten glass, which join below and along bottom edge 56 of forming body 42 to produce a single ribbon of glass 58 that is drawn in a draw or flow direction 60. As glass ribbon 58 is drawn in draw or flow direction 60, a beam 152 of at least one laser source 150 is directed onto a side of the glass ribbon 58, such as the side intended to be the B-side surface or second major surface 164 of glass sheet 62. [0036] In one embodiment, the beam 152 of the laser source 150 is focused on the surface of the glass ribbon 58. In another embodiment, the beam 152 of the laser source 150 is focused below a surface of the glass ribbon 58, in the thickness of the glass ribbon 58. The laser source 150 is generally operated at a wavelength and power that prevents significant ablation of glass from the glass ribbon 58 and prevents the beam 152 of the laser source 150 from penetrating through the glass ribbon 58. However, in some embodiments, slight ablation of the surface of the glass ribbon 58 may occur while the glass ribbon is in a viscous state without the associated formation of particulate debris from the surface of the glass ribbon 58. In these embodiments, reflow of the glass ribbon 58 following impingement of the laser beam 152 results in the formation of a plurality of texturing features.

[0037] FIG. 4 shows a schematic cross-section view of a portion of an exemplary glass sheet 62 having a first major surface 162 and a second major surface 164 that includes a plurality of texturing features 166. Texturing features 166 extend from the second major surface 164, or B-side surface, of the glass sheet 62. A peak-to-valley height of texturing features 166 is shown in FIG. 4 as H and a center-to-center pitch between adjacent texturing features 166 is shown in FIG. 4 as P. As used herein, “peak-to-valley height” refers to the distance in thickness direction (e.g., a direction normal to at least one of the first or second major surface) between the portion of a texturing feature that is closest to the plane of the glass sheet major surface (e.g., second major surface 164) and the portion of a texturing feature that is farthest from the plane of the glass sheet major surface. As used herein, “center-to-center pitch between adjacent texturing features” refers to the shortest distance between the portions of adjacent texturing features that are farthest from the plane of the glass sheet major surface (e.g., second major surface 164).

[0038] FIG. 5 shows a schematic top view of a portion of an exemplary glass sheet 62 that includes a plurality of texturing features 166. A center-to-center pitch between adjacent texturing features is shown in FIG. 5 as P. The surface area of the portion of glass sheet 62 shown in FIG. 5 is the product of the dimensions X and Y and a density of texturing features 166 within that surface area can be obtained by counting the observed texturing features (shown in FIG. 5 as five texturing features) within the surface area and dividing by the surface area.

[0039] Embodiments disclosed herein include directing a laser beam of at least one laser source onto at least the second major surface of a glass article, such as a glass ribbon, such that the beam imparts a plurality of texturing features on the second major surface, the plurality of texturing features having a peak-to-valley height H ranging from about 5 nanometers to about 40 nanometers, such as from about 10 nanometers to about 35 nanometers, and further such as from about 15 nanometers to about 30 nanometers. [0040] In certain exemplary embodiments, a density of the plurality of texturing features on the second major surface is at least about 0.1 per square micron, such as at least about 0.2 per square micron, and further such as at least about 0.5 per square micron, and yet further such as at least about 1 per square micron, such as from about 0.1 to about 100 per square micron, such as from about 0.2 to about 50 per square micron, and further such as from about 0.5 to about 10 per square micron.

[0041] In certain exemplary embodiments, a center-to-center pitch P between adjacent texturing features on the second major surface ranges from about 0.1 micron to about 20 microns in at least one direction, such as from about 0.2 microns to about 10 microns in at least one direction, and further such as from about 0.5 microns to about 5 microns in at least one direction.

[0042] In certain exemplary embodiments, the surface roughness Ra of the second major surface is at least about 0.5 nanometers, such as at least about 0.6 nanometers, and further such as at least about 0.7 nanometers, such as from about 0.5 nanometers to about 1.0 nanometer, as measured by atomic force microscopy (AFM). Ra is calculated as the arithmetical mean deviation of a surface profile.

[0043] In certain exemplary embodiments, a viscosity of the glass article when directing the laser beam of the at least one laser source onto at least the second major surface of the glass article is less than about 10¹³ Poise (annealing point), such as between about 10⁴ Poise (working point) and about 10¹³ Poise, and further such as between about 10⁷⁶ Poise (softening point) and about 10¹³ Poise.

[0044] In certain exemplary embodiments, a temperature of the glass article when directing the laser beam of the at least one laser source on at least the second major surface of the glass article is at least about 800°C, such as from about 800°C to about 1,000°C.

[0045] In certain exemplary embodiments, a thickness of the glass article between the first major surface and the second major surface is less than or equal to about 0.5 millimeters, such as from about 0.1 millimeter to about 0.5 millimeters and further such as from about 0.2 millimeters to about 0.4 millimeters.

[0046] In certain exemplary embodiments, the laser source comprises a CO2 laser operated to direct a laser beam comprising a power of from about 1 watt to about 5 watts, such as from about 2 watts to about 4 watts. The laser beam can be scanned across a dimension of the glass article, for example a width of the glass ribbon in a direction orthogonal to the draw direction at a scan speed of from about 1 centimeter per second to about 5 centimeters per second, such as from about 2 centimeters per second to about 4 centimeters per second. Scanning of the laser beam can be accomplished, for example, by using galvanometer-driven optics (e.g., mirrors) that direct the laser beam along a predetermined path.

[0047] Operating the laser source within such power ranges and scan speeds onto at least the second major surface of a glass article, such as a glass ribbon having a viscosity of less than about 10¹³ Poise and/or a temperature of at least about 800°C, can enable the formation of texturing feature topography described herein with respect to, for example, one or more of a peak-to-valley height H, density, center-to-center pitch P, or surface roughness Ra.

[0048] Embodiments disclosed herein may be used with a variety of glass compositions. Such compositions may, for example, include a glass composition, such as an alkali free glass composition, comprising 58-65 weight percent (wt%) SiCh, 14-20wt% AI2O3, 8-12wt% B2O3, l-3wt% MgO, 5-10wt% CaO, and 0.5-2wt% SrO. Such compositions may also include a glass composition, such as an alkali free glass composition, comprising 58-65wt% S1O2, 16- 22wt% AI2O3, l-5wt% B2O3, l-4wt% MgO, 2-6wt% CaO, l-4wt% SrO, and 5-10wt% BaO. Such compositions may further include a glass composition, such as an alkali free glass composition, comprising 57-61wt% S1O2, 17-21wt% AI2O3, 5-8wt% B2O3, l-5wt% MgO, 3- 9wt% CaO, 0-6wt% SrO, and 0-7wt% BaO. Such compositions may additionally include a glass composition, such as an alkali containing glass composition, comprising 55-72wt% S1O2, 12-24wt% AI2O3, 10-18wt% Na₂0, 0-10wt% B2O3, 0-5wt% K₂0, 0-5wt% MgO, and 0- 5wt% CaO, which, in certain embodiments, may also include l-5wt% K2O and l-5wt%

MgO.

[0049] Embodiments disclosed herein can result in substantial surface voltage reduction of glass substrates, which can, in turn, enable reduced gate damage to TFT devices deposited on the A-side surface of the glass substrate as well as reduced particulate matter, such as dust or other particulate debris, on the surfaces of glass substrates. In particular, texturing features having the peak-to-valley height H, density, and/or center-to-center pitch P within the ranges of embodiments disclosed herein can enable sufficient electric field variation to effectuate improved surface voltage reduction levels as compared to texturing features having peak-to- valley height H, density, and/or center-to-center pitch P outside of these ranges.

[0050] While the above embodiments have been described with reference to a fusion down draw process, it is to be understood that such embodiments are also applicable to other glass forming processes, such as float processes, slot draw processes, up-draw processes, tube drawing processes, and press-rolling processes.

[0051] It will be apparent to those skilled in the art that various modifications and variations can be made to embodiment of the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present disclosure cover such modifications and variations provided they come within the scope of the appended claims and their equivalents.

Claims

What is claimed is:

1. A method of making a glass article comprising: melting raw materials into molten glass; forming the glass article from the molten glass, the glass article comprising a first major surface and an opposing second major surface; and directing a beam of at least one laser source onto at least the second major surface of the glass article such that the beam imparts a plurality of texturing features on the second major surface, the plurality of texturing features having a peak-to-valley height H ranging from about 5 nanometers to about 40 nanometers.

2. The method of claim 1, wherein a density of the plurality of texturing features on the second major surface is at least about 0.1 per square micron.

3. The method of claim 1, wherein a center-to-center pitch P between adjacent texturing features on the second major surface ranges from about 0.1 micron to about 20 microns in at least one direction.

4. The method of claim 1, wherein a surface roughness Ra of the second major surface is at least about 0.5 nanometers.

5. The method of claim 1, wherein a viscosity of the glass article when directing the beam of the at least one laser source onto at least the second major surface of the glass article is less than about 10¹³ Poise.

6. The method of claim 1, wherein a temperature of the glass article when directing the beam of the at least one laser source on at least the second major surface of the glass article is at least about 800°C.

7. The method of claim 1, wherein the laser source comprises a CO2 laser operated to direct a laser beam comprising a power of from about 1 watt to about 5 watts at a scan speed of from about 1 centimeter per second to about 5 centimeters per second.

8. The method of claim 1, wherein a thickness of the glass article between the first major surface and the second major surface is less than or equal to about 0.5 millimeters.

9. The method of claim 1, wherein the glass substrate comprises an alkali free glass composition comprising 58-65wt% S1O₂, 14-20wt% AI₂O₃, 8-12wt% B₂O₃, l-3wt% MgO, 5-10wt% CaO, and 0.5-2wt% SrO.

10. The method of claim 1, wherein the glass substrate comprises an alkali free glass composition comprising 58-65wt% S1O₂, 16-22wt% AI₂O₃, l-5wt% B₂O₃, l-4wt% MgO, 2-6wt% CaO, l-4wt% SrO, and 5-10wt% BaO.

11. The method of claim 1, wherein the glass substrate comprises an alkali free glass composition comprising 57-6 lwt% S1O₂, 17-21wt% AI₂O₃, 5-8wt% B₂O₃, l-5wt% MgO, 3-9wt% CaO, 0-6wt% SrO, and 0-7wt% BaO.

12. The method of claim 1, wherein the glass substrate comprises a glass composition comprising 55-72wt% S1O2, 12-24wt% AI2O3, 10-18wt% Na₂0, 0-10wt% B2O3, 0-5 wt% K2O, 0-5 wt% MgO, and 0-5 wt% CaO, 1- 5wt% K2O, and l-5wt% MgO.

13. A glass article made by the method of claim 1.

14. An electronic device comprising the glass article of claim 13.

15. A method of treating a glass article comprising: directing a beam of at least one laser source onto a major surface of the glass article such that the beam imparts a plurality of texturing features on the major surface, the plurality of texturing features having a peak-to- valley height H ranging from about 5 nanometers to about 40 nanometers.

16. The method of claim 15, wherein a density of the plurality of texturing features on the major surface is at least about 0.1 per square micron.

17. The method of claim 15, wherein a center-to-center pitch P between adjacent texturing features on the major surface ranges from about 0.1 micron to about 20 microns in at least one direction.

18. The method of claim 15, wherein a surface roughness Ra of the major surface is at least about 0.5 nanometers.

19. The method of claim 15, wherein a viscosity of the glass article when directing the beam of the at least one laser source onto the major surface is less than about 10¹³ Poise.

20. The method of claim 15, wherein a temperature of the glass article when directing the beam of the at least one laser source on the major surface is at least about 800°C.

21. The method of claim 15, wherein the laser source comprises a CO2 laser operated to direct a laser beam comprising a power of from about 1 watt to about 5 watts at a scan speed of from about 1 centimeter per second to about 5 centimeters per second.

22. The method of claim 15, wherein a thickness of the glass article between the major surface and an opposing major surface is less than or equal to about 0.5 millimeters.

23. The method of claim 15, wherein the glass substrate comprises an alkali free glass composition comprising 58-65wt% S1O₂, 14-20wt% AI₂O₃, 8-12wt% B₂O₃, l-3wt% MgO, 5-10wt% CaO, and 0.5-2wt% SrO.

24. The method of claim 15, wherein the glass substrate comprises an alkali free glass composition comprising 58-65wt% S1O₂, 16-22wt% AI₂O₃, l-5wt% B₂O₃, l-4wt% MgO, 2-6wt% CaO, l-4wt% SrO, and 5-10wt% BaO.

25. The method of claim 15, wherein the glass substrate comprises an alkali free glass composition comprising 57-6 lwt% S1O₂, 17-21wt% AI₂O₃, 5-8wt% B₂O₃, l-5wt% MgO, 3-9wt% CaO, 0-6wt% SrO, and 0-7wt% BaO.

26. The method of claim 15, wherein the glass substrate comprises a glass composition comprising 55-72wt% S1O2, 12-24wt% AI2O3, 10-18wt% Na₂0, 0-10wt% B2O3, 0-5 wt% K2O, 0-5 wt% MgO, and 0-5 wt% CaO, 1- 5wt% K2O, and l-5wt% MgO.