Coated article having anti-fingerprint coating or surface-modified layer and method of making same

Abstract

Described herein are coated articles comprising a fluorine-free surface modification layer. In aspects, the surface modification layer includes a partial silica-like network having a ratio of Si-O-Si bonds to Si atoms in the anti-fingerprint coating of from about 2 to about 3. Additionally or alternatively, the surface modification layer further includes an alkylsilane at the outer surface and bonded to Si-O groups in the silica-like network. The method includes evaporating a functionalized polyhedral oligomeric silsesquioxane onto the first major surface. The method includes impinging an ion beam on the first major surface. Alternatively, the method includes disposing and heating a solution including a polysilazane or a polyhedral oligomeric silsesquioxane on the first major surface. In aspects, a method includes reacting a material at the first major surface with an alkylsilane.

Description

[0001] Priority Claims

[0002] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 598,993, filed on Nov. 15, 2023, and U.S. Provisional Application No. 63 / 431,065, filed on Dec. 8, 2022, under 35 U.S.C. § 119. The entire contents of each of these applications are hereby incorporated by reference herein for all purposes. Technical Field

[0003] The present disclosure generally relates to coated articles having a surface modification layer (e.g., a fingerprint-resistant coating) and methods of manufacturing the same, and more particularly to coated articles including a fluorine-free surface modification layer (e.g., a fingerprint-resistant coating) and methods of manufacturing the coated articles. Background Art

[0004] Glass, glass-ceramics, and ceramic materials are commonly used in a variety of consumer electronic products that include display devices such as liquid crystal displays (LCDs), electrophoretic displays (EPDs), organic light-emitting diode displays (OLEDs), plasma display panels (PDPs), and the like. For example, chemically strengthened glass is beneficial for many touchscreen products, including cell phones, music players, e-book readers, notepads, tablet computers, laptop computers, automated teller machines, and other similar devices. Many of these glass, glass-ceramic, and ceramic materials are also used in the displays and display devices of consumer electronic products that do not have touchscreen capabilities but are prone to direct human contact, including desktop computers, laptop computers, elevator screens, device displays, and the like. Glass, glass-ceramics, and ceramic materials are typically processed based on the end-use application of the material to provide aesthetic and functional properties. For example, anti-reflection, anti-glare, and fingerprint-resistant treatments are common treatments used on materials in touchscreen products.

[0005] The durability of some types of treatments (e.g., fingerprint-resistant coatings) can be limited, especially when used in combination with other treatments (e.g., anti-reflection coatings). The material selection for fingerprint-resistant and / or easy-to-clean (ETC) treatments typically relies on the ability of the treatment material on the surface to repel materials such as water, dust, and environmental debris, including sebum, oils, and proteins. Fingerprint-resistant and / or ETC treatments experience wear over time, such as from repeated touching, sliding, cleaning, etc. during use, which can affect the ability of the surface of the fingerprint-resistant and / or ETC treatment to maintain the ability to repel materials. It is known to use fluorosilanes, such as fluoroether silanes, which can be bonded to the surface as a single layer or multiple layers to form a coating with a thickness of 2 nm to 5 nm. Once this nanoscale coating is worn off, the surface no longer exhibits the repellent properties.

[0006] Accordingly, there is a need for a new surface modification layer (e.g., an anti-fingerprint coating) that can be used with glass, glass-ceramic, and / or ceramic articles having improved abrasion resistance and / or can be used in combination with other treatments (e.g., an anti-reflection coating). This disclosure addresses this need and other needs. SUMMARY OF THE INVENTION

[0007] Coated articles, surface modification layers (e.g., anti-fingerprint coatings), and methods of making the same are described herein. The surface modification layer (e.g., anti-fingerprint coating) can reduce the visibility and / or color shift associated with the placement of fingerprints thereon. Providing a low total surface energy of the surface modification layer (e.g., anti-fingerprint coating) (including a low dispersive surface energy and / or a low polar surface energy) can enable oils (e.g., fingerprint oils) to disperse on the anti-fingerprint surface (e.g., oleophilic), which can reduce the visibility and / or color shift associated with fingerprints. For example, providing an alkylsilane can reduce the surface energy (e.g., total surface energy, dispersive surface energy, polar surface energy) of the surface modification layer (e.g., anti-fingerprint coating), which can make the surface modification layer (e.g., anti-fingerprint coating) oleophilic. Providing a low hexadecane contact angle (e.g., about 30° or less) and / or a low diiodomethane contact angle (e.g., about 60° or less) can reduce the visibility and / or color shift associated with fingerprints by enabling fingerprint oils to disperse on the surface modification (e.g., anti-fingerprint coating) rather than coalescing into distinct droplets. Providing a high water contact angle (e.g., about 100° or greater) can enhance the removal of water-containing materials (e.g., water droplets, sweat droplets) from the surface modification (e.g., anti-fingerprint coating). Thus, the surface modification (e.g., anti-fingerprint coating) can be hydrophobic and oleophilic.

[0008] The surface modification layer (e.g., anti-fingerprint coating) provided in accordance with aspects of the present disclosure can exhibit good abrasion resistance (e.g., a wear water contact angle of about 90° or greater after 2,000 cycles, 3,000 cycles, and / or 3,500 cycles in a steel wool abrasion test, and a cheesecloth abrasion water contact angle of about 90° after 200,000 cycles in a cheesecloth abrasion test), thereby maintaining, for example, hydrophobic and / or oleophilic properties. The surface modification layer (e.g., anti-fingerprint coating) can exhibit good adhesion to a surface disposed, for example, on a substrate surface or an optical stack. Providing a thickness of the surface modification layer (e.g., anti-fingerprint coating) of about 100 nm to 600 nm or 1 nm to 75 nm can increase the durability of the surface modification layer (e.g., anti-fingerprint coating).

[0009] In various aspects, forming a surface modification layer (e.g., a fingerprint-resistant coating) can include evaporating functionalized POSS onto a substrate and bombarding the substrate with an ion beam. The properties of the coating can be controlled by the discharge current of the ion beam. For a KRI EH-400 end Hall ion source operating at 100 V in an AngstromEvovac chamber, providing a discharge current of about 0.25 A or greater can facilitate the formation of the coating, e.g., generating an ion beam with sufficient energy such that the functionalized POSS reacts with other functionalized POSS and / or the first major surface of the substrate at a perceivable rate (e.g., compared to a lower discharge current). Providing a discharge current of about 1 A or less to the ion beam source facilitates the deposition of the condensed POSS material. The ion beam discharge can promote the condensation of the functionalized POSS, converting at least a portion of the cage structure of the functionalized POSS into a partial Si-O-Si network. Evaporate the functionalized POSS and subject it to an ion beam to produce a partially condensed silica-like network at room temperature or near room temperature. Alternatively, the substrate onto which the thermally evaporated functionalized POSS condenses and is bombarded with the ion beam can be heated. The substrate temperature during POSS deposition is 250 °C or less, 200 °C or less, 100 °C or less, or preferably 50 °C or less. Alternatively, the partially condensed structure can be heated to 400 °C to 700 °C to produce a dense, high-modulus silica-like network, but this will result in poor wear properties. Thus, provide a maximum temperature of about 250 °C or less (e.g., about 220 °C or less, about 200 °C or less, about 180 °C or less, or about 160 °C or less) (e.g., by evaporating the functionalized POSS, bombarding with an ion beam, and subsequently functionalizing with silane) to obtain a surface modification layer (e.g., a fingerprint-resistant coating) with good abrasion resistance.

[0010] The surface modification layer (e.g., a fingerprint-resistant coating) can be formed by treating the partially condensed silica-like network with an alkylsilane, which can be done in situ (i.e., in the same chamber as the POSS deposition) or in a second chamber. The partially condensed silica-like network can be exposed to the vapor of the alkylsilane at an elevated temperature (e.g., about 100 °C to about 200 °C). Prior to treatment with a silane (e.g., an alkylsilane), the partially condensed silica-like network can optionally be subjected to plasma activation of the surface in an O2, air, or Ar plasma. The silane evaporation can be carried out at atmospheric pressure or under reduced pressure. Alternatively, the silane can be applied to the partially condensed silica-like network in solution form (e.g., dip coating). The plasma activation can be carried out at atmospheric pressure or under reduced pressure. Reacting the initial coating with a methoxysilane, chlorosilane, trialkoxysilane, trichlorosilane, or a combination thereof (e.g., dichloromethoxysilane, chlorodimethoxysilane) can ensure good bonding of the silane to the initial coating and achieve a low surface energy (e.g., a total surface energy of about 30 mN / m or less, a polar surface energy of about 5 mN / m or less).

[0011] As discussed in the examples below, it has been found that a surface modification layer (e.g., an anti-fingerprint coating) according to the present disclosure having an elastic modulus of from about 9 GPa to about 41 GPa has unexpectedly improved abrasion resistance. Providing a partial silica-like network can render the surface modification layer (e.g., an anti-fingerprint coating) hard (e.g., having an elastic modulus of about 9 GPa or greater), while maintaining sufficient flexibility to withstand wear. Additionally, as demonstrated by the results of steel wool abrasion tests, rubber abrasion tests, and cheesecloth abrasion tests, the surface modification layer (e.g., an anti-fingerprint coating) of the present disclosure can withstand wear and maintain a good contact angle. Providing a fluorine-free surface modification layer (e.g., a fluorine-free anti-fingerprint coating) can be produced more inexpensively and / or be more environmentally friendly.

[0012] The substrate can include a glass-based, glass-ceramic, and / or ceramic-based material, which can provide good dimensional stability, good impact resistance, and / or good puncture resistance. The glass-based, glass-ceramic, and / or ceramic-based substrate can include one or more compressive stress zones, which can further provide increased impact resistance and / or increased puncture resistance.

[0013] Some example aspects of the present disclosure are described below, and it should be understood that any of the features of the various aspects can be used alone or in combination with each other.

[0014] Aspect 1. A coated article comprising:

[0015] A substrate comprising a first major surface;

[0016] An anti-fingerprint coating disposed on the first major surface, the anti-fingerprint coating comprising the outer surface of the coated article, the anti-fingerprint coating having a thickness of from about 10 nanometers to about 600 nanometers, the anti-fingerprint coating comprising a partial silica-like network having a ratio of Si-O-Si bonds to Si atoms in the anti-fingerprint coating of from about 2 to about 3, and the anti-fingerprint coating being fluorine-free.

[0017] Aspect 2. The coated article according to aspect 1, wherein the anti-fingerprint coating has a refractive index in the range of from about 1.38 to about 1.55.

[0018] Aspect 3. The coated article according to any one of aspects 1 to 2, wherein the anti-fingerprint coating has an elastic modulus in the range of from about 9 gigapascals to about 70 gigapascals.

[0019] Aspect 4. The coated article according to any one of aspects 1 to 3, wherein the anti-fingerprint coating further comprises an alkylsilane at the outer surface and bonded to Si-O groups in the anti-fingerprint coating.

[0020] Aspect 5. The coated article according to aspect 4, wherein the alkylsilane comprises a C4-C 34 alkyl group.

[0021] Aspect 6. The coated article according to any one of aspects 4 to 5, wherein the alkylsilane comprises isooctylsilane, dodecylsilane, octadecylsilane, or a combination thereof.

[0022] Aspect 7. The coated article according to any one of aspects 4 to 5, wherein the fingerprint-resistant coating further comprises a nitrogen atom bonded to a silicon atom.

[0023] Article 8. The coated article according to any one of aspects 1 to 7, wherein the fingerprint-resistant coating comprises hydrogenated silicon or silanol.

[0024] Aspect 9. The coated article according to any one of aspects 1 to 8, further comprising an antireflection coating positioned between the fingerprint-resistant coating and the substrate.

[0025] Aspect 10. The coated article according to any one of aspects 1 to 8, further comprising a gradient coating, the gradient coating comprising a refractive index gradient, the gradient coating being positioned between the fingerprint-resistant coating and the substrate.

[0026] Aspect 11. The coated article according to any one of aspects 1 to 10, wherein the fingerprint-resistant coating comprises a diiodomethane contact angle of about 60° or greater.

[0027] Aspect 12. The coated article according to any one of aspects 1 to 11, wherein the fingerprint-resistant coating comprises a worn water contact angle of about 90° after 2,000 cycles of wear in a steel wool abrasion test.

[0028] Aspect 13. The coated article according to any one of aspects 1 to 12, wherein the fingerprint-resistant coating comprises a water contact angle of about 100° or greater.

[0029] Aspect 14. The coated article according to any one of aspects 1 to 13, wherein the fingerprint-resistant coating wets hexadecane or comprises a hexadecane contact angle of about 30° or less.

[0030] Aspect 15. The coated article according to any one of aspects 1 to 14, wherein the fingerprint-resistant coating comprises a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

[0031] Aspect 16. The coated article according to any one of aspects 1 to 15, wherein the fingerprint-resistant coating comprises a total surface energy of about 30 millinewtons per meter (mN / m) or less.

[0032] Aspect 17. The coated article according to any one of aspects 1 to 16, wherein the fingerprint-resistant coating has a fingerprint-resistant abrasion water contact angle of about 90° or greater after undergoing 200,000 cycles in a cheesecloth abrasion test.

[0033] Aspect 18. The coated article according to any one of aspects 1 to 17, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material. In an exemplary aspect, the glass-based material, the glass-ceramic material, or the ceramic-based material is transparent, color-transparent, opaque, color-opaque, translucent, or color-translucent.

[0034] Aspect 19. A coated article, comprising:

[0035] A substrate comprising a first major surface; and

[0036] A fingerprint-resistant coating disposed on the first major surface, the fingerprint-resistant coating comprising the outer surface of the coated article, the fingerprint-resistant coating having a thickness of about 10 nanometers to about 600 nanometers, the fingerprint-resistant coating comprising a partial silica-like network and hydrogenated silicon or silanol, and the fingerprint-resistant coating being fluorine-free.

[0037] Aspect 20. The coated article according to aspect 19, wherein the fingerprint-resistant coating has a modulus of elasticity in the range of about 9 gigapascals to about 70 gigapascals.

[0038] Aspect 21. The coated article according to any one of aspects 19 to 20, wherein the fingerprint-resistant coating has a refractive index of about 1.38 to about 1.55.

[0039] Aspect 22. The coated article according to any one of aspects 19 to \alpha, wherein the fingerprint-resistant coating further comprises nitrogen atoms bonded to silicon atoms.

[0040] Aspect 23. The coated article according to any one of aspects 19 to 22, wherein the fingerprint-resistant coating further comprises an alkylsilane at the outer surface and bonded to Si—O groups in the fingerprint-resistant coating.

[0041] Aspect 24. The coated article according to aspect 23, wherein the alkylsilane comprises a C4-C 34 alkyl group.

[0042] Aspect 25. The coated article according to any one of aspects 23 to 24, wherein the alkylsilane comprises isooctylsilane, dodecylsilane, octadecylsilane, or a combination thereof.

[0043] It should be noted that there is an error in the original text where "aspect 19 to \alpha" should be corrected to a specific range or other correct expression. The above translation is based on the existing text as accurately as possible.Aspect 26. The coated article according to any one of aspects 19 to 25 further comprises an anti-reflection coating positioned between the fingerprint-resistant coating and the substrate.

[0044] Aspect 27. The coated article according to any one of aspects 19 to 26 further comprises a gradient coating comprising a refractive index gradient, the gradient coating being positioned between the fingerprint-resistant coating and the substrate.

[0045] Aspect 28. The coated article according to any one of aspects 19 to 27, wherein the fingerprint-resistant coating comprises a diiodomethane contact angle of about 60° or greater.

[0046] Aspect 29. The coated article according to any one of aspects 19 to 28, wherein the fingerprint-resistant coating comprises a worn water contact angle of about 90° after 2,000 cycles of abrasion in a steel wool abrasion test.

[0047] Aspect 30. The coated article according to any one of aspects 19 to 29, wherein the fingerprint-resistant coating comprises a water contact angle of about 100° or greater.

[0048] Aspect 31. The coated article according to any one of aspects 19 to 30, wherein the fingerprint-resistant coating wets hexadecane or comprises a hexadecane contact angle of about 30° or less.

[0049] Aspect 32. The coated article according to any one of aspects 19 to 31, wherein the fingerprint-resistant coating comprises a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

[0050] Aspect 33. The coated article according to any one of aspects 19 to 32, wherein the fingerprint-resistant coating comprises a total surface energy of about 30 millinewtons per meter (mN / m) or less.

[0051] Aspect 34. The coated article according to any one of aspects 19 to 33, wherein the fingerprint-resistant coating comprises a cotton cloth abrasion water contact angle of about 90° or greater after 200,000 cycles of abrasion in a cotton cloth abrasion test.

[0052] Aspect 35. The coated article according to any one of aspects 19 to 34, wherein the fingerprint-resistant coating further comprises at least one of the following:

[0053] from about 50% to about 90% of the silicon atoms are in a silica-like network; or

[0054] the ratio of Si-O-Si bonds to Si atoms is from about 2 to about 3.

[0055] Aspect 36. The coated article according to any one of aspects 19 to 35, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material. In an exemplary aspect, the glass-based material, the glass-ceramic material, or the ceramic-based material is transparent, color-transparent, opaque, color-opaque, translucent, or color-translucent.

[0056] Aspect 37. A method of forming a coated article, comprising:

[0057] Evaporating a functionalized polyhedral oligomeric silsesquioxane onto a first major surface of a substrate;

[0058] Impinging an ion beam on the first major surface of the substrate, the impinging occurring in a chamber having a chamber pressure in the range of about 10 -4 Pascals to about 1 Pascal, and the impinging converting about 50% to about 90% of the silicon atoms in the cage structure of the functionalized polyhedral oligomeric silsesquioxane to a partial Si-O-Si bond network; and then

[0059] Reacting the material at the first major surface of the substrate with an alkylsilane to form an anti-fingerprint coating, the alkylsilane comprising 4 or more carbons.

[0060] Aspect 38. The method according to aspect 37, wherein the functionalized polyhedral oligomeric silsesquioxane is at least partially functionalized with at least one olefin comprising 2 to 8 carbons.

[0061] Aspect 39. The method according to aspect 38, wherein the functionalized polyhedral oligomeric silsesquioxane is fully functionalized with an olefin comprising 2 to 8 carbons.

[0062] Aspect 40. The method according to any one of aspects 37 to 38, wherein the functionalized polyhedral oligomeric silsesquioxane is at least partially functionalized with an alkyl or aromatic group.

[0063] Aspect 41. The method according to any one of aspects 37 to 40, wherein the reaction comprises heating the alkylsilane at a temperature of about 80 °C to about 250 °C for a period of about 10 minutes to about 8 hours.

[0064] Aspect 42. The method according to any one of aspects 37 to 41, wherein the alkylsilane comprises isooctyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, or a combination thereof.

[0065] Aspect 43. The method according to any one of aspects 37 to 41, wherein the silane is trimethoxysilane, triethoxysilane, trichlorosilane, dichloromethoxysilane, or chlorodimethoxysilane.

[0066] Aspect 44. The method according to any one of aspects 37 to 43, wherein the evaporation of the functionalized polyhedral oligomeric silsesquioxane and the impingement occur simultaneously.

[0067] Aspect 45. The method according to any one of aspects 37 to 44, wherein the ion beam comprises argon ions or oxygen ions.

[0068] Aspect 46. The method according to any one of aspects 37 to 45, wherein the fingerprint-resistant coating comprises from about 50% to about 90% silicon atoms in a silica-like network.

[0069] Aspect 47. The method according to any one of aspects 37 to 46, wherein the ratio of Si-O-Si bonds to Si atoms is from about 2 to about 3.

[0070] Aspect 48. The method according to any one of aspects 37 to 47, wherein the fingerprint-resistant coating comprises a wear water contact angle of about 90° after 2,000 cycles of wear in a steel wool abrasion test.

[0071] Aspect 49. The method according to any one of aspects 37 to 48, wherein the fingerprint-resistant coating has a thickness from about 10 nanometers to about 600 nanometers.

[0072] Aspect 50. The method according to any one of aspects 37 to 49, wherein the fingerprint-resistant coating has a refractive index in the range from about 1.38 to about 1.55.

[0073] Aspect 51. The method according to any one of aspects 37 to 50, wherein the fingerprint-resistant coating has a modulus of elasticity in the range from about 9 gigapascals to about 70 gigapascals.

[0074] Aspect 52. The method according to any one of aspects 37 to 51, wherein the fingerprint-resistant coating has a total surface energy of about 30 millinewtons per meter (mN / m) or less.

[0075] Aspect 53. The method according to any one of aspects 37 to 52, wherein the fingerprint-resistant coating has a dispersive surface energy of about 30 millinewtons per meter (mN / m) or less.

[0076] Aspect 54. The method according to any one of aspects 37 to 53, wherein the fingerprint-resistant coating has a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

[0077] Aspect 55. The method according to any one of aspects 37 to 54, wherein the fingerprint-resistant coating has a water contact angle of about 100° or greater.

[0078] Aspect 56. The method according to any one of aspects 37 to 55, wherein the fingerprint-resistant coating comprises a fingerprint-resistant cotton rubbing water contact angle of about 90° or greater after undergoing 200,000 cycles in a cotton rubbing test.

[0079] Aspect 57. The method according to any one of aspects 37 to 56, wherein the fingerprint-resistant coating comprises a surface roughness Ra of about 1 nm or less.

[0080] Aspect 58. The method according to any one of aspects 37 to 57, wherein the fingerprint-resistant coating is fluorine-free.

[0081] Aspect 59. The method according to any one of aspects 37 to 58, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material. In an exemplary aspect, the glass-based material, the glass-ceramic material, or the ceramic-based material is transparent, color-transparent, opaque, color-opaque, translucent, or color-translucent.

[0082] Aspect 60. The method according to any one of aspects 37 to 59, further comprising an anti-reflection coating positioned between the fingerprint-resistant coating and the substrate.

[0083] Aspect 61. The method according to any one of aspects 37 to 59, further comprising a gradient coating, the gradient coating comprising a refractive index gradient, the gradient coating positioned between the fingerprint-resistant coating and the substrate.

[0084] Aspect 62. A method of forming a coated article, comprising:

[0085] Placing a solution above a first major surface of a substrate, the solution comprising a polysilazane or a polyhedral oligomeric silsesquioxane;

[0086] Heating the solution at a temperature of about 150 °C to about 400 °C for a period of about 5 minutes to about 120 minutes; and

[0087] Reacting the material at the first major surface of the substrate with an alkylsilane comprising 4 or more carbons to form a fingerprint-resistant coating.

[0088] Aspect 63. The method according to aspect 62, wherein the concentration of the polysilazane or the polyhedral oligomeric silsesquioxane is in the range of about 0.2 wt% to about 25 wt%.

[0089] Aspect 64. The method according to any one of aspects 62 to 63, wherein the temperature is in the range of about 150 °C to about 250 °C.

[0090] Aspect 65. The method according to any one of aspects 62 to 64, wherein the reaction comprises heating the alkylsilane at a temperature of about 80 °C to about 250 °C for a period of about 10 minutes to about 8 hours.

[0091] Aspect 66. The method according to any one of aspects 62 to 65, wherein the alkylsilane comprises isooctyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, or a combination thereof.

[0092] Aspect 67. The method according to any one of aspects 62 to 66, wherein the silane is trimethoxysilane, triethoxysilane, trichlorosilane, dichloromethoxysilane, or chlorodimethoxysilane.

[0093] Aspect 68. The method according to any one of aspects 62 to 67, wherein the fingerprint-resistant coating comprises a diiodomethane contact angle of about 60° or greater.

[0094] Aspect 69. The method according to any one of aspects 62 to 68, wherein the fingerprint-resistant coating wets hexadecane or comprises a hexadecane contact angle of about 30° or less.

[0095] Aspect 70. The method according to any one of aspects 62 to 69, wherein the heating forms the fingerprint-resistant coating into a partially silica-like network and hydrogenated silicon or silanol.

[0096] Aspect 71. The method according to any one of aspects 62 to 70, wherein the heating to form the fingerprint-resistant coating comprises at least one of the following:

[0097] About 50% to about 90% of the silicon atoms are in the silica-like network; or

[0098] The ratio of Si-O-Si bonds to Si atoms is about 2 to about 3.

[0099] Aspect 72. The method according to any one of aspects 62 to 71, wherein the fingerprint-resistant coating comprises a thickness of about 10 nanometers to about 600 nanometers.

[0100] Aspect 73. The method according to any one of aspects 62 to 72, wherein the fingerprint-resistant coating comprises a refractive index of about 1.38 to about 1.55.

[0101] Aspect 74. The method according to any one of aspects 62 to 73, wherein the fingerprint-resistant coating comprises a modulus of elasticity in the range of about 9 gigapascals to about 70 gigapascals.

[0102] Aspect 75. The method according to any one of aspects 62 to 74, wherein the fingerprint-resistant coating comprises a total surface energy of about 30 millinewtons per meter (mN / m) or less.

[0103] Aspect 76. The method of any one of aspects 62 to 75, wherein the anti-fingerprint coating comprises a distributed surface energy of about 30 millinewtons per meter (mN / m) or less.

[0104] Aspect 77. The method of any one of aspects 62 to 76, wherein the anti-fingerprint coating comprises a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

[0105] Aspect 78. The method of any one of aspects 62 to 77, wherein the anti-fingerprint coating comprises a water contact angle of about 100° or greater.

[0106] Aspect 79. The method of any one of aspects 62 to 78, wherein the anti-fingerprint coating comprises a cheesecloth abrasion water contact angle of about 90° or greater after being subjected to 200,000 cycles in a cheesecloth abrasion test.

[0107] Aspect 80. The method according to any one of aspects 62 to 79, wherein the anti-fingerprint coating comprises a surface roughness Ra of about 1 nm or less.

[0108] Aspect 81. The method according to any one of aspects 62 to 80, wherein the anti-fingerprint coating is fluorine-free.

[0109] Aspect 82. The method of any one of Aspects 62 to 81, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material. In exemplary aspects, the glass-based material, the glass-ceramic material, or the ceramic-based material is transparent, colored transparent, opaque, colored opaque, translucent, or colored translucent.

[0110] Aspect 83. The method of any one of aspects 62 to 82, further comprising an anti-reflective coating positioned between the anti-fingerprint coating and the substrate.

[0111] Aspect 84. The method according to any one of aspects 62 to 83, further comprising a gradient coating comprising a refractive index gradient, the gradient coating being positioned between the anti-fingerprint coating and the substrate.

[0112] Aspect 85. The method according to any one of aspects 37 to 84, wherein the anti-fingerprint coating further comprises nitrogen atoms bonded to silicon atoms.

[0113] Aspect 86. A coated article comprising:

[0114] a substrate comprising a first major surface;

[0115] An anti-fingerprint coating is disposed on the first major surface, the anti-fingerprint coating comprising the outer surface of the coated article, the anti-fingerprint coating having a thickness of from about 10 nanometers to about 600 nanometers, the anti-fingerprint coating comprising a partial silica-like network having a ratio of Si-O-Si bonds to Si atoms in the anti-fingerprint coating of from about 2 to about 3, the anti-fingerprint coating being fluorine-free, and the anti-fingerprint coating further comprising an alkylsilane at the outer surface and bonded to the Si-O groups in the anti-fingerprint coating.

[0116] Aspect 87. A method of forming a coated article, comprising:

[0117] Evaporating a functionalized polyhedral oligomeric silsesquioxane onto a first major surface of a substrate;

[0118] Impinging an ion beam on the first major surface of the substrate, the impinging occurring in a chamber having a chamber pressure in the range of from about 10 -4 Pascals to about Pa, and the impinging converting from about 50% to about 90% of the silicon atoms from the cage structure in the functionalized polyhedral oligomeric silsesquioxane to a Si-O-Si bond network; and then

[0119] Reacting the material at the first major surface of the substrate with an alkylsilane comprising 4 or more carbons to form an anti-fingerprint coating.

[0120] Aspect 88. A method of forming a coated article, comprising:

[0121] Disposing a solution above a first major surface of a substrate, the solution comprising a polysilazane or a polyhedral oligomeric silsesquioxane;

[0122] Heating the solution at a temperature of from about 150 °C to about 400 °C for a period of from about 5 minutes to about 120 minutes; and

[0123] Reacting the material at the first major surface of the substrate with an alkylsilane comprising 4 or more carbons to form an anti-fingerprint coating.

[0124] Aspect 89. The coated article according to any one of aspects 1 to 36, wherein the anti-fingerprint coating exhibits a rubber wear water contact angle of about 100° or greater after undergoing 5,000 cycles in a rubber wear test.

[0125] Aspect 90. The coated article according to any one of aspects 1 to 36 or 89 (inclusive), further comprising an optical stack positioned between the fingerprint-resistant coating and the substrate, wherein the optical stack comprises an anti-reflection coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflection coating, or an edge filter coating.

[0126] Aspect 91. The coated article according to aspect 90, wherein the optical stack has a thickness of from about 10 nanometers to about 10 micrometers.

[0127] Aspect 92. The coated article according to aspect 91, wherein the thickness of the optical stack is from about 50 nanometers to about 5 micrometers.

[0128] Aspect 93. The coated article according to aspect 91, wherein the thickness of the optical stack is from about 50 nanometers to about 500 nanometers.

[0129] Aspect 94. The coated article according to any one of aspects 90 to 93, wherein the optical stack comprises a scratch-resistant layer, and wherein the scratch-resistant layer has a thickness of 0.05 micrometers to 3 micrometers.

[0130] Aspect 95. The coated article according to any one of aspects 90 to 94, wherein the coated article comprising the optical stack and the fingerprint-resistant coating exhibits a hardness of 8 gigapascals or greater as measured by a Berkovich indenter hardness test.

[0131] Aspect 96. The coated article according to aspect 95, wherein the coated article comprising the optical stack and the fingerprint-resistant coating exhibits a hardness of 12 gigapascals or greater as measured by the Berkovich indenter hardness test.

[0132] Aspect 97. The coated article according to any one of aspects 90 to 96, wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O5.

[0133] Aspect 98. The coated article according to any one of aspects 90 to 97, wherein the optical stack comprises two or more layers having different refractive indices, the two or more layers comprising at least a first low refractive index (low RI) layer and a second high refractive index (high RI) layer, the absolute value of the difference between the first low RI layer and the second high RI layer being 0.2 or greater, and further wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O.

[0134] Aspect 99. The coated article according to any one of aspects 1 to 36 or 89 to 98, wherein the substrate is a textured substrate.

[0135] Aspect 100. The coated article according to any one of aspects 1 to 36 or 89 to 99 (inclusive), wherein the alkylsilane comprises isooctylalkyl, dodecylalkyl, octadecylalkyl, or a combination thereof.

[0136] Aspect 101. A coated article comprising:

[0137] A substrate comprising a first major surface;

[0138] An alkylsilane on the first major surface, the alkylsilane comprising the outer surface of the coated article, the alkylsilane having a thickness of from about 1 nanometer to about 75 nanometers, and the alkylsilane being fluorine-free.

[0139] Aspect 102. The coated article according to aspect 101, wherein the alkylsilane comprises C4-C 34 alkyl.

[0140] Aspect 103. The coated article according to aspect 101, wherein the alkylsilane comprises isooctylalkyl, dodecylalkyl, octadecylalkyl, or a combination thereof.

[0141] Aspect 104. The coated article according to aspect 101, wherein the alkylsilane comprises octadecylalkyl.

[0142] Aspect 105. The coated article according to any one of aspects 101 to 105, wherein the outer surface exhibits a water contact angle of 100° or greater.

[0143] Aspect 106. The coated article according to aspect 105, wherein the outer surface exhibits the water contact angle of 102° to 110°.

[0144] Aspect 107. The coated article according to any one of aspects 101 to 106, wherein the outer surface exhibits a diiodomethane contact angle of about 60° or greater.

[0145] Aspect 108. The coated article according to any one of aspects 101 to 107, wherein the outer surface exhibits a coefficient of friction of 0.25 or less.

[0146] Aspect 109. The coated article according to any one of aspects 101 to 108, wherein the alkylsilane comprises a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

[0147] Aspect 110. The coated article according to any one of aspects 101 to 109, wherein the alkylsilane has a total surface energy of about 30 millinewtons per meter (mN / m) or less.

[0148] Aspect 111. The coated article according to any one of aspects 101 to 110, wherein the alkylsilane has a denim abrasion water contact angle of about 90° or greater after undergoing 200,000 cycles in a denim abrasion test.

[0149] Aspect 112. The coated article according to any one of aspects 101 to 111, wherein the alkylsilane exhibits a rubber abrasion water contact angle of about 100° or greater after undergoing 5,000 cycles in a rubber abrasion test.

[0150] Aspect 113. The coated article according to any one of aspects 101 to 112, further comprising an optical stack positioned between the alkylsilane and the substrate, wherein the optical stack comprises an anti-reflection coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multilayer high-reflection coating, or an edge filter coating.

[0151] Aspect 114. The coated article according to aspect 113, wherein the optical stack has a thickness of about 10 nanometers to about 10 micrometers.

[0152] Aspect 115. The coated article according to aspect 114, wherein the thickness of the optical stack is about 50 nanometers to about 5 micrometers.

[0153] Aspect 116. The coated article according to aspect 114, wherein the thickness of the optical stack is about 50 nanometers to about 500 nanometers.

[0154] Aspect 117. The coated article according to any one of aspects 113 to 116, wherein the optical stack comprises a scratch-resistant layer, and wherein the scratch-resistant layer has a thickness of 0.05 micrometers to 3 micrometers.

[0155] Aspect 118. The coated article according to any one of aspects 113 to 117, wherein the coated article comprising the optical stack and the alkylsilane exhibits a hardness of 8 gigapascals or greater as measured by a Berkovich indenter hardness test.

[0156] Aspect 119. The coated article according to aspect 118, wherein the coated article comprising the optical stack and the alkylsilane exhibits the hardness of 12 gigapascals or greater as measured by the Berkovich indenter hardness test.

[0157] Aspect 120. The coated article according to any one of aspects 113 to 119, wherein the optical stack comprises one or more of silicon oxide, silicon nitride, silicon oxynitride, and Nb2O5.

[0158] Aspect 121. The coated article according to any one of aspects 113 to 120, wherein the optical stack comprises two or more layers having different refractive indices, the two or more layers comprising at least a first low refractive index (low RI) layer and a second high refractive index (high RI) layer, the absolute value of the difference between the first low RI layer and the second high RI layer being 0.2 or greater, and further wherein the optical stack comprises one or more of silicon oxide, silicon nitride, silicon oxynitride, and Nb2O.

[0159] Aspect 122. The coated article according to any one of aspects 101 to 121, wherein the substrate is a textured substrate.

[0160] Aspect 123. The coated article according to any one of aspects 101 to 122, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material.

[0161] Aspect 124. The coated article according to aspect 123, wherein the glass-based material, the glass-ceramic material, or the ceramic-based material is transparent, color-transparent, opaque, color-opaque, translucent, or color-translucent.

[0162] Aspect 125. The method according to any one of aspects 37 to 85, wherein the alkylsilane comprises isooctylalkyl, dodecylalkyl, octadecylalkyl, or a combination thereof.

[0163] Aspect 126. The method according to any one of aspects 37 to 85 or 125 (inclusive), wherein the surface modification layer exhibits a rubber wear water contact angle of about 100° or greater after 5,000 cycles in a rubber wear test.

[0164] Aspect 127. The method according to any one of aspects 37 to 85 or 125 to 126 (inclusive), further comprising an optical stack positioned between the surface modification layer and the substrate, wherein the optical stack comprises an anti-reflection coating, a bandpass filter coating, an edge neutral mirror, a beam splitter coating, a multilayer high reflection coating, or an edge filter coating.

[0165] Aspect 128. The method according to aspect 127, wherein the optical stack has a thickness of about 10 nanometers to about 10 micrometers.

[0166] Aspect 129. The method according to aspect 128, wherein the thickness of the optical stack is from about 50 nanometers to about 5 micrometers.

[0167] Aspect 130. The method according to aspect 128, wherein the thickness of the optical stack is from about 50 nanometers to about 500 nanometers.

[0168] Aspect 131. The method according to any one of aspects 125 to 130, wherein the optical stack comprises a scratch-resistant layer, and wherein the scratch-resistant layer has a thickness of from 0.05 micrometers to 3 micrometers.

[0169] Aspect 132. The method according to any one of aspects 125 to 131, wherein the coated article comprising the optical stack and the surface modification layer exhibits a hardness of 8 gigapascals or greater as measured by a Vickers indenter hardness test.

[0170] Aspect 133. The method according to aspect 132, wherein the coated article comprising the optical stack and the surface modification layer exhibits a hardness of 12 gigapascals or greater as measured by the Vickers indenter hardness test.

[0171] Aspect 134. The method according to any one of aspects 125 to 133, wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O5.

[0172] Aspect 135. The method according to any one of aspects 125 to 134, wherein the optical stack comprises two or more layers having different refractive indices, the two or more layers comprising at least a first low refractive index (low RI) layer and a second high refractive index (high RI) layer, the absolute value of the difference between the first low RI layer and the second high RI layer being 0.2 or greater, and further wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O.

[0173] Aspect 136. The method according to any one of aspects 37 to 85 or 125 to 135, wherein the substrate is a textured substrate.

[0174] Aspect 137. A method of forming a coated article, comprising:

[0175] reacting a material at a first major surface of a substrate with an alkylsilane to form a surface modification layer, the alkylsilane comprising an alkyl group having 4 or more carbons,

[0176] wherein the surface modification layer exhibits a water contact angle of 100° or greater.

[0177] Aspect 138. The method according to aspect 137, wherein the alkyl group comprises isooctyl alkyl, dodecyl alkyl, octadecyl alkyl, or a combination thereof.

[0178] Aspect 139. The method according to aspect 137, wherein the alkyl group comprises octadecyl alkyl.

[0179] Aspect 140. The method according to any one of aspects 137 to 139, wherein the alkylsilane comprises isooctyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, or a combination thereof.

[0180] Aspect 141. The method according to any one of aspects 137 to 140, wherein the silane is trimethoxysilane, triethoxysilane, trichlorosilane, dichloromethoxysilane, or chlorodimethoxysilane.

[0181] Aspect 142. The method according to any one of aspects 137 to 141, wherein the outer surface exhibits a water contact angle of 100° or greater.

[0182] Aspect 143. The method according to aspect 142, wherein the outer surface exhibits the water contact angle of 102° to 110°.

[0183] Aspect 144. The method according to any one of aspects 137 to 143, wherein the outer surface exhibits a diiodomethane contact angle of about 60° or greater.

[0184] Aspect 145. The method according to any one of aspects 137 to 144, wherein the outer surface exhibits a coefficient of friction of 0.25 or less.

[0185] Aspect 146. The method according to any one of aspects 137 to 145, wherein the surface modification layer comprises a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

[0186] Aspect 147. The method according to any one of aspects 137 to 146, wherein the surface modification layer comprises a total surface energy of about 30 millinewtons per meter (mN / m) or less.

[0187] Aspect 148. The method according to any one of aspects 137 to 147, wherein the thickness of the surface modification layer is from 1 nanometer to 75 nanometers.

[0188] Aspect 149. The coated article according to any one of aspects 137 to 148, wherein the surface modification layer comprises a coarse cloth abrasion water contact angle of about 90° or greater after undergoing 200,000 cycles in a coarse cloth abrasion test.

[0189] Aspect 150. The coated article according to any one of aspects 137 to 149, wherein the surface modification layer exhibits a rubber wear water contact angle of about 100° or greater after undergoing 5,000 cycles in a rubber wear test.

[0190] Aspect 151. The coated article according to any one of aspects 137 to 150, further comprising an optical stack positioned between the surface modification layer and the substrate, wherein the optical stack comprises an anti-reflection coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high reflection coating, or an edge filter coating.

[0191] Aspect 152. The coated article according to aspect 151, wherein the optical stack has a thickness of about 10 nanometers to about 10 micrometers.

[0192] Aspect 153. The coated article according to aspect 152, wherein the thickness of the optical stack is about 50 nanometers to about 5 micrometers.

[0193] Aspect 154. The coated article according to aspect 152, wherein the thickness of the optical stack is about 50 nanometers to about 500 nanometers.

[0194] Aspect 155. The coated article according to any one of aspects 151 to 154, wherein the optical stack comprises a scratch-resistant layer, and wherein the scratch-resistant layer has a thickness of 0.05 micrometers to 3 micrometers.

[0195] Aspect 156. The coated article according to any one of aspects 151 to 155, wherein the coated article comprising the optical stack and the surface modification layer exhibits a hardness of 8 gigapascals or greater as measured by a Berkovich indenter hardness test.

[0196] Aspect 157. The coated article according to aspect 156, wherein the coated article comprising the optical stack and the surface modification layer exhibits the hardness of 12 gigapascals or greater as measured by a Berkovich indenter hardness test.

[0197] Aspect 158. The coated article according to any one of aspects 151 to 157, wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O5.

[0198] Aspect 159. The coated article according to any one of aspects 151 to 158, wherein the optical stack comprises two or more layers having different refractive indices, the two or more layers comprising at least a first low refractive index (low RI) layer and a second high refractive index (high RI) layer, the absolute value of the difference between the first low RI layer and the second high RI layer being 0.2 or greater, and further wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O.

[0199] Aspect 160. The coated article according to any one of aspects 137 to 159, wherein the substrate is a textured substrate.

[0200] Aspect 161. The coated article according to any one of aspects 137 to 160, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material.

[0201] Aspect 162. The coated article according to aspect 161, wherein the glass-based material, the glass-ceramic material, or the ceramic-based material is transparent, color-transparent, opaque, color-opaque, translucent, or color-translucent.

[0202] Aspect 163. A coated article comprising:

[0203] A substrate comprising a first major surface;

[0204] A surface modification layer disposed above the first major surface, the surface modification layer comprising the outer surface of the coated article, the surface modification layer having a thickness of from about 10 nanometers to about 600 nanometers, the surface modification layer comprising a partial silica-like network having a ratio of Si-O-Si bonds to Si atoms in the surface modification layer of from about 2 to about 3, the surface modification layer being fluorine-free, and the surface modification layer further comprising an alkylsilane at the outer surface and bonded to the Si-O groups in the surface modification layer.

[0205] Aspect 164. The coated article according to aspect 163, wherein the surface modification layer has a refractive index in the range of from about 1.38 to about 1.55.

[0206] Aspect 165. The coated article according to any one of aspects 163 to 164, wherein the surface modification layer has a modulus of elasticity in the range of from about 9 gigapascals to about 70 gigapascals.

[0207] Aspect 166. The coated article according to any one of aspects 163 to 165, wherein the alkylsilane comprises a C4-C 34 alkyl group.

[0208] Aspect 167. The coated article according to any one of aspects 163 to 166, wherein the alkylsilane comprises isooctylalkyl, dodecylalkyl, octadecylalkyl, or a combination thereof.

[0209] Aspect 168. The coated article according to any one of aspects 163 to 167, wherein the surface modification layer further comprises a nitrogen atom bonded to a silicon atom.

[0210] Aspect 169. The coated article according to any one of aspects 163 to 168, wherein the surface modification layer comprises hydrosilicon or silanol.

[0211] Aspect 170. The coated article according to any one of aspects 163 to 169, wherein the surface modification layer exhibits a diiodomethane contact angle of about 60° or greater.

[0212] Aspect 171. The coated article according to any one of aspects 163 to 170, wherein the surface modification layer exhibits a water contact angle of about 100° or greater.

[0213] Aspect 172. The coated article according to any one of aspects 163 to 171, wherein the surface modification layer wets hexadecane or exhibits a hexadecane contact angle of about 30° or less.

[0214] Aspect 173. The coated article according to any one of aspects 163 to 172, wherein the surface modification layer comprises a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

[0215] Aspect 174. The coated article according to any one of aspects 163 to 173, wherein the surface modification layer comprises a total surface energy of about 30 millinewtons per meter (mN / m) or less.

[0216] Aspect 175. The coated article according to any one of aspects 163 to 174, wherein the surface modification layer exhibits a worn water contact angle of about 90° after 2,000 cycles in a steel wool abrasion test.

[0217] Aspect 176. The coated article according to any one of aspects 163 to 175, wherein the surface modification layer exhibits a coarse cloth wear water contact angle of about 90° or greater after 200,000 cycles in a coarse cloth abrasion test.

[0218] Aspect 177. The coated article according to any one of aspects 163 to 176, wherein the surface modification layer exhibits a rubber wear water contact angle of about 100° or greater after 5,000 cycles in a rubber abrasion test.

[0219] Aspect 178. The coated article according to any one of aspects 163 to 177, further comprising an anti-reflection coating positioned between the surface modification layer and the substrate.

[0220] Aspect 179. The coated article according to any one of aspects 163 to 177, further comprising a gradient coating comprising a refractive index gradient, the gradient coating being positioned between the surface modification layer and the substrate.

[0221] Aspect 180. The coated article according to any one of aspects 163 to 177, further comprising an optical stack positioned between the surface modification layer and the substrate, wherein the optical stack comprises an anti-reflection coating, a bandpass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high reflection coating, or an edge filter coating.

[0222] Aspect 181. The coated article according to aspect 180, wherein the optical stack has a thickness of from about 10 nanometers to about 10 micrometers.

[0223] Aspect 182. The coated article according to aspect 181, wherein the thickness of the optical stack is from about 50 nanometers to about 5 micrometers.

[0224] Aspect 183. The coated article according to aspect 181, wherein the thickness of the optical stack is from about 50 nanometers to about 500 nanometers.

[0225] Aspect 184. The coated article according to any one of aspects 180 to 182, wherein the optical stack comprises a scratch-resistant layer, and wherein the scratch-resistant layer has a thickness of from 0.05 micrometers to 3 micrometers.

[0226] Aspect 185. The coated article according to any one of aspects 180 to 183, wherein the coated article comprising the optical stack and the surface modification layer exhibits a hardness of 8 gigapascals or greater as measured by a Vickers indenter hardness test.

[0227] Aspect 186. The coated article according to aspect 185, wherein the coated article comprising the optical stack and the surface modification layer exhibits a hardness of 12 gigapascals or greater as measured by a Vickers indenter hardness test.

[0228] Aspect 187. The coated article according to any one of aspects 180 to 186, wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O5.

[0229] Aspect 188. The coated article according to any one of aspects 180 to 187, wherein the optical stack includes two or more layers having different refractive indices, the two or more layers at least including a first low refractive index (low RI) layer and a second high refractive index (high RI) layer, the absolute value of the difference between the first low RI layer and the second high RI layer being 0.2 or greater, and further wherein the optical stack includes one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O.

[0230] Aspect 189. The coated article according to any one of aspects 163 to 188, wherein the substrate is a textured substrate.

[0231] Aspect 190. The coated article according to any one of aspects 163 to 189, wherein the substrate includes a glass-based material, a glass-ceramic material, or a ceramic-based material.

[0232] Aspect 191. The coated article according to aspect 190, wherein the glass-based material, the glass-ceramic material, or the ceramic-based material is transparent, color-transparent, opaque, color-opaque, translucent, or color-translucent.

[0233] Aspect 192. A method of forming a coated article, comprising:

[0234] Evaporating a functionalized polyhedral oligomeric silsesquioxane onto a first major surface of a substrate;

[0235] Impinging an ion beam onto the first major surface of the substrate, the impinging occurring in a chamber having a chamber pressure in the range of about 10 -4 Pascals to about 1 Pascal, and the impinging converting from about 50% to about 90% of the silicon atoms from the cage structure in the functionalized polyhedral oligomeric silsesquioxane into a Si-O-Si bond network; and then

[0236] Reacting the material at the first major surface of the substrate with an alkylsilane to form a surface modification layer, the alkylsilane including 4 or more carbons.

[0237] Aspect 193. The method according to aspect 192, wherein the functionalized polyhedral oligomeric silsesquioxane is at least partially functionalized with at least one olefin including 2 to 8 carbons.

[0238] Aspect 194. The method according to aspect 193, wherein the functionalized polyhedral oligomeric silsesquioxane is completely functionalized with an olefin including 2 to 8 carbons.

[0239] Aspect 195. The method according to any one of aspects 192 to 194, wherein the functionalized polyhedral oligomeric silsesquioxane is at least partially functionalized with an alkyl or aromatic group.

[0240] Aspect 196. The method according to any one of aspects 192 to 195, wherein the reaction comprises heating the alkylsilane at a temperature of about 80 °C to about 250 °C for a period of about 10 minutes to about 8 hours.

[0241] Aspect 197. The method according to any one of aspects 192 to 196, wherein the alkylsilane comprises isooctylalkyl, dodecylalkyl, octadecylalkyl, or a combination thereof.

[0242] Aspect 198. The method according to any one of aspects 192 to 197, wherein the silane is trimethoxysilane, triethoxysilane, trichlorosilane, dichloromethoxysilane, or chlorodimethoxysilane.

[0243] Aspect 199. The method according to any one of aspects 192 to 198, wherein the evaporation of the functionalized polyhedral oligomeric silsesquioxane and the impingement occur simultaneously.

[0244] Aspect 200. The method according to any one of aspects 192 to 199, wherein the evaporation of the functionalized polyhedral oligomeric silsesquioxane comprises an evaporation rate of about 0.01 nanometers per second (nm / s) to about 0.2 nm / s.

[0245] Aspect 201. The method according to any one of claims 192 to 200, wherein the ion beam comprises argon ions or oxygen ions.

[0246] Aspect 202. The method according to any one of aspects 192 to 201, wherein the ratio of Si-O-Si bonds to Si atoms is about 2 to about 3.

[0247] Aspect 203. The method according to any one of aspects 192 to 202, wherein the surface modification layer comprises a wear water contact angle of about 90° after 2,000 cycles of wear in a steel wool abrasion test.

[0248] Aspect 204. The method according to any one of aspects 192 to 203, wherein the surface modification layer comprises a thickness of about 10 nanometers to about 600 nanometers.

[0249] Aspect 205. The method according to any one of aspects 192 to 204, wherein the surface modification layer comprises a refractive index in the range of about 1.38 to about 1.55.

[0250] Aspect 206. The method according to any one of aspects 192 to 205, wherein the surface modification layer has a modulus of elasticity in the range of about 9 gigapascals to about 70 gigapascals.

[0251] Aspect 207. The method according to any one of aspects 192 to 206, wherein the surface modification layer has a total surface energy of about 30 millinewtons per meter (mN / m) or less.

[0252] Aspect 208. The method according to any one of aspects 192 to 207, wherein the surface modification layer has a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

[0253] Aspect 209. The method according to any one of aspects 192 to 208, wherein the surface modification layer has a water contact angle of about 100° or greater.

[0254] Aspect 210. The method according to any one of aspects 192 to 209, wherein the surface modification layer has a denim abrasion water contact angle of about 90° or greater after undergoing 200,000 cycles in a denim abrasion test.

[0255] Aspect 211. The coated article according to any one of aspects 192 to 210, wherein the surface modification layer exhibits a rubber abrasion water contact angle of about 100° or greater after undergoing 5,000 cycles in a rubber abrasion test.

[0256] Aspect 212. The method according to any one of aspects 192 to 211, wherein the surface modification layer has a surface roughness Ra of about 1 nm or less.

[0257] Aspect 213. The method according to any one of aspects 192 to 212, wherein the surface modification layer is fluorine-free.

[0258] Aspect 214. The method according to any one of aspects 192 to 213, further comprising an optical stack positioned between the surface modification layer and the substrate, wherein the optical stack comprises an anti-reflection coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflection coating, or an edge filter coating.

[0259] Aspect 215. The method according to aspect 214, wherein the optical stack thickness is from about 10 nanometers to about 10 micrometers.

[0260] Aspect 216. The method according to aspect 215, wherein the optical stack comprises a scratch-resistant layer, and the scratch-resistant layer has a thickness of 0.05 micrometers to 3 micrometers.

[0261] Aspect 217. The method according to any one of aspects 214 to 216, wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, and / or silicon oxynitride-containing.

[0262] Aspect 218. The method according to any one of aspects 214 to 217, wherein the optical stack has two or more layers of different refractive indices, a first low RI layer and a second high RI layer, wherein the absolute value of the difference between the first low RI layer and the second high RI layer is 0.2 or greater, and further wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, and / or silicon oxynitride-containing.

[0263] Aspect 219. The method according to any one of aspects 214 to 218, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material. Description of the Drawings

[0264] The above and other features and advantages of the aspects of the present disclosure will be better understood when the following detailed description is read with reference to the accompanying drawings, in which:

[0265] Figure 1 and Figures 2A to 2C is a schematic diagram of an exemplary coated article according to the aspects;

[0266] Figure 3 is a schematic plan view of an exemplary consumer electronic device according to the aspects;

[0267] Figure 4 is Figure 3 a schematic perspective view of an exemplary consumer electronic device of

[0268] Figure 5 schematically shows a functionalized polyhedral oligomeric silsesquioxane (POSS) compound;

[0269] Figure 6 schematically shows the reaction of polysilazane (PHPS);

[0270] Figures 7 to 8 is a flowchart showing an exemplary method of manufacturing a coated article according to the aspects of the present disclosure;

[0271] Figure 9 schematically shows one or more steps in a method of manufacturing a coated article, which includes evaporating functionalized POSS and impinging an ion beam on a first major surface of a substrate;

[0272] Figure 10 schematically shows a step in a method of manufacturing a coated article, which includes reacting a material at a first major surface with a functionalized silane;

[0273] Figure 11 Schematically shows steps in a method of manufacturing a coated article, which includes disposing a solution above a first major surface of a substrate;

[0274] Figure 12 Schematically shows steps in a method of manufacturing a coated article, which includes heating the solution on the first major surface;

[0275] Figure 13 Schematically shows that for Examples A to B and Comparative Examples AA to CC, the transmittance (%) on the vertical axis (y-axis) varies with the optical wavelength on the horizontal axis (x-axis);

[0276] Figure 14 Schematically shows that for Examples A to B, the refractive index (left vertical axis - left y-axis) and the extinction coefficient (right vertical axis - right x-axis) vary with the optical wavelength on the horizontal axis (x-axis);

[0277] Figure 15 Schematically shows that for Examples A to C and Comparative Example CC, the normalized absorbance on the vertical axis (y-axis) varies with the wave number (cm -1 ) on the horizontal axis (x-axis) in an infrared (IR) absorption spectrum;

[0278] Figures 16 to 17 Schematically shows that for Examples A to B and Comparative Example CC, the intensity (vertical axis - y-axis) of the charge-to-mass ratio (horizontal axis - x-axis) from secondary ion mass spectrometry (SIMS);

[0279] Figure 18 Schematically shows that for Examples A to B and Comparative Example CC, the surface composition (in atomic %) determined by X-ray photoelectron spectroscopy (XPS) on the vertical axis (y-axis);

[0280] Figures 19 to 20 Schematically shows that for Examples A to B and Comparative Example CC, the intensity (vertical axis - y-axis) of the binding energy distribution (horizontal axis - x-axis) determined by XPS;

[0281] Figure 21 Schematically shows that for Example B, the intensity (vertical axis - y-axis) of the 29 Si chemical shift (horizontal axis - x-axis) measured using solid-state nuclear magnetic resonance (NMR) (SS-NMR);

[0282] Figure 22 Schematically shows that for Examples D to E, G to H, and Comparative Examples EE and HH, the water contact angle (°) in a steel wool abrasion test (vertical axis - y-axis), where the points are after 0 cycles, 2000 cycles, and 3500 cycles;

[0283] Figure 23 Schematically shows the relationship between the modulus of elasticity (gigapascals (GPa)) on the vertical axis (y-axis) and the curing temperature (°C) on the horizontal axis (x-axis) of a polysilazane material;

[0284] Figure 24 Schematically shows the water contact angle (°) (vertical axis - y-axis) in the steel wool abrasion test for Examples D and J and Comparative Example II;

[0285] Figure 25 Schematically shows that for Examples K to N, the water contact angle (°) (vertical axis - y-axis) in the rubber abrasion test varies with the number of abrasion cycles (horizontal axis - x-axis);

[0286] Figure 26 Schematically shows that for Examples K and M, the water contact angle (°) (vertical axis - y-axis) in the steel wool abrasion test varies with the number of abrasion cycles (horizontal axis - x-axis);

[0287] Figure 27 Schematically shows the infrared (IR) absorption spectra for Examples O to S, where the horizontal axis (x-axis) corresponds to the wave number (cm -1 ) and the vertical axis (y-axis) corresponds to the normalized absorbance;

[0288] Figure 28 Schematically shows that for Examples O to S, the hydroxyl ratio on the vertical axis (y-axis) varies with the deposition rate in A / s on the horizontal axis (x-axis);

[0289] Figure 29 Schematically shows the molar ratio of hydrogen to silicon (vertical axis - y-axis) measured by dynamic secondary ion mass spectrometry (D-SIMS) for Examples 1 to 10 and Comparative Examples JJ to KK; and

[0290] Figure 30 Schematically shows the water contact angle per 100,000 cycles in the cheesecloth abrasion test for Examples 11 to 12 (vertical axis - y-axis).

[0291] Throughout this disclosure, the drawings are used to emphasize certain aspects. Thus, unless otherwise explicitly indicated, it should not be assumed that the relative sizes of the different regions, parts, and substrates shown in the drawings are in proportion to their actual relative sizes. Detailed Description

[0292] Aspects will now be described more fully hereinafter with reference to the drawings, in which example aspects are shown. Wherever possible, the same reference numerals are used throughout the drawings to refer to the same or similar components.

[0293] Figure 1 andFigures 2A to 2C A view of a coated article 101, 201, 211, or 221 in accordance with aspects of the present disclosure is shown, the coated article including a surface modification layer (e.g., an anti-fingerprint coating 113) disposed over a substrate 103. Unless otherwise indicated, discussion of features of one surface modification layer (e.g., an anti-fingerprint coating) or aspects of a coated article may equally apply to corresponding features of any aspect of the present disclosure. For example, the same component numbers throughout the present disclosure may indicate that, in some aspects, the identified features are the same, and unless otherwise indicated, discussion of an identified feature of one aspect may equally apply to an identified feature of any other aspect of the present disclosure.

[0294] As Figure 1 and Figures 2A to 2C shown, the substrate 103 includes a first major surface 105 and a second major surface 107 opposite the first major surface 105. As shown, the first major surface 105 may extend along a first plane 104, and / or the second major surface 107 may extend along a second plane 106. In aspects, as shown, the second plane 106 may be parallel to the first plane 104. As used herein, the substrate thickness 109 is positioned between the first major surface 105 and the second major surface 107 as the distance between the first plane 104 and the second plane 106. In aspects, the substrate thickness 109 may be about 10 micrometers (μm) or greater, about 25 μm or greater, about 40 μm or greater, about 60 μm or greater, about 70 μm or greater, about 80 μm or greater, about 90 μm or greater, about 100 μm or greater, about 125 μm or greater, about 150 μm or greater, about 200 μm or greater, about 300 μm or greater, about 2 millimeters (mm) or less, about 1 mm or less, about 800 μm or less, about 500 μm or less, about 300 μm or less, about 200 μm or less, about 180 μm or less, or about 160 μm or less. In aspects, the substrate thickness 109 may be in the range of about 10 μm to about 2 mm, about 25 μm to about 2 mm, about 40 μm to about 2 mm, about 60 μm to about 2 mm, about 70 μm to about 2 mm, about 70 μm to about 1 mm, about 70 μm to about 800 μm, about 80 μm to about 500 μm, about 90 μm to 500 μm, about 100 μm to about 200 μm, about 125 μm to about 200 μm, about 150 μm to about 200 μm, about 150 μm to about 160 μm or any range or sub-range therebetween. Alternatively, the substrate thickness 109 may be in the range of about 1 millimeter (mm) to about 5 mm, about 1 mm to about 3 mm or any range or sub-range therebetween.

[0295] The substrate 103 may include a glass-based material, a glass-ceramic material, and / or a ceramic-based material having a pencil hardness of 8H or greater, such as 9H or greater. As used herein, pencil hardness is measured using ASTM D3363-20 with a standard lead grade pencil. Providing a glass-based material, a glass-ceramic material, and / or a ceramic-based material as the substrate may enhance puncture resistance and / or impact resistance. As used herein, "glass-based" encompasses both glass and glass-ceramics, where the glass-ceramic has one or more crystalline phases and an amorphous residual glass phase. A glass-based material (e.g., a glass-based substrate) may include an amorphous material (e.g., glass) and optionally one or more crystalline materials (e.g., ceramics). Exemplary glass-based materials may be alkali-free glass and / or include a low content of alkali metals (e.g., R2O is about 10 mol% or less, where R2O includes Li2O, Na2O, and K2O). As used herein, "ceramic-based" encompasses both ceramics and glass-ceramics, where the glass-ceramic has one or more crystalline phases and an amorphous residual glass phase. In various aspects, the ceramic material may include one or more oxides, nitrides, oxynitrides, carbides, borides, and / or silicides. Throughout this disclosure, the elastic modulus (e.g., Young's modulus) of the substrate 103 is measured using ISO 527-1:2019. In various aspects, the substrate 103 may include an elastic modulus in the range of about 10 GPa to about 100 GPa, about 40 GPa to about 100 GPa, about 60 GPa to about 100 GPa, about 60 GPa to about 80 GPa, about 80 GPa to about 100 GPa, or any range or sub-range therebetween.

[0296] In various aspects, the substrate 103 may be optically transparent. As used herein, "optically transparent" or "optically clear" means an average transmittance of 70% or greater through a 1.0 mm thick sheet of the material in the wavelength range of 400 nm to 750 nm. In various aspects, an "optically transparent material" or "optically clear material" may have an average transmittance of 75% or greater, 80% or greater, 85% or greater, or 90% or greater, 91% or greater, 92% or greater, 94% or greater, 96% or greater through a 1.0 mm thick sheet of the material in the wavelength range of 400 nm to 750 nm. The average transmittance in the wavelength range of 400 nm to 700 nm is calculated by measuring the transmittance at integer wavelengths from about 400 nm to about 700 nm and averaging the measured values.

[0297] In some aspects, in addition to being transparent, the substrate 103 may also be color-transparent, opaque, color-opaque, translucent, or color-translucent. As used herein, "opaque" and "translucent" may mean the following: Opacity is a measure of the non-transmittance of visible light. An opaque object is neither transparent(Allows all light to pass through), nor is it translucent (Allows some light to pass through). When light shines on the interface between two substances, typically, some may be reflected, some absorbed, some scattered, and the rest transmitted. Opaque substances transmit very little light and thus reflect, scatter, or absorb most of the light. Opacity depends on the frequency of the light being considered. For example, some types of glass while being transparent within visual range are largely opaque to ultraviolet light. Additionally, colored transparent, colored opaque, and colored translucent can be any of a variety of colors, including, for example, black, white, green, yellow, pink, red, blue, orange, purple, brown, etc.

[0298] In various aspects, coated articles 101, 201, 211, or 221, including glass-based substrates, glass-ceramic substrates, and / or ceramic-based substrates, may include one or more compressive stress regions. In various aspects, the compressive stress regions may be produced by chemical strengthening. Chemical strengthening may include an ion exchange process in which ions in the surface layer are replaced or exchanged with larger ions having the same valence or oxidation state. Methods of chemical strengthening will be discussed later. Without wishing to be bound by theory, chemical strengthening of substrate 103 may achieve good impact resistance, good puncture resistance, and / or enable a small bending radius, e.g., where compressive stress from chemical strengthening counteracts bend-induced tensile stress on the outermost surface of the substrate. The compressive stress region may extend to a depth referred to as the depth of compression (DOC) in a portion of the first part and / or the second part. As used herein, the depth of compression means the depth at which the stress in the chemically strengthened substrate and / or portion described herein changes from compressive stress to tensile stress. Depending on the ion exchange treatment and the thickness of the article being measured, the depth of compression may be measured by a surface stress meter or a scatter light polariscope (SCALP, where the values reported herein were obtained using the SCALP-5 manufactured by Glasstress Co., Estonia). In the case where the stress in the substrate and / or portion is produced by exchanging potassium ions into the substrate, a surface stress meter, such as the FSM-6000 (Orihara Industrial Co., Ltd. (Japan)), is used to measure the depth of compression. Unless otherwise specified, the compressive stress (including surface CS) is measured using a surface stress meter (FSM) with a commercially available instrument such as the FSM-6000 manufactured by Orihara. Surface stress measurement relies on an accurate measurement of the stress optical coefficient (SOC) related to the birefringence of the glass. Unless otherwise specified, the SOC is measured according to Procedure C (glass disk method) described in ASTM standard C770-16, entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient", the content of which is incorporated herein by reference in its entirety. In the case where the stress is produced by exchanging sodium ions into the substrate and the article being measured is thicker than about 400 μm, the depth of compression and the center tension (CT) are measured using SCALP. In the case where the stress in the substrate and / or portion is produced by exchanging potassium ions and sodium ions into the substrate and / or portion and the article being measured is thicker than about 400 μm, the depth of compression and CT are measured by SCALP. Without wishing to be bound by theory, the exchange depth of sodium may indicate the depth of compression, while the exchange depth of potassium ions may indicate the change in the magnitude of the compressive stress (but not the change in stress from compressive to tensile).A graphical representation of the stress distribution can also be derived using the refraction near field (RNF; the RNF method is described in U.S. Patent No. 8,854,623, titled "Systems and methods for measuring a profile characteristic of a glass sample", which is incorporated herein by reference in its entirety). When using the RNF method to derive a graphical representation of the stress distribution, the maximum center tension value provided by the SCALP is utilized in the RNF method. The graphical representation of the stress distribution derived by the RNF is force balanced and calibrated to the maximum center tension value provided by the SCALP measurement. As used herein, "depth of layer" (DOL) means the depth to which ions have been exchanged into the substrate and / or part (e.g., sodium, potassium). Throughout this disclosure, the DOL is measured in accordance with ASTM C-1422. Without wishing to be bound by theory, the DOL is generally greater than or equal to the corresponding DOC. Throughout this disclosure, when the maximum center tension cannot be directly measured by the SCALP (such as when the article being measured is thinner than about 400 μm), the maximum center tension can be approximated by dividing the product of the maximum compressive stress and the compression depth by the difference between the substrate thickness and twice the compression depth, where the compressive stress and the compression depth are measured by the FSM.

[0299] In various aspects, the substrate 103 may include a first compressive stress region at a first major surface 105, which may extend from the first major surface 105 to a first compressive depth. In various aspects, the substrate 103 may include a second compressive stress region at a second major surface 107, which may extend from the second major surface 107 to a second compressive depth. In various aspects, as a percentage of the substrate thickness 109, the first compressive depth and / or the second compressive depth may be about 5% or greater, about 10% or greater, about 12% or greater, about 15% or greater, about 17% or greater, about 30% or less, about 25% or less, about 22% or less, about 20% or less, about 17% or less, or about 15% or less. In various aspects, as a percentage of the substrate thickness 109, the first compressive depth and / or the second compressive depth may be in the range of about 5% to about 30%, about 10% to about 25%, about 10% to about 22%, about 12% to about 20%, about 12% to about 17%, about 15% to about 17% or any range or sub-range therebetween. In various aspects, the first compressive depth and / or the second compressive depth may be about 1 μm or greater, about 10 μm or greater, about 15 μm or greater, about 20 μm or greater, about 25 μm or greater, about 30 μm or greater, about 200 μm or less, about 150 μm or less, about 100 μm or less, about 60 μm or less, about 45 μm or less, about 30 μm or less, or about 20 μm or less. In various aspects, the first compressive depth and / or the second compressive depth may be in the range of about 1 μm to about 200 μm, about 1 μm to about 150 μm, about 10 μm to about 100 μm, about 15 μm to about 600 μm, about 20 μm to about 45 μm, about 20 μm to about 30 μm or any range or sub-range therebetween. By providing a first portion including a first glass base, a glass-ceramic, and / or a ceramic-based portion, the first portion including a first compressive depth and / or a second compressive depth of about 1% to about 30% of a first thickness, good impact resistance and / or puncture resistance may be achieved.

[0300] In various aspects, the first compressive stress zone may include a maximum first compressive stress, and / or the second compressive stress zone may include a maximum second compressive stress. In additional aspects, the maximum first compressive stress and / or the maximum second compressive stress may be about 100 megapascals (MPa) or greater, about 300 MPa or greater, 400 MPa or greater, about 500 MPa or greater, about 600 MPa or greater, about 700 MPa or greater, about 1,500 MPa or less, about 1,200 MPa or less, about 1,000 MPa or less, or about 800 MPa or less. In additional aspects, the maximum first compressive stress and / or the maximum second compressive stress may be in the range of about 100 MPa to about 1,500 MPa, about 100 MPa to about 1,200 MPa, about 300 MPa to about 1,200 MPa, about 300 MPa to about 1,000 MPa, about 400 MPa to about 1,000 MPa, about 500 MPa to about 1,000 MPa, about 600 MPa to about 900 MPa, about 700 MPa to about 800 MPa or any range or sub-range therebetween. By providing a maximum first compressive stress and / or a maximum second compressive stress of about 100 MPa to about 1,500 MPa, good impact resistance and / or puncture resistance can be achieved.

[0301] In various aspects, the substrate 103 may include a tensile stress zone. The tensile stress zone may be located between the first compressive stress zone and the second compressive stress zone. In various aspects, the tensile stress zone may include a maximum tensile stress. In additional aspects, the maximum first stress may be about 10 MPa or greater, about 20 MPa or greater, about 30 MPa or greater, about 100 MPa or less, about 80 MPa or less, or about 60 MPa or less. In additional aspects, the maximum tensile stress may be in the range of about 10 MPa to about 100 MPa, about 10 MPa to about 80 MPa, about 10 MPa to about 60 MPa, about 20 MPa to about 100 MPa, about 20 MPa to about 80 MPa, about 20 MPa to about 60 MPa, about 30 MPa to about 100 MPa, about 30 MPa to about 80 MPa, about 30 MPa to about 60 MPa or any range or sub-range therebetween. Providing a maximum tensile stress of about 10 MPa to about 100 MPa can achieve good impact resistance and / or puncture resistance.

[0302] As used herein, if a first layer and / or component is described as being "disposed over" a second layer and / or component, there may or may not be other layers between the first layer and / or component and the second layer and / or component. Additionally, as used herein, "disposed over" does not refer to a relative position with reference to gravity. For example, the first layer and / or component may be considered to be "disposed over" the second layer and / or component when the first layer and / or component is positioned below, above, or to one side of the second layer and / or component. As used herein, a first layer and / or component being described as "bonded to" a second layer and / or component means that the layers and / or components are bonded to each other by direct contact and / or a bond between the two layers and / or components or by an adhesive layer. As used herein, a first layer and / or component being described as "in contact with" a second layer and / or component or "contacting" the second layer and / or component refers to direct contact and includes the situation where the layers and / or components are bonded to each other. As used herein, a first layer and / or component being described as "disposed on" a second layer and / or component means that there are no other layers or bonds between them other than an optional coupling agent layer. Thus, a first layer disposed over a second layer may be further disposed on the second layer, in contact with the second layer, and / or bonded to the second layer.

[0303] In various aspects, as Figures 2A to 2C shown, the coated article 201, 211, or 221 may include an optical stack 203 that includes a third major surface 205 disposed on a first major surface 105 of a substrate 103. As shown, the optical stack 203 may include a fourth major surface 207 opposite the third major surface 205, where a stack thickness 209 is defined between the third major surface and the fourth major surface. In various aspects, the stack thickness 209 may be about 10 nanometers (nm) or greater, about 50 nm or greater, about 100 nm or greater, about 300 nm or greater, about 500 nm or greater, about 700 nm or greater, about 1 μm or greater, about 10 μm or less, about 5 μm or less, about 2 μm or less, or about 1 μm or less. In various aspects, the stack thickness 209 may be in the range of about 10 nm to about 10 μm, about 50 nm to about 5 μm, about 100 nm to about 2 μm, about 300 nm to about 1 μm, about 500 nm to about 1 μm, or any range or sub-range therebetween. In an exemplary aspect, the stack thickness 209 may be in the range of 10 nm to 10 μm, 50 nm to 5 μm, or 50 nm to 500 nm.

[0304] In other aspects, the optical stack 203 may include an anti-reflection (AR) coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflection coating, and / or an edge filter coating. For example, the anti-reflection coating of the optical stack 203 may be positioned between the surface modification layer (e.g., the anti-fingerprint coating 113) and the substrate 103. In yet other aspects, the optical stack 203 (e.g., the anti-reflection coating) may include two or more layers having different refractive index values, such as a first low refractive index (RI) of about 1.3 to about 1.6 and a second high refractive index (RI) of about 1.6 to about 3.0. In still other aspects, two or more layers of the optical stack 203 may form alternative layer groups, such as 2 or more, 3 or more, 5 or more, or 10 or more, such as 2 to 15 periods, 2 to 10 periods, 2 to 12 periods, 3 to 8 periods, 3 to 6 periods, or any range or sub-range therebetween.

[0305] In various aspects, as Figure 2B shown, the coated article 211 includes an optical stack 203a that includes a plurality of silicon oxide-containing layers, silicon nitride-containing layers, and / or silicon oxynitride-containing layers. For example, the optical stack 203a may be an anti-reflection coating. As shown, the optical stack 203a may include one or more periods 213 that include two or more layers having different refractive indices, such as a first low RI layer 215a and a second high RI layer 217a. For example, Figure 2B the optical stack 203a shown in x N y has 2 periods 213 that include a first low RI layer 215a and 215b (L) and a second high RI layer 217a and 217b (H), which alternate in the following layer sequence: L / H / L / H, but H / L / H / L may be provided in other aspects. The absolute value of the difference between the first low RI layer 215a and the second high RI layer 217a may be about 0.01 or greater, about 0.05 or greater, about 0.1 or greater, or even 0.2 or greater. Exemplary materials for the first low RI layer 215a include SiO2, Al2O3, GeO2, SiO2, AlO x N y 、SiO u Al v O x N y 、MgO, and MgAl2O4. Exemplary materials for the second high RI layer 217a include Si u Al v O x N y 、AlN, oxygen-doped SiN x 、SiN x, Si3N4, AlO x N y , SiO x N y , Ta2O5, Nb2O5, HfO2, TiO2, ZrO2, Y2O3, ZrO2, Al2O3, and diamond-like carbon. The oxygen content of the material of one or more high RI layers 130B can be minimized, particularly in SiN x or AlN x materials. The foregoing materials can be hydrogenated up to about 30 wt%. As used herein, it should be understood that subscripts (e.g., "u", "v", "x", "y", and "z") are in the range greater than 0 to 1, where the sum of the subscripts is 1 to represent an "atomic fractional formula". See, for example: (i) Charles Kittel, Introduction to Solid State Physics, 7th Edition, John Wiley & Sons, Inc., NY, 1996, pp. 611 - 627; (ii) Smart and Moore, Solid State Chemistry, An introduction, Chapman & Hall University and Professional Division, London, 1992, pp. 136 - 151; and (iii) James F. Shackelford, Introduction to Materials Science for Engineers, 6th Edition, Pearson Prentice Hall, New Jersey, 2005, pp. 404 - 418. The balance of the material (i.e., 1 minus the sum of the subscripts) is the first atom (e.g., SiN where x = 0.57 x effectively corresponds to Si 0.43 N 0.57 , which is the same as Si3N4). In addition, the sum of all subscripts is greater than 0.

[0306] In various aspects, the optical stack 203a can include an anti - reflection structure, an anti - reflection coating, or an external optical film described in U.S. Patent No. 10,948,629, U.S. Patent Application Publication No. 2022 / 0011468, and / or WIPO Publication WO 2022 / 125846, issued on March 16, 2021, which are incorporated herein by reference in their entirety. In various aspects, as Figure 2BAs shown, the optical stack 203a may include a capping layer 219. In additional aspects, the capping layer 219 may include a low refractive index material, which may be the same material as the first low RI layer 215a. In additional aspects, the capping layer 219 may include silicon-containing oxides (e.g., silicon dioxide), silicon-containing nitrides (e.g., oxide-doped silicon nitride, silicon nitride, etc.), and silicon-containing oxynitrides (e.g., silicon oxynitride). An exemplary aspect of the capping layer is silicon dioxide (SiO2). In some aspects, as shown, the layer of the optical stack 203 closest to the substrate 103 may be a low refractive index layer (i.e., the first low RI layer 215a), and the layer closest to the surface modification layer (e.g., the anti-fingerprint coating 113) may be a low refractive index layer (e.g., the capping layer 219). An exemplary combination of materials for the optical stack is SiO2 for the first low RI layer, silicon nitride (e.g., Si3N4, SiN x ) or silicon oxynitride (SiO x N y ) for the second high RI layer, and silicon dioxide (SiO2) for the capping layer.

[0307] In various aspects, the coated article 211 can include a stack thickness 209a corresponding to the physical thickness of the optical stack 203a, which is in the range of from about 50 nm to less than 500 nm, from about 75 nm to about 490 nm, from about 100 nm to about 180 nm, from about 125 nm to about 475 nm, from about 150 nm to about 450 nm, from about 175 nm to about 425 nm, from about 200 nm to about 400 nm, from about 225 nm to about 375 nm, from about 250 nm to about 350 nm, from about 250 nm to about 340 nm, or any range or sub-range therebetween. As used herein, the term "optical thickness" is determined by (n*d), where "n" refers to the RI of the sub-layer and "d" refers to the physical thickness of the layer. In various aspects, at least one layer in the optical stack 203a can have an optical thickness in the range of from about 2 nm to about 200 nm, from about 10 nm to about 100 nm, from about 15 nm to about 90 nm, from about 50 nm to about 80 nm, or any range or sub-range therebetween. In additional aspects, the first low RI layers 215a and 215b in the period 213 of the optical stack 203 can be within the ranges mentioned in the previous sentence or more of the ranges. In various aspects, the combined physical thickness of the second high RI layers 217a and 217b can be about 90 nm or greater, about 100 nm or greater, about 120 nm or greater, about 130 nm or greater, about 150 nm or greater, or less than 500 nm. For example, the combined physical thickness of the second high RI layers 217a and 217b can be in the range of from about 90 nm to less than 500 nm, from about 100 nm to about 300 nm, from about 120 nm to about 200 nm, or any range or sub-range therebetween. In various aspects, as a percentage of the physical thickness of the stack thickness 209a, the combined physical thickness of the second high RI layers 217a and 217b can be about 30% or greater, about 35% or greater, about 40% or greater, or about 45% or greater, such as in the range of from about 35% to about 75%, from about 40% to about 65%, from about 45% to about 55%, or any range or sub-range therebetween.

[0308] In various aspects, the optical stack 203a of the coated article 211 can include a residual stress of less than about +50 MPa (tensile) to about -1000 MPa (compressive). In some embodiments of the article 100, the anti-reflection coating is characterized by a residual stress of about -50 MPa to about -1000 MPa (compressive) or about -75 MPa to about -800 MPa (compressive). Unless otherwise indicated, the residual stress in the anti-reflection coating is obtained by measuring the curvature of the substrate 103 before and after depositing the anti-reflection coating and then calculating the residual film stress according to the Stoney equation, as known and understood by those of ordinary skill in the art of the present disclosure.

[0309] In various aspects, the optical stack 203a and / or the coated article 211 may exhibit a visible light specular average reflectance of about 1% or less, about 0.9% or less, about 0.8% or less, about 0.7% or less, about 0.6% or less, about 0.5% or less, about 0.4% or less, about 0.3% or less, or about 0.2% or less in the optical wavelength region. These specular average reflectance values may be exhibited at incident illumination angles in the range of about 0° to about 20°, about 0° to about 40°, or about 0° to about 60°. As used herein, "specular average reflectance" simulates the response of the human eye by weighting the reflectance versus the wavelength spectrum according to the sensitivity of the human eye. According to known conventions, such as the CIE color space convention, the specular average reflectance may also be referred to as the luminance of the reflected light or the tristimulus Y value. The specular average reflectance <R p > is defined as the spectral reflectance R(λ) multiplied by the illuminant spectrum I(λ) and the color matching function of the CIE related to the spectral response of the eye:

[0310]

[0311] Additionally, the article exhibits a CIE a* value of about -10 to +2 in terms of reflectance and a CIE b* value of -10 to +2 in terms of reflectance, with the CIE a* value and the CIE b* value each measured at a normal incident illumination angle on the optical film structure. In various aspects, the optical stack 203a and / or the coated article 211 may exhibit a specular average light transmittance of about 90% or greater, 92% or greater, 94% or greater, 96% or greater, or 98% or greater in the optical wavelength region. In some embodiments, the optical stack 203a and / or the coated article 211 exhibits an average light transmittance of about 87% or greater, 88% or greater, 89% or greater, 90% or greater, 91% or greater, 92% or greater, 93% or greater, 94% or greater, or 95% or greater in the optical wavelength region of the infrared spectrum from 800 nm to 1000 nm, 900 nm to 1000 nm, or 930 nm to 950 nm. In various aspects, the optical stack 203a and / or the coated article 211 may exhibit a hardness of 8 GPa or greater measured at an indentation depth of about 100 nm, or a maximum hardness of 9 GPa or greater measured in the range of indentation depths from about 100 nm to about 500 nm, with the hardness and the maximum hardness measured by a Berkovich indenter hardness test (as defined below).

[0312] In various aspects, as Figure 2BAs shown, the coated article 211 includes an optical stack 203a that includes an optical film 231, a scratch-resistant layer 233, and an optional capping layer 229. In various aspects, the optical stack 203b can include a scratch-resistant coating, an anti-reflection coating, and / or an optical film structure as described in U.S. Patent No. 9,328,016, issued May 3, 2016; U.S. Patent No. 9,684,097, issued June 20, 2017; U.S. Patent No. 9,703,011, issued July 11, 2017; U.S. Patent No. 9,079,802, issued July 14, 2015; U.S. Patent No. 9,726,786, issued August 8, 2017; and U.S. Patent No. 10,416,352, issued September 17, 2019, which are incorporated herein by reference in their entirety. For example, the optical stack 203b can be an anti-reflection coating and / or a scratch-resistant coating.

[0313] In further aspects, as Figure 2C shown, the optical film 130 of the optical stack 203b can include one or more periods 223 that include two or more layers having different refractive indices, such as a first low RI layer 225 and a second high RI layer 227. For example, Figure 2C the optical stack 203b shown has 3 periods 223 that form an optical film 231 having alternating first low RI layers 225 and second high RI layers 227. In still further aspects, the optical film 231 can include any number of periods within one or more of the ranges discussed above for the optical stack 203a. The absolute value of the difference between the first low RI layer 225 and the second high RI layer 227 can be about 0.01 or greater, about 0.05 or greater, about 0.1 or greater, or even 0.2 or greater. In further aspects, the first low RI layer 225 can include any of the materials discussed above for the first low RI layer 215a, such as silicon dioxide (SiO2). In further aspects, the second high RI layer 227 can include any of the materials discussed above for the second high RI layer 217a, such as SiO x N y。In other aspects, the layers of the first low RI sub-layer 225 and / or the second high RI sub-layer 227 may have an optical thickness (n*d) in the range of about 2 nm to about 200 nm, about 10 nm to about 100 nm, about 15 nm to about 100 nm, or any range or sub-range therebetween. In yet other aspects, all layers in the optical film 130 or all second high RI layers in the optical film 130 may have an optical thickness within one or more of the ranges mentioned in the previous sentence. In yet other aspects, the layers of the first low RI sub-layer 225 and / or the second high RI sub-layer 227 may have a physical thickness in the range of about 10 nm to about 800 nm, about 10 nm to about 500 nm, about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 20 nm to about 100 nm, or any range or sub-range therebetween. In yet other aspects, the optical stack 203 and / or any one of the layers or segments therein (e.g., the optical film 231, the scratch-resistant layer 233, the optional capping layer 229) may exhibit an extinction coefficient of about 10 -4 or less (at a wavelength of about 400 nm).

[0314] In other aspects, as Figure 2C shown, the scratch-resistant layer 233 may comprise an inorganic carbide, nitride, oxide, diamond-like material, or a combination thereof. Examples of suitable materials for the scratch-resistant layer 233 include metal oxides, metal nitrides, metal oxynitrides, metal carbides, metal carbon oxides, and / or combinations thereof. Exemplary metals include B, Al, Si, Ti, V, Cr, Y, Zr, Nb, Mo, Sn, Hf, Ta, and W. Specific examples of materials that may be used for the scratch-resistant layer 233 may include Al2O3, AlN, AlO x N y 、Si3N4、SiO x N y 、Si u Al v O x N y 、diamond, diamond-like carbon, Si x C y 、Si x O y C z 、ZrO2、TiO x N y or a combination thereof. In yet other aspects, the scratch-resistant layer 233 may include the same material as the second high RI layer 227, such as SiO x N y。In yet another aspect, the physical thickness of the scratch-resistant layer and / or the optical stack can be from about 0.05 μm to about 3 μm, from about 0.1 μm to about 3 μm, from about 0.2 μm to about 3 μm, from about 0.3 μm to about 2.2 μm, from about 0.5 μm to about 2.1 μm, from about 1 μm to about 2.1 μm, from about 1.8 μm to about 2.1 μm, or any range or sub-range therebetween. In an exemplary aspect, the physical thickness of the scratch-resistant layer can be 0.05 μm to 3 μm, 0.3 μm to 2.2 μm, or 1 μm to 2.1 μm. The scratch-resistant layer 233 and / or the optical stack 203b can exhibit a hardness of about 8 GPa or greater, about 10 GPa or greater, about 13 GPa or greater, or about 17 GPa or greater, as measured by a Vickers indenter hardness test (described below).

[0315] Although not shown, it should be understood that the scratch-resistant layer can be sandwiched by portions of the optical film. For example, 3 or more cycles can be positioned between the scratch-resistant layer and the substrate, and 2 or more cycles can be positioned between the scratch-resistant layer and the surface modification layer (e.g., the anti-fingerprint coating).

[0316] In another aspect, as Figure 2C shown, the optical stack 203b can include a capping layer 229 disposed over (e.g., on top of) the scratch-resistant layer. In yet another aspect, the capping layer 229 can comprise a low refractive index material such as SiO2, Al2O3, GeO2, SiO2, AlO x N y 、SiO x N y 、Si u Al v O x N y 、MgO, MgF2, BaF2, CaF2, DyF3, YbF3, YF3, or CeF3. In another aspect, the capping layer 229 can include the same material as the first high RI layer 225, such as SiO2. In another aspect, the thickness of the capping layer 229 can be from about 10 nm to about 120 nm, from about 20 nm to about 115 nm, from about 50 nm to about 110 nm, from about 80 nm to about 110 nm, from about 90 nm to about 105 nm, or any range or sub-range therebetween. The capping layer 229 can exhibit an inherent hardness in the range of about 7 GPa to about 10 GPa, as measured by a Vickers indenter hardness test (measured on the surface of a layer of the same material as the capping layer, formed in the same manner, but having a thickness of about 1 micron or greater).

[0317] In other aspects, the stack thickness 209b corresponding to the physical thickness of the optical stack 203b can be in the range of about 0.5 μm to about 3 μm, about 1 μm to about 3 μm, about 1.2 μm to about 3 μm, about 1.5 μm to about 3 μm, about 2 μm to about 2.6 μm, or any range or sub-range therebetween. In other aspects, the optical stack 203b can exhibit an average light reflectance of about 0.5% or less, about 0.25% or less, about 0.1% or less, or even 0.05% or less in the optical wavelength region. In other aspects, the optical stack 203b can exhibit an average transmittance or average reflectance with an average oscillation amplitude of about 5 percentage points or less in the optical wavelength region. In other aspects, the optical stack 203b can exhibit an average light transmittance of 80% or greater, 82% or greater, 85% or greater, 90% or greater, 90.5% or greater, 91% or greater, 91.5% or greater, 92% or greater, 92.5% or greater, 93% or greater, 93.5% or greater, 94% or greater, 94.5% or greater, or 95% or greater.

[0318] The optical stacks 203, 203a, or 203b can be formed using various deposition methods, such as vacuum deposition techniques, chemical vapor deposition (e.g., plasma-enhanced chemical vapor deposition (PECVD), low-pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, and plasma-enhanced atmospheric pressure chemical vapor deposition), physical vapor deposition (e.g., reactive or non-reactive sputtering or laser ablation), thermal or electron beam evaporation, and / or atomic layer deposition. Liquid-based methods, such as printing, spraying, or slot coating, can also be used. In the case of using vacuum deposition, an in-line process can be used to form the optical stacks 203, 203a, or 203b in a single deposition run. In various aspects, the vacuum deposition can be performed through a linear PECVD source. In various aspects, the optical stacks 203, 203a, or 203b can be prepared using a sputtering process (e.g., a reactive sputtering process), a chemical vapor deposition (CVD) process, a plasma-enhanced chemical vapor deposition process, or a combination of these processes. In various aspects, the optical stacks 203a or 203b, including one or more low RI layers 215a, 215b, or 225 and one or more high RI layers 217a, 217b, or 227, can be prepared according to a reactive sputtering process. According to some embodiments, the optical stacks 203a or 203b (including the low RI layers 215a, 215b, or 225, the high RI layers 217a, 217b, or 227, and the capping layer 219 or 229) can be manufactured using metal-mode reactive sputtering in a drum coater. The reactive sputtering process conditions are defined through careful experimentation to achieve the desired combination of hardness, refractive index, optical transparency, low color, and controlled film stress.

[0319] In another aspect, the optical stack 203 may include a gradient coating that includes a refractive index gradient. For example, the gradient coating of the optical stack 203 may be positioned between a surface modification layer (e.g., an anti-fingerprint coating 113) and the substrate 103. In yet another aspect, the refractive index gradient may span a refractive index value range of about 0.2 or greater, about 0.3 or greater, about 0.4 or greater, about 1 or less, about 0.8 or less, about 0.6 or less, or about 0.5 or less, such as about 0.2 to about 1, about 0.3 to about 0.8, about 0.4 to about 0.6, or any range or sub-range therebetween. In yet another aspect, the gradient coating may include a concentration gradient of one or more of oxygen, nitrogen, and / or silicon. However, it should be understood that other functional coatings may be provided in the optical stack 203 to achieve the predetermined optical properties of the coated article 201, 211, or 221.

[0320] According to one or more aspects, an anti-reflection coating may be used in combination with an anti-glare (AG) surface. The anti-glare surface treatment can affect the performance of the anti-reflection coating. Therefore, selecting an appropriate anti-glare surface can be important for optimal performance, especially in difficult use environments such as the interior of a vehicle. In such environments, it may be beneficial for the anti-glare surface on the protective glass cover to have minimal flash and provide an appropriate anti-glare effect and touch feel while meeting the required contrast ratio (CR) in sunlight. For example, samples with a chemically etched ultra-low flash (ULS) AG surface may be prepared on a glass substrate made of Gorilla glass, the glass substrate having an anti-reflection coating and an easy-to-clean (ETC) coating according to embodiments of the present disclosure to provide a stable color appearance with a wide viewing angle, thereby facilitating visibility in sunlight.

[0321] The chemically etched ultra-low flash (ULS) AG surface may be achieved by using a chemical etching method on Gorilla An anti-glare surface is prepared on a glass substrate, and the chemical etching method achieves ultra-low flash performance suitable for high-resolution displays of up to 300 pixels per inch (PPI). The optical properties of the anti-glare glass can be analyzed, including the contributions with and without specular reflection (i.e., excluding the specular reflection component (SCE) or including the specular reflection component (SCI)), transmission haze, gloss, image clarity (DOI), and flash. Additional information regarding these properties and how these measurements are performed can be found in (1) C. Li and T. Ishikawa, Effective Surface Treatment on the Cover Glass for Auto-Interior Applications, SID Symposium Digest of Technical Papers Volume 1, Issue 36.4, page 467 (2016); (2) J. Gollier, G. A. Piech, S. D. Hart, J. A. West, H. Hovagimian, E. M. Kosik Williams, A. Stillwell, and J. Ferwerda, Display Sparkle Measurement and Human Response, SID Symposium Digest of Technical Papers Volume 44, Issue 1 (2013); and (3) J. Ferwerda, A. Stillwell, H. Hovagimian, and E. M. Kosik Williams, Perception of sparkle in anti-glare display screen, Journal of the SID, Vol 22, Issue 2 (2014), the contents of which are incorporated herein by reference.

[0322] The balance of five metrics of SCE / SCI (see previous paragraph), haze, gloss, Image Clarity (DOI), and flash is important for maximizing the benefits of anti-glare for display readability, tactile feel on a glass surface, and aesthetic appearance in applications such as high-performance touch displays in vehicle interiors. Flash is the interaction of the anti-glare surface with the micro-scattering of the LCD pixels to produce bright spots that degrade image quality, especially at high resolutions. A method with a Pixel Power Deviation with reference (PPDr) can be used to characterize the flash effect to examine the flash effect on displays of different resolutions. For example, an ultra-low flash anti-glare glass with less than 1% PPDr will have an invisible flash effect on displays less than 300 pixels per inch (PPI). However, depending on the end user's preference and depending on the display content, up to 4% PPDr may be acceptable. In a vehicle or automotive interior setting, from about 120 PPI to about 300 PPI is acceptable, and displays above 300 PPI have diminishing values.

[0323] In various aspects, the anti-glare surface of the substrate 103 and / or the optical stacks 203, 203a, and / or 203b can include, for example, a textured surface with particles, a mechanically roughened surface, and / or a chemically roughened surface. In additional aspects, the anti-glare and / or textured surface can be formed by treating the corresponding surface with an anti-glare treatment. Exemplary aspects of the anti-glare treatment include chemical or physical surface treatment to form irregularities and / or etching the surface (e.g., with hydrofluoric acid) to produce etched regions that exhibit anti-glare properties.

[0324] Throughout the present disclosure, the hardness of the optical stack is measured using "Berkovich indentation hardness testing". As used herein, "Berkovich indentation hardness testing" measures the hardness of a material by indenting a surface (e.g., the fourth major surface 207) with a diamond Berkovich indenter to form an indentation having an indentation depth in the range of from about 50 nm to about 1000 nm (or the entire thickness of the optical stack 203, 203a, or 203b, whichever is smaller), and measuring the hardness from this indentation at various points along the entire indentation depth range, along a specified section of this indentation depth (e.g., in the depth range of from about 100 nm to about 500 nm), or at a specific indentation depth (e.g., at a depth of 100 nm, at a depth of 500 nm, etc.) using the methods set forth in Oliver, W.C. and Pharr, G.M., "An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments", J. Mater. Res., Vol. 7, No. 6, 1992, 1564 - 1583; and Oliver, W.C. and Pharr, G.M., "Measurement of Hardness and Elastic Modulus by Instrument Indentation: Advances in Understanding and Refinements to Methodology", J. Mater. Res., Vol. 19, No. 1, 2004, 3 - 20. Additionally, when measuring hardness within an indentation depth range (e.g., in the depth range of from about 100 nm to about 500 nm), the result may be reported as the maximum hardness within the specified range, where the maximum value is selected from the measurements taken at each depth within the range. As used herein, both "hardness" and "maximum hardness" refer to the measured hardness value, rather than the average of the hardness values. Similarly, when measuring hardness at an indentation depth, the hardness value obtained from the Berkovich indentation hardness test is given for the specific indentation depth.

[0325] Through a Berkovich indenter hardness test at an indentation depth of about 100 nm, the optical stack 203, 203a, or 203b (if present) may include a hardness greater than about 8 GPa. Through a Berkovich indenter hardness test at an indentation depth of about 100 nm, the optical stack 203 may exhibit a hardness of about 8 GPa or greater, about 9 GPa or greater, about 10 GPa or greater, about 11 GPa or greater, about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, or about 15 GPa or greater. For example, through a Berkovich indenter hardness test at an indentation depth of about 100 nm, the optical stack 203 or 203a including a surface modification layer (e.g., the fingerprint-resistant coating 113) as described herein may exhibit a hardness of about 8 GPa or greater, about 10 GPa or greater, or about 12 GPa or greater. In various aspects, the optical stack 203 or 203b may exhibit a hardness in the range of about 8 GPa to about 30 GPa, about 10 GPa to about 25 GPa, about 12 GPa to about 20 GPa, about 16 GPa to about 20 GPa, or any range or sub-range therebetween. These measured hardness values may be exhibited by the optical stack 203, 203a, or 203b and / or the coated article 101, 201, 211, or 221 at an indentation depth of about 50 nm or greater or about 100 nm or greater (e.g., about 100 nm to about 300 nm, about 100 nm to about 400 nm, about 100 nm to about 500 nm, about 100 nm to about 600 nm, about 200 nm to about 300 nm, about 200 nm to about 400 nm, about 200 nm to about 500 nm, or about 200 nm to about 600 nm). Similarly, the maximum hardness value of about 8 GPa or greater, about 9 GPa or greater, about 10 GPa or greater, about 11 GPa or greater, about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, or about 15 GPa or greater through a Berkovich indenter hardness test may be exhibited by the optical stack 203 and / or the coated article 101, 201, 211, or 221 at an indentation depth of about 50 nm or greater or about 100 nm or greater (e.g., about 100 nm to about 300 nm, about 100 nm to about 400 nm, about 100 nm to about 500 nm, about 100 nm to about 600 nm, about 200 nm to about 300 nm, about 200 nm to about 400 nm, about 200 nm to about 500 nm, or about 200 nm to about 600 nm).

[0326] As Figure 1 and Figures 2A to 2CAs shown, the coated articles 101, 201, 221 or 221 include a surface modification layer (e.g., an anti-fingerprint coating 113) disposed above the first major surface 105 of the substrate 103. The surface modification layer (e.g., an anti-fingerprint coating 113) includes an inner surface 117 facing the first major surface 105 of the substrate 103. In various aspects, as Figure 1 shown, the surface modification layer (e.g., an anti-fingerprint coating 113) (e.g., the inner surface 117) can be disposed on and / or bonded to the first major surface 105 of the substrate 103. In various aspects, as Figure 1 and Figures 2A to 2C shown, the surface modification layer (e.g., an anti-fingerprint coating 113) includes an outer surface 115, which forms the outer surface of the coated articles 101, 201, 211 or 221. Thus, a user will interact with the coated articles 101, 201, 211 or 221 by, for example, touching the outer surface 115 or viewing an image through the outer surface 115. The anti-fingerprint thickness 119 is defined as the average distance between the inner surface 117 and the outer surface 115. In various aspects, the anti-fingerprint thickness 119 can be about 10 nm or greater, about 20 nm or greater, about 50 nm or greater, about 100 nm or greater, about 200 nm or greater, about 600 nm or less, about 500 nm or less, about 400 nm or less, about 350 nm or less, or about 300 nm or less. In various aspects, the anti-fingerprint thickness 119 can be in the range of about 10 nm to about 600 nm, about 20 nm to about 500 nm, about 50 nm to about 400 nm, about 100 nm to about 350 nm, about 200 nm to about 300 nm or any range or sub-range therebetween. The anti-fingerprint thickness 119 is determined from cross-sectional scanning electron microscope (SEM) images.

[0327] Throughout this disclosure, a "surface modification layer" refers to a layer characterized by altering the physical properties or other behavior of a coated article. For example, the surface modification layer can modify one or more of the water contact angle, oleic acid contact angle, visibility of fingerprints (e.g., simulated fingerprints), and / or the ability to remove fingerprints (e.g., by wiping).

[0328] In various aspects, the surface modification layer can be an anti-fingerprint coating. Throughout this disclosure, a surface modification layer is an "anti-fingerprint" coating if the coating on the substrate can reduce the visibility of fingerprint oil disposed thereon, reduce the color shift of fingerprint oil, and / or reduce the droplet formation of fingerprint oil relative to a substrate without the coating. As used herein, the visibility of a fingerprint refers to the absolute value of the difference in brightness (e.g., CIELAB L* value) between a portion of the anti-fingerprint coating having fingerprint oil and another portion of the anti-fingerprint coating not having fingerprint oil. As used herein, the color shift of a substrate refers to the measured color of √((a1*-a2*) 2+(b1 * - b2 *) 2 ) The difference, where a* refers to the CIELAB a* value, b* refers to the CIELAB b* value, subscript 1 refers to a portion of the fingerprint-resistant coating without fingerprint oil, and subscript 2 refers to a portion of the fingerprint-resistant coating with fingerprint oil. The fingerprint-resistant coating can reduce droplet formation by being lipophilic, which can increase the visibility and / or color shift of the fingerprint oil, as defined below. Additionally, the fingerprint-resistant coating may be able to remove water-containing materials (e.g., water droplets, sweat droplets) from the coating, e.g., by being hydrophobic, as defined below. In another aspect, the fingerprint-resistant coating can exhibit a water contact angle (e.g., formed) of 90° to 120°, an oleic acid contact angle (e.g., formed) of 40° or less, and a coefficient of friction of 0.25 or less. In another aspect, the easy-to-clean coating can be substantially fluorine-free and / or fluorine-containing. In various aspects, the diiodomethane contact angle of the fingerprint-resistant coating (e.g., formed) can be about 60° or greater, about 62° or greater, about 65° or greater, about 80° or less, about 75° or less, about 73° or less, or about 70° or less. In various aspects, the diiodomethane contact angle of the fingerprint-resistant coating (e.g., formed) can be in the range of about 60° to about 80°, about 62° to about 75°, about 65° to about 72°, or any range or sub-range therebetween. In various aspects, the fingerprint-resistant coating can be lipophilic. In various aspects, the hexadecane contact angle and / or oleic acid contact angle of the fingerprint-resistant coating (e.g., formed) can be about 45° or less, about 40° or less, about 30° or less, about 25° or less, about 20° or less, or the fingerprint-resistant coating can wet hexadecane and / or oleic acid. In another aspect, the fingerprint-resistant coating (e.g., formed) wets hexadecane and / or oleic acid. Providing a low diiodomethane contact angle (e.g., about 60° or less) and / or a low hexadecane contact angle (e.g., about 30° or less) can reduce the visibility and / or color shift associated with fingerprints by allowing the fingerprint oil to disperse on the fingerprint-resistant coating rather than coalescing into distinct droplets.

[0329] In various aspects, the surface modification layer can be a fingerprint hiding coating. Throughout this disclosure, a "fingerprint hiding coating" can reduce the visibility of fingerprint oil disposed thereon and / or reduce the color shift of fingerprint oil relative to a glass-based substrate without the coating. As used herein, the visibility of a fingerprint refers to the absolute value of the difference in brightness (e.g., CIELAB L* value) between a portion of the fingerprint hiding coating with fingerprint oil and another portion of the fingerprint hiding coating without fingerprint oil. As used herein, the color shift of a glass-based substrate refers to the measured color as √((a1 * - a2 *) 2 +(b1 * - b2 *) 2) where a* refers to the CIELAB a* value, b* refers to the CIELAB b* value, the subscript 1 refers to a portion of the fingerprint hiding coating that does not have fingerprint oil, and the subscript 2 refers to a portion of the fingerprint hiding coating that has fingerprint oil. Specifically, the fingerprint hiding coating can cause the fingerprint oil to spread above the surface of the fingerprint hiding coating. Reducing the thickness of the fingerprint oil droplets and / or increasing the area of the fingerprint hiding coating covered by the fingerprint oil can reduce the color shift and / or visibility associated with the fingerprint oil. The fingerprint hiding coating that can be lipophilic will contrast with other coatings (e.g., fingerprint resistant coatings) that can reduce droplet formation by being oleophobic. Additionally, the fingerprint hiding coating may be able to remove water-containing materials (e.g., water droplets, sweat droplets) from the coating, for example, by being hydrophobic, as discussed herein. In another aspect, the fingerprint hiding coating can exhibit a water contact angle (e.g., formed) of 90° to 120°, an oleic acid contact angle (e.g., formed) of 40° or less, and a coefficient of friction of 0.25 or less. In another aspect, the fingerprint hiding coating can be a fluorine-containing material. Alternatively, in another aspect, the fingerprint hiding coating can be substantially fluorine-free and / or fluorine-free. In another aspect, the finger hiding coating can exhibit a cetane contact angle (or wet cetane) of 20° or less and / or a diiodomethane contact angle of 60° or greater.

[0330] In various aspects, the surface modification layer can be an easy-to-clean coating. Throughout this disclosure, a surface modification layer is an "easy-to-clean" coating if the coating on the glass-based substrate repels materials disposed thereon and / or facilitates the removal of materials relative to a glass-based substrate without the coating. As used herein, the ability to repel materials is determined based on the contact angle, where a higher contact angle is associated with greater repellency. As used herein, the ability to remove materials is measured by wiping a material disposed on a surface (e.g., the coating or the glass-based substrate) with a coarse cotton cloth (see details of the coarse cotton cloth abrasion test, which is modified to have the material disposed on the surface prior to wiping) and monitoring the visibility of the material. A reduced visibility (e.g., fewer wiping cycles to achieve a predetermined reduction in visibility) is associated with a coating that facilitates the removal of materials disposed thereon. In additional aspects, the easy-to-clean coating can exhibit a (e.g., formed) water contact angle of 90° to 120°, an (e.g., formed) oleic acid contact angle of 50° or greater, and a coefficient of friction of 0.25 or less. In additional aspects, the easy-to-clean coating can be a fluorine-containing material. Alternatively, in additional aspects, the easy-to-clean coating can be substantially fluorine-free and / or fluorine-free. In various aspects, the diiodomethane contact angle of the fingerprint-resistant coating (e.g., formed) can be about 60° or greater, about 62° or greater, about 65° or greater, about 80° or less, about 75° or less, about 73° or less, or about 70° or less. In various aspects, the diiodomethane contact angle of the fingerprint-resistant coating (e.g., formed) can be in the range of about 60° to about 80°, about 62° to about 75°, about 65° to about 72°, or any range or sub-range therebetween. In various aspects, the fingerprint-resistant coating can be lipophilic. In various aspects, the hexadecane contact angle of the fingerprint-resistant coating (e.g., formed) can be about 45° or less, about 40° or less, about 30° or less, about 25° or less, about 20° or less, or the fingerprint-resistant coating can wet hexadecane. In additional aspects, the fingerprint-resistant coating (e.g., formed) wets hexadecane. Providing a low diiodomethane contact angle (e.g., about 60° or less) and / or a low hexadecane contact angle (e.g., about 30° or less) can reduce the visibility and / or color shift associated with fingerprints by enabling fingerprint oils to disperse on the surface modification layer rather than coalescing into distinct droplets.

[0331] Throughout the present disclosure, the elastic modulus (e.g., Young's modulus) of the fingerprint-resistant coating is determined using nanoindentation with a Berkovich diamond indenter tip. See: Fischer-Cripps, A.C., “Critical Review of Analysis and Interpretation of Nanoindentation Test Data,” Surface & Coatings Technology, 200, 4153–4165 (2006); and Hay, J., Agee, P and Herbert, E., “Continuous Stiffness measurement During Instrumented Indentation Testing, Experimental Techniques,” 34(3) 86-94 (2010). For the coating, an instantaneous estimate of the elastic modulus is measured as varying with indentation depth. The elastic modulus is taken as the maximum of the instantaneous estimates of the elastic modulus measured within 5 nm from the outer surface subtracted from the fingerprint-resistant thickness of 119. Without wishing to be bound by theory, if the coating has sufficient thickness, then the coating of that property can then be isolated from adjacent coatings based on the resulting response profile varying with depth. The extraction of reliable nanoindentation data is based on well-established protocols described in the references mentioned above. Otherwise, these metrics are affected by significant errors. In various aspects, the elastic modulus of the surface modification layer (e.g., the fingerprint-resistant coating 113) can be about 9 GPa or greater, about 10 GPa or greater, about 12 GPa or greater, about 15 GPa or greater, about 20 GPa or greater, about 25 GPa or greater, about 70 GPa or less, about 60 GPa or less, about 50 GPa or less, about 40 GPa or less, about 38 GPa or less, about 35 GPa or less, about 30 GPa or less, or about 25 GPa or less. In various aspects, the elastic modulus of the surface modification layer (e.g., the fingerprint-resistant coating 113) can be in the range of about 9 GPa to about 70 GPa, about 9 GPa to about 60 GPa, about 9 GPa to about 50 GPa, about 10 GPa to about 40 GPa, about 12 GPa to about 38 GPa, about 15 GPa to about 35 GPa, about 20 GPa to about 30 GPa or any range or sub-range therebetween. As discussed in the examples below, it has been found that a surface modification layer (e.g., a fingerprint-resistant coating) having an elastic modulus of about 9 GPa to about 40 GPa has unexpectedly improved wear resistance.

[0332] In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) and / or the coated article 101, 201, 211, or 221 can include an average transmittance of about 80% or greater, about 85% or greater, about 88% or greater, about 89% or greater, about 90% or greater, about 91% or greater, about 92% or greater, or about 93% or greater (as described above). In various aspects, the average transmittance of the surface modification layer (e.g., the fingerprint-resistant coating 113) and / or the coated article 101, 201, 211, or 221 can be in the range of about 80% to 100%, about 85% to about 99%, about 88% to about 97%, about 89% to about 97%, about 90% to about 96%, about 91% to about 95%, about 92% to about 94%, or any range or sub-range therebetween. In various aspects, the transmittance of the surface modification layer (e.g., the fingerprint-resistant coating 113) and / or the coated article 101, 201, 211, or 221 at 550 nm can be within one or more of the ranges mentioned above for the average transmittance in this paragraph.

[0333] As used herein, haze refers to the transmission haze measured according to ASTM D1003-21 through the surface modification layer (e.g., the fingerprint-resistant coating 113) and / or through the coated article 101, 201, 211, or 221 (through the outer surface 115) at 0° relative to the direction orthogonal to the outer surface 115. The haze is measured using a HAZE-GARD PLUS available from BYK Gardner having an orifice above the source port. The orifice has a diameter of 8 mm. The CIE C illuminant is used as the light source for illuminating the surface modification layer (e.g., the fingerprint-resistant coating 113) and / or for passing through the coated article 101, 201, 211, or 221. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) and / or the coated article 101, 201, 211, or 221 includes a haze of about 5% or less, about 2% or less, about 1.5% or less, about 1% or less, about 0.5% or less, or about 0.1% or less, such as in the range of about 0.01% to about 5%, about 0.01% to about 2%, about 0.05% to about 1.5%, about 0.05% to about 1%, about 0.1% to about 0.5%, or any range or sub-range therebetween.

[0334] Throughout this disclosure, the coefficient of friction refers to the dynamic coefficient of friction measured in accordance with ASTM D1894-14. Unless otherwise indicated, "coefficient of friction" refers to "dynamic coefficient of friction". In various aspects, the outer surface 115 of the surface modification layer (e.g., the fingerprint-resistant coating 113) can include a dynamic coefficient of friction of about 0.25 or less, about 0.22 or less, about 0.20 or less, about 0.18 or less, or about 0.15 or less. In various aspects, the outer surface 115 of the surface modification layer (e.g., the fingerprint-resistant coating 113) can include a dynamic coefficient of friction within the range of 0.05 to about 0.25, about 0.10 to about 0.22, about 0.12 to about 0.20, about 0.15 to about 0.18, or any range or sub-range therebetween.

[0335] Throughout this disclosure, the contact angle of a droplet of the corresponding liquid (not treated with plasma or corona) disposed on the outer surface is determined using a 30-gauge needle, wherein the contact angle is measured using a goniometer in accordance with ASTM D5946. If the contact angle cannot be reliably determined due to high droplet spreading corresponding to a contact angle of 15° or less, the coating is said to "wet" the droplet material. As used herein, the water contact angle is measured using a drop of deionized water. As used herein, if the coating has a water contact angle of 100° or greater, the coating is "hydrophobic". As used herein, if the coating has a water contact angle of 130° or greater, the coating is "superhydrophobic". As used herein, a "formed" coating refers to a coating that has not been subjected to abrasives (e.g., see the steel wool abrasion test and the cheesecloth abrasion test below). As used herein, if the coating has a cetane contact angle of less than 60°, the coating is "oleophilic".

[0336] In various aspects, the surface modification layer can be an anti-fingerprint coating. In various aspects, the anti-fingerprint coating 113 (e.g., as formed) is hydrophobic, but not superhydrophobic. In various aspects, the water contact angle of the anti-fingerprint coating 113 (e.g., as formed) can be about 90° or greater, about 100° or greater, about 102° or greater, about 105° or greater, about 110° or greater, about 115° or greater, about 120° or less, about 115° or less, or about 110° or less. In various aspects, the water contact angle of the anti-fingerprint coating 113 (e.g., as formed) can be in the range of about 90° to about 120°, about 100° to about 115°, about 102° to about 110°, about 105° to about 110°, or any range or sub-range therebetween. In various aspects, the diiodomethane contact angle of the anti-fingerprint coating 113 (e.g., as formed) can be about 60° or greater, about 62° or greater, about 65° or greater, about 80° or less, about 75° or less, about 73° or less, or about 70° or less. In various aspects, the diiodomethane contact angle of the anti-fingerprint coating 113 (e.g., as formed) can be in the range of about 60° to about 80°, about 62° to about 75°, about 65° to about 72°, or any range or sub-range therebetween. In various aspects, the anti-fingerprint coating 113 can be lipophilic. In various aspects, the hexadecane contact angle of the anti-fingerprint coating 113 (e.g., as formed) can be about 45° or less, about 40° or less, about 30° or less, about 25° or less, about 20° or less, or the anti-fingerprint coating 113 can wet hexadecane. In additional aspects, the anti-fingerprint coating 113 (e.g., as formed) wets hexadecane. Providing a low diiodomethane contact angle (e.g., about 60° or less) and / or a low hexadecane contact angle (e.g., about 30° or less) can reduce the visibility and / or color shift associated with fingerprints by allowing fingerprint oils to disperse on the anti-fingerprint coating rather than coalescing into distinct droplets. Providing a high water contact angle (e.g., about 100° or greater) can enhance the removal of water-containing materials (e.g., water droplets, sweat droplets) from the anti-fingerprint coating.

[0337] Throughout the present disclosure, the Wu model is used to calculate surface energy (e.g., total surface energy) and its components (e.g., polar surface energy, dispersive surface energy) based on contact angle measurements, as described above. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may have a total surface energy of about 35 millinewtons per meter (mN / m) or less, about 32 mN / m or less, about 30 mN / m or less, about 29 mN / m or less, about 28 mN / m or less, or about 27 mN / m or less. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may have a total surface energy within the range of about 20 mN / m to about 35 mN / m, about 22 mN / m to about 32 mN / m, about 25 mN / m to about 30 mN / m, about 25 mN / m to about 29 mN / m, about 26 mN / m to about 28 mN / m, or any range or sub-range therebetween. In various aspects, the fingerprint-resistant coating 113 may have a dispersive surface energy of about 30 mN / m or less, about 28 mN / m or less, about 26 mN / m or less, about 25 mN / m or less, about 24 mN / m or less, or about 23 mN / m or less. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may have a dispersive surface energy within the range of about 15 mN / m to about 30 mN / m, about 18 mN / m to about 28 mN / m, about 20 mN / m to about 26 mN / m, about 22 mN / m to about 25 mN / m, or any range or sub-range therebetween. In various aspects, the fingerprint-resistant coating 113 may have a polar surface energy of about 6 mN / m or less, about 4 mN / m or less, about 3 mN / m or less, or about 2 mN / m or less. In various aspects, the fingerprint-resistant coating 113 may have a dispersive surface energy within the range of about 0.5 mN / m to about 6 mN / m, about 1 mN / m to about 4 mN / m, about 1 mN / m to about 3 mN / m, about 1.5 mN / m to about 2 mN / m, or any range or sub-range therebetween. Providing a low total surface energy (including low dispersive surface energy and / or low polar surface energy) allows oil (e.g., fingerprint oil) to disperse on the fingerprint-resistant surface (e.g., oleophilic), which can reduce the visibility and / or color shift associated with fingerprints.

[0338] Throughout the present disclosure, a "steel wool abrasion test" is used to determine the durability of a coating. For the steel wool abrasion test, steel wool (Bonstar #0000) is cut into strips (25 mm × 12 mm) and placed on an aluminum foil sheet and baked in an oven at 100 °C for 2 hours. The steel wool strips are assembled to an attachment (10 mm × 10 mm) of an abrasion testing machine (5750, Taber Industries) using cable ties. A total weight of 720 grams is added to the Taber arm to produce a total applied load of 1 kilogram. The stroke length is set to 25 mm, the speed is set to 40 cycles per minute, and the test occurs at 23 °C. The area to be abraded is marked on the back of the sample for tracking. Samples of the coating are secured in the abrasion and subjected to 2,000 cycles, 3,000 cycles, or 3,500 cycles. After the coating has been abraded a predetermined number of cycles, the abraded water contact angle is measured according to the method for contact angle described above. Unless otherwise indicated, the abraded water contact angle is calculated as the average of 12 water contact angle measurements taken at positions evenly spaced along the abraded area. A high contact angle (e.g., about 85° or greater, about 90° or greater) indicates that the surface modification layer (e.g., fingerprint-resistant coating) has withstood the steel wool abrasion test. A decrease in the contact angle below 70 degrees is associated with the loss of the surface modification layer (e.g., fingerprint-resistant coating). In various aspects, the abraded water contact angle after 2,000 cycles, 3,000 cycles, and / or 3,500 cycles in the steel wool abrasion test may be about 85° or greater, about 88° or greater, or about 90° or greater.

[0339] Throughout the present disclosure, a "calico abrasion test" is also used to determine the durability of a coating. In the calico abrasion test, four layers of calico wrap (Crockmeter Squares for American Standards, 200877; SDL Atlas USA, Rock Hill, SC) are attached to a cylindrical tip with a radius of 2 cm of a linear Taber abrasion tester (Model 5750; Taber Industries, North Tonawanda, NY), with a constant load of 750 grams. The path length of each slide is 15 mm, where each cycle includes a forward and backward slide to return the tip to its original position, after which the next cycle is performed. The speed is 30 cycles per minute, and the test occurs at 23 °C. After the coating has been abraded for 200,000 cycles, the calico abrasion water contact angle is measured according to the method for contact angle described above. In various aspects, the calico abrasion water contact angle of the surface modification layer (e.g., the fingerprint-resistant coating 113) can be about 100° or greater, about 105° or greater, or about 110° or greater. In various aspects, the difference between the water contact angle of the surface modification layer (e.g., the fingerprint-resistant coating) (formed) and the calico abrasion water contact angle (after 200,000 cycles) can be about 15° or less, about 12° or less, about 10° or less, or about 8° or less. As indicated by the results of the steel wool abrasion test and the calico abrasion test, the surface modification layer (e.g., the fingerprint-resistant coating) of the present disclosure can withstand abrasion and maintain a good contact angle.

[0340] Throughout the present disclosure, "rubber wear testing" is also used to determine the durability of the coating. In the rubber wear test, a rubber rod with a diameter of 6 mm by 20 mm is attached to the cylindrical tip of a linear Taber wear tester (model 5750; Taber Industries, North Tonawanda, NY), where 5 mm of the length of the rubber is exposed to contact the coating and under a constant load of 1 kg. The path length of each slide is 15 mm, where each cycle includes a forward and backward slide to return the tip to its original position, after which the next cycle is performed. The speed is 40 cycles per minute, and the test occurs at 23°C. After the coating has been worn for 5,000 cycles, the rubber wear water contact angle is measured according to the method for contact angle described above. In various aspects, the rubber wear water contact angle of the surface modification layer (e.g., the fingerprint-resistant coating 113) can be about 80° or greater, about 85° or greater, about 90° or greater, about 95° or greater, about 100° or greater, about 105° or greater, or about 110° or greater. In various aspects, the difference between the water contact angle of the surface modification layer (e.g., the fingerprint-resistant coating) (formed) and the rubber wear water contact angle (after 3,000 cycles) can be about 15° or less, about 12° or less, about 10° or less, or about 8° or less.

[0341] As used herein, "surface roughness" refers to the Ra surface roughness, which is the arithmetic mean of the absolute deviations of the surface profile from the mean position in a direction orthogonal to the surface of the test area. The Ra surface roughness value of a 2 μm × 2 μm test area is obtained using an atomic force microscope (AFM). In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) can include a surface roughness Ra (e.g., formed) of about 1 nm or less, 0.8 nm or less, 0.7 nm or less, about 0.6 nm or less, about 0.5 nm or less, about 0.1 nm or greater, about 0.2 nm or greater, about 0.3 nm or greater, or about 0.4 nm or greater. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) can include a surface roughness Ra (e.g., formed) in the range of about 0.1 nm to about 1 nm, about 0.2 nm to about 0.8 nm, about 0.3 nm to about 0.7 nm, about 0.4 nm to about 0.5 nm, or any range or sub-range therebetween.

[0342] Throughout the present disclosure, the refractive index of the coatings and films is measured by ellipsometry using a Woollam M-2000 and modeled using Wollam CompleteEase software. Unless otherwise specified, the refractive index is measured at 550 nm. In various aspects, the refractive index of the surface modification layer (e.g., the fingerprint-resistant coating 113) can be about 1.38 or greater, about 1.4 or greater, about 1.42 or greater, about 1.44 or greater, about 1.48 or greater, about 1.5 or greater, about 1.55 or less, about 1.53 or less, about 1.49 or less, about 1.44 or less, about 1.42 or less, or about 1.4 or less. In various aspects, the refractive index of the surface modification layer (e.g., the fingerprint-resistant coating 113) can be in the range of about 1.38 to about 1.55, about 1.42 to about 1.55, about 1.44 to about 1.55, about 1.44 to about 1.53, about 1.48 to about 1.51 or any range or sub-range therebetween. In various aspects, the refractive index of the substrate 103 can be greater than or less than the refractive index of the surface modification layer (e.g., the fingerprint-resistant coating 113). As discussed below, different compositions of the surface modification layer (e.g., the fingerprint-resistant coating 113) can have different refractive index values or ranges.

[0343] In various aspects, the visibility of a fingerprint on the surface modification layer (e.g., the fingerprint-resistant coating 113) as the absolute value of the difference between the CIELAB L* values of a portion of the surface modification layer (e.g., the fingerprint-resistant coating 113) with and without fingerprint oil as defined above can be about 15 or less, about 10 or less, about 8 or less, about 5 or less, about 2 or less. In various aspects, the visibility of a fingerprint on the surface modification layer (e.g., the fingerprint-resistant coating 113) can be in the range of 0 to 15, about 0.5 to about 10, about 1 to about 8, about 2 to about 5 or any range or sub-range therebetween. In various aspects, the color shift of a fingerprint on the surface modification layer (e.g., the fingerprint-resistant coating 113) as defined above as √((a1* - a2*) 2 +(b1* - b2*) 2 ) can be about 15 or less, about 10 or less, about 8 or less, about 5 or less, about 2 or less. In various aspects, the color shift of a fingerprint on the surface modification layer (e.g., the fingerprint-resistant coating 113) can be in the range of 0 to 15, about 0.5 to about 10, about 1 to about 8, about 2 to about 5 or any range or sub-range therebetween.

[0344] As used herein, X-ray photoelectron spectroscopy (XPS) is used to determine the elemental composition of a surface modification layer (e.g., a fingerprint-resistant coating). In various aspects, the fingerprint-resistant coating can be fluorine-free. In various aspects, the surface modification layer (e.g., fingerprint-resistant coating 113) can include silicon atoms, oxygen atoms, carbon atoms, and hydrogen atoms. In additional aspects, the surface modification layer (e.g., fingerprint-resistant coating 113) can further include nitrogen atoms. In additional aspects, the oxygen atoms in the surface modification layer (e.g., fingerprint-resistant coating) can be more prevalent than any other atoms detected by XPS in the surface modification layer (e.g., fingerprint-resistant coating). In additional aspects, the surface modification layer (e.g., fingerprint-resistant coating) can include about 30 atomic % carbon or less, about 25 atomic % carbon or less, about 10 atomic % carbon or less, about 2 atomic % carbon or more, or about 5 atomic % carbon or more. Providing a fluorine-free surface modification layer (e.g., fluorine-free fingerprint-resistant coating 113) can be produced more inexpensively and / or be more environmentally friendly.

[0345] In various aspects, the surface modification layer (e.g., fingerprint-resistant coating) can include a partial silica-like network. A silica-like network refers to the coordination of silicon atoms bonded together by oxygen atoms with four Si-O bonds of the silicon atoms, which corresponds to the SiO2 network. As used herein, the fraction of silicon atoms in the silica-like network is determined by Fourier transform infrared (FTIR) spectroscopy based on the absorbance associated with the Si-O-Si bond (e.g., about 1000 cm -1 to 1060 cm -1 ) relative to the intensity of all Si-O-Si bonds (including the T-type stretching of POSS at about 1105 cm -1 ). In various aspects, the percentage of silicon atoms in the silica-like network in the surface modification layer (e.g., fingerprint-resistant coating 113) can be about 50% or greater, about 60% or greater, about 65% or greater, about 70% or greater, about 90% or less, about 80% or less, about 75% or less, or about 70% or less. In various aspects, the percentage of silicon atoms in the silica-like network in the surface modification layer (e.g., fingerprint-resistant coating 113) can be in the range of about 50% to about 90%, about 60% to about 80%, about 65% to about 75%, or any range or sub-range therebetween. Providing a partial silica-like network can make the surface modification layer (e.g., fingerprint-resistant coating) hard (e.g., having a modulus of elasticity of about 9 GPa or greater), while maintaining sufficient flexibility to withstand wear.

[0346] The ratio of Si-O-Si bonds to silicon atoms in the coating can be measured using: (a) XPS to determine the amount of Si-O bonds relative to the total amount of Si based on the Si 2p fine structure; or (b) 29Si solid-state nuclear magnetic resonance (NMR), which is based on fitting the observed chemical shifts to six Gaussian curves corresponding to different coordination structures (e.g., T units, D units, M units, and three Q units with different numbers of hydroxyl groups), where the functional groups bonded to silicon atoms can be replaced by organic groups (e.g., carbon). In various aspects, the ratio of Si-O-Si bonds to silicon atoms can be about 2 or greater, about 2.2 or greater, about 2.4 or greater, about 2.6 or greater, about 3 or less, about 2.9 or less, about 2.8 or less, or about 2.75 or less. In various aspects, the ratio of Si-O-Si bonds to silicon atoms can be in the range of about 2 to about 3, about 2.2 to about 2.9, about 2.4 to about 2.8, about 2.6 to about 2.75 or any range or sub-range therebetween.

[0347] In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) can be included at the outer surface 115 and at least one alkylsilane bonded to the Si-O groups in the surface modification layer (e.g., the fingerprint-resistant coating 113). In additional aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) can be one alkylsilane thick, but in other aspects, multiple alkylsilanes can react to form a composite alkylsilane with the surface modification layer (e.g., the fingerprint-resistant coating 113). As used herein, "alkylsilane" refers to a compound that includes an alkyl chain directly bonded to the silicon atom of a silane group or a surface silanol (e.g., of a substrate or an underlying optical stack), and the silane group can be bonded to other silane groups (e.g., to form a siloxane or siloxane-like network). In additional aspects, the alkylsilane can include from 4 to about 34 carbons (i.e., C4-C 34 alkyl), such as from 6 to 34 carbons (i.e., C6-C 34 alkyl), from 8 to 20 carbons (i.e., C8-C 20 alkyl). Exemplary aspects of alkylsilanes include isooctylsilane (e.g., isooctyltrimethoxysilane), dodecylsilane (e.g., dodecyltrimethoxysilane), octadecylsilane (e.g., octadecyltrimethoxysilane), or combinations thereof. In additional aspects, the silane can be methoxysilane (e.g., trimethoxysilane) and / or trialkoxysilane. In additional aspects, the silane can be trimethoxysilane, triethoxysilane, trichlorosilane, or combinations thereof (e.g., dichloromethoxysilane, chlorodimethoxysilane). In various aspects, the alkylsilane can include an alkyl group that includes from 4 to about 34 carbons (i.e., C4-C 34 alkyl) (e.g., from 6 to 34 carbons (i.e., C6-C 34 alkyl), from 8 to 20 carbons (i.e., C8-C 20(alkyl)), for example, isooctylalkyl, dodecylalkyl, octadecylalkyl, or a combination thereof. An exemplary aspect of the alkyl is octadecylalkyl. Providing the alkylsilane can reduce the surface energy (e.g., total surface energy, dispersive surface energy, polar surface energy) of the surface modification layer (e.g., anti-fingerprint coating), which can render the surface modification layer (e.g., anti-fingerprint coating) lipophilic. Reacting the initial coating with methoxysilane and / or trialkoxysilane can bond well to the initial coating and achieve a low surface energy (e.g., a total surface energy of about 30 mN / m or less, a polar surface energy of about 5 mN / m or less).

[0348] The surface modification layer (e.g., the fingerprint-resistant coating 113) may include one or more of the following: (1) the percentage of silicon atoms within one or more of the ranges discussed above (e.g., from about 50% to about 90%) in the silica-like network, or (2) the ratio of Si-O-Si bonds to silicon atoms within one or more of the ranges discussed above (e.g., from about 2 to about 3). In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating) may include a partially silica-like network and hydrogenated silicon or silanol. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may have a refractive index within the range of about 1.38 to about 1.55, about 1.42 to about 1.55, about 1.44 to about 1.55, about 1.44 to about 1.53, about 1.48 to about 1.51 or any range or sub-range therebetween. Alternatively, the surface modification layer (e.g., the fingerprint-resistant coating 113) may have a refractive index within the range of about 1.38 to about 1.44, about 1.39 to about 1.43, about 1.40 to about 1.42 or any range or sub-range therebetween. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may include nitrogen atoms, such as nitrogen atoms bonded to silicon atoms. For example, the surface modification layer (e.g., the fingerprint-resistant coating 113) may be the product of a polysilazane on the first major surface 105 of the at least partially cured substrate 103, which polysilazane may react with a silane after at least partial curing. Alternatively, the surface modification layer (e.g., the fingerprint-resistant coating 113) may be nitrogen-free. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may be the product of functionalized polyhedral oligomeric silsesquioxane (POSS) (defined below) disposed on the first major surface and bombarding the first major surface 105 of the substrate with an ion beam during and / or after reacting with a silane. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may be the result of a POSS (e.g., hydrogen POSS) compound on the first major surface 105 of the thermally cured substrate 103, which POSS compound may react with a silane after thermal curing. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may include at least one alkylsilane at the outer surface 115 and bonded to the Si-O groups in the surface modification layer (e.g., the fingerprint-resistant coating 113), which may include one or more of the silanes discussed above. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may be free of fluorine and / or nitrogen. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may consist of carbon, oxygen, silicon, hydrogen, and oxygen.

[0349] In various aspects, the silica-like network of the present disclosure can be readily distinguished from other silicon-containing oxides (e.g., silica capping layers) by the properties discussed herein (e.g., hydroxyl content, hardness, refractive index, power spectral density of the surface, surface roughness Ra). For example, the silica-like network can include a greater hydroxyl content than the hydroxyl content of the capping layer; and / or the silica-like network can exhibit a lower hardness, a lower elastic modulus, and / or a higher refractive index than the corresponding properties of the capping layer.

[0350] One way to quantify the amount (e.g., density) of hydroxyl groups in a surface modification layer (e.g., beneath an alkylsilane) is based on the molar ratio determined by secondary ion mass spectrometry (SIMS). Unless otherwise indicated, the sample is cleaned with a low-energy Ar gas cluster ion beam (GCIB) source prior to SIMS analysis. Static SIMS can be used to measure the molar ratio at the surface. Unless otherwise indicated, the molar ratio is for the bulk of the surface modification layer using dynamic SIMS (D-SIMS). Different from static SIMS, dynamic SIMS erodes the surface to provide depth-resolved compositional information. As used herein, D-SIMS is performed using a time-of-flight secondary ion mass spectrometer (ToF-SIMS) with a dual-beam configuration. Unless otherwise indicated, the TOF-SIMS used for the results reported herein is the TOF-SIMS M6 instrument (available from IONTOF GmbH) equipped with a Nanoprobe50 bismuth source. The TOF-SIMS M6 instrument operates in a dual-beam configuration, where the analysis beam is a 30 kiloelectron volt (keV) Bi3 + beam with a current of approximately 0.1 pA, and the sputter beam is a 2 keV Cs with a current of approximately 120 nA + . The sputter beam is configured to form a sputter “pit” of 300 μm × 300 μm, and the analysis beam is configured to impinge on a 75 μm × 75 μm area centered on the sputter “pit”. Charge compensation is achieved using an electron flood gun operating at a 20 nA beam current, 20 eV electron energy, and a 1.5 mm spot size focused on the location where the analysis beam impinges. The chamber is evacuated to a pressure of 5 × 10 -7 pascals (5 × 10 -9 mbar), and then brought to and maintained at a pressure of 5 × 10 -5 pascals (5 × 10 -7 mbar) using argon gas (e.g., 99.99999% purity). Data is collected in negative ion mode, where the analyzer is in the “general” mode, the analyzer energy is 3000 V, and the cycle time is 100 microseconds. The data is processed using Surface Lab software (version 7.3.125519, available from IONTOF GmbH). To obtain 16 O 1 H- , 18 O - and 28 Si - signals to obtain a molar ratio, 18 O - with 17 O - the known isotope ratio between is used for calculation and subtracted from the 16 O 1 H - signal. The normalized intensity is defined as the mass interference-corrected 17 O - H signal divided by the 16 O 1 H signal divided by the 28 Si - signal. The normalized intensity ( 16 O 1 H - / 28 Si - ) is further corrected to remove the background signal (as determined from the normalized intensity ( 16 O 1 H - / 28 Si - ) measured simultaneously from a GE type 124 fused silica) to determine the "corrected signal". A calibration curve (derived from a series of natural mid-ocean ridge basalt (MORB) glasses with known -OH concentrations and other silica and silicate minerals covering the range 0.0 wt% to 1.98 wt%) is used to convert the corrected signal to the molar ratio of hydrogen to silicon ("molar ratio"), where the equation is "molar ratio" = 1.26 * "corrected signal" - 0.025.

[0351] Throughout this disclosure, "mole ratio" refers to the mole ratio of hydrogen to silicon (i.e., the molar amount of hydrogen divided by the molar amount of silicon), as determined by SIMS analysis of the material (e.g., the surface modification layer underlying the alkylsilane). Without wishing to be bound by theory, it is believed that hydrogen indicates hydroxyl groups (e.g., silanols, Si-O-H). In various aspects, the (hydrogen to silicon) mole ratio of the surface modification layer underlying the alkylsilane can be about 0.2 or greater (e.g., about 0.2 or greater), about 0.21 or greater, about 0.22 or greater, about 0.23 or greater, about 0.24 or greater, about 0.25 or greater, about 0.45 or less, about 0.4 or less, about 0.37 or less, about 0.35 or less, about 0.32 or less, about 0.30 or less, or about 0.28 or less. In various aspects, the (hydrogen to silicon) mole ratio can be in the range of about 0.2 to about 0.45, about 0.20 to about 0.4 (e.g., about 0.2 to about 0.4), about 0.21 to about 0.37, about 0.22 to about 0.35, about 0.23 to about 0.32, about 0.24 to about 0.32, about 0.24 to about 0.30, about 0.25 to about 0.28, or any range or sub-range therebetween. In an exemplary aspect, the mole ratio of hydrogen to silicon can be in the range of 0.20 to 0.4 or about 0.22 to about 0.35. For example, as discussed below with reference to Figure 29 the surface modification layers according to various aspects of the present disclosure (e.g., Examples 1 to 10) exhibit a mole ratio of hydrogen to silicon of 0.20 or greater, about 0.20 to 0.4, or about 0.22 to about 0.35. In contrast, conventional methods of silica deposition (Comparative Examples JJ to KK) have a mole ratio of about 0.10 or less, meaning that Examples 1 to 10 have at least about twice (2×) the mole ratio of Comparative Examples JJ to KK. In various aspects, the mole ratio at the surface can be within any of the ranges described above in this paragraph. In various aspects, the (hydrogen to silicon) mole ratio of the surface modification layer can be 2 or greater, 2.5 or greater, 3 or greater, 4 or greater, 10 or less, 7 or less, 5 or less, or 4 or less times greater than the mole ratio of the reactively sputtered silica layer. In various aspects, the (hydrogen to silicon) mole ratio of the surface modification layer can be about 2 to 10, 2 to 7, 2.5 to 5, 2.5 to 4, 3 to 4 times greater than the mole ratio of the reactively sputtered silica layer, or any range or sub-range therebetween.

[0352] Another way to quantify the amount (e.g., density) of hydroxyl groups in a silica-like network layer (e.g., the surface modification layer underlying the alkylsilane) is based on the absorbance measured in infrared (IR) spectroscopy. Without wishing to be bound by theory, it can be from about 3200 cm -1 to about 3500 cm -1See a broad absorbance associated with an alcohol (e.g., hydroxyl (OH) stretch, e.g., in silanol - Si - O - H), e.g., having a peak centered at 3420 cm -1 ; and see a broad absorbance at 1059 cm -1 , which is attributed to the Si - O - Si structure. As used herein, the "hydroxyl ratio" is the peak absorbance of the broad hydroxyl signal (centered at 3420 cm -1 ) divided by the peak absorbance of the Si - O - Si signal (centered at about 1060 cm -1 ). In various aspects, the hydroxyl ratio (e.g., of the surface modification layer under the alkylsilane) can be about 0.005 or greater, about 0.008 or greater, about 0.010 or greater (e.g., about 0.01 or greater), about 0.07 or less, about 0.06 or less, about 0.05 or less, or about 0.045 or less. In various aspects, the hydroxyl ratio (e.g., of the surface modification layer under the alkylsilane) can be in the range of about 0.005 to about 0.07, about 0.005 to about 0.06, about 0.008 to about 0.5, about 0.01 to about 0.045 or any range or sub - range therebetween. Without wishing to be bound by theory, the hydroxyl ratio of a reactively sputtered silica layer is much lower than the hydroxyl ratio (e.g., of the surface modification layer under the alkylsilane) discussed herein. In various aspects, the hydroxyl ratio of the surface modification layer (e.g., the surface modification layer under the alkylsilane) can be 2 or more, 3 or more, 4 or more, 5 or more, 8 or more, 20 or less, 15 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, or 4 or less times greater than the hydroxyl ratio of the reactively sputtered silica layer. In various aspects, the hydroxyl ratio of the surface modification layer (e.g., the surface modification layer under the alkylsilane) can be 2 to 20, 3 to 20, 4 to 15, 5 to 15, 8 to 12, 8 to 10 times greater than the hydroxyl ratio of the reactively sputtered silica layer or any range or sub - range therebetween. In various aspects, in various aspects, the hydroxyl ratio of the surface modification layer (e.g., the surface modification layer under the alkylsilane) can be about 10 or less times greater than the hydroxyl ratio of the reactively sputtered silica layer, e.g., 2 to 10, 3 to 8, 3 to 6, 3 to 5, 3 to 4 times greater than the hydroxyl ratio of the reactively sputtered silica layer or any range or sub - range therebetween.

[0353] Alternatively, another embodiment of the present disclosure includes the above in Figure 1 and Figures 2A to 2Ca surface modification layer (e.g., the fingerprint-resistant coating 113) in any of the configurations discussed herein, but the surface modification layer (e.g., the fingerprint-resistant coating 113) may include a smaller fingerprint-resistant thickness 119 and / or not contain a significant amount of silica or a partially silica-like network. For example, the surface modification layer (e.g., the fingerprint-resistant coating 113) may be a product of depositing an alkylsilane (e.g., within one or more of the ranges discussed below) without using a POSS or polysilazane compound. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may include an alkylsilane at the outer surface 115, which may contain any of the corresponding alkyl groups discussed above (e.g., including 4 carbons to about 34 carbons (i.e., C4-C 34 alkyl), such as 6 carbons to 34 carbons (i.e., C6-C 34 alkyl), 8 carbons to 20 carbons (i.e., C8-C 20 alkyl)). In additional aspects, the alkyl group may be an isooctyl alkyl, dodecyl alkyl, octadecyl alkyl, or a combination thereof. An exemplary aspect of the alkyl group is an octadecyl alkyl. In various aspects, the fingerprint-resistant thickness 119 may be about 1 nm or greater, about 2 nm or greater, about 3 nm or greater, about 5 nm or greater, about 8 nm or greater, about 10 nm or greater, about 75 nm or less, about 50 nm or less, about 25 nm or less, about 15 nm or less, about 10 nm or less, about 8 nm or less, or about 5 nm or less. In various aspects, the fingerprint-resistant thickness 119 may be in the range of about 1 nm to about 75 nm, about 1 nm to about 50 nm, about 1 nm to about 25 nm, about 1 nm to about 15 nm, about 2 nm to about 10 nm, about 2 nm to about 8 nm, about 2 nm to about 5 nm, about 3 nm to about 5 nm, or any range or sub-range therebetween. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating 113) may exhibit a water contact angle (e.g., about 100° or greater, or 102° to 110°), a diiodomethane contact angle (e.g., about 60° or greater), a coefficient of friction (e.g., about 0.25 or less), a polar surface energy (e.g., about 3 mN / m or less), a total surface energy (e.g., about 30 mN / m or less), a cotton cloth abrasion water contact angle (e.g., about 90° or greater after undergoing 200,000 cycles in a cotton cloth abrasion test), and / or a rubber abrasion water contact angle (e.g., about 80° or greater, about 90° or greater, or about 100° to about 110° after undergoing 5,000 cycles in a rubber abrasion test) within one or more of the corresponding ranges discussed above.

[0354] Aspects of the present disclosure may include consumer electronic products. The consumer electronic products may include a front surface, a rear surface, and side surfaces. The consumer electronic products may further include electrical components at least partially within a housing. The electrical components may include a controller, a memory, and a display. The display may be at or adjacent to the front surface of the housing. The display may include a liquid crystal display (LCD), an electrophoretic display (EPD), an organic light emitting diode (OLED) display, or a plasma display panel (PDP). The consumer electronic products may include a cover substrate disposed above the display. In aspects, at least one of a portion of the housing or the cover substrate includes a coated article and / or a surface modification layer (e.g., a fingerprint-resistant coating) discussed throughout the present disclosure. The consumer electronic products may include portable electronic devices such as smartphones, tablet computers, wearable devices, or portable computers.

[0355] The coated articles and / or surface modification layers (e.g., fingerprint-resistant coatings) disclosed herein may be incorporated into another article, e.g., an article having a display (or a display article) (e.g., a consumer electronic product, including a mobile phone, a tablet computer, a computer, a navigation system, a wearable device (e.g., a watch), etc.), a building article, a transportation article (e.g., an automobile, a train, an airplane, a sea vessel, etc.), an electrical appliance article, or any article that may benefit from a certain transparency, scratch resistance, abrasion resistance, or a combination thereof. Exemplary articles having any of the coated articles and / or surface modification layers (e.g., fingerprint-resistant coatings) disclosed herein are shown in Figures 3 to 4 Specifically, Figures 3 to 4 a consumer electronic device 300 is shown, which includes a housing 302 having a front surface 304, a rear surface 306, and side surfaces 308. Although not shown, the consumer electronic device may include electrical components at least partially inside or completely within the housing. For example, the electrical components at least include a controller, a memory, and a display. As Figures 3 to 4 shown in

[0356] Reference will be made to Figures 7 to 8 the flowcharts in Figures 9 to 12 and the example method steps shown in

[0357] Aspects of a method of manufacturing a foldable device and / or a foldable substrate in accordance with aspects of the present disclosure will now be discussed with reference to Figure 5 and Figures 9 to 10 andFigure 7 The flowchart in Figure 7 is used to discuss an example aspect of manufacturing the coated articles 101, 201, 211, or 221. In a first step 701, the method may begin by obtaining a substrate 103. In various aspects, the substrate 103 may be provided by purchasing or otherwise obtaining the substrate or by forming the substrate. In various aspects, the substrate 103 may include a glass-based material, a glass-ceramic material, and / or a ceramic-based material. In additional aspects, the glass-based material, the glass-ceramic material, and / or the ceramic-based material may be provided by forming them using various tape casting processes, such as slot drawing, down-drawing, melt down-drawing, up-drawing, roll pressing, re-drawing, or floating. In additional aspects, a ceramic-based substrate may be provided by heating a glass-based substrate to crystallize one or more ceramic crystals. The substrate 103 includes a first major surface 105 that may extend along a first plane 104. In various aspects, as Figure 1 indicated in Figure 1 , an optical stack 203 that includes an anti-reflection coating and / or a gradient coating that includes a refractive index gradient may be disposed on and / or bonded to the first major surface 105. Although Figures 9 to 10 not shown in Figures 9 to 10 , it should be understood that the optical stack 203 may be disposed on the first major surface 105. In various aspects, the substrate 103 may be chemically strengthened with one or more compressive stress zones (or central tension zones), and the compressive stress zones include any of the aspects related to the compressive depth, the maximum compressive stress, and / or the tensile stress discussed above for the corresponding properties.

[0358] In various aspects, step 701 may further include obtaining a functionalized polyhedral oligomeric silsesquioxane (POSS). As used herein, polyhedral oligomeric silsesquioxane (POSS) refers to a functionalized oligomeric silsesquioxane composed of RSiO 1.5 monomers. Exemplary aspects of the functionalized POSS may include 6, 8, 10, or 12 RSiO 1.5 monomers, but other aspects are possible. For example, a functionalized oligomeric silsesquioxane composed of 8 RSiO 1.5 monomers is an octahedral functionalized POSS (e.g., polyoctahedral silsesquioxane). Figure 5 A functionalized POSS, namely an octahedral functionalized POSS, is shown, where R is a functional group that may be independently selected from the functional groups discussed below.

[0359] In various aspects, the functionalized oligosilsesquioxane can be formed by the condensation reaction of silanes. As used herein, the condensation reaction produces R2O by-products, where R can include any of the R units discussed below and can also include hydrogen (e.g., having a hydroxyl or water by-product). For example, a silane (e.g., R3OSi) can react to form a terminal RSiO2 monomer. For example, a terminal RSiO2 monomer can react with another RSiO2 monomer (e.g., terminal, non-terminal) to form an RSiO 1.5 monomer, as the oxygen atom of one monomer forms a bond with the silicon atom of the other monomer, thereby producing a condensation by-product. It should be understood that the RSiO 1.5 silsesquioxane monomer is different from the siloxane monomer, which can include M-type siloxane monomers (e.g., R3SiO 0.5 ), D-type siloxane monomers (e.g., R2SiO2) and / or silica-type siloxane monomers (SiO2).

[0360] The functionalized oligosilsesquioxane can be functionalized by one or more functional groups. For the methods discussed in the flowcharts in the reference Figure 7 (e.g., thermal evaporation of the functionalized oligosilsesquioxane), the functional groups that functionalize the functionalized oligosilsesquioxane may not include hydrogen. In various aspects, the functional groups that functionalize the functionalized oligosilsesquioxane may not include bisphenol, fluorinated functional groups, isocyanates, epoxides, glycidyl, ethylene oxide, sulfur-containing functional groups (e.g., thiols), acid anhydrides, acrylates, methacrylates, and / or alkynes. In various aspects, the functional groups that functionalize the functionalized oligosilsesquioxane are alkyl, alkenyl, aromatic (e.g., phenyl), silane (e.g., alkylsilyl), or a combination thereof. As used herein, an alkyl contains a saturated hydrocarbon having carbon-carbon single bonds and hydrogen bonded to carbon atoms. In various aspects, the alkyl functional group can range from 1 to 10 carbons (i.e., C1-C8 alkyl), 1 to 8 carbons (i.e., C1-C8 alkyl), e.g., 1 to 4 carbons (i.e., C2-C4 alkyl). Exemplary aspects of the alkyl functional group include methyl and isobutyl. An exemplary aspect of the aromatic functional group is phenyl. An exemplary aspect of the silane includes dimethylsilyl. As used herein, an alkenyl contains an unsaturated hydrocarbon having one or more carbon-carbon double bonds. The alkene can optionally contain one or more carbon-carbon single bonds (e.g., an alkyl chain in the alkenyl). In yet another aspect, the functionalized POSS can be at least partially functionalized by an alkene having 2 to 8 carbons (i.e., C2-C8 alkene). Being at least partially functionalized by a functional group B means that Figure 5 one or more of the R groups shown in Figure 595% or more of all of the R groups shown are B. Exemplary aspects of olefin-functionalized POSS are vinyl POSS, such as partially vinyl-functionalized vinyl / isobutyl POSS (OL1123 available from Hybrid Plastics) or octavinyl POSS (OL1170 available from Hybrid Plastics). Exemplary aspects of aromatic-functionalized POSS are octaphenyl POSS (MS0840 available from Hybrid Plastics). Exemplary aspects of alkyl-functionalized POSS are octamethyl POSS (MS0830 available from Hybrid Plastics) and octakis(isobutyl) POSS (MS0825 available from Hybrid Plastics). Providing short chains (e.g., about 8 carbons or fewer) for functionalizing the functionalized POSS can enable the functionalized POSS to evaporate during step 703. Providing one or more of the functional groups for functionalizing the functionalized POSS as discussed above can reduce the reactivity of the functionalized POSS (e.g., by sterically hindering the interaction between the functionalized POSS) before the functionalized POSS is bombarded with an ion beam and / or placed on a substrate, which can enable the production of a partially condensed silica-like network.

[0361] Alternatively, for example, when referring to Figure 8 the flowchart in (e.g., applying the functionalized oligosilsesquioxane as a solution), the functional group for functionalizing the functionalized oligosilsesquioxane can be hydrogen or an alkyl group. In aspects, the functional group for functionalizing the functionalized oligosilsesquioxane may not include bisphenol, fluorine-containing functional groups, isocyanates, epoxides, glycidyl groups, ethylene oxide, sulfur-containing functional groups (e.g., thiols), acid anhydrides, acrylates, methacrylates, and / or alkynes. In aspects, the functional group for functionalizing the functionalized oligosilsesquioxane is hydrogen, an alkyl group, an alkenyl group, an aromatic group, a silane, or a combination thereof. For example, in addition to hydrogen, the functional group can be one or more of the functional groups discussed above in the previous paragraph. In further aspects, the functional group for functionalizing the functionalized oligosilsesquioxane can consist of carbon and / or hydrogen. In still further aspects, the functionalized oligosilsesquioxane can be at least partially hydrogen-functionalized and / or fully hydrogen-functionalized. In additional aspects, the functionalized POSS can be at least partially functionalized with an olefin having 2 to 8 carbons (i.e., a C2-C8 olefin), such as ethylene, propylene, butene, pentene, hexene, heptane, or octene. In still additional aspects, the functionalized POSS can be at least partially functionalized with an olefin having 2 to 8 carbons (i.e., a C2-C8 olefin).

[0362] Throughout this disclosure, dynamic light scattering is used to measure the effective diameter of molecules (e.g., functionalized POSS) according to ISO 22412:2017. In various aspects, the effective diameter of the functionalized POSS can be about 20 nm or less, about 15 nm or less, about 10 nm or less, about 6 nm or less, about 1 nm or greater, about 2 nm or greater, or about 4 nm or greater. In various aspects, the effective diameter of the functionalized POSS can be in the range of about 1 nm to about 20 nm, about 1 nm to about 15 nm, about 2 nm to about 15 nm, about 2 nm to about 10 nm, about 4 nm to about 10 nm, about 4 nm to about 6 nm, about 1 nm to about 6 nm, about 2 nm to about 6 nm or any range or sub-range therebetween. In additional aspects, the average effective diameter of the functionalized POSS can be within one or more of the ranges discussed above in this paragraph. In additional aspects, substantially all and / or all of the functionalized POSS can be within one or more of the ranges of the effective diameter of the functionalized oligosilsesquioxanes discussed above.

[0363] After step 701, as Figure 9 shown, the method can proceed to step 703, which includes evaporating the functionalized POSS onto the first major surface 105 of the substrate 103. In various aspects, as shown, step 703 can include placing the substrate 103 in a chamber 903 (e.g., a vacuum chamber) that can be maintained under reduced pressure. In various aspects, the reduced pressure can be about 50,000 pascals (Pa) or less, about 1,000 Pa or less, about 1 Pa or less, about 0.5 Pa or less, about 10 -6 Pa or greater, about 10 -4 Pa or greater, or about 10 -3 Pa. In various aspects, the reduced pressure can be in the range of about 10 -6 Pa to about 1,000 Pa, about 10 -4 to about 1 Pa, about 10 -3 to about 0.5 Pa, about 10 -3 Pa to about 10 -1Any range or sub-range within or between Pa. In various aspects, the pressure in chamber 903 (e.g., reduced pressure) can be maintained by operating one or more of valves 905 and 925. In additional aspects, the pressure in chamber 903 can be reduced or maintained by opening valve 905 connected to pump 907, which can remove gas from chamber 903. In additional aspects, the pressure in chamber 903 can be increased or maintained by opening valve 925 connected to gas source 921, which adds gas to the chamber, as indicated by arrow 923. In various aspects, gas source 921 can provide non-reactive gas (e.g., argon, helium, krypton), oxygen, nitrogen, air, or a combination thereof. Providing reduced pressure during evaporation of functionalized POSS can increase the evaporation rate and / or enable the use of a wide range of functionalized POSS materials.

[0364] As Figure 9 shown, functionalized POSS 913 can be positioned in container 911, which is placed within chamber 903. In chamber 903, functionalized POSS 913 can evaporate (as indicated by arrow 915) into the gas phase (as indicated by 917), which can be deposited on the first major surface 105 of substrate 103 (as indicated by arrow 919). Exemplary aspects of container 911 include a Knudsen cell or effusion cell. In various aspects, container 911 can be maintained at a temperature of about 50 °C or greater, about 65 °C or greater, about 75 °C or greater, about 90 °C or greater, about 110 °C or less, about 200 °C or less, about 170 °C or less, about 150 °C or less, about 135 °C or less, about 120 °C or less, or about 110 °C or less. In various aspects, container 911 can be maintained at a temperature within or between any range or sub-range within the ranges of about 50 °C to about 200 °C, about 65 °C to about 170 °C, about 75 °C to about 150 °C, about 90 °C to about 135 °C, about 110 °C to about 135 °C. Heating the container can promote evaporation of the functionalized POSS, which can increase the deposition rate.

[0365] In various aspects, the deposition rate of the functionalized POSS 913 can be monitored using a sensor that includes a surface positioned a predetermined distance from a surface (e.g., the first major surface 105 of the substrate 103). In additional aspects, the sensor can be configured to detect a nanogram mass difference of the material deposited on the surface, where the increase in the mass and the predetermined surface area of the surface can be used to determine the effective deposition rate. It should be understood that the "effective deposition rate" is not necessarily the actual deposition rate on the surface (e.g., the first major surface 105), and in fact, the actual deposition rate may be overestimated by up to two or three times. An exemplary aspect of the sensor is a quartz crystal microbalance (QCM). As used herein, the "deposition rate" or "evaporation rate" refers to the effective deposition rate measured by a QCM positioned 500 mm below the surface and 150 mm above the vessel 911.

[0366] Although not shown, it is to be understood that if the optical stack 203 is disposed on the first major surface 105, the functionalized POSS 913 will be disposed above the first major surface 105 and on the optical stack 203. In various aspects, the evaporation rate of the functionalized POSS 913 onto the first major surface 105 can be about 0.01 nanometers per second (nm / s) (0.1 Å / s) or greater, about 0.03 nm / s (0.3 Å / s) or greater, about 0.05 nm / s (0.5 Å / s) or greater, about 0.1 nm / s or greater (1 Å / s), about 0.5 nm / s or less (5 Å / s), about 0.3 nm / s (3 Å / s) or less, about 0.2 nm / s (2 Å / s) or less, or about 0.15 nm / s (1.5 Å / s) or less. In various aspects, the evaporation rate of the functionalized POSS 913 onto the first major surface 105 can be in the range of about 0.01 nm / s to about 0.5 nm / s, about 0.03 nm / s to about 0.3 nm / s, about 0.05 nm / s to about 0.2 nm / s, about 0.1 nm / s to about 0.15 nm / s or any range or sub-range therebetween. Controlling the evaporation rate within one or more of the ranges mentioned above can effectively (e.g., rapidly) deposit a substantially uniform functionalized POSS coating on the first major surface. In various aspects, at the end of step 703, the thickness of the functionalized POSS disposed on the first major surface 105 can be within one or more of the ranges discussed above with reference to the anti-fingerprint thickness 119. Without wishing to be bound by theory, it is believed that the evaporation and deposition of the functionalized POSS onto the first major surface itself do not chemically (e.g., covalently) bond the functionalized POSS to the first major surface or modify the structure of the functionalized POSS. Exemplary aspects of the vessel 911 in the Radak II cell can be used in the chamber 903, such as an Angstrom Engineering Evovac chamber. Although not shown, it is to be understood that if the optical stack 203 is disposed on the first major surface 105, the functionalized POSS 913 will be disposed above the first major surface 105 and on the optical stack 203.

[0367] After (or simultaneous with) step 703, as Figure 9 shown, the method can proceed to step 705, which includes impinging an ion beam traveling as a plume 933 onto the first major surface 105 of the substrate 103. As shown, the substrate 103 can be in the chamber 903, which can be the same chamber 903 as discussed above with reference to step 703. In various aspects, as Figure 9As shown, the beam source 931 can be configured to emit an ion beam that travels as a plume 933 and impinges on the first major surface 105 of the substrate 103. The beam source 931 can be operated such that the ion beam traveling as the plume 933 impacts the entire first major surface 105. In various aspects, the ion beam source 931 can include an end Hall ion source, a grid ion source, or an inductively coupled plasma (ICP) ion source. An exemplary aspect of the beam source 931 is an end Hall ion source. In various aspects, the beam source 931 can generate an ion beam using a discharge current. Without wishing to be bound by theory, it is believed that the degree of reaction (e.g., from functionalized POSS to a partially silica-like network) is affected by the ion beam energy and the discharge current. In additional aspects, the discharge current can be about 0.25 amperes (A) or greater, about 0.3 A or greater, about 0.35 A or greater, about 1 A or less, about 0.75 A or less, or about 0.5 A or less. In additional aspects, the discharge current can be in the range of about 0.25 A to about 1 A, about 0.3 A to about 0.75 A, about 0.35 A to about 0.5 A, or any range or sub-range therebetween. In various aspects, the beam source 931 can operate at a voltage of about 100 volts (V), such as in the range of about 50 V to about 220 V, about 70 V to about 120 V, about 90 V to about 110 V, or any range or sub-range therebetween. In various aspects, the ion beam can include oxygen ions, argon ions, or a combination thereof. The composition of the ion beam can be adjusted by selecting the gas source 921 and controlling the amount of gas released from the gas source 921 (e.g., using the valve 925). In various aspects, the chamber 903 (e.g., a vacuum chamber) can be maintained under a reduced pressure within one or more of the ranges discussed above for the reduced pressure in step 703 (e.g., about 10 -8 Pa to about 10 - 7 Pa).

[0368] Without wishing to be bound by theory, it is believed that the ion beam breaks the cage structure of the functionalized POSS, volatilizes the functional groups that functionalize the functionalized POSS, and / or causes the functionalized POSS to bond to the surface on which it is disposed (e.g., the first major surface 105 or the fourth major surface 207 of the optical stack 203 if present) as shown in Figure 9 . At the end of step 705, the formed coating 1033 (see Figure 10 ) can include a partially silica-like network, e.g., where the percentage of silicon atoms in the silica-like network in the coating is within one or more of the ranges discussed above for the percentage of silica atoms in the silica-like network in the surface modification layer (e.g., the anti-fingerprint coating). Additionally or alternatively, at the end of step 705, the formed coating 1033 (see Figure 10)The ratio of Si-O-Si bonds to silicon atoms may be within one or more of the ranges discussed above for the ratio of Si-O-Si bonds to silicon atoms. In additional aspects, in step 705, impinging an ion beam can convert at least a fraction of the silicon atoms in the cage structure of the functionalized POSS into a partial Si-O-Si network (i.e., Si-O-Si bonds). In yet additional aspects, the fraction of silicon atoms converted in step 705 can be in the range of about 50% to about 90%, about 60% to about 80%, about 65% to about 75%, or any range or sub-range therebetween. In various aspects, the coating thickness 1039 of the coating 1033 defined between the opposing surfaces 1035 and 1037 can be within one or more of the ranges discussed above for the anti-fingerprint thickness 119.

[0369] In various aspects, the evaporation of the functionalized POSS 913 in step 703 and the impinging of the ion beam traveling along the beam path in step 705 can occur simultaneously. As used herein, steps 703 and 705 occurring "simultaneously" means that there is at least one point in time at which the activities of steps 703 and 705 both occur. It should be understood that if one of the steps starts before the other step ends and / or if one of the steps ends before the other step ends, it can still be simultaneous, but in additional aspects, both steps 703 and 705 can start simultaneously and / or end simultaneously. As Figure 9 shown, the container 911 (e.g., a Knudsen cell or effusion cell), the substrate 103, and at least a portion of the beam path can be positioned within the chamber 903 such that the gas phase (as indicated by 917) and / or the functionalized POSS 913 disposed on the first major surface 105 can be impinged upon by the ion beam traveling along the beam path. Performing steps 703 and 705 simultaneously can facilitate the formation of a coating 1033 that has good adhesion to the substrate 103 and / or is relatively uniform (see Figure 10 ). Providing a discharge current of about 0.25 A or greater can facilitate the formation of the coating 1033 (see Figure 10 ), for example, generating an ion beam with sufficient energy such that the functionalized POSS reacts with other functionalized POSS and / or the first major surface 105 of the substrate 103 at a perceivable rate (e.g., compared to a lower discharge current). Providing a discharge current of about 1 A or less can provide an ion beam that is not so strong as to remove any POSS material deposited by evaporation. Additionally, performing steps 703 and 705 simultaneously can reduce the processing time.

[0370] In various aspects, after step 705, as Figure 10 shown, the method can proceed to step 707, which includes reacting a material (e.g., the coating 1033) at the first major surface 105 of the substrate 103 with an alkylsilane to form a surface-modified layer (e.g., an anti-fingerprint coating).Figure 10 Disclosed is a silanization method. The method can be carried out at atmospheric pressure and / or at a pressure within one or more of the ranges discussed above for step 703. For example, chamber 1003 can be an inert ampoule, which is heated by an oven at about 60 °C to about 200 °C (e.g., about 60 °C or greater, about 80 °C or greater, about 90 °C or greater, about 100 °C or greater, about 120 °C or greater, about 140 °C or greater, about 250 °C or less, about 220 °C or less, about 200 °C or less, about 180 °C or less, or about 160 °C or less). The sample is optionally plasma-treated with O2 or Ar plasma for surface activation and placed in an ampoule with a drop of silane, sealed and heated for about 2 hours to about 5 hours. Providing an elevated temperature when evaporating the silane and reacting the silane with the coating can increase the evaporation rate, enabling the use of a wide range of silanes, increasing the reaction rate or reactivity of the silane, and / or promoting the formation of covalent bonding with the surface 1035 of the partially condensed silica film 1033. Alternatively, the alkylsilane can react with the surface (e.g., the first major surface, the surface of the optical stack, or the silica-like network formed by IAD) under ambient conditions (e.g., about 25 °C to about 30 °C) to form a surface modification layer.

[0371] Another embodiment that we have also shown is to use a low-vacuum chamber with a vapor source, such as the YES-1124P (available from Yield Engineering Systems). Other manufacturers have similar systems. For example, the chamber can be heated to a temperature of about 100 °C to about 200 °C and evacuated to a pressure of about 10 Pa. The substrate is optionally exposed to an Ar or O2 capacitively coupled plasma generated by low-frequency or high-frequency RF. After pumping down to the base pressure, the silane precursor vapor is introduced into the chamber. One method of silane evaporation is to use a liquid evaporator. The liquid can be injected into a heated evaporation cell with independent temperature control by a pulse pump, where the liquid is evaporated and travels through an independently heated channel into the chamber. With independent temperature control, condensation in the channel can be prevented. The evaporation of the silane can raise the chamber pressure by about 1 Pa to about 100 Pa, and the substrate is exposed to the vapor for a period of time (e.g., about 2 minutes to about 20 minutes), and the chamber is pumped out to remove excess vapor and condensation products.

[0372] In another embodiment, the high-vacuum coating chamber is similar to Figure 9The substrate is cleaned with an end Hall or ICP ion source, and silane is evaporated from a liquid injection source similar to the liquid injection source described above, or desorbed from an adsorbate (usually enclosed in a can) using a heat source such as a resistively heated tungsten boat, effusion or Knudsen cell, or an electron beam evaporator. The deposition rate and total thickness can be monitored in these systems using a quartz crystal monitor (QCM). This type of chamber is typically used to produce fluorinated ETC coatings on handheld devices such as mobile phones.

[0373] In various aspects, silane 1013 can include alkylsilane. In additional aspects, the alkylsilane can include four or more carbons, such as 4 to 34 carbons (e.g., C4-C 34 alkyl), 6 to 20 carbons (e.g., C6-C 34 alkyl), 8 to 18 carbons (e.g., C8-C 18 alkyl), 8 to 12 carbons (e.g., C8-C 12 alkyl) or any range or sub-range therebetween. Exemplary aspects of alkylsilane include isooctyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, or combinations thereof. In various aspects, the alkylsilane can include an alkyl group that includes 4 to about 34 carbons (i.e., C4-C 34 alkyl) (e.g., 6 to 34 carbons (i.e., C6-C 34 alkyl), 8 to 20 carbons (i.e., C8-C 20 alkyl)), e.g., isooctyl alkyl, dodecyl alkyl, octadecyl alkyl, or combinations thereof. An exemplary aspect of the alkyl group is octadecyl alkyl. Providing alkylsilane can reduce the surface energy of the coating (e.g., total surface energy, dispersive surface energy, polar surface energy), which can make the resulting fingerprint-resistant coating oleophilic. At the end of step 707, the silane can bond to the material of coating 1033 to form a surface modification layer (e.g., fingerprint-resistant coating 113) (see Figure 1 and Figures 2A to 2C ).

[0374] In various aspects, after step 707, the method can proceed to step 709, which includes assembling the coated article including the surface modification layer (e.g., fingerprint-resistant coating 113) into a consumer electronic device. For example, the surface modification layer (e.g., fingerprint-resistant coating 113) can include the outer surface of the display portion of a display device and / or a touch sensor. For example, the surface modification layer (e.g., fingerprint-resistant coating 113) can include the outer surface of at least a portion of a consumer electronic device.

[0375] After step 707 or 709, the method can proceed to step 711, where the method of manufacturing the coated article can be completed. In various aspects, the method of manufacturing a coated article according to aspects of the present disclosure can proceed alongFigure 7 The steps 701, 703, 705, 707, 709, and 711 of the flowchart in are carried out in sequence as discussed above. In various aspects, for example, if the method of manufacturing a coated article is completed at the end of step 707, the method can follow arrow 706 from step 707 to step 711. Any of the above options can be combined to manufacture a foldable device according to an embodiment of the present disclosure.

[0376] It is known that POSS materials can be cured at high temperatures (e.g., about 600 °C or greater). However, the method discussed above with reference to Figure 7 the flowchart in can subject the functionalized POSS to a maximum temperature of about 250 °C or less (e.g., about 220 °C or less, about 200 °C or less, about 180 °C or less, about 160 °C or less, about 120 °C or less, or about 50 °C or less) (e.g., by evaporation of the functionalized POSS, bombardment with an ion beam, and subsequent silane functionalization) to obtain a surface modification layer (e.g., the fingerprint-resistant coating 113). Thus, the properties of the surface modification layer (e.g., the fingerprint-resistant coating 113) formed in this manner can exhibit a partially silica-like network (e.g., about 50% to about 90%) that can be formed by higher temperature treatment, rather than a substantially complete silica-like network. As discussed below, the increased elastic modulus associated with exposing the functionalized POSS material to higher temperatures is associated with poor wear resistance.

[0377] As discussed above with reference to Figure 7At the end of the method described by the flowcharts herein, the coated articles 101, 201, 211, or 221 and / or the surface modification layer (e.g., the fingerprint-resistant coating) may include any one or more of the aspects discussed above. For example, the surface modification layer (e.g., the fingerprint-resistant coating) may be fluorine-free and / or nitrogen-free. The surface modification layer (e.g., the fingerprint-resistant coating) may include a water contact angle, a diiodomethane contact angle, and / or a hexadecane contact angle within one or more of the corresponding ranges discussed above. The surface modification layer (e.g., the fingerprint-resistant coating) may include a worn water contact angle after 2,000 cycles, 3,000 cycles, or 35,000 cycles of wear in the steel wool abrasion test and / or a muslin abrasion water contact angle after 200,000 cycles of wear in the muslin abrasion test within one or more of the corresponding ranges discussed above. The surface modification layer (e.g., the fingerprint-resistant coating) may include a total surface energy, a dispersive surface energy, and / or a polar surface energy within one or more of the corresponding ranges discussed above. The surface modification layer (e.g., the fingerprint-resistant coating) may include a modulus of elasticity, a surface roughness Ra, and / or a fingerprint-resistant thickness within one or more of the corresponding ranges discussed above. The surface modification layer (e.g., the fingerprint-resistant coating) may include a refractive index within the range of about 1.38 to about 1.55, about 1.44 to about 1.55, about 1.44 to about 1.53, about 1.48 to about 1.51 or any range or sub-range therebetween. In various aspects, the percentage of silicon atoms in the silica-like network may be within one or more of the ranges discussed above (e.g., about 50% to about 90%). In various aspects, the ratio of Si-O-Si bonds to silicon atoms may be within one or more of the ranges discussed above (e.g., about 2 to about 3).

[0378] Reference will now be made to Figure 6 and Figures 10 to 12 as well as Figure 8 the flowcharts herein to discuss example aspects of manufacturing the coated articles 101, 201, 211, or 221. In a first step 801, the method may begin by obtaining a substrate 103. In various aspects, the substrate 103 may be provided by purchasing or otherwise obtaining the substrate or by forming the substrate. In various aspects, the substrate 103 may include a glass-based material, a glass-ceramic material, and / or a ceramic-based material. In additional aspects, the base material, glass-ceramic material, and / or ceramic-based material may be provided by forming it using various tape casting processes such as slot drawing, down-drawing, melt down-drawing, up-drawing, roll pressing, re-drawing, or floating. In additional aspects, a ceramic-based substrate may be provided by heating a glass-based substrate to crystallize one or more ceramic crystals. The substrate 103 includes a first major surface 105 that may extend along a first plane 104. In various aspects, as Figure 1As indicated, an optical stack 203 including an anti-reflection coating and / or a gradient coating including a refractive index gradient can be disposed on and / or bonded to the first major surface 105. Although Figures 11 to 12 not shown in, it should be understood that the optical stack 203 can be disposed on the first major surface 105. In various aspects, the substrate 103 can be chemically strengthened with one or more compressive stress regions (or central tensile regions), the compressive stress regions including any one of the aspects related to the compressive depth, maximum compressive stress, and / or tensile stress discussed above for the corresponding properties.

[0379] In various aspects, step 801 can include obtaining the material of the precursor solution 1103 (see Figure 11 ), or obtaining a precursor solution. In additional aspects, the precursor solution 1103 can include a functionalized polyhedral oligomeric silsesquioxane (POSS) (see Figure 5 ), as discussed above with reference to step 701. In yet additional aspects, the functionalized POSS can be at least partially and / or fully hydrogen-functionalized, which can be abbreviated as POSS. In additional aspects, the precursor solution can include a polysilazane. As used herein, "polysilazane" is a polymer including a backbone of silicon and nitrogen. An exemplary polysilazane is a perhydropolysilazane. For example, as Figure 6 shown by the upper compound in, the polysilazane can be composed of alternating silicon atoms and nitrogen atoms in the backbone of the polysilazane, with hydrogen atoms bonded to the backbone. In additional aspects, the concentration of the polysilazane or POSS in the precursor solution 1103 can be about 0.1 wt% or greater, about 0.2 wt% or greater, about 0.5 wt% or greater, about 1 wt% or greater, about 1.5 wt% or greater, about 2 wt% or greater, about 25 wt% or less, about 15 wt% or less, about 6 wt% or less, about 5 wt% or less, about 4 wt% or less, about 3 wt% or less, about 2.5 wt% or less, or about 2 wt% or less. In additional aspects, the concentration of the polysilazane or POSS in the precursor solution 1103 can be in the range of about 0.1 wt% to about 25 wt%, about 0.2 wt% to about 25 wt%, about 0.2 wt% to about 15 wt%, about 0.2 wt% to about 6 wt%, about 0.2 wt% to about 5 wt%, about 0.5 wt% to about 4 wt%, about 1 wt% to about 3 wt%, about 1.5 wt% to about 2.5 wt%, or any range or sub-range therebetween.

[0380] After step 801, as Figure 11As shown, the method may proceed to step 803, which includes disposing precursor solution 1103 above a first major surface 105 of substrate 103. The precursor solution 1103 may include polysilazane or POSS at a concentration within one or more of the ranges discussed in the previous paragraph. In various aspects, as Figure 11 shown, the precursor solution 1103 may be dispensed (e.g., deposited) from a container 1101 (such as a conduit, flexible tube, micropipette, inkjet printhead, or syringe) above (e.g., onto) the first major surface 105 of substrate 103 to form a precursor layer 1105. In additional aspects, as shown, step 803 may include spin coating the precursor solution 1103 above (e.g., onto) the first major surface 105, for example, by disposing the second major surface 107 of the substrate above a surface 1115 of a holder 1113, and the holder may rotate (as shown by arrow 1119) while and / or after the precursor solution 1103 is disposed above the first major surface 105. In yet additional aspects, the holder 1113 may rotate at 200 revolutions per minute (rpm) or greater, about 500 rpm or greater, about 700 rpm or greater, about 4,000 rpm or less, about 2,500 rpm or less, or about 1,500 rpm or less. In yet additional aspects, the holder 1113 may rotate at 200 rpm to about 4,000 rpm, about 500 rpm to about 2,500 rpm, about 700 rpm to about 1,500 rpm, or any range or sub-range therebetween. Spin coating the precursor solution may form a substantially uniform precursor layer above the first major surface of the substrate.

[0381] After step 803, as Figure 12 shown, the method may proceed to step 805, which includes heating the precursor layer 1105 of the precursor solution 1103 at a first temperature (see Figure 11)Continue for a first time period to form the coating 1033. In various aspects, as shown, the substrate 103 can be placed in an oven 1201 maintained at a first temperature for the first time period. In various aspects, the first temperature can be about 150 °C or greater, about 170 °C or greater, about 190 °C or greater, about 400 °C or less, about 300 °C or less, about 250 °C or less, about 230 °C or less, or about 210 °C or less. In various aspects, the first temperature can be in the range of about 150 °C to about 400 °C, about 150 °C to about 300 °C, about 150 °C to about 250 °C, about 170 °C to about 230 °C, about 190 °C to about 210 °C or any range or sub-range therebetween. In various aspects, the first time period can be about 5 minutes or more, about 10 minutes or more, about 20 minutes or more, about 25 minutes or more, about 2 hours or less, about 1.5 hours or less, about 1 hour or less, or about 40 minutes or less. In various aspects, the first time period can be in the range of about 5 minutes to about 2 hours, about 10 minutes to about 1.5 hours, about 20 minutes to about 1 hour, about 25 minutes to about 40 minutes or any range or sub-range therebetween. In various aspects, the precursor solution 1103 can include a catalyst or be catalyst-free. In various aspects, in addition to polysilazane or POSS, the precursor solution 1103 can contain silane. The silane can include any of the aspects discussed above for silane.

[0382] Without wishing to be bound by theory, heating the precursor layer of the precursor solution can remove solvent and / or partially cure the polysilazane or POSS from the precursor layer, for example to form a partially silica-like network. For example, heating POSS can cause the silicon-oxygen network to rearrange into a silica-like network and / or bond to the surface (e.g., the first major surface 105) on which the precursor solution is disposed. For example, as Figure 6 shown, the polysilazane can undergo a reaction in which ammonia and hydrogen are released and oxygen and water are consumed to transform from a structure with an alternating silicon-nitrogen backbone to a silica-like network with silicon-oxygen bonds. Since the polysilazane can only partially undergo this reaction, at the end of step 805, the coating 1033 can include silicon, oxygen, nitrogen, and / or hydrogen. Additionally, it should be understood that these reactions can continue in subsequent steps (e.g., step 807).

[0383] After step 805, as Figure 10As shown, the method can proceed to step 807, which includes reacting a material (e.g., coating 1033) at the first major surface 105 of substrate 103 with an alkylsilane to form a surface modification layer (e.g., a fingerprint-resistant coating). In another aspect, as shown, substrate 103 can be placed in chamber 1003, which can be the same as chamber 903 discussed above with reference to step 703 and / or step 705. In another aspect, chamber 1003 can be maintained under reduced pressure, which can be within one or more of the ranges discussed above for the reduced pressure in step 703. In various aspects, chamber 1003 can be maintained at a temperature within one or more of the ranges discussed above for the temperature in step 705. Providing reduced pressure and / or elevated temperature when evaporating the silane and reacting the silane with the coating can increase the evaporation rate, enabling the use of a wide range of silanes, increasing the reaction rate or reactivity of the silane, and / or promoting the formation of a silica-like network. As Figure 10 shown, silane 1013 can be positioned in container 1011 placed within chamber 1003. In chamber 1003, silane 1013 can evaporate (as indicated by arrow 1015) into a gas phase (as indicated by 1017), and the gas phase can be disposed on the outer surface 1035 of coating 1033 (as indicated by arrow 1019). In various aspects, the evaporation rate of silane 1013 can be within one or more of the evaporation rates discussed above with reference to step 705, and controlling the evaporation rate within one or more of those ranges can effectively (e.g., rapidly) deposit the silane and react the silane with the material of the coating (e.g., on the first major surface). In various aspects, silane 1013 can be heated for a period of time within one or more of the corresponding ranges discussed above with reference to step 705. Silane 1013 can include any one or more of the silanes discussed above with reference to step 705. For example, the silane can be an alkylsilane. The alkylsilane can include 4 or more carbons (e.g., C4-C 34 alkyl, C6-C 34 alkyl, C6-C 20 alkyl, C8-C 18 alkyl or C8-C 12 alkyl). Exemplary aspects of the alkylsilane include isooctyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, or combinations thereof. In various aspects, the alkylsilane can include an alkyl group that includes 4 carbons to about 34 carbons (i.e., C4-C 34 alkyl) (e.g., 6 carbons to 34 carbons (i.e., C6-C 34 alkyl), 8 carbons to 20 carbons (i.e., C8-C 20(alkyl)), for example, isooctyl alkyl, dodecyl alkyl, octadecyl alkyl, or combinations thereof. An exemplary aspect of the alkyl is octadecyl alkyl. The silane can be a disilane and / or a trisilane, which can be bonded to the remainder of the coating at more than one location. For example, the disilane and / or trisilane can include multiple silyl groups at the same end of the silane, which can help orient the functional groups of the silane. Providing the alkylsilane can reduce the surface energy of the coating (e.g., total surface energy, dispersive surface energy, polar surface energy), which can make the resulting fingerprint-resistant coating lipophilic. At the end of step 807, the silane can be bonded to the material of coating 1033 to form a surface modification layer (e.g., fingerprint-resistant coating 113) (see Figure 1 and Figures 2A to 2C ).

[0384] Alternatively, although not shown, reacting the material at the first major surface of the substrate with an alkyl substrate to form a surface modification layer (e.g., fingerprint-resistant coating) can include (a) disposing the silane on the substrate as a solution and then (b) heating the substrate to react the silane with the material at the first major surface of the substrate. For example, disposing the silane on the substrate can include dip coating the substrate with a solution including the silane, can include spin coating the substrate with a solution including the silane, spraying the substrate with a solution including the silane, or printing on the substrate with a solution including the silane. In aspects, the silane solution can include silane in an amount of about 0.1 wt% or greater, about 0.2 wt% or greater, about 0.5 wt% or greater, about 1 wt% or greater, about 25 wt% or less, about 15 wt% or less, about 6 wt% or less, about 5 wt% or less, or about 2 wt% or less, based on the wt% of the silane solution. In aspects, the silane solution can include silane in an amount that can range from about 0.1 wt% to about 25 wt%, about 0.2 wt% to about 25 wt%, about 0.2 wt% to about 15 wt%, about 0.2 wt% to about 6 wt%, about 0.2 wt% to about 5 wt%, about 0.5 wt% to about 5 wt%, about 1 wt% to about 2 wt%, or any range or sub-range therebetween. In aspects, the silane can include any one or more of the silanes mentioned in the previous paragraph.

[0385] In aspects, after step 807, the method can proceed to step 809, which includes assembling the coated article including the surface modification layer (e.g., fingerprint-resistant coating 113) into a consumer electronic device. For example, the surface modification layer (e.g., fingerprint-resistant coating 113) can include the outer surface of the display portion of a display device and / or a touch sensor. For example, the surface modification layer (e.g., fingerprint-resistant coating 113) can include the outer surface of at least a portion of a consumer electronic device.

[0386] After step 807 or 809, the method may proceed to step 811, where the method of manufacturing the coated article may be completed. In various aspects, the method of manufacturing a coated article according to aspects of the present disclosure may proceed sequentially through steps 801, 803, 805, 807, 809, and 811 of the flowchart in Figure 8 as discussed above. In various aspects, for example, if the method of manufacturing the coated article is completed at the end of step 807, the method may follow arrow 802 from step 807 to step 811. In various aspects, for example, if the precursor solution contains silane in addition to polysilazane or POSS, the method may follow arrow 804 from step 805 to step 811. Any of the above options may be combined to manufacture a foldable device according to an embodiment of the present disclosure.

[0387] At the end of the method discussed above with reference to the flowchart in Figure 7 the coated articles 101, 201, 211, or 221 and / or the surface modification layer (e.g., the fingerprint-resistant coating) may include any one or more of the aspects discussed above. For example, the surface modification layer (e.g., the fingerprint-resistant coating) may be fluorine-free. The surface modification layer (e.g., the fingerprint-resistant coating) may include a water contact angle, a diiodomethane contact angle, and / or a hexadecane contact angle within one or more of the corresponding ranges discussed above. The surface modification layer (e.g., the fingerprint-resistant coating) may include a worn water contact angle after 2,000 cycles, 3,000 cycles, or 3,500 cycles of wear in a steel wool abrasion test and / or a cotton cloth worn water contact angle after 200,000 cycles of wear in a cotton cloth abrasion test within one or more of the corresponding ranges discussed above. The surface modification layer (e.g., the fingerprint-resistant coating) may include a total surface energy, a dispersive surface energy, and / or a polar surface energy within one or more of the corresponding ranges discussed above. The surface modification layer (e.g., the fingerprint-resistant coating) may include a modulus of elasticity, a surface roughness Ra, and / or a fingerprint-resistant thickness within one or more of the corresponding ranges discussed above. The surface modification layer (e.g., the fingerprint-resistant coating) may include a refractive index within a range of about 1.38 to about 1.44, about 1.39 to about 1.43, about 1.4 to about 1.42, or any range or sub-range therebetween. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating) may include a partially silica-like network and hydrogenated silicon or silanol.

[0388] Alternatively, another embodiment of the present disclosure may include a surface modification layer (e.g., the fingerprint-resistant coating 113) of the coated articles 101, 201, 211, and / or 211 having a smaller fingerprint-resistant thickness 119 and / or not having an apparent silica or partially silica-like network. For example, referring to Figure 7The flow chart shown in, although not shown, the method can proceed directly from step 701 to step 707, which includes disposing (e.g., reacting) an alkylsilane with the surface of an article (e.g., a substrate) to form a surface modification layer (e.g., a fingerprint-resistant coating). For example, referring to Figure 8 The flow chart shown in, although not shown, the method can proceed directly from step 801 to step 807, which includes disposing (e.g., reacting) an alkylsilane with the surface of an article (e.g., a substrate) to form a surface modification layer (e.g., a fingerprint-resistant coating). In various aspects, the alkylsilane can include any of the materials discussed above with reference to step 707 and / or 807. In additional aspects, the alkylsilane can include an alkyl group, the alkyl group including 4 to about 34 carbons (i.e., C4-C 34 alkyl), such as 6 to 34 carbons (i.e., C6-C 34 alkyl), 8 to 20 carbons (i.e., C8-C 20 alkyl). In yet additional aspects, the alkyl group can be isooctylalkyl, dodecylalkyl, octadecylalkyl, or a combination thereof. An exemplary aspect of the alkyl group is octadecylalkyl. In various aspects, the deposition conditions can be as described above with reference to step 707 and / or 807 and / or with reference to Figure 10within any of the corresponding ranges discussed. Alternatively, an alkylsilane can be sprayed (e.g., coated) onto the surface of an article (e.g., a substrate). In other aspects, the alkylsilane can be heated to form a surface modification layer (e.g., a fingerprint-resistant coating). As discussed above, the alkylsilane can form a surface modification layer by (1) heating under the conditions discussed above for step 707 and / or (2) reacting with a surface (e.g., a first major surface, the surface of an optical stack) under ambient conditions (e.g., from about 25°C to about 30°C). In various aspects, the fingerprint-resistant thickness of the surface modification layer (e.g., the fingerprint-resistant coating) can be in the range of about 1 nm to about 75 nm, about 1 nm to about 50 nm, about 1 nm to about 25 nm, about 1 nm to about 15 nm, about 2 nm to about 10 nm, about 2 nm to about 8 nm, about 2 nm to about 5 nm, about 3 nm to about 5 nm, or any range or sub-range therebetween. In various aspects, the surface modification layer (e.g., the fingerprint-resistant coating, the alkylsilane) can exhibit a water contact angle (e.g., about 100° or greater, or from 102° to 110°), a diiodomethane contact angle (e.g., about 60° or greater), a coefficient of friction (e.g., about 0.25 or less), a polar surface energy (e.g., about 3 mN / m or less), a total surface energy (e.g., about 30 mN / m or less), a cotton cloth abrasion water contact angle (e.g., about 90° or greater after undergoing 200,000 cycles in a cotton cloth abrasion test), and / or a rubber abrasion water contact angle (e.g., about 80° or greater, about 90° or greater, or from about 100° to about 110° after undergoing 5,000 cycles in a rubber abrasion test) within one or more of the corresponding ranges discussed above.

[0389] Examples

[0390] Various aspects will be further illustrated by the following examples. Examples A - C and AA - CC include glass-based substrates with a thickness of 0.55 mm (Composition 1, having a nominal composition in wt%: 61.9 SiO2, 19.7 Al2O3, 12.9 Na2O, 3.9 B2O3, 1.5 MgO, and 0.1 K2O). Examples D - J and Comparative Examples DD - II include glass-based substrates with a thickness of 1 mm (Composition 1). Examples K - M and 1 - 12 and Comparative Examples JJ - KK include glass-based substrates with a thickness of 0.55 mm (Composition 2, having a nominal composition in wt%: 67.6 SiO2, 12.7 Al2O3, 13.6 Na2O, 3.7 B2O3, 2.3 MgO, and 0.1 Sn2O). Examples O - S include silicon substrates analyzed by infrared spectroscopy.

[0391] Comparative example AA is only a glass-based substrate. Comparative example BB includes a SiO2 coating disposed on the glass-based substrate using high-density plasma chemical vapor deposition (HDPCVD). Comparative examples AA to BB have a water contact angle of <60°. Comparative example CC includes an OV-POSS coating disposed on the glass-based substrate by thermal evaporation of octavinyl POSS (OV-POSS) at a rate of 0.2 nm / s. Unless otherwise indicated, thermal evaporation of the functionalized POSS is carried out using a Radak II cell in an Angstrom Engineering Evovac chamber.

[0392] Figure 15 Displays an infrared (IR) absorption spectrum, where the horizontal axis 1501 (i.e., the x-axis) corresponds to the wave number in reciprocal centimeters (cm -1 ) and the vertical axis 1503 (i.e., the y-axis) corresponds to the normalized absorbance. Curve 1515 represents the obtained normalized absorbance of OV-POSS, where the large peak at approximately 1105 cm 1.5 corresponding to the Si-O-Si bond of the T-type (RSiO -1 ) units in the POSS cage and the smaller peaks around 1270 cm -1 , 1010 cm -1 and 980 cm -1 are visible. Curve 1505 represents the absorbance of comparative example CC, where OV-POSS is thermally evaporated onto the glass-based substrate. Curves 1505 and 1515 are the same, indicating that the OV-POSS thermally evaporated onto the glass-based substrate has not reacted with itself or the glass-based substrate. In addition, the coatings of the comparative examples are easily removed with a fingernail and exhibit poor abrasion resistance.

[0393] As used in this section, the ion beam is formed by an end-Hall source (KRI 400 from Kaufman & Robinson) operating at a voltage of 100 V. To explore the effect of ion beam intensity on coating formation during evaporation of OV-POSS at 0.1 A / s, the discharge current is adjusted while the chamber pressure is maintained at approximately 1.3×10 -2 Pa of argon (Ar) (maintained at a flow rate of 2.7 sccm Ar). At a discharge current of 2.5 A, no coating was observed. The discharge current was reduced until coating formation was observed, which occurred at a discharge current of approximately 1 A. It is believed that the ion beam removes and / or decomposes OV-POSS at the same rate or faster than the deposition of OV-POSS by thermal evaporation. In addition, while the chamber pressure is maintained at approximately 2.7×10 -2When oxygen (O2) at Pa (maintained at a flow rate of 7 sccm O2) is used, coatings are formed with different discharge currents. The discharge current is increased from 0 A to determine the minimum discharge current to obtain a coating that may not be easily removed with a fingernail, which results in a minimum discharge current of about 0.25 A. Therefore, it is believed that an end Hall source can be used to form a coating with a discharge current of about 0.25 A to about 1 A.

[0394] Table 1 shows the properties of Examples A to C and Comparative Examples AA to CC. In Table 1, "IAD" refers to ion-assisted deposition and refers to the use of an ion beam in combination with evaporation. In Table 1, the reported refractive index values and extinction coefficient values are obtained at an optical wavelength of 550 nm. As described above, the thickness of the coating is measured using SEM and reported in Table 1.

[0395] Examples A to C are formed by thermally evaporating OV-POSS at a rate of about 0.07 nm / s (0.7 A / s) (slightly lower than Comparative Example CC due to the ion beam) and simultaneously impinging an ion beam formed by an end Hall source (KRI 400 from Kaufman & Robinson) operating at a voltage of 100 V and a discharge current of 0.25 A. For Example A, the chamber pressure is about 1.3×10 -2 Pa of argon (Ar) (maintained at a flow rate of 2.7 sccm Ar). For Example B, the chamber pressure is about 2.7×10 -2 Pa of oxygen (O2) (maintained at a flow rate of 7 sccm O2). For Example C, the chamber pressure is about 4×10 -2 Pa of a 70 mol% Ar 30 mol% O2 mixture (maintained at a flow rate of 10 sccm mixture). In Examples A to C, evaporation and ion beam treatment continue until a coating of about 400 nm is obtained.

[0396] Table 1: Properties of Examples A to C and Comparative Examples AA to CC

[0397]

[0398]

[0399] Return to Figure 15 , curves ********, ********, and ******** correspond to Examples A to C respectively. As shown, curves ********, ********, and ******** have large peaks in the range of about 1000 cm -1 to about 1060 cm -1 that do not exist to this extent in curve ******** or ********. This peak is attributed to the formation of Q-type (i.e., silica-like) Si-O-Si bonds, indicating that the ion beam treatment transforms OV-POSS. In fact, at 1105 cm -1The intensity of the surrounding peaks decreases from curve 1505 to curve 1507 to curve 1509 to curve 1511. This indicates that the ion beam treatment at least partially destroys the cage structure, e.g., by transforming the T-type structure into the Q-type structure. In addition, a larger fraction of oxygen in the chamber (and thus in the ion beam) is associated with a larger destruction of the T-type structure.

[0400] Based on the IR peaks, as discussed above, the silica-type network % is calculated and reported in Table 1. In addition, as discussed above, the elastic modulus of the coating is measured using nanoindentation and reported in Table 1. As shown, the elastic modulus increases as the fraction of the coating in the silica-like network increases. Example A includes an elastic modulus of 20 GPa and approximately 65% of the coating is in the silica-type network. Example B includes an elastic modulus of 30 GPa and approximately 85% of the coating is in the silica-type network. Based on the increased fraction of the silica-type network in Example B relative to Example A, it appears that the oxygen ion beam achieves a greater degree of reaction (from OV-POSS to the silica-type network) than the argon ion beam (and thermal evaporation does not result in this reaction).

[0401] Figure 14 Shown for Examples A to B are the refractive index and extinction coefficient curves as a function of optical wavelength. The horizontal axis 1401 (i.e., the x-axis) represents the optical wavelength in nm. The left vertical axis 1403 (i.e., the left y-axis) represents the refractive index, and curves 1405 and 1407 correspond to the refractive index curves for Examples A to B, respectively. The right vertical axis 1413 (i.e., the right y-axis) represents the extinction coefficient, and curves 1415 and 1417 correspond to the extinction coefficient curves for Examples A to B, respectively. As shown, in Table 1 and Figure 14 Example B (curve 1407; 1.48) has a larger refractive index than Example A (curve 1405; 1.55), which can be attributed to the greater destruction of the POSS cage structure by the oxygen ion beam compared to the argon ion beam, resulting in a more silica-like structure. As Figure 14 shown in, the extinction coefficient of Example B (curve 1417) drops to zero before an optical wavelength of 250 nm and remains there throughout the visible spectrum, which is associated with low absorption of visible light. For Example A (curve 1415), the extinction coefficient decreases as the optical wavelength increases, but the extinction coefficient at 550 nm is still approximately 0.006.

[0402] Figure 13 Shown for Examples A to B and Comparative Examples AA to CC are the transmittance as a function of optical wavelength. The horizontal axis 1301 (i.e., the x-axis) corresponds to the optical wavelength in nm, and the vertical axis 1303 (i.e., the y-axis) corresponds to the transmittance %. As Figure 13As shown, curves 1305, 1307, and 1309 (Comparative Examples AA to CC, respectively) have substantially the same transmittance in the visible spectrum. Curve 1313 (Example B) has a reduced transmittance for optical wavelengths less than 400 nm, but for optical wavelengths of about 400 nm or greater, the transmittance is approximately the same as that of Comparative Examples AA to CC. Curve 1311 (Example A) has a reduced transmittance for optical wavelengths less than 600 nm, but for optical wavelengths of about 600 nm or greater, the transmittance is approximately the same as that of Comparative Examples AA to CC. Based on Figures 13 to 14 these results shown, the coatings produced by the oxygen ion beam have a reduced extinction coefficient and an increased transmittance compared to the coatings produced by the argon ion beam.

[0403] Figures 16 to 17 Shows the mass-to-charge distributions from secondary ion mass spectrometry (SIMS) (i.e., static SIMS) for Examples A to B and Comparative Example CC. Horizontal axes 1601 and 1701 (i.e., the x-axes) represent the positive mass-to-charge ratio, where horizontal axis 1601 (i.e., the x-axis) spans from 0 to 250, and horizontal axis 1701 (i.e., the x-axis) spans from 250 to 650. Before analyzing with SIMS, the sample was cleaned with a low-energy Ar gas cluster ion beam (GCIB) source. Vertical axes 1603 and 1703 (i.e., the y-axes) represent the number of counts observed. In Figures 16 to 17 this figure, each distribution in the same figure shares the same horizontal axis (i.e., the x-axis), while the vertical axis (i.e., the y-axis) is reset at the horizontal line. Distributions 1605 and 1705 correspond to Comparative Example CC, distributions 1607 and 1707 correspond to Comparative Example A, and distributions 1609 and 1709 correspond to Example B. In Figure 17 this figure, peak 1711 corresponds to OV-POSS, and peaks 1713a and 1713b correspond to large fragments of OV-POSS, which is consistent with the above observation that the evaporation of OV-POSS alone does not physically bond or otherwise react with the first major surface of the substrate. Peak 1617 corresponds to phthalate. Peak 1611 corresponds to Si, and peak 1613 corresponds to SiOH. Regions 1615 and 1715 mainly correspond to silicate clusters. Specifically, peaks 1719a, 1719b, and 1719c correspond to dehydrogenated silicate clusters, which are only present in distributions 1609 and 1709 and are thought to be associated with a higher content of the silica-like network.

[0404] Figure 18Shows the elemental compositions of Examples A to B and Comparative Example CC determined by X-ray photoelectron spectroscopy (XPS). As shown, rectangle 1805 corresponds to Example A, rectangle 1807 corresponds to Example B, and rectangle 1809 corresponds to Comparative Example CC. The vertical axis 1803 (i.e., the y-axis) represents atomic %. All examples have 0.1 atomic % or less of argon and nitrogen. Rectangle 1809 (Example CC) has the most carbon and the least oxygen. Compared with about 45 atomic % carbon in rectangle 1809, rectangle 1805 (Example A) has about half the carbon (about 23 atomic %), while rectangle 1807 (Example B) has about 5 atomic % carbon. It is believed that the 5 atomic % carbon content is roughly the content of background environmental contaminants present when analyzing the sample. Rectangle 1807 (Example B) has the least carbon and the least oxygen, which corresponds to a greater degree of reaction caused by the oxygen ion beam, for example, resulting in the removal of vinyl functional groups at the outer surface. For Examples A to B and Comparative Example CC, the silicon amounts are roughly the same.

[0405] Figure 19 Shows the binding energy distribution from XPS of electrons in the 2p orbital of silicon atoms for Examples A to B and Comparative Example CC, and Figure 20 shows the binding energy corresponding to the fine structure of carbon atoms. The horizontal axes 1901 and 2001 (i.e., the x-axis) correspond to the binding energy in electron volts (eV), and the vertical axes 1903 and 2003 (i.e., the y-axis) correspond to the intensity. Figure 19 Shows the binding energy distribution of the 2p orbital of silicon atoms. Curve 1905 corresponds to Comparative Example CC, which has the highest binding energy, which is lower than the binding energy of the pure Si-CH=CH2 bond but greater than the binding energy of the pure silica-like network. Curves 1907 and 1909 correspond to Examples A to B respectively, which are symmetric and have the same peak binding energy, which is roughly the same as the reference value of the pure silica-like network, which is consistent with the reduced carbon observed for Figure 18 these examples. Curve 1907 (Example A) is narrower than curve 1909 (Example B), which indicates a more uniform structure consistent with a greater degree of reaction caused by the oxygen ion beam.

[0406] Figure 20The binding energy corresponding to the fine structure of the carbon atoms is shown. Curves 2005, 2015, and 2025 correspond to Examples A to B and Comparative Example CC, respectively. Region 2031 corresponds to a carbon single bond (e.g., with another carbon atom or with a hydrogen atom), while region 2033 corresponds to a carbon-carbon double bond. As shown, only curve 2025 (Comparative Example CC) has significant intensity in region 2033, which is consistent with the above explanation of the ion beam treatment reaction and / or removal of vinyl functional groups. As shown, the large peak in region 2031 can be fitted as the sum of several smaller curves (e.g., Gaussian). In region 2031, curve 2025 is the largest, followed by curve 2005, and then 2015, which is consistent with the above explanation of the ion beam treatment reaction and / or removal of vinyl functional groups. Figure 18 The carbon content detected in the

[0407] Figure 21 Figure 5 shows the results from solid-state nuclear magnetic resonance (NMR) (SS-NMR) of a sample prepared as in Example B but using 8 deposition cycles to a thickness of 2.7 μm on a Si-coated KBr substrate to improve signal resolution. 29 Si chemical shift. A 2.7 μm thick coating was scraped off from a glass substrate and analyzed using SS-NMR to remove the contribution from the glass substrate. The horizontal axis 2101 (i.e., the x-axis) is 29 The Si chemical shift is plotted on the vertical axis 2103 (i.e., the y-axis) as intensity. Curve 2105 is the total signal detected, which is fitted using six smaller curves (e.g., Gaussian) 2111, 2113, 2115, 2117, 2119, and 2121. 29 Si chemical shifts, these curves can be assigned to different structures. For example, curve 2121 is associated with the M-type structure (e.g., (SiO)Si(OH)3), and curve 2119 is associated with the T-type structure found in POSS (e.g., (SiO)3Si(R) or RSiO 1.5 ), curve 2117 is associated with the D-type structure (e.g., (SiO)2Si(OH)(R)), and curves 2111, 2113, and 2115 are associated with the Q-type structure (e.g., with (SiO) x Si(OH) 4-x Based on these fitted curves and the assignment of associated regions, ratios of 1.4Si-OH / Si, 0.14Si-R / Si (where R is an organic group), and 2.72Si-O-Si / Si were determined. The low amount of Si-R bonds is consistent with the oxygen ion beam reducing the organic content of OV-POSS. The large predominance of Q-type structures indicates a large (but incomplete - e.g., about 50% to about 90%) silica-type network formed using the deposition conditions of Example B.

[0408] The adhesiveness of Examples A to C and Comparative Examples AA to BB was tested by placing a 2-μm thick silicon nitride (SiN x ) coating thereon, wherein before placing the silicon nitride coating, the surface of the coating was cleaned with (a) a Branson inductively coupled plasma (ICP) asher (Branson L3200 ICP plasma asher) operating with oxygen at 300 sccm at a chamber pressure of 600 W and 160 Pa for 10 minutes and / or (b) a Versaline HDPCVD (available from Plasma-Therm) operating with oxygen at 50 sccm at a chamber pressure of 2,000 W and about 1 Pa for 1 minute. Three parallel 20-mm long scratches were made using diamond scribing, which penetrated all the coatings to reach the first major surface of the glass substrate. Then, the coating was covered with 0.1 wt% Triton X-100 in deionized water for 1 minute, and thereafter, the coating was brushed 25 times perpendicular to the scratches in two directions using a plastic razor blade. The formed samples were examined using an optical microscope (100-fold magnification), and then, after the samples were scratched, covered, and brushed, signs of bubbles or other delamination were examined. The 2-μm thick silicon nitride coating made it clearer whether delamination occurred and subjected the coating to various stresses that would be encountered when used in combination with other coatings (e.g., antireflection, gradient refractive index).

[0409] Table 2 presents the results of this adhesiveness test. Comparative Examples AA to BB did not show bubbles and had 0 or 1 delamination. For Examples A and C, Branson cleaning prevented the bubbles that were seen without it and reduced the number of delaminations from 50 or 28 to 4 or 5. For Example B, no bubbles were observed for any condition with 0 or 1 delamination. Unexpectedly, Example B (oxygen ion beam) would not provide bubbles and 0 or 1 delamination under these harsh conditions.

[0410] Table 2: Adhesiveness Test of Examples A to B and Comparative Examples AA to CC

[0411]

[0412]

[0413] The chemical stability of Examples A to B and Comparative Example BB was tested by measuring the change in thickness and refractive index after the coatings were sequentially subjected to (1) a 2 wt% alkaline detergent solution (Semi Clean KG) at 50°C for 20 minutes and (2) deionized water for 20 minutes. All samples exhibited a thickness loss of less than 7 nm and less than 2%, with Example A having a thickness loss of about 1.2 nm, Example B having a thickness loss of about 6.7 nm (1.4%), and Comparative Example BB having a thickness loss of 5.1 nm (1.7%). All examples exhibited a refractive index change of less than 0.002, with Example A increasing its refractive index by 0.0008, Example B increasing its refractive index by 0.004, and Comparative Example BB decreasing its refractive index by 0.0013. This indicates that the chemical stability of Examples A to B is comparable to (if not better than) that of the silica coating (Comparative Example BB).

[0414] The thermal stability of Examples A and B was evaluated by heating the samples at 200°C, 300°C, or 400°C for 10 minutes. For all conditions, the thickness change was less than 5%. At 300°C, the thickness change of Example A was less than 3%, and the thickness change of Example B was about 1%. At 200°C, the thickness change of Example B was less than 2.5%, and the thickness change of Example A was less than 0.5%. Similarly, the IR spectra after these heat treatments (not shown) were essentially the same, with the normalized absorbance changing from 500 cm -1 Up to 1500cm -1 The change in is less than 0.05. This indicates that the coating is thermally stable. However, as discussed above, it is believed that prolonged heating at high temperatures can form a larger amount of silica-like network (e.g., greater than 90%), which is detrimental to wear resistance.

[0415] Table 3 presents the contact angle and surface energy values for Examples D to I and Comparative Examples DD to GG, which were prepared by depositing an initial coating and then optionally reacting this coating with evaporated silane. The initial coatings for Examples D to F were formed by evaporating OV-POSS at 0.78 A / s while impinging an oxygen ion beam generated by an end-Hall source (KRI EH-400) at 100 V with a discharge current of 0.25 and a charge of 5.3×10 -5 The chamber pressure was operated at 100 Pa of oxygen (O2) (maintained at a flow rate of 3 sccm O2), which resulted in a thickness of about 105 nm, a refractive index of 1.486, and a relatively strong OH stretch ("High OH") by FTIR. The initial coatings of Examples G to I were formed by evaporating OV-PSS at 18.9 A / s while impinging on an oxygen ion beam generated by an end-Hall source (KRI EH-400) operated at 100 V with a discharge current of 0.25 and a 5.3×10 -5Chamber pressure operation with oxygen (O2) at 1 Pa (maintained at a flow rate of 3 sccm O2), which has a slight gray color attributed to residual vinyl, as confirmed by FTIR showing C═C vinyl stretching and relatively weak O-H stretching (“low OH”). Subsequently, the initial coating (e.g., low OH, high OH) was placed upright in a Salvillex PFA vial together with 25 μL of silane placed away from the sample; after the cap was fixed, it was heated at 170 °C for 5 hours, after which the cap was removed and the sample was allowed to cool naturally to room temperature (e.g., about 25 °C).

[0416] As used in Table 3, “18TMS” refers to octadecyltrimethoxysilane, “i8TMS” refers to isooctyltrimethoxysilane, “12TES” refers to dodecyltriethoxysilane, and “ETMS” refers to ethoxytrimethylsilane. 18TMS, i8TMS, 12TES, and ETMS are alkylsilanes (e.g., trialkoxyalkylsilanes). 18TMS, i8TMS, and 12TES are methoxysilanes, while ETMS is an ethoxysilane. “POTS” refers to heptadecafluoro-1,1,2,2-tetrahydrotrimethoxysilane, which is a fluorosilane. As used herein, “WCA” refers to the water contact angle (formed), “HDCA” refers to the hexadecane contact angle (formed), and “DIMCA” refers to the diiodomethane contact angle (formed).

[0417] As Figure 3 shown, Comparative Examples DD and GG are not hydrophobic, having a total surface energy of 40 mN / m or greater and a polar surface energy of 7 mN / m or greater, indicating that the initial coating of OV-POSS alone would not be suitable as an anti-fingerprint coating. In addition, Comparative Examples FF and II are not hydrophobic, having a total surface energy of 34 mN / m or greater and a polar surface energy of 8 mN / m or greater, indicating that a single ethoxysilane may not be suitable for functionalizing the initial coating of OV-POSS to form an anti-fingerprint coating. On the other hand, Comparative Examples EE and HH use fluorosilanes, which produce hydrophobic water contact angles, low total surface energies, and low polar surface energies.

[0418] Table 3: Contact Angles and Surface Energies of Examples

[0419]

[0420]

[0421] Examples D to I are hydrophobic, where the water contact angle is 90° or greater and 95° or greater. Examples D to F and I have a water contact angle of 100° or greater. Examples D to I are lipophilic. Examples D to I wet hexadecane or have a hexadecane-water contact of 45° or less. Examples D to H wet hexadecane or have a hexadecane-water contact angle of 40° or less or about 35° or less. Examples D to G wet hexadecane or have a hexadecane-water contact angle of 30° or less. This indicates a "high OH" initial coating (e.g., lower evaporation rate with functionalized POSS). Examples D to F and G to I have a diiodomethane contact angle of about 60° to about 80°. Examples D to F and H to I have a total surface energy of 30 mN / m or less. Examples D to I have a dispersive surface energy of 30 mN / m or less. Examples D to I have a polar surface energy of 5 mN / m or less. Examples D to F and I have a surface energy of 4 mN / m or less. Examples D and F have a polar surface energy of 3 mN / m or less. Compared with Comparative Examples EE and HH (fluorosilanes), Examples D to I are more lipophilic (lower hexadecane contact angle) and have a lower diiodomethane contact angle, indicating that Examples D and F are more suitable for fingerprint-resistant applications compared to Comparative Examples EE and HH.

[0422] Figure 22 and Figure 24 And Table 4 presents the results of the steel wool abrasion test for Examples D to E, G to H, and J and Comparative Examples EE and HH to II. The vertical axis 2203 or 2403 (i.e., the y-axis) is the water contact angle in degrees. For Comparative Example EE, the contact angle decreased by about 21° from formation to 3,500 cycles, while for Comparative Examples HH and II, the contact angle decreased by more than 40°. As discussed above, Examples D to E, G to H, and J are hydrophobic (as formed). After 2,500 cycles and after 3,500 cycles, Examples D and J remained hydrophobic. In fact, after 3,500 cycles, the water contact angle of Example D decreased only 3° to 5° (compared to more than 40° for Comparative Examples HH and II or 21° for Comparative Example EE), indicating that Examples D and J have good abrasion resistance and can maintain a high water contact angle after abrasion.

[0423] Table 4: Results of the steel wool abrasion test

[0424]

[0425]

[0426] Figure 23Shows the elastic modulus obtained by spin - coating a perhydropolysilazane (polysilazane) solution at 1,000 revolutions per minute (rpm) for 30 seconds on a glass - based substrate including Composition 1 for heating, and then heating at various temperatures for 30 minutes. The horizontal axis 2301 (i.e., the x - axis) is the curing temperature in °C, and the vertical axis 2303 (i.e., the y - axis) is the elastic modulus in GPa. For curve 2305, the perhydropolysilazane solution contains a catalyst (Durazane 2850 available from Merck). For curve 2307, the perhydropolysilazane solution does not contain a catalyst (Durazane 2250 available from Merck). As shown, curve 2305 obtains an elastic modulus of more than 15 GPa at a temperature of about 175 °C or higher, and the curve obtains an elastic modulus of less than about 40 GPa at a temperature of about 250 °C or lower. As shown, curve 2307 obtains an elastic modulus of about 9 GPa or higher at a temperature of about 175 °C or higher, and curve 2307 obtains an elastic modulus of less than about 40 GPa at a temperature of less than 400 °C (e.g., about 350 °C or lower). At lower curing temperatures, the catalyzed polysilazane coating exhibits a much higher elastic modulus compared to the uncatalyzed polysilazane material, indicating that the catalyzed material cures to a greater extent than the uncatalyzed material. At higher curing temperatures (e.g., 400 °C), the difference in elastic modulus between the uncatalyzed material and the catalyzed material is minimal, indicating that the catalyst is less effective and / or not necessary for accelerating curing at these higher temperatures. For the catalyzed perhydropolysilazane, the refractive index after heating at 175 °C is about 1.44, which increases to 1.45 after heating at 400 °C. For the uncatalyzed perhydropolysilazane, the refractive index after heating at 175 °C is about 1.505, and decreases to about 1.435 after heating at 400 °C.

[0427] In Example J, a precursor solution including 3 volume % (%v / v) perhydropolysilazane (PHPS) without a catalyst in dibutyl ether (Durazane 2250) was spin - coated on a glass - based substrate including Composition 2 at 1,000 rpm for 30 seconds, and then heated at 250 °C for 30 minutes to form an initial coating. The PHPS film of Example J was functionalized with 18TS applied by dip - coating, adding a solution of 2 vol % of 18TMS to toluene. The sample was immersed in this solution for 30 minutes. Subsequently, the sample was transferred to an oven set at 150 °C for 30 minutes. If necessary, the sample was wiped with a toluene - soaked wipe to remove visible haze. As shown in Table 3, the resulting coating has a water contact angle (formed) of 103°, a hexadecane contact angle of 17°, and a diiodomethane contact angle of 65°. Example J is hydrophobic and lipophilic. Example J has a total surface energy of 28.6 mN / m, a dispersive surface energy of 26.1 mN / m, and a polar surface energy of 2.6 mN / m. As shown in Table 4 and Figure 24As shown, Example J maintains a hydrophobic surface with a water contact angle of 97° after 2,000 cycles and 3,500 cycles in the steel wool abrasion test, where the water contact angle only decreases by 5° as a result of the steel wool abrasion test.

[0428] A precursor solution comprising 1 volume % (% v / v) of hydrogen POSS was spin-coated on a glass-based substrate comprising Composition 2 at 1200 rpm for 30 seconds and then heated at 400 °C or at 600 °C for 30 minutes. When heated at 400 °C, the cured hydrogen POSS coating has an elastic modulus of about 9.4 GPa. When heated at 600 °C, the cured hydrogen POSS coating has an elastic modulus of about 56.5 GPa. It is predicted that improved abrasion resistance can be obtained by curing the hydrogen POSS solution at a temperature of about 400 °C to about 530 °C. Additionally, it is expected that this will also apply to solutions containing one or more of hydrogen POSS and the silanes discussed above.

[0429] Figure 25 Schematically shows the water contact angles in the rubber abrasion test for Examples K to N. Example K includes a layer formed from 18TMS (octadecyltrimethoxysilane) (25 μL of 18TMS, and the glass-based substrate is heated at 170 °C for 5 hours) directly deposited on a glass-based substrate (Composition 2). Example L includes a layer formed from 18TMS (octadecyltrimethoxysilane) (25 μL of 18TMS, and the article is heated at 170 °C for 5 hours) deposited on the optical stack shown in Table 5, which is in turn deposited on a glass-based substrate (Composition 2). Table 5 shows the composition of the optical stacks in Examples L and N (corresponding to the order of the deposited layers - meaning the first row is closest to the glass-based substrate and the last row is farthest from the glass-based substrate). In Table 5, the substrate (i.e., the glass-based substrate) and air are shown to assist in orienting the optical stack, but the substrate and air are not actually elements of the optical stack. In Table 5, "SiON" refers to silicon oxynitride (i.e., SiO x N y -x>0, y>O - and x + y is less than or equal to 1), and "SiN x " refers to silicon nitride, which can have a composition of atoms with a non-stoichiometric (i.e., other than Si3N4) ratio. Example M includes the material of Example D directly deposited on a glass-based substrate (Composition 2) (formed by evaporating OV-POSS at 0.78 Å / s while impinging an oxygen ion beam generated by an end Hall source (KRI EH-400), the end Hall source operating at 100 V with a discharge current of 0.25 and 5.3×10 -5Chamber pressure operation with oxygen (O2) at [[Pa]] (maintained at a flow rate of 3 sccm O2); subsequently, 25 μL of 18TMS and the article were heated at 170 °C for 5 hours). Example N includes the material of Example D disposed on the optical stack shown in Table 5 (formed by evaporating OV-POSS at 0.78 A / s while impinging an oxygen ion beam generated by an end Hall source (KRI EH-400), the end Hall source having a discharge current of 0.25 at 100 V and 5.3×10 -5 Chamber pressure operation with oxygen (O2) at [[Pa]] (maintained at a flow rate of 3 sccm O2); subsequently, 25 μL of 18TMS and the article were heated at 170 °C for 5 hours), and the optical stack is in turn disposed on a glass-based substrate (Composition 2).

[0430] Table 5: Composition of the optical stacks of Examples L and N

[0431] material refractive index thickness (nm) (substrate) 1.50 <![CDATA[SiO2]]> 1.48 20.0 SiON 1.94 8.0 <![CDATA[SiO2]]> 1.48 64.0 SiON 1.94 20.0 <![CDATA[SiO2]]> 1.48 49.2 SiON 1.94 35.9 <![CDATA[SiO2]]> 1.48 26.4 SiON 1.94 50.6 <![CDATA[SiO2]]> 1.48 8.0 SiON 1.94 1500. <![CDATA[SiO2]]> 1.48 16.0 <![CDATA[SiN x > 2.01 39.4 <![CDATA[SiO2]]> 1.48 50.4 <![CDATA[SiN x > 2.01 25.2 <![CDATA[SiO2]]> 1.48 85.6 <![CDATA[SiN x > 2.01 26.0 <![CDATA[SiO2]]> 1.48 45.1 <![CDATA[SiN x > 2.01 154.4 <![CDATA[SiO2]]> 1.48 101.5 (air) 1.00

[0432] In Figure 25 , the horizontal axis 2501 (i.e., the x-axis) corresponds to the number of cycles in the rubber wear test (as defined above), and the vertical axis 2503 (i.e., the y-axis) corresponds to the water contact angle. Curve 2507 corresponds to Example L, which has a formed water contact angle of approximately 93° and a water contact angle of less than 85 °C after only 500 cycles. In contrast, curves 2505, 2509, and 2511 (corresponding to Examples K, M, and N, respectively) maintain a water contact angle of approximately 100° or greater within 5,000 cycles tested in the rubber wear test. Additionally, Examples K and N maintain a water contact angle of approximately 105° within 5,000 cycles tested in the rubber wear test.

[0433] Figure 26 Schematically shows the water contact angle in the steel wool wear test for Examples K and M. In Figure 26 , the horizontal axis 2601 (i.e., the x-axis) corresponds to the number of cycles in the steel wool wear test (as defined above), and the vertical axis 2503 (i.e., the y-axis) corresponds to the water contact angle. Curve 2605 corresponds to Example K, which shows that the surface modification layer (e.g., the fingerprint-proof coating) does not withstand 500 cycles in the steel wool wear test (having a water contact angle of less than 80 °C). In contrast, Example M (curve 2607) maintains a water contact angle of 100° or greater (e.g., approximately 105°) within at least 2,000 cycles, at least 3,000 cycles, at least 3,500 cycles, and all 5,000 cycles tested in the steel wool wear test.

[0434] Figure 27Present the infrared (IR) spectra of Examples O to S. Examples O to S were formed on a silicon substrate by thermally evaporating octaisobutyl POSS (OB-POSS) from a Radak II cell and bombarding the evaporated OB-POSS with an ion beam formed by an end Hall source (KRI 400 from Kaufman & Robinson), the end Hall source operating at a voltage of 60 V and a discharge current of 0.25 amperes (A); the chamber pressure was maintained at about 6.7×10 -3 Pa (5×10 -5 Torr) of oxygen (O2) (maintained at a flow rate of 6.6 sccm O2). As used in this section, the "deposition rate" was measured by a QCM positioned 500 nm above the Radak II cell and 150 nm below the surface. Examples O to S had different deposition rates, namely, 0.5 A / s, 0.7 A / s, 0.9 A / s, 1.3 A / s, and 2.0 A / s, respectively.

[0435] The IR spectra were measured using a Nicolet iS50 FTIR spectrometer (Thermo Scientific) with a DTGS (deuterated triglycine sulfate) detector element, where the absorbance was measured at a resolution of 4 wavenumbers (cm -1 ) and averaged from 256 individual scans. In Figure 27 , the horizontal axis 2701 (i.e., the x-axis) corresponded to the wavenumber (cm -1 ), and the vertical axis 2703 (i.e., the y-axis) corresponded to the normalized absorbance. Curve 2705 corresponded to the absorbance of Example O and a deposition rate of 0.5 A / s; curve 2707 corresponded to the absorbance of Example P and a deposition rate of 0.7 A / s; curve 2709 corresponded to the absorbance of Example Q and a deposition rate of 0.9 A / s; curve 2711 corresponded to the absorbance of Example R and a deposition rate of 1.3 A / s; and curve 2713 corresponded to the absorbance of Example S and a deposition rate of 2.0 A / s.

[0436] Figure 27 Present the entire wavenumber range measured from 400 cm -1 to 4000 cm -1 In 1059 cm -1A broad absorbance at 2723 is seen, which is attributed to the Si-O-Si structure. Modeling (based on the model of Devine, J. Non. Cryst. Sol. 152 (1993): 50-58) indicates that the peak corresponds to a Si-O-Si bond angle of 136° at a fictive temperature of approximately 5300K. This corresponds to a highly strained non-equilibrium structure in the surface modification layer from Example O to S. The fictive temperature calculated here is higher than the temperature typically seen in sputtered silica films. Additionally, curves 2705, 2707, 2709, 2711, and 2713 differ in absorbance (absorbance range 2721) from approximately 800 cm -1 to approximately 980 cm -1 , which is attributed to C-H stretching from the organic functional groups on the functionalized POSS. As the deposition rate increases from Example P to Example S (from curve 2707 to curve 2713), the amount of residual organic material appears to increase.

[0437] Furthermore, the OH stretching associated with free water is seen as absorbance 2727 around the curve at 3550 cm -1 . The free water absorption increases with increasing deposition rate (e.g., from curve 2705 to curve 2713). Although not shown, it was observed that after vacuum annealing at 200 °C for 1 hour, the free water absorption of Example S (2.0 A / s) largely disappeared. Additionally, the hydroxyl (OH) stretching associated with alcohols (e.g., silanol - Si - O - H) is seen as a broad absorbance 2725 from approximately 3200 cm -1 to approximately 3500 cm -1 . The magnitude of the broad absorbance 2725 (associated with hydroxyl groups) also increases with increasing deposition rate (e.g., from curve 2705 to curve 2713).

[0438] Figure 28 The relationship between the deposition rate and the "hydroxyl ratio" is presented for Examples O to S, where the "hydroxyl ratio" is the peak absorbance of the broad hydroxyl signal (centered at 3420 cm -1 ) divided by the peak absorbance of the Si - O - Si signal (centered at approximately 1060 cm -1 ). As shown in Figure 27 , the peak of the Si - O - Si absorbance is much stronger than the hydroxyl absorbance. In Figure 28In [reference], the horizontal axis 2801 corresponds to the deposition rate in A / s (measured by QCM), and the vertical axis 2803 (i.e., the y-axis) is the value of the "hydroxyl ratio" defined above. The points 2805 (circles) correspond to the hydroxyl ratios of Examples O to S. As shown, the hydroxyl ratio increases with increasing deposition rate (from Example O to Example S). Examples O to S have a hydroxyl ratio of 0.005 to 0.07. Examples O to R have a hydroxyl ratio of 0.005 to 0.06 (e.g., 0.008 to 0.05 or 0.01 to 0.045). Although not shown, the hydroxyl ratio of the reactively sputtered silica layer is much lower than Figure 28 the hydroxyl ratio shown in [reference]. For example, the hydroxyl ratio of the surface-modified layer (e.g., Examples O to S) is 2 to 20 (e.g., 3 to 10 or 3 to 5) times greater than the hydroxyl ratio of the reactively sputtered silica layer.

[0439] Figure Presented in Examples 1 to 10 and Comparative Examples JJ to KK is the molar ratio of hydrogen to silicon measured by SIMS. In ​ [reference], the vertical axis 2903 (i.e., the y-axis) is the molar ratio of hydrogen to silicon. As discussed above, it is believed that hydrogen indicates hydroxyl groups (e.g., silanols, Si-O-H). As discussed above, D-SIMS was performed using a time-of-flight secondary ion mass spectrometer (ToF-SIMS) with a dual-beam configuration. Unless otherwise indicated, the ToF-SIMS used for the results reported herein is the ToF-SIMS M6 instrument equipped with a Nanoprobe50 bismuth source (available from IONTOF GmbH). The ToF-SIMS M6 instrument operates in a dual-beam configuration, where the analysis beam is a 30 keV Bi3 + beam with a current of approximately 0.1 pA, and the sputter beam is a 2 keV Cs + . The sputter beam is configured to form a sputter "pit" of 300 μm × 300 μm, and the analysis beam is configured to strike a 75 μm × 75 μm region centered on the sputter "pit". Charge compensation is achieved using an electron flood gun operating at a beam current of 20 nA, an electron energy of 20 eV, and a spot size of 1.5 mm focused on the location where the analysis beam strikes. The chamber is evacuated to a pressure of 5 × 10 -7 Pascals (5 × 10 -9 mbar), and then filled with argon (e.g., 99.99999% purity) to reach and maintain a pressure of 5 × 10 -5 Pascals (5 × 10 -7Pressure in millibars). Data was collected in negative ion mode, where the analyzer was in "general" mode, the analyzer energy was 3000 V, and the cycle time was 100 microseconds. Data was processed using Surface Lab software (version 7.3.125519, available from IONTOF GmbH). To obtain the molar ratio from 16 O 1 H - 、 18 O - and 28 Si - signals, the known isotope ratio between 18 O - and 17 O - was used for calculation and interference from 16 O 1 H - signals was subtracted. The normalized intensity was defined as the mass interference-corrected 17 O - H signal divided by the 16 O 1 H signal divided by the 28 Si - signal. The initial 16 O 1 H - / 28 Si - ratio was further corrected to remove background signals (as determined from the normalized intensity measured simultaneously from a GE type 124 fused silica ([[]] 16 O 1 H - / 28 Si - )) to determine the "corrected signal". A calibration curve (derived from a series of natural mid-ocean ridge basalt (MORB) glasses with known -OH concentrations and other silica and silicate minerals covering the range 0.0 wt% to 1.98 wt%) was used to convert the normalized intensity ([[]] 16 O 1 H - / 28 Si - ) to the hydrogen to silicon molar ratio ("molar ratio"), where the equation was "molar ratio" = 1.26 * "corrected signal" - 0.025.

[0440] Table 6 shows the deposition conditions for Examples 1 to 10 and Comparative Examples JJ to KK. As used in Examples 1 to 10 in this section, the ion-assisted deposition (IAD) process involves thermally evaporating functionalized POSS using a Radak II cell in an Angstrom Engineering Evovac chamber; the ion beam is formed by an end Hall source (KRI 400 from Kaufman & Robinson) operating at a voltage of 60 V and a discharge current of 0.25 amperes (A); the chamber pressure is about 6.7×10 -3 Pa (5×10 -5 Torr) of oxygen (O2) (maintained at a flow rate of 6.6 sccm O2); and the "deposition rate" is measured by a QCM positioned 500 nm above the Radak II cell and 150 nm below the surface. Example 1 was formed by spin-coating a 1 volume % (% v / v) solution of hydrogen POSS (i.e., ​ POSS where R = H in ​ ) (HSQ) on a glass-based substrate at 1,200 rpm for 30 seconds, followed by heating at 400 °C for 30 minutes. Example 2 was formed by spin-coating a 3 volume % (% v / v) solution of perhydropolysilazane (PHPS - see ​ POSS where R = isobutyl in ​ ) without a catalyst in dibutyl ether (Durazane 2250) on a glass-based substrate at 1,000 rpm for 30 seconds, followed by heating at 250 °C for 30 minutes. Examples 3 to 7 used octaisobutyl-functionalized POSS (OBPOSS) (i.e.,

[0441] POSS where R = isobutyl in

[0442]

[0443] Table 6: Deposition Conditions for Examples 35 to 44 and Comparative Examples JJ to KK

[0442]

[0443] The dashed line 2905 corresponds to a hydrogen to silicon molar ratio of 0.20. As ​ shown, Comparative Examples JJ to KK have a hydrogen to silicon molar ratio of about 0.10 (about half of the dashed line 2905). As ​ shown, Examples 1 to 10 all have a molar ratio of 0.2 or greater. Thus, Examples 1 to 10 have at least about twice (2×) the molar ratio of Comparative Examples JJ to KK. Increasing the deposition rate of OBPSS (Examples 3 to 7) generally increases the molar ratio. However, increasing the thickness formed by OVPSS IAD from 50 nm to 200 nm (Examples 8 to 10) slightly decreases or essentially does not change the molar ratio. In addition, Examples 2 to 6 and 8 to 10 have a molar ratio of 0.2 to 0.4 or 0.22 to 0.35.

[0444] ​ Presents the water contact angles before and after 100,000 to 400,000 wear cycles in the cheesecloth wear test for Examples 11 to 12. Examples 11 to 12 include the optical stacks shown in Table 7 (corresponding to the order of the deposited layers - meaning the first row is closest to the glass substrate and the last row is farthest from the glass substrate). For Example 11, a surface modification layer was formed by directly placing 18TMS on the optical stack (placing 25 μL of silane away from the sample; after the lid was fixed, it was heated at 170 °C for 5 hours). For Example 12, octaisobutyl-functionalized POSS (OBPOSS) (i.e., ​ the POSS where R = isobutyl in

[0445] Table 7: Composition of the optical stacks of Examples 11 to 12

[0446]

[0447]

[0448] In ​In it, the vertical axis 3003 (i.e., the y-axis) corresponds to the water contact angle in degrees. Point 3005 corresponds to the water contact angle of Example 11, where line 3017 shows the trend from as-formed (0 cycles), 100,000 cycles, and 200,000 cycles (from left to right). As shown, the water contact angle decreases to less than 90° (e.g., about 75°) after 100,000 cycles and further decreases to less than 75° after 200,000 cycles. Point 3015 corresponds to the water contact angle of Example 12, where line 3017 shows the trend from as-formed (0 cycles) to 400,000 cycles (where the points correspond to the water contact angle after every 100,000 cycles). As shown, for all cycles measured (e.g., after 100,000 cycles, after 200,000 cycles, after 300,000 cycles, and after 400,000 cycles), point 3015 (Example 12) maintains a water contact angle greater than 90°, greater than 95°, greater than 98°, greater than 100°, and greater than 105° (e.g., about 110° or greater). The difference between the initial water contact angle and the worn contact angle (e.g., after 200,000 cycles) is less than 10° (e.g., about 5° or less).

[0449] The above observations can be combined to provide a surface modification layer (e.g., a fingerprint-resistant layer) or a coated article containing it, which can reduce the visibility and / or color shift associated with placing fingerprints thereon. Providing a low total surface energy of the surface modification layer (e.g., a fingerprint-resistant coating), including a low dispersive surface energy and / or a low polar surface energy, can enable oils (e.g., fingerprint oils) to disperse on the fingerprint-resistant surface (e.g., oleophilic), which can reduce the visibility and / or color shift associated with fingerprints. For example, providing an alkylsilane can reduce the surface energy (e.g., total surface energy, dispersive surface energy, polar surface energy) of the surface modification layer (e.g., a fingerprint-resistant coating), which can make the surface modification layer (e.g., a fingerprint-resistant coating) oleophilic. Providing a low hexadecane contact angle (e.g., about 30° or less) and / or a low diiodomethane contact angle (e.g., about 60° or less) can reduce the visibility and / or color shift associated with fingerprints by enabling fingerprint oils to disperse on the surface modification (e.g., a fingerprint-resistant coating) rather than coalescing into distinct droplets. Providing a high water contact angle (e.g., about 100° or greater) can enhance the removal of water-containing materials (e.g., water droplets, sweat droplets) from the surface modification (e.g., a fingerprint-resistant coating). Thus, the surface modification (e.g., a fingerprint-resistant coating) can be hydrophobic and oleophilic.

[0450] Surface modification layers (e.g., anti-fingerprint coatings) according to aspects of the present disclosure can exhibit good abrasion resistance (e.g., a wear water contact angle of about 90° or greater after 2,000 cycles, 3,000 cycles, and / or 3,500 cycles in a steel wool abrasion test, and a denim abrasion water contact angle of about 90° after 200,000 cycles in a denim abrasion test), thereby maintaining, for example, hydrophobic and / or oleophilic properties. The surface modification layer (e.g., anti-fingerprint coating) can exhibit good adhesion to surfaces disposed on, for example, a substrate surface or an optical stack. Providing a thickness of the surface modification layer (e.g., anti-fingerprint coating) of about 100 nm to 600 nm or 1 nm to 75 nm can increase the durability of the surface modification layer (e.g., anti-fingerprint coating).

[0451] In aspects, forming a surface modification layer (e.g., anti-fingerprint coating) can include evaporating a functionalized POSS onto a substrate and impinging the substrate with an ion beam. The properties of the coating can be controlled by the discharge current of the ion beam. For a KRI EH-400 end Hall ion source operating at 100 V in an Angstrom Evovac chamber, providing a discharge current of about 0.25 A or greater can facilitate coating formation, e.g., generating an ion beam with sufficient energy such that the functionalized POSS reacts with other functionalized POSS and / or the first major surface of the substrate at a perceivable rate (e.g., compared to a lower discharge current). Providing a discharge current of about 1 A or less to the ion beam source facilitates deposition of the condensed POSS material. Ion beam discharge can promote condensation of the functionalized POSS, converting at least a portion of the cage structure of the functionalized POSS into a partial Si-O-Si network. Evaporate the functionalized POSS and subject it to an ion beam to produce a partially condensed silica-like network at room temperature or near room temperature. Alternatively, the substrate on which the thermally evaporated functionalized POSS condenses and is impinged by the ion beam can be heated. The substrate temperature during POSS deposition is 250 °C or less, 200 °C or less, 100 °C or less, or preferably 50 °C or less. Alternatively, the partially condensed structure can be heated to 400 °C to 700 °C to produce a dense high-modulus silica-like network, but this will result in poor wear performance. Thus, providing a maximum temperature of about 250 °C or less (e.g., about 220 °C or less, about 200 °C or less, about 180 °C or less, or about 160 °C or less) (e.g., by evaporating the functionalized POSS, impinging with an ion beam, and subsequently functionalizing with silane) to obtain a surface modification layer (e.g., anti-fingerprint coating) with good abrasion resistance.

[0452] A surface modification layer (e.g., an anti-fingerprint coating) can be formed by treating a partially condensed silica-like network with an alkylsilane, which can be carried out in-situ (i.e., in the same chamber as the POSS deposition) or in a second chamber. The partially condensed silica-like network can be exposed to the vapor of an alkylsilane at an elevated temperature (e.g., about 100 °C to about 200 °C). Before treatment with a silane (e.g., an alkylsilane), the partially condensed silica-like network can optionally be subjected to plasma activation of the surface in O2, air, or Ar plasma. The silane evaporation can be carried out at atmospheric pressure or under reduced pressure. Alternatively, the silane can be applied to the partially condensed silica-like network in solution form (e.g., dip coating). The plasma activation can be carried out at atmospheric pressure or under reduced pressure. Reacting the initial coating with a methoxysilane, chlorosilane, trialkoxysilane, trichlorosilane, or a combination thereof (e.g., dichloromethoxysilane, chlorodimethoxysilane) can ensure good bonding of the silane to the initial coating and achieve a low surface energy (e.g., a total surface energy of about 30 mN / m or less, a polar surface energy of about 5 mN / m or less).

[0453] As discussed above in the examples, it has been found that a surface modification layer (e.g., an anti-fingerprint coating) according to the present disclosure having an elastic modulus of about 9 GPa to about 41 GPa has unexpectedly improved abrasion resistance. Providing a partially silica-like network can enable the surface modification layer (e.g., an anti-fingerprint coating) to be hard (e.g., having an elastic modulus of about 9 GPa or greater), while maintaining sufficient flexibility to withstand wear. Additionally, as demonstrated by the results of steel wool abrasion tests, rubber abrasion tests, and cheesecloth abrasion tests, the surface modification layer (e.g., an anti-fingerprint coating) of the present disclosure can withstand wear and maintain a good contact angle. Providing a fluorine-free surface modification layer (e.g., a fluorine-free anti-fingerprint coating) can be produced more inexpensively and / or be more environmentally friendly.

[0454] The substrate can include a glass-based, glass-ceramic, and / or ceramic-based material, which can provide good dimensional stability, good impact resistance, and / or good puncture resistance. The glass-based, glass-ceramic, and / or ceramic-based substrate can include one or more compressive stress zones, which can further provide increased impact resistance and / or increased puncture resistance.

[0455] As used herein, directional terms - such as up, down, right, left, front, back, top, bottom - refer only to the drawings as depicted and are not intended to imply absolute orientation.

[0456] It should be understood that the various disclosed aspects may involve features, elements, or steps described in connection with those aspects. It should also be understood that although features, elements, or steps are described in connection with one aspect, they can be interchanged or combined with alternative aspects in various combinations or arrangements not shown.

[0457] It should also be understood that, as used herein, the terms "the", "a", or "an" mean "at least one", and unless explicitly indicated to the contrary, should not be limited to "only one". For example, unless the context clearly indicates otherwise, a reference to "a component" includes aspects having two or more such components. Similarly, "plurality" is intended to mean "more than one".

[0458] As used herein, the term "about" means that a quantity, size, formulation, parameter, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller as desired, thereby reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those of skill in the art. A range may be expressed herein as from "about" a particular value, and / or to "about" another particular value. When expressing such a range, aspects include from the one particular value and / or to the other particular value. Similarly, when a value is expressed as an approximation by use of the antecedent "about", it should be understood that the particular value forms another aspect. Whether or not the numerical value or endpoint of a range in the specification is recited with "about", the numerical value or endpoint of the range is intended to include two aspects: one modified by "about", and one not modified by "about". It should also be understood that each endpoint of a range is significant relative to the other endpoint and independent of the other endpoint.

[0459] As used herein, the terms "substantially", "essentially" and their variants are intended to indicate that the described feature is equal to or approximately equal to a value or description. For example, a "substantially flat" surface is intended to mean a flat or approximately flat surface. Additionally, as defined above, "substantially similar" is intended to mean that two values are equal or approximately equal. In aspects, "substantially similar" may represent values within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.

[0460] Unless otherwise expressly stated, no method set forth herein is intended to be construed as requiring that its steps be performed in a particular order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or where it is not otherwise specifically stated in the claims or description that the steps are to be limited to a particular order, no particular order is intended to be inferred.

[0461] Although various features, elements, or steps of particular aspects may be disclosed using the transitional phrase "comprising", it should be understood that alternative aspects are implied, including those that may be described using the transitional phrases "consisting of" or "consisting essentially of". Thus, for example, an implied alternative aspect of an apparatus including A + B + C includes the aspect where the apparatus consists of A + B + C and the aspect where the apparatus consists essentially of A + B + C. As used herein, unless otherwise indicated, the terms "comprising" and "including" and their variants should be construed as synonymous and open-ended.

[0462] The above aspects and the features of those aspects are illustrative, and may be provided alone or in any combination with any one or more features of other aspects provided herein without departing from the scope of the present disclosure. That is, it should be understood that the various disclosed embodiments may relate to the specific features or elements described in connection with the specific embodiments. It should also be understood that although a specific feature or element is described in connection with one specific embodiment, it may be interchanged or combined with alternative embodiments in various combinations or arrangements not shown.

[0463] It will be apparent to those skilled in the art that various modifications and variations can be made to the present disclosure without departing from the spirit and scope of the present disclosure. Accordingly, it is intended that the present disclosure cover the modifications and variations of the aspects herein provided that they come within the scope of the appended claims and their equivalents.

Claims

1. A coated article, the coated article comprising: A substrate, the substrate comprising a first major surface; An anti-fingerprint coating disposed on the first major surface, the anti-fingerprint coating comprising the outer surface of the coated article, the anti-fingerprint coating having a thickness of from about 10 nanometers to about 600 nanometers, the anti-fingerprint coating comprising a partial silica-like network having a ratio of Si-O-Si bonds to Si atoms in the anti-fingerprint coating of from about 2 to about 3, the anti-fingerprint coating being fluorine-free, and the anti-fingerprint coating further comprising an alkylsilane at the outer surface and bonded to Si-O groups in the anti-fingerprint coating.

2. The coated article according to claim 1, wherein the anti-fingerprint coating has a refractive index in the range of from about 1.38 to about 1.

55.

3. The coated article according to any one of claims 1 to 2, wherein the anti-fingerprint coating has a modulus of elasticity in the range of from about 9 gigapascals to about 70 gigapascals.

4. The coated article according to any one of claims 1 to 3, wherein the alkylsilane comprises a C4-C 34 alkyl group.

5. The coated article according to any one of claims 1 to 4, wherein the alkylsilane comprises isooctylsilane, dodecylsilane, octadecylsilane, or a combination thereof.

6. The coated article according to any one of claims 1 to 5, wherein the anti-fingerprint coating further comprises nitrogen atoms bonded to silicon atoms.

7. The coated article according to any one of claims 1 to 6, wherein the anti-fingerprint coating comprises silicon hydride or silanol.

8. The coated article according to any one of claims 1 to 7, wherein the anti-fingerprint coating exhibits a diiodomethane contact angle of about 60° or greater.

9. The coated article according to any one of claims 1 to 8, wherein the anti-fingerprint coating exhibits a water contact angle of about 100° or greater.

10. The coated article according to any one of claims 1 to 9, wherein the anti-fingerprint coating wets hexadecane or exhibits a hexadecane contact angle of about 30° or less.

11. The coated article according to any one of claims 1 to 10, wherein the anti-fingerprint coating has a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

12. The coated article according to any one of claims 1 to 11, wherein the anti-fingerprint coating has a total surface energy of about 30 millinewtons per meter (mN / m) or less.

13. The coated article according to any one of claims 1 to 12, wherein the anti-fingerprint coating exhibits a worn water contact angle of about 90° after 2,000 cycles of wear in a steel wool abrasion test.

14. The coated article according to any one of claims 1 to 13, wherein the anti-fingerprint coating exhibits a coarse cloth worn water contact angle of about 90° or greater after 200,000 cycles of abrasion in a coarse cloth abrasion test.

15. The coated article according to any one of claims 1 to 14, wherein the anti-fingerprint coating exhibits a rubber worn water contact angle of about 100° or greater after 5,000 cycles of abrasion in a rubber abrasion test.

16. The coated article according to any one of claims 1 to 15, wherein the coated article further comprises an antireflection coating positioned between the fingerprint-resistant coating and the substrate.

17. The coated article according to any one of claims 1 to 15, wherein the coated article further comprises a gradient coating, the gradient coating comprising a refractive index gradient, the gradient coating being positioned between the fingerprint-resistant coating and the substrate.

18. The coated article according to any one of claims 1 to 15, wherein the coated article further comprises an optical stack positioned between the fingerprint-resistant coating and the substrate, wherein the optical stack comprises an antireflection coating, a bandpass filter coating, an edge neutral mirror, a beam splitter coating, a multilayer high reflection coating, or an edge filter coating.

19. The coated article according to claim 18, wherein the optical stack has a thickness of from about 10 nanometers to about 10 micrometers.

20. The coated article according to claim 19, wherein the thickness of the optical stack is from about 50 nanometers to about 5 micrometers.

21. The coated article according to claim 19, wherein the thickness of the optical stack is from about 50 nanometers to about 500 nanometers.

22. The coated article according to any one of claims 18 to 21, wherein the optical stack comprises a scratch-resistant layer, and wherein the scratch-resistant layer has a thickness of from 0.05 micrometers to 3 micrometers.

23. The coated article according to any one of claims 18 to 22, wherein the coated article comprising the optical stack and the fingerprint-resistant coating exhibits a hardness of 8 gigapascals or greater as measured by a Berkovich indenter hardness test.

24. The coated article according to claim 23, wherein the coated article comprising the optical stack and the fingerprint-resistant coating exhibits a hardness of 12 gigapascals or greater as measured by the Berkovich indenter hardness test.

25. The coated article according to any one of claims 18 to 24, wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O5.

26. The coated article according to any one of claims 18 to 25, wherein the optical stack comprises two or more layers having different refractive indices, the two or more layers comprising at least a first low refractive index (low RI) layer and a second high refractive index (high RI) layer, the absolute value of the difference between the first low RI layer and the second high RI layer being 0.2 or greater, and further wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O.

27. The coated article according to any one of claims 1 to 26, wherein the substrate is a textured substrate.

28. The coated article according to claim 27, wherein the coated article further comprises an antireflection coating or a gradient coating positioned between the fingerprint-resistant coating and the textured substrate.

29. The coated article according to any one of claims 1 to 28, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material.

30. The coated article according to claim 29, wherein the glass-based material, the glass-ceramic material, or the ceramic-based material is transparent, color-transparent, opaque, color-opaque, translucent, or color-translucent.

31. A coated article, the coated article comprising: a substrate, the substrate comprising a first major surface; an alkylsilane disposed on the first major surface, the alkylsilane comprising the outer surface of the coated article, the alkylsilane layer having a thickness of from about 1 nanometer to about 75 nanometers, and the alkylsilane being fluorine-free.

32. The coated article according to claim 31, wherein the alkylsilane comprises a C4-C 34 alkyl group.

33. The coated article according to claim 31, wherein the alkylsilane comprises octadecylalkyl.

34. The coated article according to any one of claims 31 to 33, wherein the outer surface exhibits a water contact angle of 100° or greater.

35. The coated article according to claim 34, wherein the outer surface exhibits the water contact angle of from 102° to 110°.

36. The coated article according to any one of claims 31 to 35, wherein the outer surface exhibits a diiodomethane contact angle of about 60° or greater.

37. The coated article according to any one of claims 31 to 36, wherein the outer surface exhibits a coefficient of friction of 0.25 or less.

38. The coated article according to any one of claims 31 to 37, wherein the alkylsilane comprises a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

39. The coated article according to any one of claims 31 to 38, wherein the alkylsilane comprises a total surface energy of about 30 millinewtons per meter (mN / m) or less.

40. The coated article according to any one of claims 31 to 39, wherein the alkylsilane comprises a scrim abrasion water contact angle of about 90° or greater after undergoing 200,000 cycles in a scrim abrasion test.

41. The coated article according to any one of claims 31 to 40, wherein the alkylsilane exhibits a rubber abrasion water contact angle of about 100° or greater after undergoing 5,000 cycles in a rubber abrasion test.

42. The coated article according to any one of claims 31 to 41, the coated article further comprising an optical stack positioned between the alkylsilane and the substrate, wherein the optical stack comprises an anti-reflection coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multilayer high-reflection coating, or an edge filter coating.

43. The coated article according to claim 42, wherein the optical stack has a thickness of from about 10 nanometers to about 10 micrometers.

44. The coated article according to claim 43, wherein the thickness of the optical stack is from about 50 nanometers to about 5 micrometers.

45. The coated article according to claim 43, wherein the thickness of the optical stack is from about 50 nanometers to about 500 nanometers.

46. The coated article according to any one of claims 42 to 45, wherein the optical stack includes a scratch-resistant layer, and wherein the scratch-resistant layer has a thickness of from 0.05 micrometers to 3 micrometers.

47. The coated article according to any one of claims 42 to 46, wherein the coated article comprising the optical stack and the alkylsilane exhibits a hardness of 8 gigapascals or greater as measured by a Berkovich indentation hardness test.

48. The coated article according to claim 47, wherein the coated article comprising the optical stack and the alkylsilane exhibits the hardness of 12 gigapascals or greater as measured by the Berkovich indentation hardness test.

49. The coated article according to any one of claims 42 to 48, wherein the optical stack includes one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O5.

50. The coated article according to any one of claims 42 to 49, wherein the optical stack includes two or more layers having different refractive indices, the two or more layers comprising at least a first low refractive index (low RI) layer and a second high refractive index (high RI) layer, the absolute value of the difference between the first low RI layer and the second high RI layer being 0.2 or greater, and further wherein the optical stack includes one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O.

51. The coated article according to any one of claims 31 to 41, wherein the substrate is a textured substrate.

52. The coated article according to claim 51, wherein the coated article further includes an antireflection coating or a gradient coating positioned between the fingerprint-resistant coating and the textured substrate.

53. The coated article according to any one of claims 31 to 52, wherein the substrate includes a glass-based material, a glass-ceramic material, or a ceramic-based material.

54. The coated article according to claim 53, wherein the glass-based material, the glass-ceramic material, or the ceramic-based material is transparent, color-transparent, opaque, color-opaque, translucent, or color-translucent.

55. A method of forming a coated article, the method comprising: evaporating a functionalized polyhedral oligomeric silsesquioxane onto a first major surface of a substrate; An ion beam is impinged on the first major surface of the substrate, and the impingement occurs in a chamber having a chamber pressure in the range of from about 10 -4 Pascals to about 1 Pascal, and the impingement converts from about 50% to about 90% of the silicon atoms from the cage structure in the functionalized polyhedral oligomeric silsesquioxane to a Si-O-Si bond network; and then reacting a material at the first major surface of the substrate with an alkylsilane to form a fingerprint-resistant coating, the alkylsilane including 4 or more carbons.

56. The method according to claim 55, wherein the functionalized polyhedral oligomeric silsesquioxane is at least partially functionalized with at least one olefin including 2 to 8 carbons.

57. The method according to claim 55, wherein the functionalized polyhedral oligomeric silsesquioxane is fully functionalized with an olefin including 2 to 8 carbons.

58. The method according to any one of claims 56 to 57, wherein the functionalized polyhedral oligomeric silsesquioxane is at least partially functionalized with an alkyl or aromatic group.

59. The method according to any one of claims 55 to 58, wherein the reaction comprises heating the alkylsilane at a temperature of from about 80 °C to about 250 °C for a period of from about 10 minutes to about 8 hours.

60. The method according to any one of claims 55 to 58, wherein the alkylsilane comprises isooctylalkyl, dodecylalkyl, octadecylalkyl, or a combination thereof.

61. The method according to any one of claims 55 to 60, wherein the silane is trimethoxysilane, triethoxysilane, trichlorosilane, dichloromethoxysilane, or chlorodimethoxysilane.

62. The method according to any one of claims 55 to 61, wherein the evaporation of the functionalized polyhedral oligomeric silsesquioxane and the impingement occur simultaneously.

63. The method according to any one of claims 55 to 62, wherein the evaporation of the functionalized polyhedral oligomeric silsesquioxane comprises an evaporation rate of from about 0.01 nanometers per second (nm / s) to about 0.2 nm / s.

64. The method according to any one of claims 55 to 63, wherein the ion beam comprises argon ions or oxygen ions.

65. The method according to any one of claims 55 to 64, wherein the ratio of Si-O-Si bonds to Si atoms is from about 2 to about 3.

66. The method according to any one of claims 55 to 65, wherein the fingerprint-resistant coating comprises a thickness of from about 10 nanometers to about 600 nanometers.

67. The method according to any one of claims 55 to 66, wherein the fingerprint-resistant coating comprises a refractive index in the range of from about 1.38 to about 1.

55.

68. The method according to any one of claims 55 to 67, wherein the fingerprint-resistant coating comprises a modulus of elasticity in the range of from about 9 gigapascals to about 70 gigapascals.

69. The method according to any one of claims 55 to 68, wherein the fingerprint-resistant coating comprises a total surface energy of about 30 millinewtons per meter (mN / m) or less.

70. The method according to any one of claims 55 to 69, wherein the fingerprint-resistant coating comprises a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

71. The method according to any one of claims 55 to 70, wherein the fingerprint-resistant coating comprises a water contact angle of about 100° or greater.

72. The method according to any one of claims 55 to 71, wherein the fingerprint-resistant coating comprises a worn water contact angle of about 90° after 2,000 cycles in a steel wool abrasion test.

73. The method according to any one of claims 55 to 72, wherein the fingerprint-resistant coating comprises a cotton cloth abrasion water contact angle of about 90° or greater after undergoing 200,000 cycles in a cotton cloth abrasion test.

74. The coated article according to any one of claims 55 to 73, wherein the fingerprint-resistant coating exhibits a rubber wear water contact angle of about 100° or greater after undergoing 5,000 cycles in a rubber wear test.

75. The method according to any one of claims 55 to 74, wherein the fingerprint-resistant coating has a surface roughness Ra of about 1 nm or less.

76. The method according to any one of claims 55 to 75, wherein the fingerprint-resistant coating is fluorine-free.

77. The method according to any one of claims 55 to 76, the method further comprising an optical stack positioned between the fingerprint-resistant coating and the substrate, wherein the optical stack comprises an anti-reflection coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflection coating, or an edge filter coating.

78. The method according to claim 77, wherein the optical stack thickness is from about 10 nanometers to about 10 micrometers.

79. The method according to claim 77, wherein the optical stack comprises a scratch-resistant layer, and the scratch-resistant layer has a thickness of 0.05 micrometers to 3 micrometers.

80. The method according to any one of claims 76 to 79, wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, and / or silicon oxynitride-containing.

81. The method according to any one of claims 76 to 80, wherein the optical stack has two or more layers of different refractive indices, a first low RI layer and a second high RI layer, wherein the absolute value of the difference between the first low RI layer and the second high RI layer is 0.2 or greater, and further wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, and / or silicon oxynitride-containing.

82. The method according to any one of claims 55 to 76, wherein the substrate is a textured substrate.

83. The method according to claim 82, wherein the coated article further comprises an anti-reflection coating or a gradient coating positioned between the fingerprint-resistant coating and the textured substrate.

84. The method according to any one of claims 55 to 83, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material.

85. A method of forming a coated article, the method comprising: disposing a solution above a first major surface of a substrate, the solution comprising a polysilazane or a polyhedral oligomeric silsesquioxane; heating the solution at a temperature of about 150 °C to about 400 °C for a period of about 5 minutes to about 120 minutes; and reacting the material at the first major surface of the substrate with an alkylsilane having 4 or more carbons to form a fingerprint-resistant coating.

86. The method according to claim 85, wherein the concentration of the polysilazane or the polyhedral oligomeric silsesquioxane is in the range of about 0.2 wt% to about 25 wt%.

87. The method according to any one of claims 85 to 86, wherein the temperature is in the range of about 150 °C to about 250 °C.

88. The method according to any one of claims 85 to 87, wherein the reaction comprises heating the alkylsilane at a temperature of from about 80 °C to about 250 °C for a period of from about 10 minutes to about 8 hours.

89. The method according to any one of claims 85 to 88, wherein the alkylsilane comprises isooctyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, or a combination thereof.

90. The method according to any one of claims 85 to 89, wherein the silane is trimethoxysilane, triethoxysilane, trichlorosilane, dichloromethoxysilane, or chlorodimethoxysilane.

91. The method according to any one of claims 85 to 88, wherein the alkylsilane comprises isooctylalkyl, dodecylalkyl, octadecylalkyl, or a combination thereof.

92. The method according to any one of claims 85 to 91, wherein the fingerprint-resistant coating comprises a diiodomethane contact angle of about 60° or greater.

93. The method according to any one of claims 85 to 92, wherein the fingerprint-resistant coating wets hexadecane or comprises a hexadecane contact angle of about 30° or less.

94. The method according to any one of claims 85 to 93, wherein the heating forms the fingerprint-resistant coating into a partially silica-like network and hydrogenated silicon or silanol.

95. The method according to any one of claims 85 to 94, wherein the heating to form the fingerprint-resistant coating comprises a ratio of Si-O-Si bonds to Si atoms of from about 2 to about 3.

96. The method according to any one of claims 85 to 95, wherein the fingerprint-resistant coating comprises a thickness of from about 10 nanometers to about 600 nanometers.

97. The method according to any one of claims 85 to 96, wherein the fingerprint-resistant coating comprises a refractive index of from about 1.38 to about 1.

55.

98. The method according to any one of claims 85 to 97, wherein the fingerprint-resistant coating comprises a modulus of elasticity in the range of from about 9 gigapascals to about 70 gigapascals.

99. The method according to any one of claims 85 to 98, wherein the fingerprint-resistant coating comprises a total surface energy of about 30 millinewtons per meter (mN / m) or less.

100. The method according to any one of claims 85 to 99, wherein the fingerprint-resistant coating comprises a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

101. The method according to any one of claims 85 to 100, wherein the fingerprint-resistant coating comprises a water contact angle of about 100° or greater.

102. The method according to any one of claims 85 to 101, wherein the fingerprint-resistant coating comprises a worn water contact angle of about 90° after 2,000 cycles of wear in a steel wool abrasion test.

103. The method according to any one of claims 85 to 102, wherein the fingerprint-resistant coating comprises a coarse cloth wear water contact angle of about 90° or greater after undergoing 200,000 cycles of wear in a coarse cloth abrasion test.

104. The coated article according to any one of claims 85 to 103, wherein the fingerprint-resistant coating exhibits a rubber wear water contact angle of about 100° or greater after undergoing 5,000 cycles in a rubber wear test.

105. The method according to any one of claims 85 to 104, wherein the fingerprint-resistant coating has a surface roughness Ra of about 1 nm or less.

106. The method according to any one of claims 85 to 105, wherein the fingerprint-resistant coating is fluorine-free.

107. The method according to any one of claims 85 to 106, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material.

108. The method according to any one of claims 85 to 107, wherein the fingerprint-resistant coating further comprises nitrogen atoms bonded to silicon atoms.

109. The method according to any one of claims 85 to 108, the method further comprising an optical stack positioned between the fingerprint-resistant coating and the substrate, wherein the optical stack comprises an anti-reflection coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high reflection coating, or an edge filter coating.

110. The method according to claim 109, wherein the optical stack thickness is from about 10 nanometers to about 10 micrometers.

111. The method according to claim 110, wherein the optical stack comprises a scratch-resistant layer, and the scratch-resistant layer has a thickness of 0.05 micrometers to 3 micrometers.

112. The method according to any one of claims 109 to 111, wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, and / or silicon oxynitride-containing.

113. The method according to any one of claims 109 to 112, wherein the optical stack has two or more layers of different refractive indices, a first low RI layer and a second high RI layer, wherein the absolute value of the difference between the first low RI layer and the second high RI layer is 0.2 or greater, and further wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, and / or silicon oxynitride-containing.

114. The method according to any one of claims 85 to 108, wherein the substrate is a textured substrate.

115. The method according to claim 114, wherein the coated article further comprises an anti-reflection coating or a gradient coating positioned between the fingerprint-resistant coating and the textured substrate.

116. A method of forming a coated article, the method comprising: reacting a material at a first major surface of a substrate with an alkylsilane to form a surface modification layer, the alkylsilane comprising an alkyl having 4 or more carbons, wherein the surface modification layer exhibits a water contact angle of 100° or greater.

117. The method according to claim 116, wherein the alkyl comprises isooctyl alkyl, dodecyl alkyl, octadecyl alkyl, or a combination thereof.

118. The method according to claim 116, wherein the alkyl comprises octadecyl alkyl.

119. The method according to any one of claims 116 to 118, wherein the alkylsilane comprises isooctyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, or a combination thereof.

120. The method according to any one of claims 116 to 119, wherein the silane is trimethoxysilane, triethoxysilane, trichlorosilane, dichloromethoxysilane, or chlorodimethoxysilane.

121. The method according to any one of claims 116 to 120, wherein the outer surface exhibits a water contact angle of 100° or greater.

122. The method according to claim 121, wherein the outer surface exhibits the water contact angle of 102° to 110°.

123. The method according to any one of claims 116 to 121, wherein the outer surface exhibits a diiodomethane contact angle of about 60° or greater.

124. The method according to any one of claims 116 to 122, wherein the outer surface exhibits a coefficient of friction of 0.25 or less.

125. The method according to any one of claims 116 to 124, wherein the surface modification layer comprises a polar surface energy of about 3 millinewtons per meter (mN / m) or less.

126. The method according to any one of claims 116 to 125, wherein the surface modification layer comprises a total surface energy of about 30 millinewtons per meter (mN / m) or less.

127. The method according to any one of claims 116 to 126, wherein the thickness of the surface modification layer is from 1 nanometer to 75 nanometers.

128. The method according to any one of claims 126 to 127, wherein the surface modification layer comprises a denim abrasion water contact angle of about 90° or greater after undergoing 200,000 cycles in a denim abrasion test.

129. The method according to any one of claims 116 to 128, wherein the surface modification layer exhibits a rubber abrasion water contact angle of about 100° or greater after undergoing 5,000 cycles in a rubber abrasion test.

130. The method according to any one of claims 116 to 129, the method further comprising an optical stack positioned between the surface modification layer and the substrate, wherein the optical stack comprises an antireflection coating, a bandpass filter coating, an edge neutral mirror, a beam splitter coating, a multilayer high reflection coating, or an edge filter coating.

131. The method according to claim 130, wherein the optical stack has a thickness of from about 10 nanometers to about 10 micrometers.

132. The method according to claim 131, wherein the thickness of the optical stack is from about 50 nanometers to about 5 micrometers.

133. The method according to claim 131, wherein the thickness of the optical stack is from about 50 nanometers to about 500 nanometers.

134. The method according to any one of claims 130 to 133, wherein the optical stack comprises a scratch-resistant layer, and wherein the scratch-resistant layer has a thickness of 0.05 micrometers to 3 micrometers.

135. The method according to any one of claims 130 to 134, wherein the coated article comprising the optical stack and the surface modification layer exhibits a hardness of 8 gigapascals or greater as measured by a Vickers indenter hardness test.

136. The method according to claim 135, wherein the coated article comprising the optical stack and the surface modification layer exhibits the hardness of 12 gigapascals or greater as measured by the Vickers indenter hardness test.

137. The method according to any one of claims 130 to 136, wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O5.

138. The method according to any one of claims 123 to 130, wherein the optical stack comprises two or more layers having different refractive indices, the two or more layers comprising at least a first low refractive index (low RI) layer and a second high refractive index (high RI) layer, the absolute value of the difference between the first low RI layer and the second high RI layer being 0.2 or greater, and further wherein the optical stack comprises one or more of silicon oxide-containing, silicon nitride-containing, silicon oxynitride-containing, and Nb2O.

139. The method according to any one of claims 116 to 122, wherein the substrate is a textured substrate.

140. The method according to claim 139, wherein the coated article further comprises an antireflection coating or a gradient coating positioned between the fingerprint-resistant coating and the textured substrate.

141. The method according to any one of claims 116 to 140, wherein the substrate comprises a glass-based material, a glass-ceramic material, or a ceramic-based material.

142. The method according to claim 141, wherein the glass-based material, the glass-ceramic material, or the ceramic-based material is transparent, color-transparent, opaque, color-opaque, translucent, or color-translucent.

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