WO2022011073A1 - Anti-glare substrate for a display article including a textured region with primary surface features and secondary surface features imparting a surface roughness that increases surface scattering - Google Patents

Anti-glare substrate for a display article including a textured region with primary surface features and secondary surface features imparting a surface roughness that increases surface scattering Download PDF

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Publication number
WO2022011073A1
WO2022011073A1 PCT/US2021/040775 US2021040775W WO2022011073A1 WO 2022011073 A1 WO2022011073 A1 WO 2022011073A1 US 2021040775 W US2021040775 W US 2021040775W WO 2022011073 A1 WO2022011073 A1 WO 2022011073A1
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Prior art keywords
surface features
primary surface
substrate
textured region
primary
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PCT/US2021/040775
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French (fr)
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WO2022011073A9 (en
Inventor
Jiangwei Feng
Corinne Elizabeth ISAAC
Shenping Li
Wageesha Senaratne
William Allen Wood
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Corning Inc
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Corning Inc
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Anticipated expiration legal-status Critical
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00Surface treatment of glass, not in the form of fibres or filaments, by etching
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11Anti-reflection coatings
    • G02B1/113Anti-reflection coatings using inorganic layer materials only
    • G02B1/115Multilayers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11Anti-reflection coatings
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/225Nitrides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02Pretreatment of the material to be coated
    • C23C14/021Cleaning or etching treatments
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04Coating on selected surface areas, e.g. using masks
    • C23C14/042Coating on selected surface areas, e.g. using masks using masks
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02Pretreatment of the material to be coated
    • C23C16/0227Pretreatment of the material to be coated by cleaning or etching
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04Coating on selected surface areas, e.g. using masks
    • C23C16/042Coating on selected surface areas, e.g. using masks using masks
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11Anti-reflection coatings
    • G02B1/118Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14Protective coatings, e.g. hard coatings
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/42Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect
    • G02B27/4205Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect having a diffractive optical element [DOE] contributing to image formation, e.g. whereby modulation transfer function MTF or optical aberrations are relevant
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/42Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect
    • G02B27/4272Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect having plural diffractive elements positioned sequentially along the optical path
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0221Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0268Diffusing elements; Afocal elements characterized by the fabrication or manufacturing method
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00Glasses, glazes or enamels with special properties
    • C03C2204/08Glass having a rough surface
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/70Properties of coatings
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • C03C2218/152Deposition methods from the vapour phase by cvd
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • C03C2218/152Deposition methods from the vapour phase by cvd
    • C03C2218/153Deposition methods from the vapour phase by cvd by plasma-enhanced cvd
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • C03C2218/154Deposition methods from the vapour phase by sputtering
    • C03C2218/155Deposition methods from the vapour phase by sputtering by reactive sputtering
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/30Aspects of methods for coating glass not covered above
    • C03C2218/34Masking
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/101Nanooptics

Definitions

  • ______ (D32630/32632), entitled “TEXTURED REGION OF A SUBSTRATE TO REDUCE SPECULAR REFLECTANCE INCORPORATING SURFACE FEATURES WITH AN ELLIPTICAL PERIMETER OR SEGMENTS THEREOF, AND METHOD OF MAKING THE SAME” and filed on ___; U.S. Patent Application Serial No. ____ (D32647), entitled “DISPLAY ARTICLES WITH DIFFRACTIVE, ANTIGLARE SURFACES AND THIN, DURABLE ANTIREFLECTION COATINGS” and filed on __________; and U.S. Patent Application Serial No.
  • ______ (D32623), entitled “DISPLAY ARTICLES WITH DIFFRACTIVE, ANTIGLARE SURFACES AND THIN, DURABLE ANTIREFLECTION COATINGS” and filed on ____.
  • the entire disclosures of each of the foregoing U.S. patent applications, publications and patent documents are incorporated herein by reference.
  • FIELD OF INVENTION [0003] The disclosure relates to an anti ⁇ glare substrate for display articles where the anti ⁇ glare substrate includes a textured region with primary surface features and secondary surface features imparting a surface roughness that increases surface scattering.
  • BACKGROUND [0004] Substrates transparent to visible light are utilized to cover displays of display articles.
  • Such display articles include smart phones, tablets, televisions, computer monitors, and the like.
  • the displays are often liquid crystal displays, organic light emitting diodes, among others.
  • the substrate protects the display, while the transparency of the substrate allows the user of the device to view the display.
  • the substrate reflecting ambient light, especially specular reflection reduces the ability of the user to view the display through the substrate. Specular reflection in this context is the mirror ⁇ like reflection of ambient light off the substrate.
  • the substrate may reflect visible light reflecting off or emitted by an object in the environment around the device. The visible light reflecting off the substrate reduces the contrast of the light from the display transmitting to the eyes of the user through the substrate.
  • Such methods of texturing i.e., sandblasting and liquid etching
  • sandblasting and liquid etching generate features on the surface with imprecise and unrepeatable geometry (the features provide the texture).
  • the geometry of the textured surface of one substrate formed via sandblasting or liquid etching can never be the same as the geometry of the textured surface of another substrate formed via sandblasting or liquid etching.
  • R a surface roughness
  • Distinctness ⁇ of ⁇ image which more aptly might be referred to as distinctness ⁇ of ⁇ reflected ⁇ image, is a measure of how distinct an image reflecting off the surface appears. The lower the distinctness ⁇ of ⁇ image, the more the textured surface is diffusely reflecting rather than specularly reflecting. Surface features can magnify various pixels of the display, which distorts the image that the user views. Pixel power deviation, also referred to as "sparkle,” is a quantification of such an effect. The lower the pixel power deviation the better.
  • Moiré interference fringes are large scale interference patterns, which, if visible, distort the image that the user sees.
  • the textured surface produces no apparent Moiré interference fringes.
  • Transmission haze is a measure of how much the textured surface is diffusing the visible light that the display emitted upon transmitting through the substrate. The greater the transmission haze, the less sharp the display appears (i.e., lowered apparent resolution).
  • Specular reflection reduction is again a measure of how much of the reflected ambient light off the textured surface is specular. The lower the better.
  • Reflection color artifacts are a sort of chromatic aberration where the textured surface diffracts light upon reflection as a function of wavelength ⁇ meaning that the reflected light, although relatively diffuse, appears segmented by color.
  • a new approach to providing a textured region of the substrate is needed ⁇ one that is reproducible from substrate ⁇ to ⁇ substrate and one that causes the textured surface to reflect ambient light sufficiently diffusely rather than specularly so as to be "antiglare" (e.g., a low distinctness ⁇ of ⁇ image, low specular reflection) but simultaneously also delivers low pixel power deviation, low transmission haze, and low reflection color artifacts.
  • the present disclosure provides a new approach that specifically places primary surface features having a specific geometry throughout a textured region according to a predetermined placement. The primary surface features cause the substrate to reflect rather diffusely and are reproducible from substrate ⁇ to ⁇ substrate because the placement of each primary surface feature is by design.
  • secondary surface features are incorporated into the textured region to increase the surface roughness to within a certain range.
  • the increased surface roughness imparts surface scattering to the textured region, which generally lowers pixel power deviation and specular reflection, and sometimes distinctness of image too.
  • a substrate for a display article comprising: (a) a primary surface; and (b) a textured region on at least a portion of the primary surface; the textured region comprising: (i) primary surface features, each comprising a perimeter parallel to a base ⁇ plane extending through the substrate disposed below the textured region, wherein the perimeter of each of the primary surface features comprises a longest dimension of at least 5 ⁇ m; and (ii) one or more sections each comprising secondary surface features having a surface roughness (R a ) within a range of 5 nm to 100 nm.
  • the substrate of the first aspect wherein the primary surface features form a pattern.
  • the substrate of any one of the first through second aspects the longest dimension of each of the primary surface features is about the same.
  • the substrate of any one of the first through third aspects wherein an arrangement of the surface features reflect a random distribution.
  • the substrate of any one of the first through fourth aspects wherein the perimeter of each primary surface features is elliptical.
  • the substrate of any one of the first through fourth aspects wherein the perimeter of each primary surface features is circular.
  • each primary surface feature provides a surface, and the surface is either concave or convex.
  • the substrate of any one of the first through seventh aspects, wherein the textured region further comprises: a surrounding portion into which the primary surface features are set or out of which the primary surface features project.
  • the substrate of any one of the first through eighth aspects wherein (i) the primary surface features that are adjacent to one another have perimeters that are separated by a distance within a range of 1 ⁇ m to 100 ⁇ m; and (ii) the primary surface features that are adjacent to one another are separated by a center ⁇ to ⁇ center distance within a range of 5 ⁇ m to 150 ⁇ m. [0021] According to a tenth aspect of the present disclosure, the substrate of any one of the first through ninth aspects, wherein each of the primary surface features comprises a change in elevation perpendicular to the base ⁇ plane that is within a range of 0.05 ⁇ m to 0.50 ⁇ m.
  • the substrate of any one of the first through sixth and eighth through tenth aspects wherein (i) each primary surface features provides a surface, and (ii) the secondary surface features are disposed on the surfaces of the primary surface features.
  • the substrate of any one of the first through sixth, ninth, and tenth aspects wherein the textured region further comprises: a surrounding portion into which the primary surface features are set into or out of which the primary surface features project; wherein, each primary surface feature provides a surface, wherein, the secondary surface features are disposed on both the surrounding portion and on the surfaces of the primary surface features, and wherein, the surface roughness at the surfaces of the primary surface features is less than the surface roughness at the surrounding portion.
  • the substrate of any one of the first through sixth, ninth, and tenth aspects further comprises: a surrounding portion into which the primary surface features are set into or out of which the primary surface features project; wherein, the secondary surface features are disposed on the surfaces of the primary surface features but not on the surrounding portion.
  • the substrate of any one of the first through thirteenth aspects wherein the substrate comprises a glass or glass ⁇ ceramic.
  • the substrate of any one of the first through fourteenth aspects wherein (i) the textured region exhibits a transmission haze within a range of 1.5% to 3.5%; (ii) the textured region exhibits a pixel power deviation within a range of 1.5% to 3.5%; (iii) the textured region exhibits a distinctness ⁇ of ⁇ image within a range of 2.% to 5.0%; and (iv) the textured region exhibits a specular reflectance within a range of 5 GU to 20 GU.
  • a method of forming a textured region of a substrate comprising: (i) forming primary surface features into a primary surface of a substrate according to a predetermined positioning of each primary surface feature thus forming a textured region, each primary surface feature comprising a largest dimension parallel to a base ⁇ plane through the substrate disposed below the primary surface of at least 5 ⁇ m; and (ii) forming secondary surface features into one or more sections of the textured region, thereby increasing the surface roughness (R a ) of the one or more sections to within a range of 5 nm to 100 nm.
  • the method of the sixteenth aspect further comprises: determining the positioning of each primary surface feature utilizing a spacing distribution algorithm.
  • forming the primary surface features into the primary surface comprises contacting the primary surface with an etchant while an etching mask is disposed on the primary surface to permit only selective etching of the substrate to form the primary surface features.
  • the method of the eighteenth aspect wherein (i) the etchant comprises hydrofluoric acid and nitric acid; and (ii) the etchant contacts the substrate for a time period within a range of 10 seconds to 60 seconds.
  • the method of any one of the sixteenth through nineteenth aspects further comprising: forming the etching mask by exposing a photorsesist material disposed on the primary surface of the substrate to a curing agent while a lithography mask is disposed on the photoresist material, the lithography mask comprising material and voids through the material to selectively expose portions of the photoresist material to the curing agent, wherein the voids of the lithography mask are positioned according to the predetermined positioning of the primary surface features.
  • the method of any one of the sixteenth through twentieth aspects wherein forming the secondary surface features into one or more sections of the textured region comprises contacting the textured region of the substrate with a second etchant, different than the etchant used to form the primary surface features.
  • the second etchant comprises acetic acid and ammonium fluoride.
  • the method of any one of the sixteenth through twenty ⁇ second aspects wherein (i) forming the primary surface features into the primary surface comprises contacting the primary surface with an etchant while an etching mask is disposed on the primary surface to permit only selective etching of the substrate to form the primary surface features, and (ii) forming the secondary surface features into one or more sections of the textured region comprises contacting the one or more sections of the textured region of the substrate with a second etchant, different than the etchant used to form the primary surface features, while the etching mask used to form the primary surface features remains on the substrate.
  • FIG. 1 is perspective view of a display article, illustrating a substrate with a textured region disposed over a display;
  • FIG. 2 is closer ⁇ up perspective view of area II of FIG. 1, illustrating the textured region of the substrate of FIG. 1 including primary surface features that are arranged in a hexagonal pattern;
  • FIG. 3 is an elevation view of a cross ⁇ section of the substrate of FIG. 1 taken through line III ⁇ III of FIG. 2, illustrating the textured region further including secondary surface features, smaller than the primary surface features, disposed on the textured region including the primary surface features;
  • FIG. 1 is perspective view of a display article, illustrating a substrate with a textured region disposed over a display
  • FIG. 2 is closer ⁇ up perspective view of area II of FIG. 1, illustrating the textured region of the substrate of FIG. 1 including primary surface features that are arranged in a hexagonal pattern
  • FIG. 3 is an elevation view of a cross ⁇ section of the substrate of FIG. 1 taken through line III ⁇ III of FIG. 2, illustrating the textured region
  • FIG. 4 is an overhead view of embodiments of a textured region, illustrating the primary surface features having an elliptical perimeter and projecting from a surrounding portion;
  • FIG. 5 is another overhead view of embodiments of a textured region, illustrating the primary surface features having a hexagonal perimeter that are arranged hexagonally but separated by a distance (wall ⁇ to ⁇ wall) and a center ⁇ to ⁇ center distance;
  • FIG. 6 is a schematic flow chart of a method of forming the textured region of FIG. 1, illustrating steps such as determining the positioning of each primary surface feature using a spacing distribution algorithm;
  • FIG. 4 is an overhead view of embodiments of a textured region, illustrating the primary surface features having an elliptical perimeter and projecting from a surrounding portion;
  • FIG. 5 is another overhead view of embodiments of a textured region, illustrating the primary surface features having a hexagonal perimeter that are arranged hexagonally but separated by a distance (wall ⁇ to ⁇ wall) and a center ⁇ to ⁇ center distance;
  • FIG. 6
  • FIG. 7A pertaining to a modeled Example 1 is a graph that illustrates distinctness ⁇ of ⁇ image generally decreasing as a function of (i) increasing change of elevation (height) of the primary surface features and (ii) increasing sigma value assigned for the secondary surface features, which is a measure of the surface scattering that the secondary surface features impart to the textured region;
  • FIG. 7B pertaining to Example 1, is a graph that illustrates the change in distinctness ⁇ of ⁇ image that the presence of the secondary surface features impart compared to if there were no secondary surface features, as a function of the assigned sigma value and height of the primary surface features;
  • FIG. 7A pertaining to a modeled Example 1
  • FIG. 7B pertaining to Example 1
  • FIG. 7B is a graph that illustrates the change in distinctness ⁇ of ⁇ image that the presence of the secondary surface features impart compared to if there were no secondary surface features, as a function of the assigned sigma value and height of the primary surface features
  • FIG. 7C pertaining to Example 1, is a graph that illustrates the sigma value that imparts the textured region with the minimum distinctness ⁇ of ⁇ image value generally decreases as a function of decreasing height of the primary surface features
  • FIG. 7D pertaining to Example 1
  • FIG. 7E pertaining to Example 1, is a graph that illustrates pixel power deviation generally decreases as a function of increasing sigma value and decreases as a function of decreasing height of the primary surface features
  • FIG. 7E pertaining to Example 1 is a graph that illustrates pixel power deviation generally decreases as a function of increasing sigma value and decreases as a function of decreasing height of the primary surface features
  • FIG. 7F pertaining to Example 1 is a graph that illustrates transmission haze generally increases as a function of increasing sigma values assigned for the secondary surface features
  • FIG. 7G pertaining to Example 1 is a graph that illustrates transmission haze generally increasing as a function of increasing sigma value assigned for the secondary surface features, but only after a threshold minimum sigma value
  • FIG. 8A pertaining to Examples 2A ⁇ 2D, reproduce atomic force microscopy images of secondary surface features with various topographies, a result of varying a composition of an etchant utilized to form the secondary surface features
  • FIG. 8A pertaining to Examples 2A ⁇ 2D, reproduce atomic force microscopy images of secondary surface features with various topographies, a result of varying a composition of an etchant utilized to form the secondary surface features
  • FIG. 8A pertaining to Examples 2A ⁇ 2D, reproduce atomic force microscopy images of secondary surface features with various topographies, a result of varying a composition of an etchant utilized to form
  • FIG. 8B pertaining to Examples 2A ⁇ 2D, is a graph that illustrates transmission haze generally increasing as a function of increasing sigma (surface scattering) value, which were variable as a function of etchant composition;
  • FIG. 9A pertaining to Examples 3A ⁇ 3B, is a graph that illustrates pixel power deviation varying as a function of orientation angle of the textured region (because of the hexagonal perimeter) of the primary surface features, and the presence of the secondary surface features lowering pixel power deviation compared to when no such secondary surface features were present;
  • FIG. 9B pertaining to Examples 3A ⁇ 3B, is a schematic diagram illustrating that orientation angle concerns the angle that an edge of the substrate forms with the display beneath the substrate; [0053] FIG.
  • FIG. 10A pertaining to Examples 4A ⁇ 4H, is a graph that illustrates that the inclusion of the secondary surface features resulted in a lower pixel power deviation and, further, that the resulting pixel power deviation can vary depending on the surface roughness (R a ) that the secondary surface features impart, and thus the composition of the etchant used to form the secondary surface features;
  • FIG. 10B pertaining to Examples 4A ⁇ 4H, is a graph that illustrates that the presence of the secondary surface features did not change measured specular reflectance compared to substrates that did not have the secondary surface features; [0055] FIG.
  • FIG. 10C pertaining to Examples 4A ⁇ 4H, is a graph that illustrates that the presence of the secondary surface features produced a lower distinctness ⁇ of ⁇ image compared to substrates that did not have the secondary surface features
  • FIG. 10D pertaining to Examples 4A ⁇ 4H, is a graph that illustrates that the presence of the secondary surface features produces greater transmission haze compared to substrates that did not have the secondary surface features, and increasingly so as the surface roughness (R a ) that the secondary surface features imparts increases;
  • FIG. 10D pertaining to Examples 4A ⁇ 4H
  • FIG. 11A pertaining to Examples 5A ⁇ 5O, is a graph that illustrates that the presence of secondary surface features resulted in a lower pixel power deviation compared to substrates that did not have the secondary surface features
  • FIG. 11B pertaining to Examples 5A ⁇ 5O, is a graph that illustrates that the presence of secondary surface features resulted in a lower specular reflectance compared to substrates that did not have the secondary surface features
  • FIG. 11C pertaining to Examples 5A ⁇ 5O, is a graph that illustrates that the presence of secondary surface features resulted in a higher distinctness ⁇ of ⁇ image compared to substrates that did not have the secondary surface features
  • FIG. 11A pertaining to Examples 5A ⁇ 5O
  • FIG. 11D pertaining to Examples 5A ⁇ 5O, is a graph that illustrates that the presence of secondary surface features resulted in a higher transmission haze compared to substrates that did not have the secondary surface features;
  • FIG. 12A pertaining to Examples 6A ⁇ 6B, are atomic force microscopy images of the primary surface features and the surrounding portion (left) and the secondary surface features (middle and right), for both when the secondary surface features were disposed only on the primary surface features (top) and when the secondary surface features were disposed over both the primary surface features and the surrounding portion (bottom);
  • FIG. 12A pertaining to Examples 6A ⁇ 6B, are atomic force microscopy images of the primary surface features and the surrounding portion (left) and the secondary surface features (middle and right), for both when the secondary surface features were disposed only on the primary surface features (top) and when the secondary surface features were disposed over both the primary surface features and the surrounding portion (bottom);
  • FIG. 12A pertaining to Examples 6A ⁇ 6B, are atomic force microscopy
  • FIG. 12B pertaining to Examples 6A ⁇ 6B, is a graph illustrating that incorporating the secondary surface features over the entire textured region resulted in a lowed pixel power deviation compared to substrates where the secondary surface features were incorporated only on the primary surface features;
  • FIG. 12C pertaining to Examples 6A ⁇ 6B, is a graph illustrating that incorporating the secondary surface features over the entire textured region resulted in a higher transmission haze compared to substrates that incorporated the secondary surface features only on the primary surface features;
  • FIG. 12C pertaining to Examples 6A ⁇ 6B, is a graph illustrating that incorporating the secondary surface features over the entire textured region resulted in a higher transmission haze compared to substrates that incorporated the secondary surface features only on the primary surface features;
  • FIG. 12D pertaining to Examples 6A ⁇ 6B, is a graph illustrating that incorporating the secondary surface features over the entire textured region did not substantially affect specular reflectance compared to substrates that incorporated the secondary surface features only on the primary surface features;
  • FIG. 12E pertaining to Examples 6A ⁇ 6B, is a graph illustrating that incorporating the secondary surface features over the entire textured region slightly affected specular reflectance compared to substrates that incorporated the secondary surface features only on the primary surface features, and increasingly so as wavelength deviated from about 455 nm;
  • FIG. 12E pertaining to Examples 6A ⁇ 6B, is a graph illustrating that incorporating the secondary surface features over the entire textured region slightly affected specular reflectance compared to substrates that incorporated the secondary surface features only on the primary surface features, and increasingly so as wavelength deviated from about 455 nm;
  • FIG. 13A pertaining to Example 7, are white light interferometer graphs illustrating the topography of the primary surface features and the surrounding portion (top) and the secondary surface features (bottom) disposed at the primary surface features (left) and the surrounding portion (right); and [0067] FIG. 13B, pertaining to Example 7, are atomic force microscopy images of the secondary surface features disposed at a primary surface feature (left) and the surrounding portion (right), illustrating that the secondary surface features at the surrounding portion imparted a higher surface roughness (R a ) than the at the primary surface features (because the surrounding portion was not previously etched and thus more sensitive to the etching that imparted the secondary surface features).
  • R a surface roughness
  • a display article 10 includes a substrate 12.
  • the display article 10 further includes a housing 14 to which the substrate 12 is coupled and a display 16 within the housing 14.
  • the substrate 12 at least partially covers the display 16 such that light that the display 16 emits transmits through the substrate 12.
  • the substrate 12 includes a primary surface 18, a textured region 20 defined on the primary surface 18, and a thickness 22 that the primary surface 18 bounds in part.
  • the primary surface 18 generally faces toward an external environment 24 surrounding the display article 10 and away from the display 16.
  • the display 16 emits visible light that transmits through the thickness 22 of the substrate 12, out the primary surface 18, and into the external environment 24.
  • the textured region 20 includes primary surface features 26.
  • a base ⁇ plane 28 extends through the substrate 12 below the textured region 20.
  • the base ⁇ plane 28 provides a conceptual reference point and is not a structural feature.
  • Each primary surface feature 26 includes a perimeter 30.
  • the perimeter 30 is parallel to the base ⁇ plane 28.
  • the perimeter 30 has a longest dimension 32.
  • the perimeter 30 is hexagonal and thus the longest dimension 32 of the perimeter 30 is the long diagonal of the hexagonal perimeter 30.
  • the longest dimension 32 is parallel to the base ⁇ plane 28 as well.
  • the longest dimension 32 of each primary surface feature 26 is at least 5 ⁇ m.
  • the perimeter 30 can be shaped other than hexagonal. In embodiments, the perimeter 30 of each of the primary surface features 26 is polygonal.
  • the perimeter 30 of each of the primary surface features 26 is elliptical (see, e.g., FIG. 4). In other embodiments, the perimeter 30 of each of the primary surface features 26 is circular.
  • the textured region 20 further includes one or more sections 34 that have secondary surface features 36.
  • the secondary surface features 36 are smaller than the primary surface features 26.
  • the secondary surface features 36 impart a surface roughness to the one or more sections 34 of the textured region 20.
  • the surface roughness imparted is 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, or 100 nm, or within any range bounded by any two of those values (e.g., 5 nm to 100 nm, and so on).
  • surface roughness (R a ) is measured with an atomic force microscope, such as an atomic force microscope controlled by a NanoNavi control station distributed by Seiko Instruments Inc.
  • each of the primary surface features 26 is by design, as opposed to the purely uncontrolled and coincidental placement of surface features via sandblasting or open etching (i.e., etching without a mask that would define the placement of each surface feature). In embodiments, such as those embodiments illustrated at FIG. 2, the primary surface features 26 form a pattern.
  • the positioning of a grouping of the primary surface features 26 repeats at the textured region 20.
  • the embodiments illustrated at FIG. 2 are a hexagonal pattern.
  • the longest dimension 32 of each of the primary surface features 26 is about the same or the same within manufacturing tolerances.
  • the primary surface features 26 do not form a pattern – that is, the arrangement of the surface features reflect a random distribution.
  • the primary surface features 26 can be randomly distributed within certain constraints, such as a center ⁇ to ⁇ center distance 38 that varies but is greater than a minimum value.
  • the longest dimension 32 of each primary surface feature 26 can be aligned not parallel to each other.
  • Each of the primary surface features 26 includes a surface 40 facing the external environment 24.
  • the primary surface 18 of the substrate 12 at the textured region 20 includes all of surfaces 40 that the primary surface features 26 provide.
  • the surface 40 of each primary surface feature 26 is concave. In other embodiments, the surface 40 of each primary surface feature 26 is convex.
  • the surfaces 40 of some primary surface features 26 of the textured region 20 are concave, while the surfaces 40 of other primary surface features 26 of the textured region 20 are convex.
  • the surface 40 of each primary surface feature 26 of the textured region 20 is planar and parallel to the base ⁇ plane 28.
  • the textured region 20 further includes a surrounding portion 42 (see, e.g., FIGS. 4 and 5).
  • the primary surface features 26 project out from the surrounding portion 42 away from the base ⁇ plane 28 and toward the external environment 24.
  • the primary surface features 26 are set into the surrounding portion 42 toward the base ⁇ plane 28 and away from the external environment 24.
  • the elevation 44 see FIG.
  • the textured region 20 may thus have a bi ⁇ modal surface structure – with one or more surfaces (e.g., the surfaces 40 of the primary surface features 26) having one mean elevation (e.g., elevation 46), and one or more surfaces (e.g., the surface provided by the surrounding portion 42) having a second mean elevation (e.g., elevation 44).
  • the perimeters 30 of primary surface features 26 that are adjacent are separated by a distance 48 (e.g., wall ⁇ to ⁇ wall distance).
  • the distance 48 is 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, 50 ⁇ m, 55 ⁇ m, 60 ⁇ m, 65 ⁇ m, 70 ⁇ m, 75 ⁇ m, 80 ⁇ m, 85 ⁇ m, 90 ⁇ m, 95 ⁇ m, or 100 ⁇ m, or within any range bounded by any two of those values (e.g., 25 ⁇ m to 75 ⁇ m, 50 ⁇ m to 60 ⁇ m, 1 ⁇ m to 100 ⁇ m, and so on).
  • primary surface features 26 that are adjacent are separated by a center ⁇ to ⁇ center distance 38 of 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, 50 ⁇ m, 55 ⁇ m, 60 ⁇ m, 65 ⁇ m, 70 ⁇ m, 75 ⁇ m, 80 ⁇ m, 85 ⁇ m, 90 ⁇ m, 95 ⁇ m, 100 ⁇ m, 110 ⁇ m, 120 ⁇ m, 130 ⁇ m, 140 ⁇ m, or 150 ⁇ m, or within any range bounded by any two of those values (e.g., 100 ⁇ m to 150 ⁇ m, 5 ⁇ m to 150 ⁇ m and so on).
  • a center ⁇ to ⁇ center distance 38 of 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 15 ⁇ m
  • Each primary surface feature 26 has a change in elevation 50 perpendicular to the base ⁇ plane 28.
  • the change in elevation 50 is the height of the primary surface feature 26.
  • the change in elevation 50 is the depth of the primary surface feature 26. In embodiments, the change in elevation 50 of each primary surface feature 26 is the same or about the same (varies by 25% or less).
  • the change in elevation 50 of each primary surface feature 26 is 0.05 ⁇ m, 0.10 ⁇ m, 0.15 ⁇ m, 0.20 ⁇ m, 0.25 ⁇ m, 0.30 ⁇ m, 0.35 ⁇ m, 0.40 ⁇ m, 0.45 ⁇ m, or 0.50 ⁇ m, or within any range bounded by any two of those values (e.g., 0.05 ⁇ m to 0.50 ⁇ m, and so on).
  • the change in elevation 50 is the distance between the two elevations.
  • the one or more sections 34 that include the secondary surface features 36 include the surfaces 40 of the primary surface features 26.
  • the secondary surface features 36 are disposed on the surface 40 of the primary surface features 26. In embodiments, the secondary surface features 36 are disposed on the surface 40 of the primary surface features 26 but not the surrounding portion 42. [0077] In embodiments, the one or more sections 34 that include the secondary surface features 36 include the surrounding portion 42 and the surfaces 40 of the primary surface features 26. In other words, in those embodiments, the secondary surface features 36 are disposed on both the surrounding portion 42 and on the surfaces 40 of the primary surface features 26. In embodiments, the section 34 that includes the secondary surface features 36 is coextensive with the textured region 20 meaning that the secondary surface features 36 are disposed throughout the entirety of the textured region 20.
  • the surface roughness (R a ) at the surfaces 40 of the primary surface features 26 is less than the surface roughness at the surrounding portion 42.
  • the parameters of the primary surface features 26, such as the change in elevation 50, longest dimension 32, shape of the perimeter 30, and center ⁇ to ⁇ center distance 38, and the addition of the secondary surface features 36 can be optimized.
  • incorporation of the primary surface features 26 alone would cause the textured region 20 to reflect ambient light with a lower distinctness ⁇ of ⁇ image but transmit light from the display 16 with a higher pixel power deviation and higher transmission haze.
  • the incorporation of the secondary surface features 36 mitigates the negative effect that the primary surface features 26 might have on pixel power deviation.
  • the surface roughness that the secondary surface features 36 impart increases the scattering of the textured region 20. This increased scattering increases the amount of diffuse reflection that the textured region 20 generates upon reflecting ambient light thus further lowering specular reflection and rehabilitating (lowering) the pixel power deviation simultaneously, and distinctness ⁇ of ⁇ image in some instances.
  • the textured region 20 can simultaneously generate low values for all of the specular reflection, distinctness ⁇ of ⁇ image, pixel power deviation, and transmission haze – something that previous methods of created the textured region 20 could not achieve.
  • the designer of the textured region 20 has many more variables with which the designer can work to optimize the textured region 20 for any given application than with previous methods such as sandblasting or open etching.
  • the substrate 12 includes a glass or glass ⁇ ceramic.
  • the substrate 12 is a multi ⁇ component glass composition having about 40 mol % to 80 mol % silica and a balance of one or more other constituents, e.g., alumina, calcium oxide, sodium oxide, boron oxide, etc.
  • the bulk composition of the substrate 12 is selected from the group consisting of aluminosilicate glass, a borosilicate glass, and a phosphosilicate glass. In other implementations, the bulk composition of the substrate 12 is selected from the group consisting of aluminosilicate glass, a borosilicate glass, a phosphosilicate glass, a soda lime glass, an alkali aluminosilicate glass, and an alkali aluminoborosilicate glass. In further implementations, the substrate 12 is a glass ⁇ based substrate, including, but not limited to, glass ⁇ ceramic materials that comprise a glass component at about 90% or greater by weight and a ceramic component.
  • the substrate 12 can be a polymer material, with durability and mechanical properties suitable for the development and retention of the textured region 20.
  • the substrate 12 has a bulk composition that comprises an alkali aluminosilicate glass that comprises alumina, at least one alkali metal and, in some embodiments, greater than 50 mol % SiO 2 , in other embodiments, at least 58 mol % SiO 2 , and in still other embodiments, at least 60 mol % SiO 2 , wherein the ratio (Al 2 O 3 (mol%) + B 2 O 3 (mol%)) / ⁇ alkali metal modifiers (mol%) > 1, where the modifiers are alkali metal oxides.
  • This glass in particular embodiments, comprises, consists essentially of, or consists of: about 58 mol % to about 72 mol % SiO 2 ; about 9 mol % to about 17 mol % Al 2 O 3 ; about 2 mol % to about 12 mol % B 2 O 3 ; about 8 mol % to about 16 mol % Na 2 O; and 0 mol % to about 4 mol % K 2 O, wherein the ratio (Al 2 O 3 (mol%) + B 2 O 3 (mol%)) / ⁇ alkali metal modifiers (mol%) > 1, where the modifiers are alkali metal oxides.
  • the substrate 12 has a bulk composition that comprises an alkali aluminosilicate glass comprising, consisting essentially of, or consisting of: about 61 mol % to about 75 mol % SiO 2 ; about 7 mol % to about 15 mol % Al 2 O 3 ; 0 mol % to about 12 mol % B 2 O 3 ; about 9 mol % to about 21 mol % Na 2 O; 0 mol % to about 4 mol % K 2 O; 0 mol % to about 7 mol % MgO; and 0 mol % to about 3 mol % CaO.
  • an alkali aluminosilicate glass comprising, consisting essentially of, or consisting of: about 61 mol % to about 75 mol % SiO 2 ; about 7 mol % to about 15 mol % Al 2 O 3 ; 0 mol % to about 12 mol % B 2 O 3 ; about 9 mol % to about
  • the substrate 12 has a bulk composition that comprises an alkali aluminosilicate glass comprising, consisting essentially of, or consisting of: about 60 mol % to about 70 mol % SiO 2 ; about 6 mol % to about 14 mol % Al 2 O 3 ; 0 mol % to about 15 mol % B 2 O 3 ; 0 mol % to about 15 mol % Li 2 O; 0 mol % to about 20 mol % Na 2 O; 0 mol % to about 10 mol % K 2 O; 0 mol % to about 8 mol % MgO; 0 mol % to about 10 mol % CaO; 0 mol % to about 5 mol % ZrO 2 ; 0 mol % to about 1 mol % SnO 2 ; 0 mol % to about 1 mol % CeO 2 ; less than about 50 ppm As 2 O 3 ; and less than about 50 ppm As
  • the substrate 12 has a bulk composition that comprises an alkali aluminosilicate glass comprising, consisting essentially of, or consisting of: about 64 mol % to about 68 mol % SiO 2 ; about 12 mol % to about 16 mol % Na 2 O; about 8 mol % to about 12 mol % Al 2 O 3 ; 0 mol % to about 3 mol % B 2 O 3 ; about 2 mol % to about 5 mol % K 2 O; about 4 mol % to about 6 mol % MgO; and 0 mol % to about 5 mol % CaO, wherein: 66 mol % ⁇ SiO 2 +B 2 O 3 +CaO ⁇ 69 mol %; Na 2 O+K 2 O+B 2 O 3 +MgO+CaO+SrO>10 mol %; 5 mol % ⁇ MgO+CaO+SrO ⁇ 8 mol %; (
  • the substrate 12 has a bulk composition that comprises SiO 2 , Al 2 O 3 , P 2 O 5 , and at least one alkali metal oxide (R 2 O), wherein 0.75>[(P 2 O 5 (mol %)+R 2 O (mol %))/M 2 O 3 (mol %)] ⁇ 1.2, where M 2 O 3 ⁇ Al 2 O 3 +B 2 O 3 .
  • R 2 O alkali metal oxide
  • [(P 2 O 5 (mol %)+R 2 O (mol %))/M 2 O 3 (mol %)] 1 and, in embodiments, the glass does not include B 2 O 3 and M 2 O 3 ⁇ Al 2 O 3 .
  • the substrate 12 comprises, in embodiments: about 40 to about 70 mol % SiO 2 ; 0 to about 28 mol % B 2 O 3 ; about 0 to about 28 mol % Al 2 O 3 ; about 1 to about 14 mol % P 2 O 5 ; and about 12 to about 16 mol % R 2 O.
  • the glass substrate comprises: about 40 to about 64 mol % SiO 2 ; 0 to about 8 mol % B 2 O 3 ; about 16 to about 28 mol % Al 2 O 3 ; about 2 to about 12 mol % P 2 O 5 ; and about 12 to about 16 mol % R 2 O.
  • the substrate 12 may further comprise at least one alkaline earth metal oxide such as, but not limited to, MgO or CaO.
  • the substrate 12 has a bulk composition that is substantially free of lithium; i.e., the glass comprises less than 1 mol % Li 2 O and, in other embodiments, less than 0.1 mol % Li 2 O and, in other embodiments, 0.01 mol % Li 2 O, and in still other embodiments, 0 mol % Li 2 O.
  • such glasses are free of at least one of arsenic, antimony, and barium; i.e., the glass comprises less than 1 mol % and, in other embodiments, less than 0.1 mol %, and in still other embodiments, 0 mol % of As 2 O 3 , Sb 2 O 3 , and/or BaO.
  • the substrate 12 has a bulk composition that comprises, consists essentially of or consists of a glass composition, such as Corning ® Eagle XG ® glass, Corning ® Gorilla ® glass, Corning ® Gorilla ® Glass 2, Corning ® Gorilla ® Glass 3, Corning ® Gorilla ® Glass 4, or Corning ® Gorilla ® Glass 5.
  • the substrate 12 has an ion ⁇ exchangeable glass composition that is strengthened by either chemical or thermal means that are known in the art.
  • the substrate 12 is chemically strengthened by ion exchange.
  • metal ions at or near the primary surface 18 of the substrate 12 are exchanged for larger metal ions having the same valence as the metal ions in the substrate 12.
  • the exchange is generally carried out by contacting the substrate 12 with an ion exchange medium, such as, for example, a molten salt bath that contains the larger metal ions.
  • the metal ions are typically monovalent metal ions, such as, for example, alkali metal ions.
  • chemical strengthening of a substrate 12 that contains sodium ions by ion exchange is accomplished by immersing the substrate 12 in an ion exchange bath comprising a molten potassium salt, such as potassium nitrate (KNO 3 ) or the like.
  • a molten potassium salt such as potassium nitrate (KNO 3 ) or the like.
  • the ions in the surface layer of the substrate 12 contiguous with the primary surface 18 and the larger ions are monovalent alkali metal cations, such as Li + (when present in the glass), Na + , K + , Rb + , and Cs + .
  • monovalent cations in the surface layer of the substrate 12 may be replaced with monovalent cations other than alkali metal cations, such as Ag + or the like.
  • the replacement of small metal ions by larger metal ions in the ion exchange process creates a compressive stress region in the substrate 12 that extends from the primary surface 18 to a depth (referred to as the “depth of layer”) that is under compressive stress.
  • This compressive stress of the substrate 12 is balanced by a tensile stress (also referred to as “central tension”) within the interior of the substrate 12.
  • the primary surface 18 of the substrate 12 described herein when strengthened by ion exchange, has a compressive stress of at least 350 MPa, and the region under compressive stress extends to a depth, i.e., depth of layer, of at least 15 ⁇ m below the primary surface 18 into the thickness 22.
  • Ion exchange processes are typically carried out by immersing the substrate 12 in a molten salt bath containing the larger ions to be exchanged with the smaller ions in the glass.
  • 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 as a result of the strengthening operation.
  • ion exchange of alkali metal ⁇ containing glasses may be achieved by immersion in at least one molten bath containing a salt, such as, but not limited to, nitrates, sulfates, and chlorides, of the larger alkali metal ion.
  • a salt such as, but not limited to, nitrates, sulfates, and chlorides
  • the temperature of the molten salt bath typically is in a range from about 380°C up to about 450°C, 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 when employed with a substrate 12 having an alkali aluminosilicate glass composition, result in a compressive stress region having a depth (depth of layer) ranging from about 5 ⁇ m up to at least 50 ⁇ m, with a compressive stress ranging from about 200 MPa up to about 800 MPa, and a central tension of less than about 100 MPa.
  • a depth depth of layer
  • the etching processes that can be employed to create the textured region 20 of the substrate 12 can remove alkali metal ions from the substrate 12 that would otherwise be replaced by a larger alkali metal ion during an ion exchange process, a preference exists for developing the compressive stress region in the display article 10 after the formation and development of the textured region 20.
  • the display article 10 exhibits a pixel power deviation (“PPD”).
  • PPD pixel power deviation
  • the PPD measurement system includes: a pixelated source comprising a plurality of pixels (e.g., a Lenovo Z50 140 ppi laptop), wherein each of the plurality of pixels has referenced indices i and j; and an imaging system optically disposed along an optical path originating from the pixelated source.
  • the imaging system comprises: an imaging device disposed along the optical path and having a pixelated sensitive area comprising a second plurality of pixels, wherein each of the second plurality of pixels is referenced with indices m and n; and a diaphragm disposed on the optical path between the pixelated source and the imaging device, wherein the diaphragm has an adjustable collection angle for an image originating in the pixelated source.
  • the image processing calculation includes: acquiring a pixelated image of the transparent sample, the pixelated image comprising a plurality of pixels; determining boundaries between adjacent pixels in the pixelated image; integrating within the boundaries to obtain an integrated energy for each source pixel in the pixelated image; and calculating a standard deviation of the integrated energy for each source pixel, wherein the standard deviation is the power per pixel dispersion.
  • PPI pixels per inch
  • the display article 10 exhibits a PPD of 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.25%, 2.5%, 2.75%, 3.0%, 3.25%, 3.5%, 3.75%, 4.0%, 4.25%, 4.5%, 4.75%, 5.0%, 5.5%, 6.0%, 6.5%, or within any range bounded by any two of those values (e.g., 0.8% to 2.0%, 0.9% to 2.25%, 2.0% to 5.0%, 4.0% to 6.0%, and so on). In embodiments, the display article 10 exhibits a PPD of less than 4.0%, less than 4.0% ⁇ less than 3.0% ⁇ or less than 2.0%.
  • the substrate 12 exhibits a distinctness ⁇ of ⁇ image (“DOI”).
  • DOE is equal to 100*(R S ⁇ R 0.3 ⁇ )/R S , where R S is the specular reflectance flux measured from incident light (at 20 ⁇ from normal) directed onto the textured region 20, and R 0.3 is the reflectance flux measured from the same incident light at 0.3 ⁇ from the specular reflectance flux, R S .
  • DOI values and measurements reported in this disclosure are obtained according to the ASTM D5767 ⁇ 18, entitled “Standard Test Method for Instrumental Measurement of Distinctness ⁇ of ⁇ Image (DOI) Gloss of Coated Surfaces using a Rhopoint IQ Gloss Haze & DOI Meter” (Rhopoint Instruments Ltd.).
  • the values are reported here as “coupled” meaning that the sample is coupled with index matching fluid to the back ⁇ side surface of the substrate during the measurement to reduce backside reflections.
  • the substrate 12 exhibits a distinctness ⁇ of ⁇ image (“DOI”) of 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 96%, 97%, 98%, 99%, or 99.9%, or within any range bounded by any two of those values (e.g., 20% to 40%, 10% to 96%, 35% to 60%, and so on).
  • DOI distinctness ⁇ of ⁇ image
  • transmission haze refers to the percentage of transmitted light scattered outside an angular cone of about ⁇ 2.5° in accordance with ASTM D1003, entitled “Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics,” the contents of which are incorporated by reference herein in their entirety. Note that although the title of ASTM D1003 refers to plastics, the standard has been applied to substrates comprising a glass material as well. For an optically smooth surface, transmission haze is generally close to zero. In embodiments, the substrate 12 exhibits a transmission haze of 0.7%, 0.8%, 0.9%.
  • the substrate 12 exhibits a specular reflectance of 1 GU, 2 GU, 3 GU, 4 GU, 5 GU, 10 GU, 15 GU, 20 GU, 25 GU, 30 GU, 40 GU, 50 GU, 60 GU, 70 GU, 80 GU, or within any range bounded by any two of those values (e.g., 1 GU to 3 GU, 5 GU to 30 GU, 50 GU to 80 GU, and so on).
  • the substrate 12 exhibits a specular reflectance that is less than less than 25 GU less than 20 GU, less than 15 GU, less than 10 GU, less than 5 GU, or less than 2 GU.
  • Specular reflectance here, noted as “c ⁇ Rspec” “or “coupled Rspec” in the Examples that follow, refers to the value obtained in gloss units (GU) using a Rhopoint IQ goniophotometer. The values are indicative of how much specular reflection is measured when the sample is optically coupled to a perfect absorber. A value of 100 GU means 4.91% specular reflection from a polished flat black glass surface of refractive index 1.567 at 20 degrees angle of incidence. [0095] Referring now to FIGS.
  • a method 100 of forming the textured region 20 is herein disclosed.
  • the method 100 includes forming the primary surface features 26 into the primary surface 18 of the substrate 12 according to a predetermined positioning of each primary surface feature 26.
  • the step 102 at least for the moment, forms the textured region 20.
  • the method 100 further includes determining the positioning of each primary surface feature 26 utilizing a spacing distribution algorithm.
  • Example spacing distribution algorithms include Poisson disk sampling, maxi ⁇ min spacing, and hard ⁇ sphere distribution. For example, Poisson disk sampling inserts a first object (e.g., a point or a circle with a diameter) into an area of a plane.
  • the algorithm inserts a second object within the area, placing the center at a random point within the area. If the placement of the second object satisfies the minimum center ⁇ to ⁇ center distance from the first object, then the second object stays in the area. The algorithm then repeats this process until no more such objects can be placed within the area that satisfies the minimum center ⁇ to ⁇ center distance.
  • the result is a random distribution, but specific placement, of the objects. From the random distribution but specific placement of the objects, the positioning of the primary surface features 26 are determined. For example, if the objects positioned via the spacing distribution algorithm are points, then the points can be the center of circles with a certain diameter, or the center of hexagons with certain geometry.
  • the points are triangulated, inellipses formed in the triangles, and then the triangulations and points are removed leaving ellipses, which can be shape of the primary surface features 26.
  • the step of 102 forming the primary surface features 26 into the primary surface 18 includes contacting the primary surface 18 with an etchant while an etching mask is disposed on the primary surface 18 to permit only selective etching of the substrate 12 to form the primary surface features 26.
  • the etching mask includes voids that allow the etchant to remove material from the primary surface 18 of the substrate 12 and, outside of the voids, the etching mask prevents the etchant from contacting the primary surface 18 of the substrate 12.
  • the voids allow the etchant to remove material and thereby to create the primary surface features 26 set into the surrounding portion 42, which the etching mask protects from the etchant.
  • the voids allow the etchant to remove material of the substrate 12 where the surrounding portion 42 is to be but not where the primary surface features 26 are to be, resulting in the primary surface features 26 projecting from the surrounding portion 42.
  • the etching mask incorporates the predetermined positioning of each primary surface feature 26 as either a positive or negative.
  • the etchant includes one or more of hydrofluoric acid and nitric acid. In embodiments, the etchant includes both hydrofluoric acid and nitric acid.
  • the etchant can be sprayed onto the substrate 12 while the etching mask is on the substrate 12.
  • the substrate 12 with the etching mask can be dipped into a vessel containing the etchant.
  • the etchant contacts the substrate 12 for a time period of 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, or 60 seconds, or within any range bounded by any two of those values (e.g., 10 seconds to 60 seconds, and so on).
  • the substrate 12 is rinsed in deionized water and dried. The longer the period of time that the etchant contacts the substrate 12, the deeper the etchant etches into the substrate 12 and thus the greater the change in elevation 50 of the primary surface features 26.
  • the method 100 further includes forming the etching mask by exposing a photoresist material disposed on the primary surface 18 of the substrate 12 to a curing agent while a lithography mask is disposed on the photoresist material.
  • the thickness of the photoresist material can vary from about 3 ⁇ m to about 20 ⁇ m depending on how the photoresist material is added to the primary surface 18 of the substrate 12.
  • the photoresist material can be added via spin coating ( ⁇ 3 ⁇ m thickness), screen coating ( ⁇ 15 ⁇ m thickness), or as a dry film ( ⁇ 20 ⁇ m thickness).
  • the lithography mask includes material and voids through the material to selectively expose portions of the photoresist material to the curing agent.
  • the voids of the lithography mask are positioned according to the predetermined positioning of the primary surface features 26, either as a positive or negative.
  • the placement of each of the primary surface features 26 is determined, such as with the spacing distribution algorithm and the lithography mask incorporates that determined placement.
  • the lithography mask then allows selective curing of the etching mask, which then incorporates that predetermined placement of the primary surface features 26.
  • the etching mask allows for selective etching of the substrate 12, which translates the determined placement of the primary surface features 26 onto the primary surface 18 of the substrate 12 as the textured region 20.
  • the method 100 further includes forming the secondary surface features 36 into the one or more sections 34 of the textured region 20.
  • This step 108 increases the surface roughness (R a ) at the one or more sections 34 to within the range of 5 nm to 100 nm.
  • the step 108 of forming the secondary surface features 36 into one or more sections 34 of the textured region 20 comprises contacting the one or more sections 34 of the textured region 20 of the substrate 12 with a second etchant.
  • the second etchant is different than the etchant that was utilized to etch the primary surface features 26 into the primary surface 18 of the substrate 12.
  • the second etchant includes acetic acid and ammonium fluoride.
  • the second etchant includes (in wt%): 85 to 98 acetic acid, 0.5 to 7.5 ammonium fluoride, and 0 to 11 water.
  • the water can be deionized water.
  • the second etchant contacts the one or more sections 34 for a time period within a range of 15 seconds to 5 minutes.
  • the second etchant contacts the one or more sections 34 while the etching mask used to form the primary surface features 26 remains on the substrate 12.
  • the method 100 is scalable and low ⁇ cost. In addition, the method 100 is repeatable and is able to reproduce the textured region 20 with the essentially the same geometry from substrate 12 to substrate 12. That is different than the previous methods, such as sand ⁇ blasting or open etching, where the geometry of the textured region 20 varied from one substrate 12 to the next.
  • Example 1 – Example 1 is computer modeling that explores the impact of the second surface features.
  • Example 1 assumes that the textured region is as illustrated in FIGS. 2 and 3, with primary surface features arranged in a hexagonal pattern.
  • Each primary surface feature has a hexagonal perimeter and an aspheric surface facing the external environment.
  • Each aspheric surface is governed by the equation: ⁇ where z(r) is the sag – the z ⁇ component of the displacement of the surface from the vertex, at the distance from z axis.
  • the z ⁇ axis is perpendicular to the base ⁇ plane.
  • the a 0 , a 4 , a 6 are all coefficients that describe the deviation of the surface from the axially symmetric quadric surface specified by R and ⁇ . If the coefficients are all zero, which they are assumed to be here, then R is the radius of curvature and ⁇ is the conic constant, as measured at the vertex. When the change in elevation of the surface along the z ⁇ axis is a negative value, then the surface of the primary surface features are concave. In contrast, when the change in elevation of surface of the primary surface features along the z ⁇ axis is positive, then the surface of the primary surface features is convex.
  • Example 1 further assumes that the secondary surface features generate a light scattering distribution that can be described by the Gaussian scattering function: ⁇ ⁇ ⁇ where, ⁇ is the angle (degree) from the specular direction, I( ⁇ ) is radiance in the ⁇ direction, I 0 is radiance in the specular direction, and ⁇ (sigma) is the standard deviation (or scattering factor) of the Gaussian distribution, in degree. As ⁇ increases, the scattering angle increases.
  • FIG. 7A reproduces a graph of the calculations of the model pertaining to distinctness ⁇ of ⁇ image. As the graph reveals, increasing change in elevation (i.e., height or depth) of the primary surface features decreases distinctness ⁇ of ⁇ image.
  • FIG. 7B reproduces a graph illustrating the difference the presence of secondary surface features on the primary surface features makes for decreasing distinctness ⁇ of ⁇ image compared to if the secondary surface features were absent.
  • the presence of the secondary surface features further decreases the distinctness ⁇ of ⁇ image, compared to if no secondary surface features were present, for all heights of the primary surface features from ⁇ 0.24 ⁇ m to + 0.24 ⁇ m.
  • the presence of the secondary surfaces features decreases the distinctness ⁇ of ⁇ image by a maximum of ⁇ 25% when the height of the primary surface features is ⁇ 0.18 ⁇ m, compared to if no secondary surface features were present.
  • 0.41 degrees
  • the graph reproduced at FIG. 7C reveals the optimum value for ⁇ , to minimize distinctness ⁇ of ⁇ image, as a function of change in elevation (height) of the primary surface features.
  • FIGS. 7D and 7E each reproduce a graph of the calculations. The graphs reveals that, as the height of the primary surface features increases, the pixel power deviation increases. However, as the value for ⁇ provided by the secondary surface features increases, for any given height of the primary surface features, the pixel power deviation decreases.
  • the secondary surface features cause scattering that evens the angular and spatial distributions of the light transmitting through the primary surface features and thus reduces the pixel power deviation.
  • the effect that the secondary surface features have on reducing pixel power deviation becomes greater as the height of the primary surface features increases.
  • the presence of the secondary surface features on the primary surface features introduces surface scattering that can reduce distinctness ⁇ of ⁇ image (for a given range of heights of the primary surface features) and generally reduces pixel power deviation.
  • the modeling software calculated transmission haze as a function of the height of the primary surface features and ⁇ value.
  • FIGS. 7F and 7G each reproduce a graph of the calculations. The graph of FIG.
  • the transmission haze is only 20%, which may be acceptable for a given application.
  • the ⁇ value is configured to be right below 0.35, the affect that the secondary features have on decreasing distinctness ⁇ of ⁇ image and pixel power deviation does not simultaneously cause an increase in transmission haze.
  • the calculated distinctness ⁇ of ⁇ image is ⁇ 74%
  • the pixel power deviation is ⁇ 2.5%
  • the transmission haze is ⁇ 1%.
  • the calculated distinctness ⁇ of ⁇ image is ⁇ 64%
  • the pixel power deviation is ⁇ 3.5%
  • the transmission haze is ⁇ 0%.
  • the calculated distinctness ⁇ of ⁇ image is ⁇ 85%
  • the pixel power deviation is ⁇ 2%
  • the transmission haze is ⁇ 0%.
  • the calculated distinctness ⁇ of ⁇ image is ⁇ 73%
  • the pixel power deviation is ⁇ 2.5%
  • the transmission haze is ⁇ 0%.
  • NH 4 F ammonium fluoride
  • Each etchant composition contacted the primary surface of the glass substrate for a time period of 2 minutes.
  • the surface roughness was determined utilizing an atomic force microscope with a 5 ⁇ m by 5 ⁇ m scan size. Images that the atomic force microscope captured for each example are reproduced at FIG. 8. The images show the secondary surface features that impart the desired surface roughness. Table 2 immediate below reports the measured surface roughness for each sample.
  • the ⁇ value, the surface scattering factor was measured for each sample.
  • the measurement method of the surface scattering factor is as follows. First, the transmission haze of a sample is measured.
  • a graph reproduced at FIG. 8B reproduces the results.
  • a reproduced at FIG. 8D sets forth measured transmission haze as a function of measured surface scattering ⁇ (sigma) value for each sample, and then a line is modeled to fit the data. The modeled line fitting measured data agrees with the ray scattering model of Example 1 that indicated that the surface scattering ⁇ value had to reach a certain value before it began to impart increased transmission haze.
  • Examples 3A and 3B – Examples 3A and 3B demonstrate the effect that the secondary surface features (imparting the surface roughness) has on pixel power deviation for samples were primary surface features are also present.
  • primary surface features were etched into a glass substrate.
  • the composition of the etchant included 1 wt% hydrofluoric acid (HF) and 2 wt% nitric acid (HNO 3 ).
  • the etchant contacted the primary surface of the glass substrate for 25 seconds, resulting the primary surface features having a depth of 150 nm from a surrounding portion.
  • a dry film resist etching mask was utilized to position the primary surface features in a hexagonal pattern set into the surrounding portion (see FIG. 5).
  • each primary surface feature was hexagonal as well. Each primary surface feature was separated by a center ⁇ to ⁇ center distance of 120 ⁇ m. Adjacent primary surface features were separated, perimeter to perimeter, by a distance of 55 ⁇ m.
  • One of the samples was retained as Example 3A and no secondary surface features were subsequently added to the sample of Example 3A [0120]
  • Example 3B the sample was subjected to a second etching step to impart secondary surface features.
  • the second etching step used an etchant with a composition of 92 wt% acetic acid, 2 wt% ammonium fluoride, and 6 wt% water (deionized). The etchant contacted the primary surface with the primary surface features for a period of time of 2 minutes.
  • the etchant formed the secondary surface features within the textured region, which imparted a surface roughness (R a ) of ⁇ 28 nm.
  • R a surface roughness
  • the pixel power deviation that the samples of both Example 3A and Example 3B generated were measured.
  • the measured pixel power deviation was sensitive to the orientation of the sample to the display pixel array, because the primary surface features had a hexagonal perimeter.
  • a graph reproduced at FIG. 9A reproduces the measured pixel power deviation for both Examples 3A and 3B as a function of the orientation angle 52 of the sample.
  • the schematic illustration at FIG. 9B shows what orientation angle means.
  • the substrate is over the display, with the textured region at the primary surface facing away from the display.
  • the display has pixels 54.
  • the substrate forms the orientation angle relative to the display.
  • Example 3B As the substrate is rotated relative to the display about an axis extending through the substrate orthogonal to the primary surface, the orientation angle changes.
  • Analysis of the graph of FIG. 9A reveals that the Example 3B, with the added secondary surface features over the primary surface features to impart surface roughness, lowered the pixel power deviation compared to Example 3A, which included only the primary surface features.
  • the secondary surface features lowered the pixel power deviation by ⁇ 0.2% to 2.5% (in absolute terms), depending on orientation angle of the substrate relative to the display.
  • the results suggest that the effect that the secondary surface features has on the pixel power deviation of the sample is a function of the geometry of the primary surface features.
  • the glass substrate was then subjected to a first etching step to etch primary surface features set into a surrounding portion.
  • Each primary surface feature had a perimeter that was circular. The diameter of the perimeter was 40 ⁇ m.
  • An etching mask was utilized to place each of the primary surface features.
  • the placement of each of the primary surface features was generated using a spacing distribution algorithm.
  • the spacing distribution algorithm required a minimum center ⁇ to ⁇ center distance between circles of 50 ⁇ m.
  • the placement of the primary surface features pursuant to the spacing distribution algorithm was thus randomized and did not form a pattern.
  • the placement of the primary surface features made pursuant to the spacing distribution algorithm was transferred to a lithograph mask, which was then used to cure AZ 4210 lithography ink disposed on the primary surface of the substrate.
  • the uncured portions of the lithograph ink was removed and the cured portion remained as the etching mask.
  • the primary surface features occupied about 50% of the area of the textured region, and the depth of the primary surface features was 0.18 ⁇ m.
  • the etchant of the first etching step comprised 1 wt% hydrofluoric acid (HF) and 2 wt% nitric acid (HNO 3 ).
  • the etchant contacted the substrate for a period of time to achieve the target 150nm depth based on etch rate.
  • For of the samples were then set aside as Example 4A ⁇ 4D and not subjected to a second etching step to impart secondary surface features.
  • the remaining four samples were assigned to be Examples 4E ⁇ 4H and each subjected to a second etching step using an etchant including acetic acid, ammonium fluoride, and water (deionized).
  • the etchant for Examples 4E and 4F had a composition of 92 wt% acetic acid, 2 wt% ammonium fluoride, and 6 wt% water (deionized).
  • the second etching step for Examples 4E and 4F formed secondary surface features that imparted a surface roughness (Ra) of ⁇ 28nm.
  • the etchant for Examples 4G and 4H had a composition of 90 wt% acetic acid, 1 wt% ammonium fluoride, and 9 wt% water (deionized). In each of Examples 4E ⁇ 4H, the etchant contacted the sample of a time period of 2 minutes.
  • the second etching step for Examples 4G and 4H formed secondary surface features that imparted a surface roughness (Ra) of ⁇ 54nm.
  • Ra surface roughness
  • the measurements are set forth in the aforementioned graphs at FIGS. 10A ⁇ 10D. Analysis of the graphs reveal that the second etching step that formed the secondary surface features that added surface roughness to the textured region resulted in a lowering of pixel power deviation and distinctness ⁇ of ⁇ image but resulted in increasing the transmission haze.
  • the higher surface roughness of that the secondary surface features imparted to Examples 4G and 4H did not result in a different scale of lowering of distinctness ⁇ of ⁇ image compared to Examples 4E and 4F.
  • the higher surface roughness of that the secondary surface features imparted to Examples 4G and 4H did result in a larger decrease in pixel power deviation compared to Examples 4E and 4F but with a larger increase in transmission haze.
  • the etchant utilized had a composition of 0.15wt% hydrofluoric acid and 1wt% nitric acid.
  • the etchant contacted the primary surface with the etching mask for a period of time set forth in Table 4 immediately below that varied among the samples.
  • the etchant formed primary surface features having an elliptical perimeter set into a surrounding portion. The depth of the primary surface features varied, and the depth for each sample is set forth below.
  • the samples of 5M ⁇ 5O were then subjected to a second etching step to form secondary surface features at the primary surface.
  • the second etching step used an etchant with a composition of 92 wt% acetic acid, 2 wt% ammonium fluoride, and 6 wt% water (deionized).
  • the etchant contacted the substrate for a time period of 120 seconds.
  • the secondary surface features so formed imparted a surface roughness (Ra) of ⁇ 28nm to the textured region at the primary surface.
  • Ra surface roughness
  • the pixel power deviation, distinctness ⁇ of ⁇ image, specular reflection, and transmission haze were measured for the sample of each of Examples 5A ⁇ 5O.
  • the measured results are set forth in the graphs of FIGS. 11A ⁇ 11D, which plot the measured value as a function of the depth of the primary surface features with the elliptical perimeter. Analysis of the graphs reveal that the secondary surface features to impart surface roughness of Examples 5M ⁇ 5O resulted in a lower pixel power deviation and specular reflectance compared to when no such secondary surface features were included in Examples 5A ⁇ 5L. However, the secondary surface features to impart surface roughness of Examples 5M ⁇ 5O resulted in a higher distinctness ⁇ of ⁇ image and transmission haze compared to when no such secondary surface features were included in Examples 5A ⁇ 5L.
  • Example 6A ⁇ 6C –Examples 6A and 6B are two different sets of samples, each with primary surface features having an elliptical perimeter, just as in Examples 5A ⁇ 5O. The difference was that for the samples of Example 6A, the etching mask used while forming the primary surface features was kept on the substrate while the second etching step was performed to generate the secondary surface features.
  • Example 6B For the samples of Example 6B, the etching mask was removed before the second etching step was performed to generate the secondary surface features.
  • the secondary surface features and the added surface roughness were formed only on surfaces provided by the primary surface features and not the surrounding portion.
  • the secondary surface features and the added surface roughness were formed on the entire textured region including both the surrounding portion and the surfaces provided by the primary surface features.
  • the images on the right show the etching depth of the secondary surface features.
  • the pixel power deviation, transparency haze, and specular reflectance of samples from both Examples 6A and 6B were measured. A Rhopoint instrument was utilized to determine specular reflectance.
  • the graphs reproduced at FIGS. 12B ⁇ 12D set forth the measured data. Analysis of the graphs reveal that the samples of Example 6B, where the etching mask was removed before the second etching step to impart second surface features throughout the entire textured region, resulted in a lower pixel power deviation but higher transmission haze compared to the samples of Example 6A, where the etching mask was maintained during the second etching step and thus the second surface features were imparted only to the surfaces provided by the primary surface features.
  • the Rhopoint instrument utilized to measure specular reflectance did not measure a difference between the samples of Examples 6A and 6B. However, the device could measure differences in specular reflectance when a 6 degree angle of incidence for the light to be reflected and a 2 degree aperture to measure the specular reflectance.
  • the graph reproduced at FIG. 12E shows the measured data for samples of Examples 6A and 6B, as well as for a sample (Example 6C) where only the primary surface features were present and did not include the secondary surface features to impart surface roughness. Analysis of the graph of FIG. 12E reveals that the presence of the secondary surface features in Examples 6A and 6B reduced specular reflectance compared to when the secondary surface features were absent in Example 6C.
  • Example 7 For Example 7, a sample was prepared similar to the samples Examples 5M ⁇ 5O, where primary surface features with an elliptical perimeter are set into a surrounding portion in a first etching step forming textured region, and then secondary surface features are etched throughout the entire textured region to increase surface roughness. The sample so prepared was then analyzed with a white light interferometer to measure the three dimensional profile of the textured region.
  • FIG. 13A illustrates the three dimensional profile that was measured. The top half illustrates relative elevation differences between primary surface features and the surrounding portion.
  • the bottom half illustrates the topography of the secondary surface features, with the topography of the secondary surface features added to the surfaces that the primary surface features are provided illustrated at the left, and the topography of the secondary surface features added to the surrounding portion illustrated at the right.
  • the three dimensional profile of the secondary features within the primary surface features is measurably different than the three dimensional profile of the secondary features at the surrounding portion – with the surrounding portion showing deeper secondary features.
  • An atomic force microscope was utilized to image and determine the surface roughness (Ra) imparted by the secondary surface features at both (i) a surface provided by a primary surface feature and (ii) at the surrounding portion. The images are reproduced at FIG. 13B.
  • the image on the left is of the secondary surface features at the surface provided by the primary surface feature, and shows a surface roughness (R a ) of 15.3 nm.
  • the image on the right is of the secondary surface features at the surrounding portion, and shows a surface roughness (R a ) of 33.5 nm.
  • the image on the right and the higher surface roughness (R a ) value at the surrounding portion matches the topography date illustrated at FIG. 13A.
  • the surrounding portion was covered by the etching mask during the formation of the primary surface features and thus had not been contacted with an etchant, unlike the primary surface features which were created by the first etching step. Thus, it is believed that the surrounding portion, previously untouched by an etchant, was more sensitive to the second etching step to impart the secondary surface features.

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Abstract

A substrate for a display article is described herein that includes (a) a primary surface; and (b) a textured region on at least a portion of the primary surface; the textured region comprising: (i) primary surface features, each comprising a perimeter parallel to a base-plane extending through the substrate disposed below the textured region, wherein the perimeter of each of the primary surface features comprises a longest dimension of at least 5 µm; and (ii) one or more sections each comprising secondary surface features having a surface roughness (Ra) within a range of 5 nm to 100 nm. In some instances, an arrangement of the surface features reflect a random distribution. A method of forming the same is disclosed.

Description

ANTI‐GLARE SUBSTRATE FOR A DISPLAY ARTICLE INCLUDING A TEXTURED REGION WITH PRIMARY SURFACE  FEATURES AND SECONDARY SURFACE FEATURES IMPARTING A SURFACE ROUGHNESS THAT INCREASES SURFACE  SCATTERING  CLAIM OF PRIORITY  [0001] This  Application  claims  the  benefit  of  priority  to  U.S.  Provisional  Application  No.  63/049,843, filed 09 July 2021, the content of which  is  incorporated herein by reference  in  its  entirety.  CROSS‐REFERENCE TO RELATED APPLICATIONS  [0002] The present application relates to, but does not claim priority to, commonly owned and  assigned U.S. Patent Application Serial No. __________ (D31977), entitled “TEXTURED REGION  TO REDUCE SPECULAR REFLECTANCE  INCLUDING A LOW REFRACTIVE  INDEX SUBSTRATE WITH  HIGHER ELEVATED SURFACES AND LOWER ELEVATED SURFACES AND A HIGH REFRACTIVE INDEX  MATERIAL DISPOSED ON THE LOWER ELEVATED SURFACES” and filed on ______________; U.S.  Patent Application Serial No. __________  (D32630/32632), entitled “TEXTURED REGION OF A  SUBSTRATE TO REDUCE SPECULAR REFLECTANCE INCORPORATING SURFACE FEATURES WITH AN  ELLIPTICAL PERIMETER OR SEGMENTS THEREOF, AND METHOD OF MAKING THE SAME” and filed  on  __________;  U.S.  Patent  Application  Serial  No.  __________  (D32647),  entitled  “DISPLAY  ARTICLES  WITH  DIFFRACTIVE,  ANTIGLARE  SURFACES  AND  THIN,  DURABLE  ANTIREFLECTION  COATINGS”  and  filed  on  __________;  and  U.S.  Patent  Application  Serial  No.  __________  (D32623),  entitled  “DISPLAY  ARTICLES WITH DIFFRACTIVE,  ANTIGLARE  SURFACES  AND  THIN,  DURABLE ANTIREFLECTION COATINGS” and filed on __________.  The entire disclosures of each  of the foregoing U.S. patent applications, publications and patent documents are incorporated  herein by reference.  FIELD OF INVENTION    [0003] The disclosure relates to an anti‐glare substrate for display articles where the anti‐glare  substrate  includes  a  textured  region  with  primary  surface  features  and  secondary  surface  features imparting a surface roughness that increases surface scattering.      BACKGROUND  [0004] Substrates transparent to visible light are utilized to cover displays of display articles.  Such  display articles include smart phones, tablets, televisions, computer monitors, and the like.  The  displays  are  often  liquid  crystal  displays,  organic  light  emitting  diodes,  among  others.    The  substrate protects the display, while the transparency of the substrate allows the user of the  device to view the display.    [0005] The substrate reflecting ambient light, especially specular reflection, reduces the ability  of the user to view the display through the substrate.  Specular reflection in this context is the  mirror‐like reflection of ambient light off the substrate.  For example, the substrate may reflect  visible  light reflecting off or emitted by an object  in the environment around the device.   The  visible  light  reflecting  off  the  substrate  reduces  the  contrast  of  the  light  from  the  display  transmitting to the eyes of the user through the substrate.  At some viewing angles, instead of  seeing the visible light that the display emits, the user sees a specularly reflected image.  Thus,  attempts  have  been made  to  reduce  specular  reflection  of  visible  ambient  light  off  of  the  substrate.  [0006] Attempts have been made to reduce specular reflection off of the substrate by texturing  the  reflecting  surface of  the  substrate.   The  resulting  surface  is  sometimes  referred  to as an  "antiglare surface."   For examples, sandblasting and liquid etching the surface of the substrate  can  texture  the  surface, which generally  causes  the  surface  to  reflect ambient  light diffusely  rather than specularly.  Diffuse reflection generally means that the surface still reflects the same  ambient  light but  the  texture of  the reflecting surface scatters  the  light upon reflection.   The  more diffuse reflection interferes less with the ability of the user to see the visible light that the  display emits.  [0007] Such methods of texturing (i.e., sandblasting and liquid etching) generate features on the  surface with  imprecise  and  unrepeatable  geometry  (the  features  provide  the  texture).    The  geometry of the textured surface of one substrate formed via sandblasting or liquid etching can  never be  the  same as  the geometry of  the  textured  surface of another  substrate  formed via  sandblasting  or  liquid  etching.    Commonly,  only  a  statistical  quantification  of  the  surface  roughness (i.e., Ra) of the textured surface of the substrate is a repeatable target of the texturing.    [0008] There are a variety of metrics by which the quality of the "antiglare" surface  is  judged.   Those metrics include (1) the distinctness‐of‐image, (2) pixel power deviation, (3) apparent Moiré  interference  fringes,  (4)  transmission  haze,  (5)  specular  reflection,  and  (6)  reflection  color  artifacts.    Distinctness‐of‐image,  which more  aptly might  be  referred  to  as  distinctness‐of‐ reflected‐image, is a measure of how distinct an image reflecting off the surface appears.  The  lower the distinctness‐of‐image, the more the textured surface is diffusely reflecting rather than  specularly reflecting.  Surface features can magnify various pixels of the display, which distorts  the  image  that  the  user  views.    Pixel  power  deviation,  also  referred  to  as  "sparkle,"  is  a  quantification  of  such  an  effect.    The  lower  the  pixel  power  deviation  the  better.   Moiré  interference fringes are large scale interference patterns, which, if visible, distort the image that  the user sees.  Preferably, the textured surface produces no apparent Moiré interference fringes.   Transmission haze  is a measure of how much the textured surface  is diffusing the visible  light  that the display emitted upon transmitting through the substrate.  The greater the transmission  haze, the less sharp the display appears (i.e., lowered apparent resolution).  Specular reflection  reduction is again a measure of how much of the reflected ambient light off the textured surface  is specular.  The lower the better.  Reflection color artifacts are a sort of chromatic aberration  where the textured surface diffracts light upon reflection as a function of wavelength ‐ meaning  that  the  reflected  light,  although  relatively  diffuse,  appears  segmented  by  color.    The  less  reflected color artifacts that the textured surface produces the better.  Some of these attributes  are discussed in greater detail below.  [0009] Targeting  a  specific  surface  roughness  alone  cannot  optimize  all  of  those  metrics  simultaneously.  A relatively high surface roughness that sandblasting or liquid etching produces  might adequately transform specular reflection into diffuse reflection.  However, the high surface  roughness  can  additionally  generate  high  transmission  haze  and  pixel  power  deviation.    A  relatively  low surface roughness, while decreasing transmission haze, might  fail to sufficiently  transform specular reflection  into diffuse reflection  ‐ defeating the "antiglare" purpose of the  texturing.  [0010] Accordingly, a new approach to providing a textured region of the substrate is needed ‐  one that is reproducible from substrate‐to‐substrate and one that causes the textured surface to  reflect ambient  light sufficiently diffusely rather than specularly so as to be "antiglare" (e.g., a  low distinctness‐of‐image,  low  specular  reflection) but  simultaneously  also delivers  low pixel  power deviation, low transmission haze, and low reflection color artifacts.   SUMMARY  [0011] The present disclosure provides a new approach that specifically places primary surface  features having a specific geometry throughout a textured region according to a predetermined  placement.  The primary surface features cause the substrate to reflect rather diffusely and are  reproducible from substrate‐to‐substrate because the placement of each primary surface feature  is by design.   In addition, secondary surface features are incorporated into the textured region  to  increase the surface roughness to within a certain range.   The  increased surface roughness  imparts surface scattering to the textured region, which generally lowers pixel power deviation  and specular reflection, and sometimes distinctness of image too.  [0012] According to a first aspect of the present disclosure, a substrate for a display article, the  substrate comprising: (a) a primary surface; and (b) a textured region on at least a portion of the  primary surface; the textured region comprising: (i) primary surface features, each comprising a  perimeter parallel to a base‐plane extending through the substrate disposed below the textured  region, wherein  the  perimeter  of  each  of  the  primary  surface  features  comprises  a  longest  dimension of at  least 5 µm; and  (ii) one or more sections each comprising secondary surface  features having a surface roughness (Ra) within a range of 5 nm to 100 nm.  [0013] According to a second aspect of the present disclosure, the substrate of the first aspect,  wherein the primary surface features form a pattern.  [0014] According to a third aspect of the present disclosure, the substrate of any one of the first  through second aspects, the longest dimension of each of the primary surface features is about  the same.  [0015] According to a fourth aspect of the present disclosure, the substrate of any one of the first  through  third  aspects,  wherein  an  arrangement  of  the  surface  features  reflect  a  random  distribution.  [0016] According to a fifth aspect of the present disclosure, the substrate of any one of the first  through fourth aspects, wherein the perimeter of each primary surface features is elliptical.  [0017] According to a sixth aspect of the present disclosure, the substrate of any one of the first  through fourth aspects, wherein the perimeter of each primary surface features is circular.  [0018] According to a seventh aspect of the present disclosure, the substrate of any one of the  first through fourth aspects, wherein each primary surface feature provides a surface, and the  surface is either concave or convex.  [0019] According to an eighth aspect of the present disclosure, the substrate of any one of the  first  through  seventh  aspects, wherein  the  textured  region  further  comprises:  a  surrounding  portion  into which  the primary  surface  features are  set or out of which  the primary  surface  features project.  [0020] According to a ninth aspect of the present disclosure, the substrate of any one of the first  through eighth aspects, wherein (i) the primary surface features that are adjacent to one another  have perimeters that are separated by a distance within a range of 1 µm to 100 µm; and (ii) the  primary surface features that are adjacent to one another are separated by a center‐to‐center  distance within a range of 5 µm to 150 µm.  [0021] According to a tenth aspect of the present disclosure, the substrate of any one of the first  through  ninth  aspects, wherein  each  of  the  primary  surface  features  comprises  a  change  in  elevation perpendicular to the base‐plane that is within a range of 0.05 µm to 0.50 µm.  [0022] According to an eleventh aspect of the present disclosure, the substrate of any one of the  first through sixth and eighth through tenth aspects, wherein (i) each primary surface features  provides a surface, and (ii) the secondary surface features are disposed on the surfaces of the  primary surface features.  [0023] According to a twelfth aspect of the present disclosure, the substrate of any one of the  first through sixth, ninth, and tenth aspects, wherein the textured region further comprises: a  surrounding portion  into which  the primary surface  features are set  into or out of which  the  primary  surface  features  project; wherein,  each  primary  surface  feature  provides  a  surface,  wherein, the secondary surface features are disposed on both the surrounding portion and on  the surfaces of the primary surface features, and wherein, the surface roughness at the surfaces  of the primary surface features is less than the surface roughness at the surrounding portion.  [0024]  According to a thirteenth aspect of the present disclosure, the substrate of any one of  the first through sixth, ninth, and tenth aspects further comprises: a surrounding portion  into  which  the primary surface  features are set  into or out of which  the primary surface  features  project; wherein,  the secondary surface  features are disposed on  the surfaces of the primary  surface features but not on the surrounding portion.  [0025]  According to a fourteenth aspect of the present disclosure, the substrate of any one of  the first through thirteenth aspects, wherein the substrate comprises a glass or glass‐ceramic.  [0026] According to a fifteenth aspect of the present disclosure, the substrate of any one of the  first  through  fourteenth aspects, wherein  (i)  the  textured  region exhibits a  transmission haze  within a range of 1.5% to 3.5%; (ii) the textured region exhibits a pixel power deviation within a  range of 1.5% to 3.5%; (iii) the textured region exhibits a distinctness‐of‐image within a range of  2.% to 5.0%; and (iv) the textured region exhibits a specular reflectance within a range of 5 GU  to 20 GU.  [0027] According to a sixteenth aspect of the present disclosure, a method of forming a textured  region of a substrate, the method comprising: (i) forming primary surface features into a primary  surface of a substrate according to a predetermined positioning of each primary surface feature  thus  forming a  textured  region, each primary surface  feature comprising a  largest dimension  parallel to a base‐plane through the substrate disposed below the primary surface of at least 5  µm; and (ii) forming secondary surface features into one or more sections of the textured region,  thereby increasing the surface roughness (Ra) of the one or more sections to within a range of 5  nm to 100 nm.   [0028] According to a seventeenth aspect of the present disclosure, the method of the sixteenth  aspect further comprises: determining the positioning of each primary surface feature utilizing a  spacing distribution algorithm.  [0029] According to an eighteenth aspect of the present disclosure, the method of any one of  the sixteenth through seventeenth aspects, wherein forming the primary surface features into  the primary surface comprises contacting the primary surface with an etchant while an etching  mask is disposed on the primary surface to permit only selective etching of the substrate to form  the primary surface features.  [0030] According to a nineteenth aspect of the present disclosure, the method of the eighteenth  aspect, wherein (i) the etchant comprises hydrofluoric acid and nitric acid; and (ii) the etchant  contacts the substrate for a time period within a range of 10 seconds to 60 seconds.  [0031] According to a twentieth aspect of the present disclosure, the method of any one of the  sixteenth through nineteenth aspects further comprising: forming the etching mask by exposing  a photorsesist material disposed on the primary surface of the substrate to a curing agent while  a  lithography mask  is disposed on  the photoresist material,  the  lithography mask comprising  material and voids through the material to selectively expose portions of the photoresist material  to the curing agent, wherein the voids of the lithography mask are positioned according to the  predetermined positioning of the primary surface features.   [0032] According to a twenty‐first aspect of the present disclosure, the method of any one of the  sixteenth through twentieth aspects, wherein forming the secondary surface features into one  or more sections of the textured region comprises contacting the textured region of the substrate  with a second etchant, different than the etchant used to form the primary surface features.  [0033] According to a twenty‐second aspect of the present disclosure, the method of any one of  the sixteenth through twenty‐first aspects, wherein the second etchant comprises acetic acid and  ammonium fluoride.  [0034] According to a twenty‐third aspect of the present disclosure, the method of any one of  the sixteenth through twenty‐second aspects, wherein (i) forming the primary surface features  into  the primary  surface  comprises  contacting  the primary  surface with  an etchant while  an  etching mask is disposed on the primary surface to permit only selective etching of the substrate  to form the primary surface features, and (ii) forming the secondary surface features into one or  more  sections of  the  textured  region  comprises  contacting  the one or more  sections of  the  textured region of the substrate with a second etchant, different than the etchant used to form  the primary surface features, while the etching mask used to form the primary surface features  remains on the substrate.  BRIEF DESCRIPTION OF THE DRAWINGS  [0035] In the figures:  [0036] FIG. 1 is perspective view of a display article, illustrating a substrate with a textured region  disposed over a display;  [0037] FIG. 2 is closer‐up perspective view of area II of FIG. 1, illustrating the textured region of  the  substrate  of  FIG.  1  including  primary  surface  features  that  are  arranged  in  a  hexagonal  pattern;  [0038] FIG. 3 is an elevation view of a cross‐section of the substrate of FIG. 1 taken through line  III‐III  of  FIG.  2,  illustrating  the  textured  region  further  including  secondary  surface  features,  smaller than the primary surface features, disposed on the textured region including the primary  surface features;  [0039] FIG. 4 is an overhead view of embodiments of a textured region, illustrating the primary  surface features having an elliptical perimeter and projecting from a surrounding portion;  [0040] FIG. 5  is another overhead view of embodiments of a  textured  region,  illustrating  the  primary  surface  features  having  a  hexagonal  perimeter  that  are  arranged  hexagonally  but  separated by a distance (wall‐to‐wall) and a center‐to‐center distance;  [0041] FIG. 6  is a schematic  flow chart of a method of  forming  the  textured  region of FIG. 1,  illustrating steps such as determining  the positioning of each primary surface  feature using a  spacing distribution algorithm;  [0042] FIG. 7A, pertaining  to a modeled Example 1,  is a graph  that  illustrates distinctness‐of‐ image generally decreasing as a  function of  (i)  increasing change of elevation  (height) of  the  primary  surface  features  and  (ii)  increasing  sigma  value  assigned  for  the  secondary  surface  features, which is a measure of the surface scattering that the secondary surface features impart  to the textured region;  [0043] FIG. 7B, pertaining to Example 1, is a graph that illustrates the change in distinctness‐of‐ image that the presence of the secondary surface features impart compared to if there were no  secondary surface features, as a function of the assigned sigma value and height of the primary  surface features;  [0044] FIG. 7C, pertaining to Example 1, is a graph that illustrates the sigma value that imparts  the  textured  region with  the minimum  distinctness‐of‐image  value  generally  decreases  as  a  function of decreasing height of the primary surface features;  [0045] FIG. 7D, pertaining  to Example 1,  is a graph  that  illustrates  that pixel power deviation  generally  increases as a function of height of the primary surface features and decreases as a  function of increasing sigma value assigned to the secondary surface features;  [0046] FIG. 7E, pertaining to Example 1, is a graph that illustrates pixel power deviation generally  decreases as a function of increasing sigma value and decreases as a function of decreasing height  of the primary surface features;  [0047] FIG. 7F, pertaining to Example 1,  is a graph that  illustrates transmission haze generally  increases as a function of increasing sigma values assigned for the secondary surface features;  [0048] FIG. 7G, pertaining to Example 1,  is a graph that  illustrates transmission haze generally  increasing as a function of increasing sigma value assigned for the secondary surface features,  but only after a threshold minimum sigma value;  [0049] FIG. 8A, pertaining  to Examples 2A‐2D,  reproduce  atomic  force microscopy  images of  secondary surface features with various topographies, a result of varying a composition of an  etchant utilized to form the secondary surface features;  [0050] FIG.  8B,  pertaining  to  Examples  2A‐2D,  is  a  graph  that  illustrates  transmission  haze  generally  increasing  as  a  function of  increasing  sigma  (surface  scattering)  value, which were  variable as a function of etchant composition;  [0051] FIG. 9A, pertaining to Examples 3A‐3B,  is a graph that  illustrates pixel power deviation  varying  as  a  function  of  orientation  angle  of  the  textured  region  (because  of  the  hexagonal  perimeter) of the primary surface features, and the presence of the secondary surface features  lowering pixel power deviation  compared  to when no  such  secondary  surface  features were  present;  [0052] FIG. 9B, pertaining to Examples 3A‐3B, is a schematic diagram illustrating that orientation  angle  concerns  the  angle  that  an  edge  of  the  substrate  forms with  the  display  beneath  the  substrate;  [0053] FIG. 10A, pertaining to Examples 4A‐4H, is a graph that illustrates that the inclusion of the  secondary  surface  features  resulted  in  a  lower  pixel  power  deviation  and,  further,  that  the  resulting  pixel  power  deviation  can  vary  depending  on  the  surface  roughness  (Ra)  that  the  secondary surface features  impart, and thus the composition of the etchant used to form the  secondary surface features;  [0054] FIG. 10B, pertaining to Examples 4A‐4H, is a graph that illustrates that the presence of the  secondary  surface  features  did  not  change  measured  specular  reflectance  compared  to  substrates that did not have the secondary surface features;  [0055] FIG. 10C, pertaining to Examples 4A‐4H, is a graph that illustrates that the presence of the  secondary surface features produced a lower distinctness‐of‐image compared to substrates that  did not have the secondary surface features;  [0056] FIG. 10D, pertaining to Examples 4A‐4H, is a graph that illustrates that the presence of the  secondary surface features produces greater transmission haze compared to substrates that did  not have the secondary surface features, and increasingly so as the surface roughness (Ra) that  the secondary surface features imparts increases;  [0057] FIG. 11A, pertaining to Examples 5A‐5O,  is a graph that  illustrates that the presence of  secondary surface features resulted in a lower pixel power deviation compared to substrates that  did not have the secondary surface features;  [0058] FIG. 11B, pertaining to Examples 5A‐5O,  is a graph that  illustrates that the presence of  secondary surface features resulted in a lower specular reflectance compared to substrates that  did not have the secondary surface features;  [0059] FIG. 11C, pertaining to Examples 5A‐5O,  is a graph that  illustrates that the presence of  secondary surface  features  resulted  in a higher distinctness‐of‐image compared  to substrates  that did not have the secondary surface features;  [0060] FIG. 11D, pertaining to Examples 5A‐5O,  is a graph that  illustrates that the presence of  secondary surface features resulted in a higher transmission haze compared to substrates that  did not have the secondary surface features;  [0061] FIG.  12A,  pertaining  to  Examples  6A‐6B,  are  atomic  force microscopy  images  of  the  primary surface features and the surrounding portion (left) and the secondary surface features  (middle and  right),  for both when  the  secondary  surface  features were disposed only on  the  primary surface features (top) and when the secondary surface features were disposed over both  the primary surface features and the surrounding portion (bottom);  [0062] FIG.  12B,  pertaining  to  Examples  6A‐6B,  is  a  graph  illustrating  that  incorporating  the  secondary  surface  features  over  the  entire  textured  region  resulted  in  a  lowed  pixel  power  deviation compared to substrates where the secondary surface features were incorporated only  on the primary surface features;  [0063] FIG.  12C,  pertaining  to  Examples  6A‐6B,  is  a  graph  illustrating  that  incorporating  the  secondary surface features over the entire textured region resulted in a higher transmission haze  compared to substrates that  incorporated the secondary surface features only on the primary  surface features;  [0064] FIG.  12D,  pertaining  to  Examples  6A‐6B,  is  a  graph  illustrating  that  incorporating  the  secondary surface features over the entire textured region did not substantially affect specular  reflectance compared to substrates that incorporated the secondary surface features only on the  primary surface features;  [0065] FIG.  12E,  pertaining  to  Examples  6A‐6B,  is  a  graph  illustrating  that  incorporating  the  secondary surface features over the entire textured region slightly affected specular reflectance  compared to substrates that  incorporated the secondary surface features only on the primary  surface features, and increasingly so as wavelength deviated from about 455 nm;  [0066] FIG. 13A, pertaining to Example 7, are white light interferometer graphs illustrating the  topography of the primary surface features and the surrounding portion (top) and the secondary  surface  features  (bottom) disposed at the primary surface features  (left) and the surrounding  portion (right); and  [0067] FIG. 13B, pertaining to Example 7, are atomic force microscopy images of the secondary  surface features disposed at a primary surface feature (left) and the surrounding portion (right),  illustrating  that  the  secondary  surface  features at  the  surrounding portion  imparted a higher  surface roughness (Ra) than the at the primary surface features (because the surrounding portion  was not previously etched and thus more sensitive to the etching that imparted the secondary  surface features).  DETAILED DESCRIPTION  [0001] Referring now to FIG. 1, a display article 10 includes a substrate 12.  In embodiments, the  display article 10 further includes a housing 14 to which the substrate 12 is coupled and a display  16 within the housing 14.   In such embodiments, the substrate 12 at  least partially covers the  display 16 such that light that the display 16 emits transmits through the substrate 12.  [0002] The  substrate  12  includes  a primary  surface  18,  a  textured  region  20 defined on  the  primary surface 18, and a thickness 22 that the primary surface 18 bounds in part.  The primary  surface 18 generally faces toward an external environment 24 surrounding the display article 10  and away  from  the display 16.   The display 16 emits  visible  light  that  transmits  through  the  thickness 22 of the substrate 12, out the primary surface 18, and into the external environment  24.    [0068] Referring now  to  FIGS. 2‐5,  in embodiments,  the  textured  region 20  includes primary  surface features 26.  A base‐plane 28 extends through the substrate 12 below the textured region  20.  The base‐plane 28 provides a conceptual reference point and is not a structural feature.  Each  primary surface feature 26  includes a perimeter 30.   The perimeter 30  is parallel to the base‐ plane 28.   The perimeter 30 has a  longest dimension 32.   For example,  in  the embodiments  illustrated at FIG. 2,  the perimeter 30  is hexagonal and  thus  the  longest dimension 32 of  the  perimeter 30 is the long diagonal of the hexagonal perimeter 30.  The longest dimension 32 is  parallel to the base‐plane 28 as well.  The longest dimension 32 of each primary surface feature  26 is at least 5 µm.  The perimeter 30 can be shaped other than hexagonal.  In embodiments, the  perimeter 30 of each of  the primary  surface  features 26  is polygonal.    In embodiments,  the  perimeter 30 of each of the primary surface features 26 is elliptical (see, e.g., FIG. 4).  In other  embodiments, the perimeter 30 of each of the primary surface features 26 is circular.     [0069] In addition, the textured region 20 further  includes one or more sections 34 that have  secondary surface features 36.  The secondary surface features 36 are smaller than the primary  surface features 26.  The secondary surface features 36 impart a surface roughness to the one or  more sections 34 of the textured region 20.  The surface roughness imparted is 5 nm, 10 nm, 15  nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80  nm, 85 nm, 90 nm, 95 nm, or 100 nm, or within any range bounded by any two of those values  (e.g., 5 nm to 100 nm, and so on).  As used herein, surface roughness (Ra) is measured with an  atomic force microscope, such as an atomic force microscope controlled by a NanoNavi control  station distributed by Seiko Instruments Inc. (Chiba, Japan), with a scan size of 5 µm by 5 µm.   Surface roughness (Ra), as opposed to other types of surface roughness values such as Rq, is the  arithmetical mean of the absolute values of the deviations from a mean  line of the measured  roughness profile.    [0070] The positioning, perimeter 30, and longest dimension 32 of each of the primary surface  features 26 is by design, as opposed to the purely uncontrolled and coincidental placement of  surface features via sandblasting or open etching (i.e., etching without a mask that would define  the placement of each surface feature).  In embodiments, such as those embodiments illustrated  at FIG. 2, the primary surface features 26 form a pattern.  In other words, the positioning of a  grouping of the primary surface features 26 repeats at the textured region 20.  The embodiments  illustrated at FIG. 2 are a hexagonal pattern.  In embodiments, the longest dimension 32 of each  of  the  primary  surface  features  26  is  about  the  same  or  the  same  within  manufacturing  tolerances.      [0071]  In other embodiments, such as those illustrated at FIG. 4, the primary surface features 26  do  not  form  a  pattern  –  that  is,  the  arrangement  of  the  surface  features  reflect  a  random  distribution.  To not form a pattern, the primary surface features 26 can be randomly distributed  within certain constraints, such as a center‐to‐center distance 38 that varies but is greater than  a minimum value.  In addition, to not form a pattern, the longest dimension 32 of each primary  surface feature 26 can be aligned not parallel to each other.   A reason to avoid arranging the  primary surface features 26 not in a pattern is to avoid the textured region 20 reflecting ambient  light with Moiré  fringe  interference patterns.   When  the primary  surface  features 26  form a  pattern, a possible consequence  is the generation of Moiré  fringe  interference patterns upon  reflection of ambient light.  [0072] Each  of  the  primary  surface  features  26  includes  a  surface  40  facing  the  external  environment 24.  The primary surface 18 of the substrate 12 at the textured region 20 includes  all of surfaces 40 that the primary surface features 26 provide.  In embodiments, such as those  illustrated at FIGS. 3 and 4, the surface 40 of each primary surface feature 26 is concave.  In other  embodiments, the surface 40 of each primary surface feature 26 is convex.  In embodiment, the  surfaces 40 of some primary surface features 26 of the textured region 20 are concave, while the  surfaces  40  of  other  primary  surface  features  26  of  the  textured  region  20  are  convex.    In  embodiments, the surface 40 of each primary surface  feature 26 of the textured region 20  is  planar and parallel to the base‐plane 28.    [0073] In embodiments, the textured region 20 further includes a surrounding portion 42 (see,  e.g.,  FIGS. 4  and 5).    In embodiments,  the primary  surface  features 26 project out  from  the  surrounding portion 42 away from the base‐plane 28 and toward the external environment 24.   In embodiments, the primary surface features 26 are set into the surrounding portion 42 toward  the base‐plane 28 and away from the external environment 24.  The elevation 44 (see FIG. 13A)  of  the  surrounding  portion  42  from  the  base‐plane  28  may  be  relatively  constant  within  manufacturing capabilities.   The elevation 46  (see FIG. 13A) of the surfaces 40 of the primary  surface feature 26 may all be approximately the same, within manufacturing capabilities.   The  textured region 20 may thus have a bi‐modal surface structure – with one or more surfaces (e.g.,  the surfaces 40 of the primary surface features 26) having one mean elevation (e.g., elevation  46), and one or more surfaces (e.g., the surface provided by the surrounding portion 42) having  a second mean elevation (e.g., elevation 44).    [0074] In embodiments, the perimeters 30 of primary surface features 26 that are adjacent are  separated by a distance 48 (e.g., wall‐to‐wall distance).  In embodiments, the distance 48 is 1 µm,  2 µm, 3 µm, 4 µm, 5 µm, 6 µm, 7 µm, 8 µm, 9 µm, 10 µm, 15 µm, 20 µm, 25 µm, 30 µm, 35 µm,  40 µm, 45 µm, 50 µm, 55 µm, 60 µm, 65 µm, 70 µm, 75 µm, 80 µm, 85 µm, 90 µm, 95 µm, or 100  µm, or within any range bounded by any two of those values (e.g., 25 µm to 75 µm, 50 µm to 60  µm, 1 µm to 100 µm, and so on).  In embodiments, primary surface features 26 that are adjacent  are separated by a center‐to‐center distance 38 of 5 µm, 6 µm, 7 µm, 8 µm, 9 µm, 10 µm, 15 µm,  20 µm, 25 µm, 30 µm, 35 µm, 40 µm, 45 µm, 50 µm, 55 µm, 60 µm, 65 µm, 70 µm, 75 µm, 80 µm,  85 µm, 90 µm, 95 µm, 100 µm, 110 µm, 120 µm, 130 µm, 140 µm, or 150 µm, or within any range  bounded by any two of those values (e.g., 100 µm to 150 µm, 5 µm to 150 µm and so on).    [0075] Each primary surface feature 26 has a change in elevation 50 perpendicular to the base‐ plane 28.  For a primary surface feature 26 that is convex or projects from the surrounding portion  42, the change  in elevation 50  is the height of the primary surface  feature 26.   For a primary  surface feature 26 that is concave or set into the surrounding portion 42, the change in elevation  50 is the depth of the primary surface feature 26.  In embodiments, the change in elevation 50  of each primary surface feature 26  is the same or about the same (varies by 25% or  less).     In  embodiments, the change in elevation 50 of each primary surface feature 26 is 0.05 µm, 0.10 µm,  0.15 µm, 0.20 µm, 0.25 µm, 0.30 µm, 0.35 µm, 0.40 µm, 0.45 µm, or 0.50 µm, or within any range  bounded by any two of those values (e.g., 0.05 µm to 0.50 µm, and so on).  When the textured  region 20 provides surfaces structured  in a bi‐modal distribution of elevations,  the change  in  elevation 50 is the distance between the two elevations.    [0076] In embodiments, the one or more sections 34 that include the secondary surface features  36  include  the  surfaces  40  of  the  primary  surface  features  26.    In  other  words,  in  those  embodiments, the secondary surface features 36 are disposed on the surface 40 of the primary  surface  features 26.    In embodiments, the secondary surface  features 36 are disposed on the  surface 40 of the primary surface features 26 but not the surrounding portion 42.    [0077] In embodiments, the one or more sections 34 that include the secondary surface features  36 include the surrounding portion 42 and the surfaces 40 of the primary surface features 26.  In  other words, in those embodiments, the secondary surface features 36 are disposed on both the  surrounding  portion  42  and  on  the  surfaces  40  of  the  primary  surface  features  26.    In  embodiments, the section 34 that includes the secondary surface features 36 is coextensive with  the textured region 20 meaning that the secondary surface features 36 are disposed throughout  the  entirety  of  the  textured  region  20.    In  embodiments,  the  surface  roughness  (Ra)  at  the  surfaces  40  of  the  primary  surface  features  26  is  less  than  the  surface  roughness  at  the  surrounding portion 42.  [0078] Through adjustment of the parameters of the primary surface features 26, such as the  change in elevation 50, longest dimension 32, shape of the perimeter 30, and center‐to‐center  distance 38, and the addition of the secondary surface features 36, the distinctness‐of‐image,  pixel  power  deviation,  and  transmission  haze  that  the  textured  region  20  generates  can  be  optimized.  In general, incorporation of the primary surface features 26 alone would cause the  textured region 20 to reflect ambient light with a lower distinctness‐of‐image but transmit light  from the display 16 with a higher pixel power deviation and higher transmission haze.  The larger  the  change  in  elevation  50  of  the  primary  surface  features  26,  the  larger  these  effects  on  distinctness of  image, pixel power deviation, and transmission haze.   The  incorporation of the  secondary surface features 36 mitigates the negative effect that the primary surface features 26  might have on pixel power deviation.  The surface roughness that the secondary surface features  36 impart increases the scattering of the textured region 20.  This increased scattering increases  the amount of diffuse reflection that the textured region 20 generates upon reflecting ambient  light  thus  further  lowering  specular  reflection  and  rehabilitating  (lowering)  the  pixel  power  deviation simultaneously, and distinctness‐of‐image in some instances.  Thus, the textured region  20  can  simultaneously  generate  low  values  for  all of  the  specular  reflection, distinctness‐of‐ image,  pixel  power  deviation,  and  transmission  haze  –  something  that  previous methods  of  created the textured region 20 could not achieve.  In addition, the designer of the textured region  20 has many more variables with which the designer can work to optimize the textured region  20 for any given application than with previous methods such as sandblasting or open etching.   [0079] In embodiments, the substrate 12 includes a glass or glass‐ceramic.  In embodiments, the  substrate 12 is a multi‐component glass composition having about 40 mol % to 80 mol % silica  and a balance of one or more other constituents, e.g., alumina, calcium oxide, sodium oxide,  boron oxide, etc.  In some implementations, the bulk composition of the substrate 12 is selected  from  the group consisting of aluminosilicate glass, a borosilicate glass, and a phosphosilicate  glass.  In other implementations, the bulk composition of the substrate 12 is selected from the  group consisting of aluminosilicate glass, a borosilicate glass, a phosphosilicate glass, a soda lime  glass,  an  alkali  aluminosilicate  glass,  and  an  alkali  aluminoborosilicate  glass.    In  further  implementations, the substrate 12 is a glass‐based substrate, including, but not limited to, glass‐ ceramic materials that comprise a glass component at about 90% or greater by weight and a  ceramic component.  In other implementations of the display article 10, the substrate 12 can be  a polymer material, with durability and mechanical properties suitable for the development and  retention of the textured region 20.    [0080] In  embodiments,  the  substrate  12  has  a  bulk  composition  that  comprises  an  alkali  aluminosilicate  glass  that  comprises  alumina,  at  least  one  alkali  metal  and,  in  some  embodiments, greater than 50 mol % SiO2, in other embodiments, at least 58 mol % SiO2, and in  still other embodiments, at least 60 mol % SiO2, wherein the ratio (Al2O3 (mol%) + B2O3 (mol%))  / ∑ alkali metal modifiers (mol%) > 1, where the modifiers are alkali metal oxides.  This glass, in  particular embodiments, comprises, consists essentially of, or consists of: about 58 mol %  to  about 72 mol % SiO2; about 9 mol % to about 17 mol % Al2O3; about 2 mol % to about 12 mol %  B2O3; about 8 mol % to about 16 mol % Na2O; and 0 mol % to about 4 mol % K2O, wherein the  ratio (Al2O3 (mol%) + B2O3 (mol%)) / ∑ alkali metal modifiers (mol%) > 1, where the modifiers are  alkali metal oxides.  [0081] In  embodiments,  the  substrate  12  has  a  bulk  composition  that  comprises  an  alkali  aluminosilicate glass comprising, consisting essentially of, or consisting of: about 61 mol % to  about 75 mol % SiO2; about 7 mol % to about 15 mol % Al2O3; 0 mol % to about 12 mol % B2O3;  about 9 mol % to about 21 mol % Na2O; 0 mol % to about 4 mol % K2O; 0 mol % to about 7 mol  % MgO; and 0 mol % to about 3 mol % CaO.  [0082] In  embodiments,  the  substrate  12  has  a  bulk  composition  that  comprises  an  alkali  aluminosilicate glass comprising, consisting essentially of, or consisting of: about 60 mol % to  about 70 mol % SiO2; about 6 mol % to about 14 mol % Al2O3; 0 mol % to about 15 mol % B2O3; 0  mol % to about 15 mol % Li2O; 0 mol % to about 20 mol % Na2O; 0 mol % to about 10 mol % K2O;  0 mol % to about 8 mol % MgO; 0 mol % to about 10 mol % CaO; 0 mol % to about 5 mol % ZrO2;  0 mol % to about 1 mol % SnO2; 0 mol % to about 1 mol % CeO2; less than about 50 ppm As2O3;  and  less  than about 50 ppm Sb2O3; wherein 12 mol %≦Li2O+Na2O+K2O≦20 mol % and 0 mol  %≦MgO+Ca≦10 mol %.  [0083] In  embodiments,  the  substrate  12  has  a  bulk  composition  that  comprises  an  alkali  aluminosilicate glass comprising, consisting essentially of, or consisting of: about 64 mol % to  about 68 mol % SiO2; about 12 mol % to about 16 mol % Na2O; about 8 mol % to about 12 mol %  Al2O3; 0 mol % to about 3 mol % B2O3; about 2 mol % to about 5 mol % K2O; about 4 mol % to  about 6 mol % MgO; and 0 mol % to about 5 mol % CaO, wherein: 66 mol %≦SiO2+B2O3+CaO≦69  mol  %;  Na2O+K2O+B2O3+MgO+CaO+SrO>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 %.  [0084] In embodiments, the substrate 12 has a bulk composition that comprises SiO2, Al2O3, P2O5,  and at least one alkali metal oxide (R2O), wherein 0.75>[(P2O(mol %)+R2O (mol %))/M2O(mol  %)]≦1.2, where M2O3═Al2O+B2O3.    In embodiments,  [(P2O(mol %)+R2O  (mol %))/M2O(mol  %)]=1 and, in embodiments, the glass does not include B2Oand M2O3═Al2O3.  The substrate 12  comprises, in embodiments: about 40 to about 70 mol % SiO2; 0 to about 28 mol % B2O3; about  0 to about 28 mol % Al2O3; about 1 to about 14 mol % P2O5; and about 12 to about 16 mol % R2O.   In some embodiments, the glass substrate comprises: about 40  to about 64 mol % SiO2; 0  to  about 8 mol % B2O3; about 16 to about 28 mol % Al2O3; about 2 to about 12 mol % P2O5; and  about 12 to about 16 mol % R2O.  The substrate 12 may further comprise at least one alkaline  earth metal oxide such as, but not limited to, MgO or CaO.  [0085] In some embodiments, the substrate 12 has a bulk composition that is substantially free  of lithium; i.e., the glass comprises less than 1 mol % Li2O and, in other embodiments, less than  0.1 mol % Li2O and, in other embodiments, 0.01 mol % Li2O, and in still other embodiments, 0  mol % Li2O.  In some embodiments, such glasses are free of at least one of arsenic, antimony, and  barium; i.e., the glass comprises less than 1 mol % and, in other embodiments, less than 0.1 mol  %, and in still other embodiments, 0 mol % of As2O3, Sb2O3, and/or BaO.  [0086] In  embodiments,  the  substrate  12  has  a  bulk  composition  that  comprises,  consists  essentially of or  consists of a  glass  composition,  such as Corning® Eagle XG® glass, Corning®  Gorilla® glass, Corning® Gorilla® Glass 2, Corning® Gorilla® Glass 3, Corning® Gorilla® Glass 4, or  Corning® Gorilla® Glass 5.  [0087] In  embodiments,  the  substrate  12  has  an  ion‐exchangeable  glass  composition  that  is  strengthened by either chemical or thermal means that are known in the art.  In embodiments,  the substrate 12 is chemically strengthened by ion exchange.  In that process, metal ions at or  near the primary surface 18 of the substrate 12 are exchanged for larger metal ions having the  same valence as the metal  ions  in the substrate 12.   The exchange  is generally carried out by  contacting the substrate 12 with an ion exchange medium, such as, for example, a molten salt  bath that contains the  larger metal  ions.   The metal  ions are typically monovalent metal  ions,  such as, for example, alkali metal ions.  In one non‐limiting example, chemical strengthening of a  substrate  12  that  contains  sodium  ions  by  ion  exchange  is  accomplished  by  immersing  the  substrate 12  in an  ion exchange bath comprising a molten potassium salt, such as potassium  nitrate  (KNO3) or the  like.    In one particular embodiment, the  ions  in the surface  layer of the  substrate 12 contiguous with the primary surface 18 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 of the substrate 12 may be replaced with monovalent  cations other than alkali metal cations, such as Ag+ or the like.    [0088] In such embodiments, the replacement of small metal ions by larger metal ions in the ion  exchange process creates a compressive stress region in the substrate 12 that extends from the  primary surface 18 to a depth  (referred to as the “depth of  layer”) that  is under compressive  stress.  This compressive stress of the substrate 12 is balanced by a tensile stress (also referred  to  as  “central  tension”) within  the  interior  of  the  substrate  12.    In  some  embodiments,  the  primary surface 18 of the substrate 12 described herein, when strengthened by  ion exchange,  has a compressive stress of at least 350 MPa, and the region under compressive stress extends  to a depth, i.e., depth of layer, of at least 15 μm below the primary surface 18 into the thickness  22.    [0089] Ion exchange processes are typically carried out by immersing the substrate 12 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 as a result of the strengthening  operation.  By way of example, ion exchange of alkali metal‐containing glasses may be achieved  by immersion in at least one molten 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 380°C up to about 450°C, 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, when employed  with a substrate 12 having an alkali aluminosilicate glass composition, result  in a compressive  stress region having a depth (depth of layer) ranging from about 5 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.  [0090] As the etching processes that can be employed to create the textured region 20 of the  substrate  12  can  remove  alkali metal  ions  from  the  substrate  12  that would  otherwise  be  replaced by a  larger alkali metal  ion during an  ion exchange process, a preference exists  for  developing  the  compressive  stress  region  in  the  display  article  10  after  the  formation  and  development of the textured region 20.  [0091] In embodiments,  the display  article 10 exhibits  a pixel power deviation  (“PPD”).   The  details of a measurement system and  image processing calculation used to obtain PPD values  described  in  U.S.  Patent  No.  9,411,180  entitled  “Apparatus  and  Method  for  Determining  Sparkle,” and the salient portions of which are related to PPD measurements are incorporated  by  reference herein  in  their entirety.   Further, unless otherwise noted,  the SMS‐1000 system  (Display‐Messtechnik & Systeme GmbH & Co. KG) is employed to generate and evaluate the PPD  measurements of  this disclosure.   The PPD measurement system  includes: a pixelated source  comprising a plurality of pixels (e.g., a Lenovo Z50 140 ppi laptop), wherein each of the plurality  of pixels has referenced indices i and j; and an imaging system optically disposed along an optical  path originating from the pixelated source.   The  imaging system comprises: an  imaging device  disposed  along  the  optical  path  and  having  a  pixelated  sensitive  area  comprising  a  second  plurality of pixels, wherein each of the second plurality of pixels is referenced with indices m and  n; and a diaphragm disposed on the optical path between the pixelated source and the imaging  device, wherein the diaphragm has an adjustable collection angle for an image originating in the  pixelated source.  The image processing calculation includes: acquiring a pixelated image of the  transparent sample, the pixelated image comprising a plurality of pixels; determining boundaries  between adjacent pixels in the pixelated image; integrating within the boundaries to obtain an  integrated  energy  for  each  source  pixel  in  the  pixelated  image;  and  calculating  a  standard  deviation of the integrated energy for each source pixel, wherein the standard deviation is the  power per pixel dispersion.  As used herein, all PPD values, attributes and limits are calculated  and evaluated with a test set‐up employing a display device having a pixel density of 140 pixels  per inch (PPI).  In embodiments, the display article 10 exhibits a PPD of 1.0%, 1.1%, 1.2%, 1.3%,  1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.25%, 2.5%, 2.75%, 3.0%, 3.25%, 3.5%, 3.75%, 4.0%,  4.25%, 4.5%, 4.75%, 5.0%, 5.5%, 6.0%, 6.5%, or within any range bounded by any two of those  values  (e.g.,  0.8%  to  2.0%,  0.9%  to  2.25%,  2.0%  to  5.0%,  4.0%  to  6.0%,  and  so  on).    In  embodiments, the display article 10 exhibits a PPD of less than 4.0%, less than 4.0%¸ less than  3.0%¸ or less than 2.0%.  [0092] In  embodiments,  the  substrate  12  exhibits  a  distinctness‐of‐image  (“DOI”).    As  used  herein, “DOI”  is equal to 100*(RS‐ R0.3˚)/RS, where RS  is the specular reflectance flux measured  from  incident  light  (at 20˚  from normal) directed onto  the  textured  region 20, and R0.3  is  the  reflectance flux measured from the same incident light at 0.3˚ from the specular reflectance flux,  RS.   Unless otherwise noted, the DOI values and measurements reported  in this disclosure are  obtained according  to  the ASTM D5767‐18, entitled  “Standard Test Method  for  Instrumental  Measurement of Distinctness‐of‐Image (DOI) Gloss of Coated Surfaces using a Rhopoint IQ Gloss  Haze & DOI Meter”  (Rhopoint  Instruments Ltd.).   The values are  reported here as “coupled”  meaning that the sample  is coupled with  index matching fluid to the back‐side surface of the  substrate  during  the  measurement  to  reduce  backside  reflections.  In  embodiments,  the  substrate 12 exhibits a distinctness‐of‐image (“DOI”) of 15%, 20%, 25%, 30%, 35%, 40%, 45%,  50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 96%, 97%, 98%, 99%, or 99.9%, or  within any range bounded by any two of those values (e.g., 20% to 40%, 10% to 96%, 35% to 60%,  and so on).  [0093] In embodiments, the substrate 12 exhibits a transmission haze.  As used herein, the term  “transmission haze” refers to the percentage of transmitted light scattered outside an angular  cone of about ±2.5° in accordance with ASTM D1003, entitled “Standard Test Method for Haze  and Luminous Transmittance of Transparent Plastics,” the contents of which are incorporated by  reference herein in their entirety.  Note that although the title of ASTM D1003 refers to plastics,  the standard has been applied to substrates comprising a glass material as well.  For an optically  smooth surface, transmission haze is generally close to zero.  In embodiments, the substrate 12  exhibits a transmission haze of 0.7%, 0.8%, 0.9%. 1.0%, 1.5%, 2%, 3%, 4%, or 5%, or within any  range bounded by any two of those values (e.g., 0.7% to 3%, 2% to 4%, and so on).  [0094] In embodiments, the substrate 12 exhibits a specular reflectance of 1 GU, 2 GU, 3 GU, 4  GU, 5 GU, 10 GU, 15 GU, 20 GU, 25 GU, 30 GU, 40 GU, 50 GU, 60 GU, 70 GU, 80 GU, or within any  range bounded by any two of those values (e.g., 1 GU to 3 GU, 5 GU to 30 GU, 50 GU to 80 GU,  and so on).  In embodiments, the substrate 12 exhibits a specular reflectance that is less than less  than 25 GU less than 20 GU, less than 15 GU, less than 10 GU, less than 5 GU, or less than 2 GU.   Specular reflectance here, noted as “c‐Rspec” “or “coupled Rspec” in the Examples that follow,  refers to the value obtained in gloss units (GU) using a Rhopoint IQ goniophotometer.  The values  are indicative of how much specular reflection is measured when the sample is optically coupled  to a perfect absorber.  A value of 100  GU means 4.91% specular reflection from a polished flat  black glass surface of refractive index 1.567 at 20 degrees angle of incidence.    [0095] Referring now to FIGS. 6‐10, a method 100 of forming the textured region 20  is herein  disclosed.  At a step 102, the method 100 includes forming the primary surface features 26 into  the primary surface 18 of  the substrate 12 according  to a predetermined positioning of each  primary surface feature 26.  The step 102, at least for the moment, forms the textured region 20.    [0096] In  embodiments,  at  a  step  104,  the  method  100  further  includes  determining  the  positioning of each primary surface feature 26 utilizing a spacing distribution algorithm.  Example  spacing distribution algorithms include Poisson disk sampling, maxi‐min spacing, and hard‐sphere  distribution.  For example, Poisson disk sampling inserts a first object (e.g., a point or a circle with  a diameter) into an area of a plane.  Then the algorithm inserts a second object within the area,  placing  the center at a  random point within  the area.    If  the placement of  the second object  satisfies the minimum center‐to‐center distance  from the  first object, then the second object  stays  in the area.   The algorithm then repeats this process until no more such objects can be  placed within  the area  that  satisfies  the minimum  center‐to‐center distance.   The  result  is a  random distribution, but specific placement, of the objects.  From the random distribution but  specific  placement  of  the  objects,  the  positioning  of  the  primary  surface  features  26  are  determined.   For example,  if the objects positioned via the spacing distribution algorithm are  points,  then  the points can be  the center of circles with a certain diameter, or  the center of  hexagons with certain geometry.  In other embodiments, the points are triangulated, inellipses  formed  in  the  triangles, and  then  the  triangulations and points are  removed  leaving ellipses,  which can be shape of the primary surface features 26.   [0097] In embodiments, the step of 102 forming the primary surface features 26 into the primary  surface 18 includes contacting the primary surface 18 with an etchant while an etching mask is  disposed on the primary surface 18 to permit only selective etching of the substrate 12 to form  the primary  surface  features 26.   The etching mask  includes  voids  that  allow  the etchant  to  remove material from the primary surface 18 of the substrate 12 and, outside of the voids, the  etching mask prevents the etchant from contacting the primary surface 18 of the substrate 12.   In embodiments,  the  voids  allow  the etchant  to  remove material  and  thereby  to  create  the  primary surface features 26 set into the surrounding portion 42, which the etching mask protects  from  the  etchant.    In  embodiments,  the  voids  allow  the  etchant  to  remove material  of  the  substrate  12 where  the  surrounding  portion  42  is  to  be  but  not where  the  primary  surface  features  26  are  to  be,  resulting  in  the  primary  surface  features  26  projecting  from  the  surrounding portion 42.  In short, the etching mask incorporates the predetermined positioning  of each primary surface feature 26 as either a positive or negative.  [0098] In embodiments, the etchant includes one or more of hydrofluoric acid and nitric acid.  In  embodiments, the etchant includes both hydrofluoric acid and nitric acid.   The etchant can be  sprayed onto the substrate 12 while the etching mask is on the substrate 12.  The substrate 12  with the etching mask can be dipped into a vessel containing the etchant.  In embodiments, the  etchant contacts the substrate 12 for a time period of 10 seconds, 20 seconds, 30 seconds, 40  seconds, 50 seconds, or 60 seconds, or within any range bounded by any two of those values  (e.g., 10 seconds to 60 seconds, and so on).  After the period of time has concluded, the substrate  12 is rinsed in deionized water and dried.  The longer the period of time that the etchant contacts  the substrate 12, the deeper the etchant etches into the substrate 12 and thus the greater the  change in elevation 50 of the primary surface features 26.     [0099] In embodiments, at a step 106, the method 100 further includes forming the etching mask  by exposing a photoresist material disposed on the primary surface 18 of the substrate 12 to a  curing agent while a lithography mask is disposed on the photoresist material.  The thickness of  the photoresist material  can  vary  from  about 3 µm  to  about  20 µm  depending on how  the  photoresist material  is added  to  the primary surface 18 of  the substrate 12.   The photoresist  material can be added via spin coating (< 3 µm thickness), screen coating (< 15 µm thickness), or  as a dry film (< 20 µm thickness).  [0100]  The  lithography mask  includes material  and  voids  through  the material  to  selectively  expose portions of the photoresist material to the curing agent.   The voids of the  lithography  mask are positioned according to the predetermined positioning of the primary surface features  26, either as a positive or negative.  The placement of each of the primary surface features 26 is  determined,  such  as  with  the  spacing  distribution  algorithm  and  the  lithography  mask  incorporates that determined placement.  The lithography mask then allows selective curing of  the etching mask, which then incorporates that predetermined placement of the primary surface  features 26.  Then finally the etching mask allows for selective etching of the substrate 12, which  translates the determined placement of the primary surface features 26 onto the primary surface  18 of the substrate 12 as the textured region 20.  The substrate 12 with the etching mask can be  baked before the etching mask contacts the etchant in order to ensure adhesion to the substrate  12.    [0101] At a step 108, which occurs after the step 102, the method 100 further includes forming  the secondary surface features 36 into the one or more sections 34 of the textured region 20.   This step 108 increases the surface roughness (Ra) at the one or more sections 34 to within the  range of 5 nm  to 100 nm.    In embodiments,  the  step 108 of  forming  the  secondary  surface  features 36 into one or more sections 34 of the textured region 20 comprises contacting the one  or more sections 34 of the textured region 20 of the substrate 12 with a second etchant.  The  second etchant is different than the etchant that was utilized to etch the primary surface features  26 into the primary surface 18 of the substrate 12.  In embodiments, the second etchant includes  acetic acid and ammonium fluoride.  In embodiments, the second etchant includes (in wt%): 85  to 98 acetic acid, 0.5 to 7.5 ammonium fluoride, and 0 to 11 water.  The water can be deionized  water.    In embodiments, the second etchant contacts the one or more sections 34 for a time  period within a range of 15 seconds to 5 minutes. In embodiments, the second etchant contacts  the one or more sections 34 while the etching mask used to form the primary surface features  26 remains on the substrate 12.  This would result in the increase of the surface roughness (Ra)  of  only  the  primary  surface  features  26  and  not  the  surrounding  portion  42,  or  only  the  surrounding portion 42 and not the primary surface features 26.   After the period of time has  concluded the substrate 12 is rinsed with deionized water and dried.  Both etching steps 102, 108  can be conducted at room temperature.  [0102] The method 100 is scalable and low‐cost.  In addition, the method 100 is repeatable and  is  able  to  reproduce  the  textured  region  20  with  the  essentially  the  same  geometry  from  substrate 12 to substrate 12.  That is different than the previous methods, such as sand‐blasting  or open etching, where the geometry of the textured region 20 varied from one substrate 12 to  the next.    [0103] EXAMPLES  [0104] Example 1 – Example 1  is computer modeling  that explores  the  impact of  the  second  surface features.  Example 1 assumes that the textured region is as illustrated in FIGS. 2 and 3,  with primary surface features arranged in a hexagonal pattern.  Each primary surface feature has  a hexagonal perimeter and an aspheric surface facing the external environment.  Each aspheric  surface is governed by the equation:  ^
Figure imgf000027_0001
where  z(r)  is the sag – the z‐component of the displacement of the surface from the vertex, at  the distance from z axis.  The z‐axis  is perpendicular to the base‐plane.   The  a0,  a4,  a6 are all  coefficients that describe the deviation of the surface from the axially symmetric quadric surface  specified by R and κ.  If the coefficients are all zero, which they are assumed to be here,  then R  is  the  radius of curvature and κ  is  the conic constant, as measured at  the vertex.   When  the  change  in elevation of the surface along the z‐axis  is a negative value, then the surface of the  primary surface features are concave.  In contrast, when the change in elevation of surface of the  primary  surface  features along  the z‐axis  is positive,  then  the  surface of  the primary  surface  features is convex.  [0105] Example 1 further assumes that the secondary surface features generate a light scattering  distribution that can be described by the Gaussian scattering function:  ଶ ^^
Figure imgf000027_0002
where,  θ  is the angle (degree) from the specular direction, I(θ) is radiance in the  θ direction, I0  is radiance in the specular direction, and  σ  (sigma) is the standard deviation (or scattering factor)  of the Gaussian distribution, in degree.  As  σ  increases, the scattering angle increases.   [0106] Zemax  ray  tracing  software  (Zemax, LLC of Kirkland, Washington, USA) was utilized  to  model  distinctness‐of‐image,  pixel  power  deviation,  and  transmission  haze  as  a  function  of  change of elevation (height) of the primary surface features and the  σ  provided by the secondary  surface features.  The modeling assumed that the substrate had a thickness of 0.3 mm, that the  refractive index of the substrate was 1.49, and the substrate had no light absorption.    [0107] FIG. 7A reproduces a graph of the calculations of the model pertaining to distinctness‐of‐ image.  As the graph reveals, increasing change in elevation (i.e., height or depth) of the primary  surface  features  decreases  distinctness‐of‐image.   When  no  secondary  surface  features  are  present (sigma = 0) on the primary surface features, then the primary surface features do not  begin to decrease distinctness‐of‐image until the change in elevation (height or depth) is greater  than 0.08 µm.  However, when secondary surface features are present on the primary surface  features,  increasing  height  of  the  primary  surface  features  instantly  causes  a  decrease  in  distinctness‐of‐image.  [0108] FIG. 7B reproduces a graph illustrating the difference the presence of secondary surface  features on the primary surface features makes for decreasing distinctness‐of‐image compared  to if the secondary surface features were absent.  When sigma=0.20 degree, the presence of the  secondary  surface  features  further  decreases  the  distinctness‐of‐image,  compared  to  if  no  secondary surface features were present, for all heights of the primary surface features from ‐ 0.24 µm  to + 0.24 µm.   The presence of  the secondary surfaces  features  (providing  σ  = 0.20  degrees) decreases  the distinctness‐of‐image by a maximum of ~29% when  the height of  the  primary  surface  features  is  ~  0.10  µm,  compared  to  if  no  secondary  surface  features were  present.    When  σ   =  0.41  degree,  the  presence  of  the  secondary  surface  features  further  decreases the distinctness‐of‐image, compared to if no secondary surface features were present,  for all heights of  the primary surface  features  from  ‐0.27 µm  to + 0.27.   The presence of  the  secondary surfaces features (providing  σ  = 0.41 degrees) decreases the distinctness‐of‐image by  a maximum of ~25% when the height of the primary surface features is ~ 0.18 µm, compared to  if no secondary surface features were present.   [0109] In short, for any given height/depth of the primary surface features, there is an optimal  σ   value to be incorporated as the secondary surface features in order to maximize the contribution  that  the  secondary  surface  features has on decreasing  the distinctness‐of‐image.   The  graph  reproduced at FIG. 7C reveals the optimum value for  σ , to minimize distinctness‐of‐image, as a  function  of  change  in  elevation  (height)  of  the  primary  surface  features.    The  smallest  distinctness‐of‐image values of 92%, 66%, 49% respectively for primary surface feature heights  of 0.00  (flat),  ‐0.10 µm, and  ‐0.14 µm are achieved with  σ  being 0.14, 0.20, and 0.28 degree,  respectively.  [0110] Next, the modeling software calculated pixel power deviation as a function of the height  of the primary surface  features and  σ  value.   FIGS. 7D and 7E each reproduce a graph of the  calculations.  The graphs reveals that, as the height of the primary surface features increases, the  pixel power deviation increases.  However, as the value for σ provided by the secondary surface  features increases, for any given height of the primary surface features, the pixel power deviation  decreases.  The secondary surface features cause scattering that evens the angular and spatial  distributions of the light transmitting through the primary surface features and thus reduces the  pixel power deviation.   The effect that the secondary surface  features have on reducing pixel  power deviation becomes greater as  the height of  the primary surface  features  increases.    In  short, the presence of the secondary surface features on the primary surface features introduces  surface  scattering  that  can  reduce distinctness‐of‐image  (for  a  given  range of heights of  the  primary surface features) and generally reduces pixel power deviation.    [0111] Finally, the modeling software calculated transmission haze as a function of the height of  the  primary  surface  features  and  σ   value.    FIGS.  7F  and  7G  each  reproduce  a  graph  of  the  calculations.  The graph of FIG. 7F reveals that increasing  σ  value increases generally increases  pixel power deviation, and  increasing the height of the primary surface features magnifies the  affect that  increasing  σ  value on increasing pixel power deviation (but only slightly).  The graph  of FIG. 7G reveals however that  σ  has to be above a certain value before  σ  causes an increase in  pixel  power  deviation.  In  the  instance  of  FIG.  7G, where  the  primary  surface  features were  assumed to have a height of ‐0.1 µm and a width of 100 µm, the  σ  only begins to increase pixel  power deviation when the value for  σ  is about 0.35 or higher.  The value for  σ  can be greater  than 0.35,  in order to further reduce pixel power deviation and distinctness‐of‐image,  if those  benefits outweigh  the  increase  in  transmission haze.    For example, even at a  σ   value of 0.7  degree, which maximizes the reduction in pixel power deviation and distinctness‐of‐image, the  transmission haze is only 20%, which may be acceptable for a given application.    [0112] Thus, as  long as  the  σ   value  is  configured  to be  right below 0.35,  the affect  that  the  secondary features have on decreasing distinctness‐of‐image and pixel power deviation does not  simultaneously cause an  increase  in  transmission haze.   For example, when  the height of  the  primary surface features are ‐0.1 µm and the  σ  value is 0.41 degree, the calculated distinctness‐ of‐image is ~74%, the pixel power deviation is ~2.5%, and the transmission haze is ~1%.  When  the  height  of  the  primary  surface  features  are  ‐0.1  µm  and  the  σ   value  is  0.2  degree,  the  calculated  distinctness‐of‐image  is  ~64%,  the  pixel  power  deviation  is  ~3.5%,  and  the  transmission haze is ~0%.  When the height of the primary surface features are ‐0.08 µm and the  σ  value is 0.41 degree, the calculated distinctness‐of‐image is ~85%, the pixel power deviation is  ~2%, and the transmission haze is ~0%.  When the height of the primary surface features are ‐ 0.08 µm and the  σ  value is 0.20 degree, the calculated distinctness‐of‐image is ~73%, the pixel  power deviation is ~2.5%, and the transmission haze is ~0%.  [0113] In  sum,  the modeling  demonstrates  that  the  incorporation  of  the  secondary  surface  features on the primary surface features to impart the surface roughness that causes a certain  scattering  level can  result  in a  low distinctness‐of‐image,  low pixel power deviation, and  low  transmission  haze  all  simultaneously  –  something  not  achievable with  previous methods  of  forming the textured region.   [0114] Examples 2A‐2D – For Examples 2A‐2D, four (4) samples of glass were prepared.   Each  sample was etched with an etchant of differing compositions to model the effect that the etchant  would have on the generation of secondary surface features to impart a surface roughness within  a range of 5 nm to 100 nm.  All compositions of the etchant included acetic acid and ammonium  fluoride  (NH4F)  in  varying weight percentages.   Table 1,  immediately, below  summarizes  the  compositions of the four etchants tested. 
Figure imgf000031_0001
Each etchant composition contacted the primary surface of the glass substrate for a time period  of 2 minutes.   [0115] After the etchant for each example etched the glass sample for the 2‐minute period of  time, the surface roughness was determined utilizing an atomic force microscope with a 5 µm by  5  µm  scan  size.    Images  that  the  atomic  force microscope  captured  for  each  example  are  reproduced at FIG. 8.  The images show the secondary surface features that impart the desired  surface roughness.  Table 2 immediate below reports the measured surface roughness for each  sample.  In addition, the σ value, the surface scattering factor, was measured for each sample.   Here,  the  measurement  method  of  the  surface  scattering  factor  is  as  follows.  First,  the  transmission haze of a sample  is measured. Then, a raytracing model with Gaussian scattering  function for describing surface scattering is used to find proper surface scattering factor which  results the same transmission haze as the measured one.  Those values too are reported in Table  2 below.   
Figure imgf000031_0002
  [0116] In general, the higher the weight percentage of water, the higher the surface roughness  that was generated during the same two minute period of time.  In turn, the higher the surface  roughness,  the  higher  the  surface  scattering  σ   value.    Thus,  the  surface  roughness  can  be  controlled via manipulating the water content of the composition of the etchant, and thus the  acetic acid and ammonium fluoride content of the composition of the etchant.    [0117] In  addition,  the  transmission  haze,  coupled  distinctness‐of‐image,  and  pixel  power  deviation was measured for each sample.  Table 3, immediately below, reproduces the results. 
Figure imgf000032_0001
Analysis of the results reveal that the higher the surface roughness, the greater the transmission  haze.    [0118] A graph reproduced at FIG. 8B reproduces the results.  In addition, a reproduced at FIG.  8D sets forth measured transmission haze as a function of measured surface scattering  σ  (sigma)  value  for each  sample,  and  then  a  line  is modeled  to  fit  the data.   The modeled  line  fitting  measured data agrees with the ray scattering model of Example 1 that indicated that the surface  scattering σ value had to reach a certain value before it began to impart increased transmission  haze.    [0119] Examples 3A and 3B – Examples 3A and 3B demonstrate the effect that the secondary  surface features (imparting the surface roughness) has on pixel power deviation for samples were  primary surface features are also present.  For the samples of both Example 3A and 3B, primary  surface features were etched into a glass substrate.  The composition of the etchant included 1  wt% hydrofluoric acid  (HF) and 2 wt% nitric acid  (HNO3).   The etchant contacted  the primary  surface of  the glass substrate  for 25 seconds,  resulting  the primary surface  features having a  depth of 150 nm  from a  surrounding portion.   A dry  film  resist etching mask was utilized  to  position the primary surface features in a hexagonal pattern set into the surrounding portion (see  FIG. 5).   The perimeter of each primary surface  feature was hexagonal as well.   Each primary  surface  feature was  separated  by  a  center‐to‐center  distance  of  120 µm.   Adjacent  primary  surface features were separated, perimeter to perimeter, by a distance of 55 µm.   One of the  samples was  retained  as  Example  3A  and  no  secondary  surface  features were  subsequently  added to the sample of Example 3A  [0120] For Example 3B, the sample was subjected to a second etching step to impart secondary  surface features.  The second etching step used an etchant with a composition of 92 wt% acetic  acid,  2 wt%  ammonium  fluoride,  and  6 wt% water  (deionized).    The  etchant  contacted  the  primary surface with the primary surface features for a period of time of 2 minutes.  The etchant  formed  the  secondary  surface  features within  the  textured  region, which  imparted a  surface  roughness (Ra) of ~28 nm.  [0121] The pixel power deviation that the samples of both Example 3A and Example 3B generated  were measured.   The measured pixel power deviation was sensitive  to the orientation of  the  sample  to  the  display  pixel  array,  because  the  primary  surface  features  had  a  hexagonal  perimeter.  A graph reproduced at FIG. 9A reproduces the measured pixel power deviation for  both Examples 3A and 3B as a function of the orientation angle 52 of the sample.  The schematic  illustration at FIG. 9B shows what orientation angle means.   In short, the substrate  is over the  display, with the textured region at the primary surface facing away from the display.  The display  has pixels 54.  The substrate forms the orientation angle relative to the display.  As the substrate  is rotated relative to the display about an axis extending through the substrate orthogonal to the  primary surface, the orientation angle changes.    [0122] Analysis of the graph of FIG. 9A reveals that the Example 3B, with the added secondary  surface features over the primary surface features to impart surface roughness, lowered the pixel  power deviation compared to Example 3A, which included only the primary surface features.  The  secondary  surface  features  lowered  the pixel power deviation by ~0.2%  to 2.5%  (in absolute  terms), depending on orientation angle of the substrate relative to the display.  For example, at  the orientation angle of 85%, the pixel power deviation of Example 3A was 6.5%, while the pixel  power deviation of Example 3B was 4.0%, for a reduction (in absolute terms) of 2.5%, (or a 41.7%  relative reduction in pixel power display, where 6.5%‐4.0%=2.5% and 2.5%/6.5%*100% is 41.7%).   The results suggest that the effect that the secondary surface features has on the pixel power  deviation of the sample is a function of the geometry of the primary surface features.  [0123] Examples 4A‐4H – For each of Examples 4A‐4H, a glass substrate was obtained having  dimensions of 4 mm by 4 mm by 0.7 mm.  The glass substrate was then subjected to a first etching  step  to  etch  primary  surface  features  set  into  a  surrounding  portion.    Each  primary  surface  feature had a perimeter that was circular.  The diameter of the perimeter was 40 µm.  An etching  mask was utilized to place each of the primary surface features.  The placement of each of the  primary  surface  features was  generated using  a  spacing distribution  algorithm.    The  spacing  distribution algorithm required a minimum center‐to‐center distance between circles of 50 µm.   The placement of the primary surface  features pursuant to the spacing distribution algorithm  was thus randomized and did not form a pattern.  The placement of the primary surface features  made pursuant to the spacing distribution algorithm was transferred to a lithograph mask, which  was then used to cure AZ 4210 lithography ink disposed on the primary surface of the substrate.   The uncured portions of the lithograph ink was removed and the cured portion remained as the  etching mask.   The primary surface  features occupied about 50% of  the area of  the  textured  region, and  the depth of  the primary  surface  features was 0.18 µm. The etchant of  the  first  etching step comprised 1 wt% hydrofluoric acid (HF) and 2 wt% nitric acid (HNO3).  The etchant  contacted the substrate for a period of time to achieve the target 150nm depth based on etch  rate.  For of the samples were then set aside as Example 4A‐4D and not subjected to a second  etching step to impart secondary surface features.    [0124] The remaining four samples were assigned to be Examples 4E‐4H and each subjected to a  second  etching  step  using  an  etchant  including  acetic  acid,  ammonium  fluoride,  and water  (deionized).  The etchant for Examples 4E and 4F had a composition of 92 wt% acetic acid, 2 wt%  ammonium fluoride, and 6 wt% water (deionized).  The second etching step for Examples 4E and  4F formed secondary surface features that  imparted a surface roughness (Ra) of ~28nm.   The  etchant  for Examples 4G and 4H had a composition of 90 wt% acetic acid, 1 wt% ammonium  fluoride, and 9 wt% water (deionized).    In each of Examples 4E‐4H, the etchant contacted the  sample of a time period of 2 minutes. The second etching step for Examples 4G and 4H formed  secondary surface features that imparted a surface roughness (Ra) of ~54nm.    [0125] Referring  now  to  FIGS.  10A‐10D,  the  pixel  power  deviation  (FIG.  10A),  the  specular  reflectance (FIG. 10B), the distinctness‐of‐image (FIG. 10C), and the transmission haze (FIG. 10D)  were measured for each example.  The measurements are set forth in the aforementioned graphs  at FIGS. 10A‐10D.   Analysis of the graphs reveal that the second etching step that formed the  secondary surface  features that added surface roughness to the textured region resulted  in a  lowering  of  pixel  power  deviation  and  distinctness‐of‐image  but  resulted  in  increasing  the  transmission haze.  The higher surface roughness of that the secondary surface features imparted  to Examples 4G and 4H did not result  in a different scale of  lowering of distinctness‐of‐image  compared to Examples 4E and 4F.  However, the higher surface roughness of that the secondary  surface features imparted to Examples 4G and 4H did result in a larger decrease in pixel power  deviation compared to Examples 4E and 4F but with a larger increase in transmission haze.  The  addition  of  the  secondary  surface  features  did  not  appear  to  affect  measured  specular  reflectance.   [0126] Examples 5A‐5O – For Examples 5A‐5O, a spacing distribution algorithm was utilized to  randomly but specifically place points within an area.  Each of the points were to be separated  by a minimum distance of 105 µm.  The points were then triangulated, an inellipse drawn in each  triangle, and then the points and triangles were removed.  The longest dimension of the ellipses  now remaining in the area were scaled down so that the ellipses occupied 50 percent of the area.   The placement of the ellipses was then transferred to a lithography mask.  The lithography mask  was used to form an etching mask on the primary surface of a glass substrate.  Each substrate  was then etched with the etching mask on the substrate.  The etchant utilized had a composition  of 0.15wt% hydrofluoric acid and 1wt% nitric acid.  The etchant contacted the primary surface  with the etching mask for a period of time set forth  in Table 4  immediately below that varied  among the samples.  The etchant formed primary surface features having an elliptical perimeter  set into a surrounding portion.  The depth of the primary surface features varied, and the depth  for each sample is set forth below.   
Figure imgf000035_0001
Figure imgf000036_0001
  [0127] After removal of the etching mask, the samples of 5M‐5O were then subjected to a second  etching step to form secondary surface features at the primary surface.  The second etching step  used an etchant with a composition of 92 wt% acetic acid, 2 wt% ammonium fluoride, and 6 wt%  water (deionized).  The etchant contacted the substrate for a time period of 120 seconds.  The  secondary  surface  features  so  formed  imparted  a  surface  roughness  (Ra)  of  ~  28nm  to  the  textured region at the primary surface.    [0128] The pixel power deviation, distinctness‐of‐image, specular  reflection, and  transmission  haze were measured for the sample of each of Examples 5A‐5O.  The measured results are set  forth in the graphs of FIGS. 11A‐11D, which plot the measured value as a function of the depth  of the primary surface features with the elliptical perimeter.  Analysis of the graphs reveal that  the secondary surface  features  to  impart surface roughness of Examples 5M‐5O resulted  in a  lower pixel power deviation  and  specular  reflectance  compared  to when no  such  secondary  surface features were included in Examples 5A‐5L.  However, the secondary surface features to  impart  surface  roughness of  Examples  5M‐5O  resulted  in  a higher distinctness‐of‐image  and  transmission  haze  compared  to when  no  such  secondary  surface  features were  included  in  Examples 5A‐5L.    In general, the  introducing of the secondary surface features to the primary  surface features can be either  increase or decrease   the distinctness‐of‐image, which depends   on the design of the primary surface features.  Unlike the model of Example 1, the design of the  primary  surface  features  of  this  experimental  sample  resulted  in  the  increasing  of  the  distinctness‐of‐image.  [0129] Example 6A‐6C –Examples 6A and 6B are two different sets of samples, each with primary  surface features having an elliptical perimeter,  just as  in Examples 5A‐5O.   The difference was  that for the samples of Example 6A, the etching mask used while forming the primary surface  features was kept on the substrate while the second etching step was performed to generate the  secondary  surface  features.   For  the  samples of Example 6B,  the etching mask was  removed  before the second etching step was performed to generate the secondary surface features.  Thus,  in the samples of Example 6A, the secondary surface features and the added surface roughness  were formed only on surfaces provided by the primary surface features and not the surrounding  portion.   In contrast, with the samples of Example 6B, the secondary surface features and the  added  surface  roughness  were  formed  on  the  entire  textured  region  including  both  the  surrounding portion and the surfaces provided by the primary surface features.    [0130] A scanning electron microscope captured images of a sample from both Example 6A and  Example 6B.  The images are reproduced at FIG. 12A.  The images on the left show the primary  surface features with the elliptical perimeters set into the surrounding portion.  The images in  the middle show the secondary surface features.  The images on the right show the etching depth  of the secondary surface features.     [0131] The pixel power deviation, transparency haze, and specular reflectance of samples from  both Examples 6A and 6B were measured.   A Rhopoint  instrument was utilized  to determine  specular  reflectance.   The graphs  reproduced at FIGS. 12B‐12D  set  forth  the measured data.   Analysis of  the  graphs  reveal  that  the  samples of  Example  6B, where  the  etching mask was  removed before the second etching step to impart second surface features throughout the entire  textured region, resulted in a lower pixel power deviation but higher transmission haze compared  to the samples of Example 6A, where the etching mask was maintained during the second etching  step and thus the second surface features were imparted only to the surfaces provided by the  primary surface features.    [0132] The  Rhopoint  instrument  utilized  to measure  specular  reflectance  did  not measure  a  difference between the samples of Examples 6A and 6B.   However, the device could measure  differences in specular reflectance when a 6 degree angle of incidence for the light to be reflected  and a 2 degree aperture to measure the specular reflectance.  The graph reproduced at FIG. 12E  shows the measured data for samples of Examples 6A and 6B, as well as for a sample (Example  6C) where only the primary surface  features were present and did not  include the secondary  surface features to impart surface roughness.  Analysis of the graph of FIG. 12E reveals that the  presence of the secondary surface features in Examples 6A and 6B reduced specular reflectance  compared to when the secondary surface features were absent in Example 6C.  The difference in  specular reflectance between Examples 6A and 6B is wavelength dependent.    [0133] Example 7 – For Example 7, a sample was prepared similar to the samples Examples 5M‐ 5O, where primary surface features with an elliptical perimeter are set into a surrounding portion  in a first etching step forming textured region, and then secondary surface features are etched  throughout the entire textured region to increase surface roughness.  The sample so prepared  was then analyzed with a white light interferometer to measure the three dimensional profile of  the textured region.  FIG. 13A illustrates the three dimensional profile that was measured.  The  top  half  illustrates  relative  elevation  differences  between  primary  surface  features  and  the  surrounding  portion.    The  bottom  half  illustrates  the  topography  of  the  secondary  surface  features, with the topography of the secondary surface features added to the surfaces that the  primary surface features are provided illustrated at the left, and the topography of the secondary  surface features added to the surrounding portion illustrated at the right.  The three dimensional  profile of the secondary features within the primary surface features is measurably different than  the three dimensional profile of the secondary features at the surrounding portion – with the  surrounding portion showing deeper secondary features.    [0134] An atomic force microscope was utilized to image and determine the surface roughness  (Ra)  imparted by  the  secondary  surface  features at both  (i) a  surface provided by a primary  surface feature and (ii) at the surrounding portion.  The images are reproduced at FIG. 13B.  The  image on the  left  is of the secondary surface  features at the surface provided by the primary  surface feature, and shows a surface roughness (Ra) of 15.3 nm.  The image on the right is of the  secondary surface features at the surrounding portion, and shows a surface roughness (Ra) of  33.5 nm.  The image on the right and the higher surface roughness (Ra) value at the surrounding  portion matches  the  topography  date  illustrated  at  FIG.  13A.    The  surrounding  portion was  covered by the etching mask during the formation of the primary surface features and thus had  not been contacted with an etchant, unlike the primary surface features which were created by  the first etching step.  Thus, it is believed that the surrounding portion, previously untouched by  an  etchant, was more  sensitive  to  the  second  etching  step  to  impart  the  secondary  surface  features.       

Claims

CLAIM(S)  What is claimed is:  1. A  substrate for a display article, the substrate comprising:  a primary surface; and  a textured region on at least a portion of the primary surface;   the textured region comprising:  primary  surface  features, each comprising a perimeter parallel  to a base‐plane  extending  through  the  substrate  disposed  below  the  textured  region,  wherein  the  perimeter of each of the primary surface features comprises a  longest dimension of at  least 5 µm; and  one or more sections each comprising secondary surface features having a surface  roughness (Ra) within a range of 5 nm to 100 nm.   
2. The substrate of claim 1, wherein  the primary surface features form a pattern.   
3. The substrate of any one of claims 1‐2, wherein  the longest dimension of each of the primary surface features is about the same.   
4. The substrate of any one of claims 1‐3, wherein  an arrangement of the surface features reflect a random distribution.   
5. The substrate of any one of claims 1‐4, wherein  the perimeter of each primary surface features is elliptical.   
6. The substrate of any one of claims 1‐4, wherein  the perimeter of each primary surface features is circular.   
7. The substrate of any one of claims 1‐4, wherein  each primary  surface  feature provides a  surface, and  the  surface  is either  concave or  convex.   
8. The substrate of any one of claims 1‐7, wherein the textured region further comprises:  a surrounding portion into which the primary surface features are set or out of which the  primary surface features project.   
9. The substrate of any one of claims 1‐8, wherein  the primary surface features that are adjacent to one another have perimeters that are  separated by a distance within a range of 1 µm to 100 µm; and  the primary surface features that are adjacent to one another are separated by a center‐ to‐center distance within a range of 5 µm to 150 µm.   
10. The substrate of any one of claims 1‐9, wherein  each of the primary surface features comprises a change in elevation perpendicular to the  base‐plane that is within a range of 0.05 µm to 0.50 µm.   
11. The substrate of any one of claims 1‐6 and 8‐10, wherein  each primary surface features provides a surface, and  the  secondary  surface  features  are  disposed  on  the  surfaces  of  the  primary  surface  features.   
12. The substrate of any one of claims 1‐6, 9, and 10, wherein the textured region further  comprises:  a surrounding portion into which the primary surface features are set into or out of which  the primary surface features project;   wherein, each primary surface feature provides a surface,  wherein, the secondary surface features are disposed on both the surrounding portion  and on the surfaces of the primary surface features, and  wherein, the surface roughness at the surfaces of the primary surface features is less than  the surface roughness at the surrounding portion.   
13. The substrate of any one of claims 1‐6, 9, and 10 further comprising:   a surrounding portion into which the primary surface features are set into or out of which  the primary surface features project;   wherein,  the  secondary  surface  features  are disposed on  the  surfaces of  the primary  surface features but not on the surrounding portion.     
14. The substrate of any one of claims 1‐13, wherein  the substrate comprises a glass or glass‐ceramic.     
15. The substrate of any one of claims 1‐14, wherein  the textured region exhibits a transmission haze within a range of 1.5% to 3.5%;  the textured region exhibits a pixel power deviation within a range of 1.5% to 3.5%;  the textured region exhibits a distinctness‐of‐image within a range of 2.% to 5.0%; and  the textured region exhibits a specular reflectance within a range of 5 GU to 20 GU.     
16. A method of forming a textured region of a substrate, the method comprising:  forming primary  surface  features  into a primary  surface of a  substrate according  to a  predetermined positioning of each primary surface feature thus forming a textured region, each  primary  surface  feature  comprising  a  largest dimension parallel  to  a base‐plane  through  the  substrate disposed below the primary surface of at least 5 µm; and  forming  secondary  surface  features  into one or more  sections of  the  textured  region,  thereby increasing the surface roughness (Ra) of the one or more sections to within a range of 5  nm to 100 nm.   
17. The method of claim 16 further comprising:  determining  the  positioning  of  each  primary  surface  feature  utilizing  a  spacing  distribution algorithm.      
18. The method of any one of claims 16‐17, wherein  forming the primary surface features into the primary surface comprises contacting the  primary surface with an etchant while an etching mask  is disposed on the primary surface  to  permit only selective etching of the substrate to form the primary surface features.   
19. The method of claim 18, wherein  the etchant comprises hydrofluoric acid and nitric acid; and  the etchant contacts the substrate for a time period within a range of 10 seconds to 60  seconds.   
20. The method of any one of claims 16‐19 further comprising:  forming the etching mask by exposing a photorsesist material disposed on the primary  surface of the substrate to a curing agent while a lithography mask is disposed on the photoresist  material, the lithography mask comprising material and voids through the material to selectively  expose  portions  of  the  photoresist material  to  the  curing  agent, wherein  the  voids  of  the  lithography mask  are  positioned  according  to  the  predetermined  positioning  of  the  primary  surface features.   
21. The method of any one of claims 16‐20, wherein  forming the secondary surface features into one or more sections of the textured region  comprises contacting the textured region of the substrate with a second etchant, different than  the etchant used to form the primary surface features.   
22. The method of any one of claims 16‐21, wherein  the second etchant comprises acetic acid and ammonium fluoride.   
23. The method of any one of claims 16‐22, wherein  forming the primary surface features into the primary surface comprises contacting the  primary surface with an etchant while an etching mask  is disposed on the primary surface  to  permit only selective etching of the substrate to form the primary surface features, and  forming the secondary surface features into one or more sections of the textured region  comprises contacting the one or more sections of the textured region of the substrate with a  second etchant, different than the etchant used to form the primary surface features, while the  etching mask used to form the primary surface features remains on the substrate.        
PCT/US2021/040775 2020-07-09 2021-07-08 Anti-glare substrate for a display article including a textured region with primary surface features and secondary surface features imparting a surface roughness that increases surface scattering Ceased WO2022011073A1 (en)

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