# Patent

## Title
Scratch-resistant articles with retained optical properties

## Abstract

One or more aspects of the disclosure pertain to an article including an optical film structure disposed on a substrate, which may include a strengthened or non-strengthened substrate that may be amorphous or crystalline, such that the article exhibits scratch resistance and retains the same or improved optical properties as the substrate, without the optical film structure disposed thereon. In one or more embodiments, the article exhibits an average transmittance of 85% or more, over the visible spectrum (e.g., 380 nm-780 nm). Embodiments of the optical film structure include aluminum-containing oxides, aluminum-containing oxy-nitrides, aluminum-containing nitrides (e.g., AlN) and combinations thereof. The optical film structures disclosed herein also include a transparent dielectric including oxides such as silicon oxide, germanium oxide, aluminum oxide and a combination thereof. Methods of forming such articles are also provided.

## Background
This application claims the benefit of priority under 35 U.S.C. §119 of U.S. Provisional Application Ser. No. 62/034,480 filed on Aug. 7, 2014, and of U.S. Provisional Application Ser. No. 61/877,568 filed on Sep. 13, 2013, the contents of which are relied upon and incorporated herein by reference in their entirety. This application is a continuation-in-part application and claims the benefit of priority under 35 U.S.C. §120 of U.S. application Ser. No. 14/267,516 filed on May 1, 2014, which in turns claims the benefit of priority under 35 U.S.C. §119 of U.S. Provisional Application Ser. No. 61/877,568 filed on Sep. 13, 2013, and of U.S. Provisional Application Ser. No. 61/820,407 filed on May 7, 2013, the contents of which are relied upon and incorporated herein by reference in their entirety.


BACKGROUND
This disclosure relates to articles for display cover glass applications having scratch-resistance and retained optical properties, and more particularly to articles that include an optical film structure comprising scratch resistance, wherein the article exhibits 85% or more average light transmittance over the visible spectrum. As defined herein, the phrase “visible spectrum” includes wavelengths in the range from about 380 nm to about 780 nm.
Cover articles are often used to protect critical devices within electronic products, to provide a user interface for input and/or display, and/or many other functions. Such products include mobile devices, such as smart phones, mp 3 players and computer tablets. Cover articles also include architectural articles, transportation articles (e.g., articles used in automotive applications, trains, aircraft, sea craft, etc.), appliance articles, or any article that requires some transparency, scratch-resistance, abrasion resistance or a combination thereof. These applications often demand scratch-resistance and strong optical performance characteristics, in terms of maximum light transmittance and minimum reflectance. Furthermore, some cover applications require that the color exhibited or perceived, in reflection and/or transmission, does not change appreciably as the viewing angle is changed. In display applications, this is because, if the color in reflection or transmission changes with viewing angle to an appreciable degree, the user of the product will perceive a change in color or brightness of the display, which can diminish the perceived quality of the display.
Known cover articles can often exhibit a variety of different types of scratches after use in harsh operating conditions. In some instances, a significant portion of those scratches are microductile scratches, which typically include a single groove in a material having extended length and with depths in the range from about 100 nm to about 500 nm. Microductile scratches may be accompanied by other types of visible damage, such as sub-surface cracking, frictive cracking, chipping and/or wear. Evidence suggests that a majority of such scratches and other visible damage is caused by sharp contact that occurs in a single contact event. Once a significant scratch appears on a cover article, the appearance of the product is degraded since the scratch causes an increase in light scattering, which may cause significant reduction in brightness, clarity and contrast of images on the display. Significant scratches can also affect the accuracy and reliability of touch sensitive displays. A portion of such scratches and other visible damage as described above may also be caused by multiple contact events (including reciprocating abrasion or wear). Thus, these scratches, and even less significant scratches, are unsightly and can affect product performance.
Single event scratch damage can be contrasted with abrasion damage. Abrasion damage is typically caused by multiple contact events, such as reciprocating sliding contact from hard counter face objects (e.g., sand, gravel and sandpaper). Abrasion damage can generate heat, which can degrade chemical bonds in the film materials and cause flaking and other types of damage to the article. In addition, since abrasion damage is often experienced over a longer term than the single events that cause scratches, the film material experiencing abrasion damage can also oxidize, which further degrades the durability of the film and thus the article. The single events that cause scratches generally do not involve the same conditions as the events that cause abrasion damage and therefore, the solutions often utilized to prevent abrasion damage may not also prevent scratches in articles. Moreover, known scratch and abrasion damage solutions often compromise the optical properties.
Accordingly, there is a need for new articles, and methods for their manufacture, which exhibit scratch resistance over a wide range of different types of scratches, abrasion resistance and good optical performance.
SUMMARY
A first aspect of this disclosure pertains to an article including a substrate having opposing major surfaces and opposing minor surfaces and an optical film structure disposed on at least one of the opposing major surfaces of the substrate forming a front face of the article. The articles according to one or more embodiments exhibit an average light transmittance of 85% or more over the visible spectrum (e.g., 380 nm 780 nm), as measured at the front face of the article. In a specific embodiment, the article exhibits a total reflectance (which includes specular and diffuse reflectance) that is the same or less than the total reflectance of the substrate without the optical film structure disposed thereon, as measured at the front face of the article. The article of one or more embodiments exhibits a substantially flat transmittance spectra (or reflectance spectra) or a transmittance (or reflectance) that is substantially constant over the visible spectrum, as measured at the front face of the article. The article may also exhibit a color in the (L*, a*, b*) colorimetry system, such that the transmittance color or reflectance coordinates distance from a reference point is less than about 2. Stated another way, the article may exhibit a transmittance color (or transmittance color coordinates) and/or a reflectance color (or reflectance color coordinates) measured at the front face of the article having a color shift of less than about 2 from a reference point, as defined herein. In one or more embodiments, the reference point may be the origin (0, 0) in the L*a*b* color space (or the color coordinates a*=0, b*=0) or the transmittance or reflectance color coordinates of the substrate. In one or more embodiments, the substrate may include an amorphous substrate, crystalline substrate or a combination thereof. In embodiments in which an amorphous substrate is utilized, the amorphous substrate can include a glass substrate that may be strengthened or non-strengthened. Examples of amorphous substrates include soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass and/or alkali aluminoborosilicate glass. Examples of crystalline substrates include strengthened glass ceramic substrates, a non-strengthened glass ceramic substrates, single crystalline substrates (e.g., single crystal substrates such as sapphire) or a combination thereof.
In accordance with one or more embodiments, the optical film structure imparts scratch resistance to the article. For example, the optical film structure may include at least one layer that has a maximum hardness of about 12 GPa or greater, as measured by a Berkovich Indenter Hardness Test described herein, along an indentation depth of about 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, or from about 100 nm to about 600 nm). In one or more embodiments, the article exhibits a hardness of about 12 GPa or greater (e.g., 16 GPa or greater), as measured by the Berkovich Indenter Hardness Test, along an indentation depth of about 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, or from about 100 nm to about 600 nm). In other embodiments, the optical film structure may exhibit a coefficient of friction of less than 0.3, when measured against a silicon carbide sphere counter surface.
The optical film structure may include a silicon-containing oxide, a silicon-containing nitride, an aluminum-containing nitride (e.g., AlN and AlxSiyN), an aluminum-containing oxy-nitride (e.g., AlOxNy and SiuAlvOxNy), an aluminum-containing oxide or combinations thereof. In some embodiments, the optical film structure includes transparent dielectric materials such as SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof. The optical film structure of one or more embodiments may have a layered structure or, more specifically, at least two layers (e.g., a first layer and a second layer) such that a first layer is disposed between the substrate and the second layer.
In one or more embodiments, the first layer of the optical film structure may include a silicon-containing oxide, a silicon-containing nitride, an aluminum-containing oxide, an aluminum-containing oxy-nitride (e.g., AlOxNy and SiuAlvONy), an aluminum-containing nitride (e.g., AlN and AlxSiyN) or combinations thereof. Specifically, the first layer may include Al2O3, AlN, AlOxNy or combinations thereof. In another option, the first layer may also include a transparent dielectric material such as SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof.
In embodiments in which the optical film structure includes AlN or AlOxNy, the AlN or AlOxNy may include an amorphous structure, a microcrystalline structure, or a combination thereof. Alternatively or additionally, the AlN or AlOxNy may include a polycrystalline structure.
In one or more embodiments, the optical film structure may incorporate one or more modifiers. Alternatively, the optical film structure may be free of modifiers. In one or more specific embodiments, at least one modifier may be incorporated into optical film structures that utilize AlN. In such embodiments, the AlN may be doped or alloyed with at least one modifier. Exemplary modifiers include BN, Ag, Cr, Mg, C and Ca. In one variant, the optical film structure exhibits conductive properties. In such embodiments, the optical film structure may incorporate a modifier including Mg and/or Ca therein.
The first layer of the optical film structure may include a first sub-layer and a second sub-layer. In such embodiments, the first sub-layer may be disposed between the second sub-layer and the substrate. In one variant, the first sub-layer may include Al2O3 and a second sub-layer may include AlN.
In one or more embodiments, the first sub-layer may include AlOxNy and the second sub-layer may include AlN. In another variant, the first layer includes three sub-layers (e.g., a first sub-layer, a second sub-layer and a third sub-layer). In such embodiments, the first sub-layer and third sub-layer may include AlN and the second sub-layer may include a transparent dielectric material such as SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof.
In one or more embodiments, the first layer of the optical film structure may include a compositional gradient. The composition gradient may include an oxygen content gradient, a nitrogen content gradient, a silicon content gradient and/or an aluminum content gradient. In one or more embodiments, the composition gradient may include a silicon/aluminum composition gradient, where the atomic % of silicon and aluminum change along the thickness of the first layer independently of one another or in relation to one another. In other embodiments, the compositional gradient may include an oxygen/nitrogen composition gradient, where the atomic % of oxygen and nitrogen change along the thickness of the first layer independently of one another or in relation to one another.
In a specific embodiment, the oxygen content and/or the silicon content of the first layer may decrease along the thickness of the first layer in a direction moving away from the substrate. In another embodiment, the aluminum and/or nitrogen content gradient may increase along the thickness of the first layer in a direction moving away from the substrate. In one or more examples, the first layer may include an oxygen content gradient and include AlN. In such embodiments, the first layer and may be free of oxygen adjacent to the second layer. In specific examples, the compositional gradient in the first layer is constant along the thickness of the first layer. In other specific examples, the compositional gradient in the first layer is not constant along the thickness of the first layer. In other more specific examples, the compositional gradient in the first layer occurs step-wise along the thickness of the first layer and the step-wise composition gradient may be constant or inconstant.
In accordance with one or more embodiments, the first layer includes a refractive index gradient. The refractive index of the first layer may increase or decrease or otherwise change along the thickness of the first layer to improve the optical properties described herein of the optical film structure and/or the article.
In one or more embodiments, second layer of the optical film structure includes a transparent dielectric material such as SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof.
Optionally, the optical film structure may include additional films or layers disposed on the second layer of the optical film structure. In one variant, the article may include a wrapped film. The wrapped film may be disposed on one or more of the opposing minor surfaces and/or one or more of the opposing major surfaces of the substrate. In embodiments in which the wrapped film is disposed on one or more of the opposing major surfaces of the substrate, the wrapped film may be disposed between the substrate and the optical film structure. The wrapped film may also form a portion of the optical film structure (e.g., the first sub-layer of the optical film structure).
The articles may optionally include a passivation film or an interlayer. In one or more embodiments, the interlayer may be disposed between the optical film structure and the substrate. In one or more alternative embodiments, the interlayer may be part of the optical film structure. For example, one or more embodiments, the interlayer may form part of the first layer or the first sub-layer of the optical film structure.
In one or more embodiments, the optical film structure may have a thickness of at least about 1 μm or at least about 2 μm. Where the optical film structure includes a layered structure, the first layer may have a thickness that is greater than the thickness of the second layer of the optical film structure.
The articles disclosed herein may include articles with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, and the like), architectural articles, transportation articles (e.g., automotive, trains, aircraft, sea craft, etc.), appliance articles, or any article that requires some transparency, scratch-resistance, abrasion resistance or a combination thereof.
A second aspect of this disclosure pertains to a method of forming an article, as described herein. In one or more embodiments, the method includes providing a substrate, as otherwise provided herein, and disposing a low-stress optical film structure on the substrate at a pressure in the range from about 0.5 mTorr to about 10 mTorr. The optical film structure and/or the article may exhibit a hardness of about 12 GPa or greater, as measured by the Berkovich Indenter Hardness Test along an indentation depth of about 50 nm or greater or about 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, or from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm). The optical film structure may have a layered structure as described herein.
In one or more embodiments, the method includes using a vacuum deposition technique to dispose the optical film structure on the substrate. The vacuum deposition technique may include chemical vapor deposition, physical vapor deposition, thermal evaporation and/or atomic layer deposition. In one or more embodiments, the method further includes increasing the conductivity of the optical film structure, by, for example, doping the optical film structure with a modifier. Exemplary modifiers that may be utilized to increase the conductivity of the optical film structure include Mg, Ca and a combination thereof. One or more embodiments of the method may include increasing the lubricity of the optical film structure. In a specific embodiment, increasing the lubricity of the optical film structure includes incorporating BN into the optical film structure. In one or more embodiments, the method may include reducing the stress of the optical film structure. In a specific embodiment, the method may include reducing the stress of the optical film structure by incorporating one or more of BN, Ag, Cr or a combination thereof into the optical film structure.
In accordance with one or more embodiments, the method may include introducing oxygen and/or nitrogen into the optical film structure. In one example, the method may optionally include creating an oxygen content gradient and/or a nitrogen content gradient in the optical film structure. In one variant, the oxygen content gradient includes an oxygen content that decreases along the thickness of the optical film structure in a direction moving away from the substrate. In one variant, the nitrogen content gradient includes a nitrogen content that increases along the thickness of the optical film structure in a direction moving away from the substrate. The method may also include creating a silicon content gradient and/or an aluminum content gradient. In one or more embodiments, the method may include depositing one or more source materials (e.g., silicon and/or aluminum) on the substrate to form the optical film structure and varying one or more process conditions such as the power supplied to the one or more source materials to create the silicon content gradient and/or the aluminum content gradient in the optical film structure. In one or more embodiments, the method includes disposing an interlayer between the optical film structure and the substrate or incorporating an interlayer into the optical film structure.
Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.
It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework to understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s), and together with the description serve to explain principles and operation of the various embodiments.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration of an article according to one or more embodiments.
FIG. 2 is an illustration of an article according to one or more embodiments.
FIG. 3 is an illustration of an article according to one or more embodiments.
FIG. 4 is an illustration of an article according to one or more embodiments.
FIG. 4A shows a specific embodiment of the article shown in FIG. 4.
FIG. 5 is an illustration of an article according to one or more embodiments.
FIG. 5A shows a specific embodiment of the article shown in FIG. 5.
FIG. 6A is a graph of the oxygen or silicon content of an article shown in FIGS. 4 and 5.
FIG. 6B is a graph of the nitrogen or aluminum content of an article shown in FIGS. 4 and 5.
FIG. 7 is a graph of the relationship between the thickness and refractive indices of the optical film structure of the article of FIG. 2.
FIG. 8 is a graph of the relationship between the thickness and refractive indices of the optical film structure of the article of FIG. 3.
FIG. 9 is a graph of the relationship between the thickness and refractive indices of the optical film structure of the article of FIG. 4.
FIG. 10A is a graph of the relationship between the thickness and refractive indices of the optical film structure of the article of FIG. 5.
FIG. 10B is a graph of the relationship between the thickness and refractive indices of the optical film structure of the article according to one or more alternative embodiments.
FIG. 11 is a contour plot showing the transmittance color of an optical film structure according to Example 1.
FIG. 12 is a contour plot showing the transmittance color of the optical film structure according to Example 2.
FIG. 13 is a contour plot showing the transmittance color of the optical film structure according to Example 3.
FIG. 14 is a contour plot showing the transmittance color of the optical film structure according to Example 4.
FIG. 15 is a contour plot showing the transmittance color of the optical film structure according to Example 5.
FIG. 16 is a contour plot showing the transmittance color of the optical film structure according to Example 6.
FIG. 17 is a contour plot showing the transmittance color of the optical film structure according to Example 7.
FIG. 18 is a contour plot showing the transmittance color of the optical film structure according to Example 8.
FIG. 19A is a contour plot of the luminosity, L*, in transmittance, for Example 1.
FIG. 19B is a plot showing the distance, d, of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 1.
FIG. 19C is a plot showing log10d of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 1.
FIG. 20A is a contour plot of the luminosity, L*, in transmittance, for Example 2.
FIG. 20B is a plot showing the distance, d, of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 2.
FIG. 20C is a plot showing log10d of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 2.
FIG. 21A is a contour plot of the luminosity, L*, in transmittance, for Example 3.
FIG. 21B is a plot showing the distance, d, of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 3.
FIG. 21C is a plot showing log10d of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 3.
FIG. 22A is a contour plot of the luminosity, L*, in transmittance, for Example 4.
FIG. 22B is a plot showing the distance, d, of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 4.
FIG. 22C is a plot showing log10d of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 4.
FIG. 23A is a contour plot of the luminosity, L*, in transmittance, for Example 5.
FIG. 23B is a plot showing the distance, d, of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 5.
FIG. 23C is a plot showing log10d of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 5.
FIG. 24A is a contour plot of the luminosity, L*, in transmittance, for Example 6.
FIG. 24B is a plot showing the distance, d, of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 6.
FIG. 24C is a plot showing log10d of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 6.
FIG. 25A is a contour plot of the luminosity, L*, in transmittance, for Example 7.
FIG. 25B is a plot showing the distance, d, of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 7.
FIG. 25C is a plot showing log10d of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 7.
FIG. 26A is a contour plot of the luminosity, L*, in transmittance, for Example 8.
FIG. 26B is a plot showing the distance, d, of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 8.
FIG. 26C is a plot showing log10d of a particular color point (a*, b*), in transmittance, corresponding to the SiO2 and Al2O3 film thicknesses as indicated by the axes from the origin (0, 0) in the L*a*b* color space for Example 8.
FIG. 27 illustrates the reflectivity % over the visible spectrum of a layer according to one or more embodiments.
FIG. 28 illustrates transmittance % over the visible spectrum of a layer according to one or more embodiments.
FIG. 29A is a contour plot of a*, in reflectance, for the optical film structure of Example 11.
FIG. 29B is a contour plot of a*, in reflectance, for the optical film structure and substrate of Example 11.
FIG. 29C is a contour plot of b*, in reflectance, for the optical film structure and substrate of Example 11.
FIG. 29D is a contour plot of b*, in reflectance, for the optical film structure and substrate of Example 11.
FIG. 29E is a contour plot of the distance of a* and b*, in reflectance, for the optical film structure and substrate of Example 11 from the origin (0, 0) in the L*a*b* color space.
FIG. 29F is a contour plot of the distance of a* and b*, in reflectance, for the optical film structure and substrate from the color coordinates of the substrate.
FIG. 30A is a contour plot of a*, in transmittance, for the optical film structure of Example 11.
FIG. 30B is a contour plot of a*, in transmittance, for the optical film structure and substrate of Example 11.
FIG. 30C is a contour plot of b*, in transmittance, for the optical film structure of Example 11.
FIG. 30D is a contour plot of b*, in transmittance, for the optical film structure and substrate of Example 11.
FIG. 30E is a contour plot of the distance of a* and b*, in transmittance, for the optical film structure and substrate of Example 11 from the origin (0, 0) in the L*a*b* color space.
FIG. 30F is a contour plot of the distance of a* and b*, in transmittance, for the optical film structure and substrate from the color coordinates of the substrate.
FIG. 31 is a graph showing the hardness measurements of four layers of the same material having different thicknesses.
FIG. 32 is a graph comparing the maximum hardness values of the four layers shown in FIG. 31.
FIG. 33 is a graph showing the relative scratch depths of an article according to one or more embodiments, a bare crystalline substrate, and a bare glass substrate.



DETAILED DESCRIPTION
Reference will now be made in detail to the embodiment(s), examples of which are illustrated in the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to refer to the same or like parts.
Referring to FIG. 1, a first aspect of the disclosure pertains to an article 100 including a substrate 110 having major opposing sides 112, 114 and opposing minor sides 116, 118 and an optical film structure 120 disposed on one of the opposing major sides 112 of the substrate 110. The optical film structure may be disposed on the other opposing major side 114 and/or one or both opposing minor sides 116, 118 in addition to or instead of being disposed on the opposing major side 112.
The term “film”, as applied to the optical film structures described herein may include one or more layers that are formed by any known method in the art, including discrete deposition or continuous deposition processes. Such layers may be in direct contact with one another. The layers may be formed from the same material or more than one different material. In one or more alternative embodiments, such layers may have intervening layers of different materials disposed therebetween. In one or more embodiments a film may include one or more contiguous and uninterrupted layers and/or one or more discontinuous and interrupted layers (i.e., a layer having different materials formed adjacent to one another).
As used herein, the term “dispose” includes coating, depositing and/or forming a material onto a surface using any known method in the art. The disposed material may constitute a layer or film as defined herein. The phrase “disposed on” includes the instance of forming a material onto a surface such that the material is in direct contact with the surface and also includes the instance where the material is formed on a surface, with one or more intervening material(s) is between the disposed material and the surface. The intervening material(s) may constitute a layer or film, as defined herein.
According to one or more embodiments, the article 100 exhibits an average transmittance of 85% or greater over the visible spectrum. In one or more embodiments, the article 100 has a total reflectance of 15% or less. As used herein, the term “transmittance” is defined as the percentage of incident optical power within a given wavelength range transmitted through a material (e.g., the article, the substrate or the optical film structure or portions thereof). The term “reflectance” is similarly defined as the percentage of incident optical power within a given wavelength range that is reflected from a material (e.g., the article, the substrate or the optical film structure or portions thereof). Transmittance and reflectance are measured using a specific linewidth. In one or more embodiments, the spectral resolution of the characterization of the transmittance and reflectance is less than 5 nm or 0.02 eV.
In one or more specific examples, the article 100 may exhibit an average transmittance of about 85% or greater, about 85.5% or greater, about 86% or greater, about 86.5% or greater, about 87% or greater, about 87.5% or greater, about 88% or greater, about 88.5% or greater, about 89% or greater, about 89.5% or greater, about 90% or greater, about 90.5% or greater, about 91% or greater, about 91.5% or greater, about 92% or greater, about 92.5% or greater, about 93% or greater, about 93.5% or greater, about 94% or greater, about 94.5% or greater, about 95% or greater, about 96% or greater, about 97% or greater, about 98% or greater, or about 99% or greater, over the visible spectrum. In one or more other examples, the article may have a total reflectance of about 15% or less, about 14% or less, about 13% or less, about 12% or less, about 11% or less, about 10% or less, about 9% or less, about 8% or less, about 7% or less, or about 6% or less. In some specific embodiments, the article has a total reflectance of about 6.8% or less, about 6.6% or less, about 6.4% or less, about 6.2% or less, about 6% or less, about 5.8% or less, about 5.6% or less, about 5.4% or less, about 5.2% or less, about 5% or less, about 4.8% or less, about 4.6% or less, about 4.4% or less, about 4.2% or less, about 4% or less, about 3.8% or less, about 3.6% or less, about 3.4% or less, about 3.2% or less, about 3% or less, about 2.8% or less, about 2.6% or less, about 2.4% or less, about 2.2% or less, about 2% or less, about 2.8% or less, about 2.6% or less, about 2.4% or less, about 2.2% or less, about 2% or less, about 1.8% or less, about 1.6% or less, about 1.4% or less, about 1.2% or less, about 1% or less, or about 0.5% or less. In accordance with one or more embodiments, the article 100 has a total reflectance that is the same or less than the total reflectance of the substrate 110. In other embodiments, the article has a total reflectance differs from the total reflectance of the substrate by less than about 20%, or 10%.
According to one or more embodiments, the article 100 exhibits an average light transmission of 85% or greater over the visible spectrum. The term “light transmission” refers to the amount of light that is transmitted through a medium. The measure of light transmission is the ratio between the light incident on the medium and the amount of light exiting the medium (that is not reflected or absorbed by the medium). In other words, light transmission is the fraction of incident light that is both not reflected and not absorbed by a medium. The term “average light transmission” refers to spectral average of the light transmission multiplied by the luminous efficiency function, as described by CIE standard observer. The article 100 may exhibit an average light transmission of 85% or greater, 85.5% or greater, 86% or greater, 86.5% or greater, 87% or greater, 87.5% or greater, 88% or greater, 88.5% or greater, 89% or greater, 89.5% 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, over the visible spectrum.
The article 100 includes a front face 101 and optical properties such that, when the article is viewed at an angle other than normal incidence from the front face, the article does not provide a reflectance color tone, or the reflectance color tone provided is neutral or colorless. In other words, observed from an angle other than directly in front of the front face 101, the reflectance is colorless. Additionally or alternatively, the reflected color from the article does not substantially vary, even if a viewing angle changes. In one or more embodiments, the article exhibits a transmittance color and/or reflectance color in the (L*, a*, b*) colorimetry system a color shift of less than about 2 from a reference point, at normal incidence for the transmitted or reflected light. As used herein, the phrase “color shift” refers to the distance between the transmittance color coordinates of the article and/or the reflectance color coordinates article, in the (L*, a*, b*) colorimetry system, and the reference point. In one or more embodiments, the reference point may be the origin (0, 0) in the L*a*b* color space (or the color coordinates a*=0, b*=0) or the transmittance color coordinates or reflectance color coordinates of the substrate 110. Where the color shift of the article is defined with respect to the substrate, the transmittance color coordinates of the article are compared to the transmittance color coordinates of the substrate and the reflectance color coordinates of the article are compared to the reflectance color coordinates of the substrate.
In one or more specific embodiments, the color shift of the transmittance color and/or the reflectance color may be less than 1 or even less than 0.5. In one or more specific embodiments, the color shift for the transmittance color and/or the reflectance color may be 1.8, 1.6, 1.4, 1.2, 0.8, 0.6, 0.4, 0.2, 0 and all ranges and sub-ranges therebetween. Where the reference point is the color coordinates a*=0, b*=0, the color shift is calculated by the equation, color coordinate distance=√((a*)2+(b*)2). Where the reference point is the color coordinates of the substrate 110, the color shift is calculated by the equation, color coordinate distance=√((a*article−a*substrate)2+(b*article−b*substrate)2).
Substrate
As shown in FIGS. 1-5, the substrate 110 includes an optical film system 120, 220, 320, 420, 520 disposed on at least one opposing major surface (112, 114). The substrate 110 includes minor surfaces 116, 118, which may or may not include a film or material disposed thereon. The substrate 110 may include an amorphous substrate, a crystalline substrate, or a combination thereof.
In some embodiments, the substrate 110 may be characterized as inorganic. In one or more embodiments, the amorphous substrate may include a glass substrate, which may be strengthened or non-strengthened. Examples of suitable glass substrates include soda lime glass substrates, alkali aluminosilicate glass substrates, alkali containing borosilicate glass substrates and alkali aluminoborosilicate glass substrates. In some variants, the glass substrates may be free of lithia. In one or more alternative embodiments, the substrate 110 may include crystalline substrates such as glass-ceramic substrates (which may be strengthened or non-strengthened) or may include a single crystal structure, such as sapphire. In one or more specific embodiments, the substrate 110 includes an amorphous base (e.g., glass) and a crystalline cladding (e.g., sapphire layer, a polycrystalline alumina layer and/or or a spinel (MgAl2O4) layer).
In some embodiments, the substrate 110 may be organic and may specifically be polymeric. Examples of suitable polymers include, without limitation: thermoplastics including polystyrene (PS) (including styrene copolymers and blends), polycarbonate (PC) (including copolymers and blends), polyesters (including copolymers and blends, including polyethyleneterephthalate and polyethyleneterephthalate copolymers), polyolefins (PO) and cyclicpolyolefins (cyclic-PO), polyvinylchloride (PVC), acrylic polymers including polymethyl methacrylate (PMMA) (including copolymers and blends), thermoplastic urethanes (TPU), polyetherimide (PEI) and blends of these polymers with each other. Other exemplary polymers include epoxy, styrenic, phenolic, melamine, and silicone resins.
The substrate 110 may be substantially planar, although other embodiments may utilize a curved or otherwise shaped or sculpted substrate. The substrate 110 may be substantially optically clear, transparent and free from light scattering. The substrate 110 may have a refractive index in the range from about 1.45 to about 1.55. As used herein, the refractive index values are with respect to a wavelength of 550 nm. The substrate 110 may be characterized as having a high average flexural strength (when compared to substrates that are not strengthened, as described herein) or high surface strain-to-failure (when compared to substrates that are not strengthened, as described herein) as measured on one or more major opposing surfaces 112, 114 of such substrates.
Additionally or alternatively, the thickness of the substrate 110 may vary along one or more of its dimensions for aesthetic and/or functional reasons. For example, the edges of the substrate 110 may be thicker as compared to more central regions of the substrate 110. The length, width and thickness dimensions of the substrate 110 may also vary according to the article application or use.
The substrate 110 may be provided using a variety of different processes. For instance, where the substrate 110 includes a glass substrate, exemplary glass substrate forming methods include float glass processes and down-draw processes such as fusion draw and slot draw.
A glass substrate prepared by a float glass process may be characterized by smooth surfaces and uniform thickness is made by floating molten glass on a bed of molten metal, typically tin. In an example process, molten glass that is fed onto the surface of the molten tin bed forms a floating glass ribbon. As the glass ribbon flows along the tin bath, the temperature is gradually decreased until the glass ribbon solidifies into a solid glass substrate that can be lifted from the tin onto rollers. Once off the bath, the glass substrate can be cooled further and annealed to reduce internal stress.
Down-draw processes produce glass substrates having a uniform thickness that possess relatively pristine surfaces. Because the average flexural strength of the glass substrate is controlled by the amount and size of surface flaws, a pristine surface that has had minimal contact has a higher initial strength. When this high strength glass substrate is then further strengthened (e.g., chemically), the resultant strength can be higher than that of a glass substrate with a surface that has been lapped and polished. Down-drawn glass substrates may be drawn to a thickness of less than about 2 mm. In addition, down drawn glass substrates have a very flat, smooth surface that can be used in its final application without costly grinding and polishing.
The fusion draw process, for example, uses a drawing tank that has a channel for accepting molten glass raw material. The channel has weirs that are open at the top along the length of the channel on both sides of the channel. When the channel fills with molten material, the molten glass overflows the weirs. Due to gravity, the molten glass flows down the outside surfaces of the drawing tank as two flowing glass films. These outside surfaces of the drawing tank extend down and inwardly so that they join at an edge below the drawing tank. The two flowing glass films join at this edge to fuse and form a single flowing glass substrate. The fusion draw method offers the advantage that, because the two glass films flowing over the channel fuse together, neither of the outside surfaces of the resulting glass substrate comes in contact with any part of the apparatus. Thus, the surface properties of the fusion drawn glass substrate are not affected by such contact.
The slot draw process is distinct from the fusion draw method. In slow draw processes, the molten raw material glass is provided to a drawing tank. The bottom of the drawing tank has an open slot with a nozzle that extends the length of the slot. The molten glass flows through the slot/nozzle and is drawn downward as a continuous substrate and into an annealing region.
In some embodiments, the compositions used for the glass substrate may be batched with 0-2 mol. % of at least one fining agent selected from a group that includes Na2SO4, NaCl, NaF, NaBr, K2SO4, KCl, KF, KBr, and SnO2.
Once formed, a glass substrate may be strengthened to form a strengthened glass substrate. It should be noted that glass ceramic substrates may also be strengthened in the same manner as glass substrates. As used herein, the term “strengthened substrate” may refer to a glass substrate or a glass ceramic substrates that has been chemically strengthened, for example through ion-exchange of larger ions for smaller ions in the surface of the glass or glass ceramic substrate. However, other strengthening methods known in the art, such as thermal tempering, may be utilized to form strengthened glass substrates.
The strengthened substrates described herein may be chemically strengthened by an ion exchange process. In the ion-exchange process, typically by immersion of a glass or glass ceramic substrate into a molten salt bath for a predetermined period of time, ions at or near the surface(s) of the glass or glass ceramic substrate are exchanged for larger metal ions from the salt bath. In one embodiment, the temperature of the molten salt bath is about 400-430° C. and the predetermined time period is about four to about eight hours. The incorporation of the larger ions into the glass or glass ceramic substrate strengthens the substrate by creating a compressive stress in a near surface region or in regions at and adjacent to the surface(s) of the substrate. A corresponding tensile stress is induced within a central region or regions at a distance from the surface(s) of the substrate to balance the compressive stress. Glass or glass ceramic substrates utilizing this strengthening process may be described more specifically as chemically-strengthened or ion-exchanged glass or glass ceramic substrates.
In one example, sodium ions in a strengthened glass or glass ceramic substrate are replaced by potassium ions from the molten bath, such as a potassium nitrate salt bath, though other alkali metal ions having larger atomic radii, such as rubidium or cesium, can replace smaller alkali metal ions in the glass. According to particular embodiments, smaller alkali metal ions in the glass or glass ceramic can be replaced by Ag+ ions. Similarly, other alkali metal salts such as, but not limited to, sulfates, phosphates, halides, and the like may be used in the ion exchange process.
The replacement of smaller ions by larger ions at a temperature below that at which the glass network can relax produces a distribution of ions across the surface(s) of the strengthened substrate that results in a stress profile. The larger volume of the incoming ion produces a compressive stress (CS) on the surface and tension (central tension, or CT) in the center of the strengthened substrate. The compressive stress is related to the central tension by the following relationship:




  CS
  =
  
    CT
    ⁡
    
      (
      
        
          t
          -
          
            2
            ⁢
            DOL
          
        
        DOL
      
      )
    
  




where t is the total thickness of the strengthened glass or glass ceramic substrate and compressive depth of layer (DOL) is the depth of exchange. Depth of exchange may be described as the depth within the strengthened glass or glass ceramic substrate (i.e., the distance from a surface of the glass substrate to a central region of the glass or glass ceramic substrate), at which ion exchange facilitated by the ion exchange process takes place.

In one embodiment, a strengthened glass or glass ceramic substrate can have a surface compressive stress of 300 MPa or greater, e.g., 400 MPa or greater, 450 MPa or greater, 500 MPa or greater, 550 MPa or greater, 600 MPa or greater, 650 MPa or greater, 700 MPa or greater, 750 MPa or greater or 800 MPa or greater. The strengthened glass or glass ceramic substrate may have a compressive depth of layer 15 μm or greater, 20 μm or greater (e.g., 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 μm or greater) and/or a central tension of 10 MPa or greater, 20 MPa or greater, 30 MPa or greater, 40 MPa or greater (e.g., 42 MPa, 45 MPa, or 50 MPa or greater) but less than 100 MPa (e.g., 95, 90, 85, 80, 75, 70, 65, 60, 55 MPa or less). In one or more specific embodiments, the strengthened glass or glass ceramic substrate has one or more of the following: a surface compressive stress greater than 500 MPa, a depth of compressive layer greater than 15 nm, and a central tension greater than 18 MPa.
Without being bound by theory, it is believed that strengthened glass or glass ceramic substrates with a surface compressive stress greater than 500 MPa and a compressive depth of layer greater than about 15 μm typically have greater strain-to-failure than non-strengthened glass or glass ceramic substrates (or, in other words, glass substrates that have not been ion exchanged or otherwise strengthened).
Example glasses that may be used in the substrate may include alkali aluminosilicate glass compositions or alkali aluminoborosilicate glass compositions, though other glass compositions are contemplated. Such glass compositions may be characterized as ion exchangeable. As used herein, “ion exchangeable” means that a substrate comprising the composition is capable of exchanging cations located at or near the surface of the substrate with cations of the same valence that are either larger or smaller in size. One example glass composition comprises SiO2, B2O3 and Na2O, where (SiO2+B2O3)≧66 mol. %, and Na2O≧9 mol. %. In an embodiment, the glass composition includes at least 6 wt. % aluminum oxide. In a further embodiment, the substrate includes a glass composition with one or more alkaline earth oxides, such that a content of alkaline earth oxides is at least 5 wt. %. Suitable glass compositions, in some embodiments, further comprise at least one of K2O, MgO, and CaO. In a particular embodiment, the glass compositions used in the substrate can comprise 61-75 mol. % SiO2; 7-15 mol. % Al2O3; 0-12 mol. % B2O3; 9-21 mol. % Na2O; 0-4 mol. % K2O; 0-7 mol. % MgO; and 0-3 mol. % CaO.
A further example glass composition suitable for the substrate comprises: 60-70 mol. % SiO2; 6-14 mol. % Al2O3; 0-15 mol. % B2O3; 0-15 mol. % Li2O; 0-20 mol. % Na2O; 0-10 mol. % K2O; 0-8 mol. % MgO; 0-10 mol. % CaO; 0-5 mol. % ZrO2; 0-1 mol. % SnO2; 0-1 mol. % CeO2; less than 50 ppm As2O3; and less than 50 ppm Sb2O3; where 12 mol. %≦(Li2O+Na2O+K2O)≦20 mol. % and 0 mol. %≦(MgO+CaO)≦10 mol. %.
A still further example glass composition suitable for the substrate comprises: 63.5-66.5 mol. % SiO2; 8-12 mol. % Al2O3; 0-3 mol. % B2O3; 0-5 mol. % Li2O; 8-18 mol. % Na2O; 0-5 mol. % K2O; 1-7 mol. % MgO; 0-2.5 mol. % CaO; 0-3 mol. % ZrO2; 0.05-0.25 mol. % SnO2; 0.05-0.5 mol. % CeO2; less than 50 ppm As2O3; and less than 50 ppm Sb2O3; where 14 mol. %≦(Li2O+Na2O+K2O)≦18 mol. % and 2 mol. %≦(MgO+CaO)≦7 mol. %.
In a particular embodiment, an alkali aluminosilicate glass composition suitable for the substrate comprises alumina, at least one alkali metal and, in some embodiments, greater than 50 mol. % SiO2, in other embodiments at least 58 mol. % SiO2, and in still other embodiments at least 60 mol. % SiO2, wherein the ratio ((Al2O3+B2O3)Σmodifiers)>1, where in the ratio the components are expressed in mol. % and the modifiers are alkali metal oxides. This glass composition, in particular embodiments, comprises: 58-72 mol. % SiO2; 9-17 mol. % Al2O3; 2-12 mol. % B2O3; 8-16 mol. % Na2O; and 0-4 mol. % K2O, wherein the ratio ((Al2O3+B2O3)Σmodifiers)>1.
In still another embodiment, the substrate may include an alkali aluminosilicate glass composition comprising: 64-68 mol. % SiO2; 12-16 mol. % Na2O; 8-12 mol. % Al2O3; 0-3 mol. % B2O3; 2-5 mol. % K2O; 4-6 mol. % MgO; and 0-5 mol. % CaO, wherein: 66 mol. %≦SiO2+B2O3+CaO≦69 mol. %; Na2O+K2O+B2O3+MgO+CaO+SrO>10 mol. %; 5 mol. %≦MgO+CaO+SrO≦8 mol. %; (Na2O+B2O3)−Al2O3≦2 mol. %; 2 mol. %≦Na2O−Al2O3≦6 mol. %; and 4 mol. %≦(Na2O+K2O)−Al2O3≦10 mol. %.
In an alternative embodiment, the substrate may comprise an alkali aluminosilicate glass composition comprising: 2 mol % or more of Al2O3 and/or ZrO2, or 4 mol % or more of Al2O3 and/or ZrO2.
Where the substrate 110 includes a crystalline substrate, the substrate may include a single crystal, which may include Al2O3. Such single crystal substrates are referred to as sapphire. Other suitable materials for a crystalline substrate include polycrystalline alumina layer and/or or a spinel (MgAl2O4).
Optionally, the crystalline substrate 100 may include a glass ceramic substrate, which may be strengthened or non-strengthened. Examples of suitable glass ceramics may include Li2O—Al2O3—SiO2 system (i.e. LAS-System) glass ceramics, MgO—Al2O3—SiO2 System (i.e. MAS-System) glass ceramics, and/or glass ceramics that include a predominant crystal phase including β-quartz solid solution, β-spodumene ss, cordierite, and lithium disilicate. The glass ceramic substrates may be strengthened using the glass substrate strengthening processes disclosed herein. In one or more embodiments, MAS-System glass ceramic substrates may be strengthened in Li2SO4 molten salt, whereby 2Li+ for Mg2+ exchange can occur.
The substrate 110 according to one or more embodiments can have a thickness ranging from about 100 μm to about 5 mm. Example substrate 110 thicknesses range from about 100 μm to about 500 μm (e.g., 100, 200, 300, 400 or 500 μm). Further example substrate 110 thicknesses range from about 500 μm to about 1000 μm (e.g., 500, 600, 700, 800, 900 or 1000 μm). The substrate 110 may have a thickness greater than about 1 mm (e.g., about 2, 3, 4, or 5 mm). In one or more specific embodiments, the substrate 110 may have a thickness of 2 mm or less or less than 1 mm. The substrate 110 may be acid polished or otherwise treated to remove or reduce the effect of surface flaws.
Optical Film Structure
In the embodiments described herein, the optical film structure is disposed on a major surface (112, 114) of the substrate 110. In some instances, the optical film structure may be disposed on one or more minor surfaces (not shown). The optical film surface forms a coated surface that forms the front face 101 of the article.
The optical film structures described herein have scratch resistance, which may be characterized by the measured hardness of the article including the optical film structure, the measured hardness of the optical film structure itself, and/or the measured hardness of one or more of the layers of the optical film structure. Hardness may be measured by a “Berkovich Indenter Hardness Test”, which includes measuring the hardness of a material on a surface thereof by indenting the surface with a diamond Berkovich indenter. The Berkovich Indenter Hardness Test includes indenting the front face 101 of the article or the surface of the optical film structure (or the surface of any one or more of the layers in the optical film structure) with the diamond Berkovich indenter to form an indent to an indentation depth in the range from about 50 nm to about 1000 nm (or the entire thickness of the optical film structure or layer, whichever is less) and measuring the maximum hardness from this indentation along the entire indentation depth range or a segment of this indentation depth (e.g., in the range from about 100 nm to about 600 nm), generally using the methods set forth in Oliver, W. C.; 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.; 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. The indentation depth is made and measured from the front face 101 of the article, the surface of the optical film structure and/or surface of any one or more of the layers in the optical film structure. As used herein, hardness refers to a maximum hardness, and not an average hardness.
Typically, in nanoindentation measurement methods (such as by using a Berkovich indenter) of a coating that is harder than the underlying substrate, the measured hardness may appear to increase initially due to development of the plastic zone at shallow indentation depths and then increases and reaches a maximum value or plateau at deeper indentation depths. Thereafter, hardness begins to decrease at even deeper indentation depths due to the effect of the underlying substrate. Where a substrate having an increased hardness compared to the coating is utilized, the same effect can be seen; however, the hardness increases at deeper indentation depths due to the effect of the underlying substrate.
The indentation depth range and the hardness values at certain indentation depth range(s) can be selected to identify a particular hardness response of the optical film structures and layers thereof, described herein, without the effect of the underlying substrate. When measuring hardness of the optical film structure (when disposed on a substrate) with a Berkovich indenter, the region of permanent deformation (plastic zone) of a material is associated with the hardness of the material. During indentation, an elastic stress field extends well beyond this region of permanent deformation. As indentation depth increases, the apparent hardness and modulus are influenced by stress field interactions with the underlying substrate. The substrate influence on hardness occurs at deeper indentation depths (i.e., typically at depths greater than about 10% of the optical film structure or layer thickness). Moreover, a further complication is that the hardness response requires a certain minimum load to develop full plasticity during the indentation process. Prior to that certain minimum load, the hardness shows a generally increasing trend.
At small indentation depths (which also may be characterized as small loads) (e.g., up to about 100 nm, or less than about 70 nm), the apparent hardness of a material appears to increase dramatically versus indentation depth. This small indentation depth regime does not represent a true metric of hardness but instead, reflects the development of the aforementioned plastic zone, which is related to the finite radius of curvature of the indenter. At intermediate indentation depths, the apparent hardness approaches maximum levels. At deeper indentation depths, the influence of the substrate becomes more pronounced as the indentation depths increase. Hardness may begin to drop dramatically once the indentation depth exceeds about 30% of the optical film structure thickness or the layer thickness.
As shown in FIG. 31, the hardness measured at intermediate indentation depths (at which hardness approaches and is maintained at maximum levels) and at deeper indentation depths depends on the thickness of a material or layer. FIG. 31 illustrates the hardness response of four different layers of AlOxNy having different thicknesses. The hardness of each layer was measured using the Berkovich Indenter Hardness Test. The 500 nm-thick layer exhibited its maximum hardness at indentation depths from about 100 nm to 180 nm, followed by a dramatic decrease in hardness at indentation depths from about 180 nm to about 200 nm, indicating the hardness of the substrate influencing the hardness measurement. The 1000 nm-thick layer exhibited a maximum hardness at indentation depths from about 100 nm to about 300 nm, followed by a dramatic decrease in hardness at indentation depths greater than about 300 nm. The 1500 nm-thick layer exhibited a maximum hardness at indentation depths from about 100 nm to about 550 nm and the 2000-nm thick layer exhibited a maximum hardness at indentation depths from about 100 nm to about 600 nm.
In some embodiments, the article, the optical film structure and/or layer(s) in the optical film structure exhibit a maximum hardness at indentation depths greater than about 100 nm or greater than about 200 nm and thus exhibit sufficient hardness to provide scratch resistance, that is not influenced by the substrate. In some embodiments, the article, the optical film structure and/or layer(s) in the optical film structure have a maximum hardness at such indentation depths and thus are resistant to specific scratches such as microductile scratches (which typically have depths of about 100 nm to about 500 nm or from about 200 nm to about 400 nm). For example, the front face 101 (or the surface of the optical film structure or any one or more layers of the optical film structure) may be resistant to microductile scratches because the article exhibits the hardness values recited herein along specific indentation depths, as measured by a Berkovich Indenter Hardness Test.
In addition, as shown in FIG. 32, the measured or apparent hardness may be maximized by tuning the thickness of the optical film structure or one or more layer(s) in the optical film structure. FIG. 32 plots the measured maximum hardness values of the layers shown in FIG. 31. For the 500 nm-thick layer, a 10% indentation depth threshold occurs at 50 nm; however, it does not appear that a fully developed plastic zone occurs until the indentation depth is greater than about 70 nm. As a result, the apparent hardness of the 500 nm-thick layer is significantly lower than the hardness of thicker films.
In one or more specific embodiments, the optical film structure has a hardness (as measured on a surface of the optical film structure, e.g., 221 of FIG. 2) of about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, about 15 GPa or greater, about 16 GPa or greater, about 17 GPa or greater, about 18 GPa or greater, about 19 GPa or greater, about 20 GPa or greater, about 22 GPa or greater, about 23 GPa or greater, about 24 GPa or greater, about 25 GPa or greater, about 26 GPa or greater, or about 27 GPa or greater (up to about 50 GPa), as measured by the Berkovich Indenter Hardness Test. Such measured hardness values may be exhibited by the optical film structure along an indentation depth of about 50 nm or greater or about 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm).
The optical film structure 120 may have at least one layer having a hardness (as measured on the surface of such layer, e.g., surface 229 of the second sub-layer 228 of FIG. 2) of about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, about 15 GPa or greater, about 16 GPa or greater, about 17 GPa or greater, about 18 GPa or greater, about 19 GPa or greater, about 20 GPa or greater, about 22 GPa or greater, about 23 GPa or greater, about 24 GPa or greater, about 25 GPa or greater, about 26 GPa or greater, or about 27 GPa or greater (up to about 50 GPa), as measured by the Berkovich Indenter Hardness Test. The hardness of such layer may be in the range from about 18 GPa to about 21 GPa, as measured by the Berkovich Indenter Hardness Test. Such measured hardness values may be exhibited by the at least one layer along an indentation depth of about 50 nm or greater or 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm). In one or more embodiments, the optical film structure includes a layer with a maximum hardness and such layer forms about 50% or more by volume of the optical film structure.
In one or more embodiments, the article (as measured on the front face 101) may exhibit a hardness of about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, about 15 GPa or greater, about 16 GPa or greater, about 17 GPa or greater, about 18 GPa or greater, about 19 GPa or greater, about 20 GPa or greater, about 22 GPa or greater, about 23 GPa or greater, about 24 GPa or greater, about 25 GPa or greater, about 26 GPa or greater, or about 27 GPa or greater (up to about 50 GPa), as measured by the Berkovich Indenter Hardness Test, along an indentation depth of about 50 nm or greater or about 100 nm or greater. In one or more embodiments, the indentation depths may be in the range from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm.
In one or more embodiments, the optical film structure has scratch resistance that is measured by a reduction in scratch depth. Specifically, articles that include the optical film structure may exhibit a reduction in scratch depth, when compared to the scratch depth in the substrate 110 without the optical film structure. When the article having an optical film structure disposed thereon is scratched using a Berkovich indenter, using a load of 160 mN at a speed of 10 μm/second for a length of at least 100 μm along the surface of the article (on the side of the optical film structure), the resulting scratch has a depth that less than the depth of a scratch formed identically (i.e., using the same indenter, load, speed, and length) on an substrate 110 (without the optical film structure disposed thereon) by at least about 30%, at least about 31%, at least about 32%, at least about 33%, at least about 34%, at least about 35%, at least about 36%, at least about 37%, at least about 38%, at least about 39%, at least about 40%, at least about 41%, at least about 42%, at least about 43%, at least about 44%, at least about 45%, at least about 46%, at least about 47%, at least about 48%, at least about 49%, at least about 50%, at least about 51%, at least about 52%, at least about 53%, at least about 54%, at least about 55%, at least about 56%, at least about 57%, at least about 58%, at least about 59%, at least about 60% (and all ranges and sub-ranges therebetween). This scratch resistant property of the optical film structure may be present where the article utilizes an amorphous substrate (e.g., strengthened glass substrate and/or a non-strengthened glass substrate), a crystalline substrate (e.g., a strengthened glass ceramic substrate, a non-strengthened glass ceramic glass substrate, and a single crystal substrate such as sapphire) or a combination thereof. In some embodiments, the scratch resistance may be present where the substrate is polymeric. In addition, this scratch resistant property of the optical film structure may be present when the article is scratched using the Berkovich indenter, at a speed of 10 μm/second for a length of at least 1 mm, at least 2 mm, at least 3 mm, at least 4 mm or at least 5 mm. In one or more embodiments, the optical film structure has scratch resistance such that, when an article including the optical film structure is scratched by a Berkovich indenter using a load of 160 mN at a speed of 10 μm/seconds for at least a length of 100 μm along the surface of the article, the resulting scratch has a scratch depth of less than 250 nm, less than 240 nm, less than 230 nm, less than 220 nm, or less than about 200 nm. The scratch depths described herein may be measured from the original and undisturbed surface of the optical film structure. In other words, the scratch depth does not include any amount of optical film structure that may be built up around the edges of the scratch due to displacement of the optical film structure materials caused by the penetration of the Berkovich indenter into the optical film structure.
The reduced scratch depth of the optical film structure, when disposed on a substrate, is shown in FIG. 33. FIG. 33 shows the scratch depth of a bare glass substrate (indicated by “G”), a bare sapphire substrate (indicated by “S”) and an article (indicated by “A”) having an optical film structure disposed on the same glass substrate as G. The optical film structure of A has the same structure as FIG. 2, described herein, with a first sub-layer of Al2O3 (having a thickness of about 115 nm), a second sub-layer of AlOxNy (having a thickness of about 2000 nm) and a second layer of SiO2 (having a thickness of about 32 nm). At all loads, the article exhibits a reduced scratch depth as compared to bare glass and bare sapphire substrates. Accordingly, embodiments of the article described herein exhibit scratch resistance such that when the article is scratched on the front face 101 with a Berkovich indenter using a load of 30 mN or 60 mN at a speed of 10 nm/seconds for at least a length of 100 μm along the surface of the article, the resulting scratch has a scratch depth of less than 100 nm or less than about 50 nm. Similarly, when the article is scratched on the front face 101 with a Berkovich indenter using a load of 125 mN at a speed of 10 nm/seconds for at least a length of 100 μm along the surface of the article, the resulting scratch has a scratch depth of less than about 200 nm, less than 150 nm, or less than 100 nm.
In one or more embodiments, the article 100 exhibits a reduction in scratch depth when compared to bare substrates 110 that include sapphire and when compared to bare substrates 110 that include chemically strengthened glass. In one or more specific embodiments, the reduction in scratch depth of the article 100 versus a bare substrate 110 that includes chemically strengthened glass is at least two times greater than the reduction in scratch depth of a bare sapphire substrate versus a bare chemically strengthened glass substrate. For example, a bare sapphire substrate may exhibit a 30-40% scratch depth reduction when compared to a bare strengthened glass substrate; however, the article exhibits a 60-75% or greater scratch depth reduction when compared to bare strengthened glass substrate. In one or more specific embodiments, the reduction in scratch depth of the article 100 is at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75% or at least 85%, and all ranges and sub-ranges therebetween, when compared to bare substrates 110 that include chemically strengthened glass. Comparison between the article 100 and the bare substrate may be performed on the same article, where the coated surface 101 is tested to evaluate the scratch depth of the article and the opposite surface of the substrate (e.g., 114, in FIG. 1) is tested evaluate the scratch depth of the bare substrate; the resulting scratch depths may be compared to determine the scratch depth reduction on the coated surface 101 with respect to the bare substrate. In one or more embodiments, the article 100 exhibits the improved reduction in scratch depth in comparison with a bare substrate having a hardness in the range from about 7 GPa to about 8 GPa, as measured by the Berkovich Indenter Hardness Test.
In one or more embodiments, the optical film structure exhibits scratch resistance that is measured by a reduction in scratch width. Specifically, articles that include the optical film structure may exhibit a reduction in scratch width, when compared to the scratch depth in the substrate 110 without the optical film structure. When the article having an optical film structure, as described herein, disposed thereon is scratched using a Berkovich indenter, using a load of 160 mN at a speed of 10 μm/second for a length of at least 100 nm along the surface of the article (on the side of the optical film structure), the resulting scratch has a width that is at least about 30%, at least about 31%, at least about 32%, at least about 33%, at least about 34%, at least about 35%, at least about 36%, at least about 37%, at least about 38%, at least about 39%, at least about 40%, at least about 41%, at least about 42%, at least about 43%, at least about 44%, at least about 45% (and all ranges and sub-ranges therebetween) less than the width of a scratch formed identically (i.e., using the same indenter, load, speed, and length) on a substrate 110, without the optical film structure disposed thereon. This scratch resistant property of the optical film structure may be present where the article utilizes an amorphous substrate (e.g., strengthened glass substrate and/or a non-strengthened glass substrate), a crystalline substrate (e.g., a strengthened glass ceramic substrate, a non-strengthened glass ceramic glass substrate, and a single crystal substrate such as sapphire) or a combination thereof. In one or more alternative embodiments, this scratch resistance may be present where the substrate is polymeric. In addition, this scratch resistant property of the optical film structure may be present when the article is scratched using the Berkovich indenter, at a speed of 10 nm/second for a length of at least 1 mm, at least 2 mm, at least 3 mm, at least 4 mm or at least 5 mm. Comparison between the article 100 and the bare substrate may be performed on the same article, where the coated surface 101 is tested to evaluate the scratch width of the article and the opposite surface of the substrate (e.g., 114, in FIG. 1) is tested evaluate the scratch depth of the bare substrate; the resulting scratch widths may be compared to determine the scratch width reduction on the coated surface 101 with respect to the bare substrate. In one or more embodiments, the article 100 exhibits the improved reduction in scratch width in comparison with a bare substrate having a hardness in the range from about 7 GPa to about 8 GPa, as measured by the Berkovich Indenter Hardness Test.
In one or more embodiments, the optical film structure has scratch resistance such that, when an article including the optical film structure is scratched by a Berkovich indenter using a load of 160 mN at a speed of 10 μm/seconds for at least a length of 100 μm along the surface of the article, the resulting scratch has a scratch width of less than about 10 μm. In some embodiments, the resulting scratch has a scratch width in the range from about 1 μm to about 10 μm, from about 2 μm to about 10 μm, from about 3 μm to about 10 μm, from about 4 μm to about 10 μm, from about 5 μm to about 10 μm, from about 1 μm to about 9 μm, from about 1 μm to about 8 μm, from about 1 μm to about 7 μm, from about 1 μm to about 6 μm, from about 2 μm to about 8 μm, from about 2 μm to about 6 μm, from about 2 μm to about 5 μm, or from about 2 μm to about 4 μm and all ranges and sub-ranges therebetween. The scratch widths described herein may be measured from the original and undisturbed surface of the optical film structure. In other words, the scratch width does not include any amount of optical film structure that may be built up around the edges of the scratch due to displacement of the optical film structure materials caused by the penetration of the Berkovich indenter into the optical film structure.
In some embodiments, the optical film reduces or minimizes the formation of microductile scratches (as described herein) and/or lateral scratches. Lateral scratches are cracks or scratches that are formed as a result of microductile scratches. Lateral scratches are similarly extended in length but are oriented transversely from the microductile scratch(es) from which they are formed. In one or more embodiments, the optical film structure provides resistance to frictive damage to the front face 101. As used herein, frictive damage includes chipping, flaking and cracking that can accompany microductile scratches. Frictive damage, however, can result in increased visibility of scratch damage and may degrade the optical properties of the article in terms of decreased transmittance and/or increased reflectance or increased light scattering. Moreover, frictive damage may result in failure of the optical film structure. Without being bound by theory, hardness alone is not an indicator of whether a coating will experience frictive damage.
In one or more embodiments, articles with optical film structures described herein may exhibit scratch resistance when evaluated using a garnet sandpaper test. The garnet sandpaper test is intended to replicate or imitate the day-to-day conditions of use of the articles described herein, when incorporated into mobile electronic devices, such as mobile phones. The articles described herein are substantially free of any scratches on the surface thereof, when observed with the naked eye, after the surface has been swiped a single time with a 150-grit garnet sandpaper (supplied by 3M) by hand.
In one or more embodiments, articles with the optical film structures described herein also exhibit resistance to scratches and other damage formed by abrasion (or multiple contact events). Various forms of abrasion test are known in the art, such as that specified in ASTM D1044-99, using abrasive media supplied by Taber Industries. Modified abrasion methods related to ASTM D1044-99 can be created using different types of abrading media, abradant geometry and motion, pressure, etc. in order to provide repeatable and measurable abrasion or wear tracks to meaningfully differentiate the abrasion resistance of different samples. For example, different test conditions will usually be appropriate for soft plastics vs. hard inorganic test samples. The embodiments described herein exhibit scratch resistance as measured by a specific modified version of the ASTM D1044-99 test referred to herein as the “Taber Test”, which provides clear and repeatable differentiation of durability between different samples, which comprise primarily hard inorganic materials. These test methods may generate a combination of micro-ductile scratches together with other damage modes mentioned above, depending on the specific sample tested. As used herein, the phrase “Taber Test” refers to a test method using a Taber Linear Abraser 5750 (TLA 5750) and accessories supplied by Taber Industries, in an environment including a temperature of about 22° C.±3° C. and Relative Humidity of up to about 70%. The TLA 5750 includes a CS-17 abraser material having a 6.7 mm diameter abraser head. Each sample was abraded according to the Taber Test and the abrasive damage was evaluated using both Haze and Bidirectional Transmittance Distribution Function (BTDF) measurements, among other methods. In the Taber Test, the procedure for abrading each sample includes placing the TLA 5750 and a flat sample support on a rigid, flat surface and securing the TLA 5750 and the sample support to the surface. Before each sample is abraded under the Taber Test, the abraser material (CS-17) is refaced using a new S-14 refacing strip adhered to glass. The abraser is subjected to 10 refacing cycles using a cycle speed of 25 cycles/minute and stroke length of 1 inch, with no additional weight added (i.e., a total weight of about 350 g is used during refacing, which is the combined weight of the spindle and collet holding the abraser). The procedure then includes operating the TLA 5750 to abrade the sample, where the sample is placed in the sample support in contact with the abraser head and supporting the weight applied to the abraser head, using a cycle speed of 25 cycles/minute, and a stroke length of 1 inch, and a weight such that the total weight applied to the sample is 850 g (i.e., a 500 g auxiliary weight is applied in addition to the 350 g combined weight of the spindle and collet). The procedure includes forming two wear tracks on each sample for repeatability, and abrading each sample for 500 cycle counts in each of the two wear tracks on each sample.
In one or more embodiments, the front face 101 of the article is abraded according to the above Taber Test and the article exhibits a haze of about 5% or less, as measured on the abraded side using a hazemeter supplied by BYK Gardner under the trademark Haze-Gard Plus®, using an aperture over the source port, the aperture having a diameter of 8 mm. In some embodiments, the haze measured after the Taber Test may be about 4% or less, about 3% or less, about 2% or less, about 1% or less, about 0.8% or less, about 0.5% or less, about 0.4% or less, about 0.3%, about 0.2% or less, or about 0.1% or less.
In one or more embodiments, the front face 101 of the article may exhibit an abrasion resistance, after being abraded by the Taber Test as measured by a light scattering measurement. In one or more embodiments, the light scattering measurement includes a bi-directional reflectance distribution function (BRDF) or bi-directional transmittance distribution function (BTDF) measurement carried out using a Radiant Zemax IS-SATM instrument. This instrument has the flexibility to measure light scattering using any input angle from normal to about 85 degrees incidence in reflection, and from normal to about 85 degrees incidence in transmission, while also capturing all scattered light output in either reflection or transmission into 2*Pi steradians (a full hemisphere in reflection or transmission). In one embodiment, the article 100 exhibits an abrasion resistance, as measured using BTDF at normal incidence and analyzing the transmitted scattered light at a selected angular range, for example from about 10° to about 80° degrees in polar angles and any angular range therein. The full azimuthal range of angles can be analyzed and integrated, or particular azimuthal angular slices can be selected, for example from about 0° and 90° azimuthally. In the case of linear abrasion, an azimuthal direction that is substantially orthogonal to the abrasion direction may be utilized so as to increase signal-to-noise of the optical scattering measurement. In one or more embodiments, the article may exhibit a scattered light intensity after the Taber Test as measured at the front face 101, of about less than about 0.1, about 0.05 or less, about 0.03 or less, about 0.02 or less, about 0.01 or less, about 0.005 or less, or about 0.003 or less (in units of 1/steradian), when using the Radiant Zemax IS-SA tool in CCBTDF mode at normal incidence in transmission, with a 2 mm aperture and a monochrometer set to 600 nm wavelength, and when evaluated at polar scattering angles in the range from about 15° to about 60° (e.g. specifically, about 20°). Normal incidence in transmission may be otherwise known as zero degrees in transmission, which may be denoted as 180° incidence by the instrument software. In one or more embodiments, the scattered light intensity may be measured along an azimuthal direction substantially orthogonal to the abraded direction of a sample abraded by the Taber Test. These optical intensity values may also correspond to less than about 1%, less than about 0.5%, less than about 0.2%, or less than about 0.1% of the input light intensity that is scattered into polar scattering angles greater than about 5 degrees, greater than about 10 degrees, greater than about 30 degrees, or greater than about 45 degrees.
Generally speaking, BTDF testing at normal incidence, as described herein, is closely related to the transmission haze measurement, in that both are measuring the amount of light that is scattered in transmission through a sample (or, in this case the article, after abrading the front face 101). BTDF measurements provide more sensitivity as well as more detailed angular information, compared to haze measurements. BTDF allows measurement of scattering into different polar and azimuthal angles, for example allowing us to selectively evaluate the scattering into azimuthal angles that are substantially orthogonal to the abrasion direction in the linear Taber test (these are the angles where light scattering from linear abrasion is the highest). Transmission haze is essentially the integration of all scattered light measured by normal incidence BTDF into the entire hemisphere of polar angles greater than about +/−2.5 degrees.
The optical film structure may include one or more layers, as shown in FIGS. 1-5. One or more of these layers may impart scratch resistant properties to the optical film structure and thus the article 100, while also providing in optical management function (e.g., providing anti-reflection and/or colorless transmittance properties). In one or more alternative embodiments, the thickest layer in the optical film structure provides scratch resistant properties to the optical film structure, and thus the article. The thickness of the layers of the optical film structure may be modified to tune the scratch resistance of the optical film structure and/or the article. Additionally or alternatively, the one or more layers of the optical film structure may include specific materials and/or material properties to tune the optical properties of the optical film structure and/or the article. For example, the layer may include transparent dielectric materials such as SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof.
The optical film structure may have a thickness of 1 μm or greater. In one or more specific embodiments, the thickness of the optical film structure may be about 2 μm or greater. In one or more alternative embodiments, the thickness of the optical film structure may be in the range from about 1 μm to about 20 μm, from about 1 μm to about 15 μm, from about 1 μm to about 10 μm, from about 1 μm to about 8 μm, from about 1 μm to about 5 μm, from about 1.5 μm to about 20 μm, from about 2 μm to about 20 μm, from about 2.5 μm to about 20 μm, from about 3 μm to about 20 μm and all ranges and sub-ranges therebetwen. In some embodiments, the optical film structure may have a thickness in the range from about 0.5 μm to about 5 μm, or from about 1 μm to about 3 μm. Specific optical film structures 120 may have a thickness of about 1.1 μm, about 1.3 μm, about 1.4 μm, about 1.5 μm, about 1.6 μm, about 1.7 μm, about 1.8 μm, about 1.9 μm, about 2.1 μm, about 2.2 μm, about 2.3 μm, about 2.4 μm, about 2.5 μm, about 2.6 μm, about 2.7 μm, about 2.8 μm, about 2.9 μm, about 3.0 μm, about 4 μm, about 5 μm, about 6 μm, about 7 μm, about 8 μm, about 9 μm, about 10 μm, about 15 μm, or about 20 μm.
The optical film structure in accordance with one or more embodiments may be substantially clear or transparent in the visible spectrum. In one or more embodiments, the optical film structure maintains or reduces the reflectivity of the article 100 and does not include any materials for purposely increasing the reflectivity of the article 100. In one or more embodiments, the optical film structure has an average refractive index in the range from about 1.8 to 2.2. In some embodiments, the optical film structure (including the first layer and/or the second layer, described herein) exhibits an extinction coefficient value, measured at 400 nm of about less than or equal to about 10−4.
The optical film structure may include one or more of the following materials: a silicon-containing oxide, a silicon-containing nitride, a silicon-containing oxy-nitride, an aluminum-containing nitride (e.g., AlN and AlxSiyN), an aluminum-containing oxy-nitride (e.g., AlOxNy and SiuAlvOxNy, where x and y are greater than zero) and an aluminum-containing oxide. In one or more embodiments, the aluminum-containing oxy-nitride material may include up to about 60 atomic % aluminum, up to about 20 atomic % oxygen and up to about 40 atomic % nitrogen. In some embodiments, the aluminum-containing oxy-nitride material may include aluminum in an amount in the range from about 45 atomic % to about 55 atomic % (e.g., about 50 atomic %), oxygen in an amount in the range from about 12 atomic % to about 20 atomic % (e.g., about 15 atomic % to about 17 atomic %), and nitrogen in an amount in the range from about 30 atomic % to about 35 atomic % (e.g., about 32 atomic % or about 33 atomic %). In some instances the amount of oxygen in the aluminum-containing oxy-nitride material may be modified to provide a desired crystallinity or crystal size (or size range). In some embodiments, the crystal size may be limited to less than about 50 nm, less than about 20 nm or less than about 10 nm. In some instances, the crystal size may be in the range from about 4 nm to about 8 nm. The amount of nitrogen may be controlled to provide a desired hardness, as measured by the Berkovich Indenter Hardness Test. An increased amount of nitrogen relative to oxygen may provide an aluminum-containing oxy-nitride layer and thus an article including the same, which exhibits higher hardness than such a layer or article that includes less nitrogen relative to the amount of oxygen. Moreover, the amount of nitrogen to oxygen may alter the refractive index and thus may influence the transmittance and color shift of the article. The foregoing compositional modifications could be applied to any of the materials used in the optical film structure including oxygen and/or nitrogen.
In one or more embodiments, SiuAlvOxNy includes composition where (u+v)=1 and (x+y)=1. In one or more embodiments, AlOxNy includes compositions where x+y=1 and x<0.5.
An example of a suitable aluminum-containing oxide includes Al2O3. In one or more embodiments, the optical film structure includes a single layer comprising AlOxNy, or SiuAlvOxNy. In one or more alternative embodiments, the optical film structure may include AlOxNy or SiuAlvOxNy, where x can be in the range from about 0 to about 1. In one or more alternative embodiments, the optical film structure may also include other metal oxides, metal nitrides, metal oxynitrides, metal carbides, metal borides, diamond-like carbon materials and/or combinations thereof. Exemplary metals, in addition to aluminum and silicon include B, Ti, V, Cr, Y, Zr, Nb, Mo, Sn, Hf, Ta and W.
In one or more embodiments, the optical film structure may include at least one of AlN, AlOxNy, SiAlN, SiuAlvOxNy and an aluminum oxide and/or a silicon oxide. Optionally, an optical film structure including AlN and an aluminum oxide may be free of an aluminum-containing oxy-nitride. In one or more alternative embodiments, the optical film structure may include AlN and an aluminum-containing oxy-nitride. Optionally, an optical film structure including AlN and an aluminum-containing oxynitrides may be free of an aluminum-containing oxide. In a specific embodiment, the optical film structure may comprise an aluminum oxy-nitride where the amount of oxygen and nitrogen may be varied such that all three of an aluminum-containing oxide, AlN and an aluminum-containing oxy-nitride are present in the optical film structure. The optical film structure may include silicon such that the optical film structure includes one or more of SiO2, SiOxNy, AlxSiyN, SiuAlvOxNy, and Si3N4 and the amount of oxygen, nitrogen, silicon and/or aluminum may be varied to provide any and all of these materials.
In one or more embodiments, the materials used in the optical film structure may be dielectric (i.e., not electrically conductive). For example, in some embodiments, the optical film structure may consist essentially of dielectric materials. In other embodiments, the optical film structure may be characterized as inorganic, and consisting essentially of inorganic materials (i.e., substantially free of organic materials). In some instances, the optical film structure may be free of IR reflecting materials or layers (i.e., substantially free of metallic layers) and/or free of pyrolytically deposited materials. In other instances, the optical film structure may be substantially free of transparent conductive oxide materials. The optical film structure may be substantially free of particulate materials.
In one or more embodiments, the materials utilized in the optical film structure may be selected to optimize the optical properties of the optical film structure. For example, Al2O3, SiO2, SiOxNy, SiuAlvOxNy, and AlOxNy may be utilized in the optical film structure to minimize the variation on the reflectance color coordinates and/or transmittance color coordinates of the article as the viewing angle is changed from normal incidence (i.e., 0 degrees) to oblique incidence, from the front face 101 of the article. Oblique incidence may be in the range from greater than 0 degrees to less than 90 degrees (e.g., 10 degrees or greater, 20 degrees or greater, 30 degrees or greater, 40 degrees or greater, 50 degrees or greater, 60 degrees or greater, 70 degrees or greater, 75 degrees or greater, 80 degrees or greater, 85 degrees or greater, 86 degrees or greater, 87 degrees or greater, 88 degrees or greater, 89 degrees or greater or 89.5 degrees or greater).
In one or more specific embodiments, the amount of oxygen and/or nitrogen in the optical film structure or the amount of oxygen and/or nitrogen in one or more layers of the optical film structure may be tuned such that the optical film structure has a refractive index of greater than 1.9 at a wavelength of about 500 nm. In one or more specific embodiments, the oxygen content and/or nitrogen content may be tuned such that the optical film structure or one or more layers of the optical film structure exhibits a refractive index that is 1.92 or greater, 1.94 or greater, 1.96 or greater, 1.98 or greater, 2.0 or greater, 2.2 or greater, 2.4 or greater or 2.5 or greater, at a wavelength of about 500 nm. The oxygen content and/or nitrogen content may be tuned in specific layers of the optical film structure. For example, the oxygen content and/or nitrogen content may be tuned in the foregoing manner in layers of the optical film structure containing AlOxNy, SiOxNy, and/or AlxSiyN.
In one or more embodiments, the materials utilized in the optical film structure may be selected to optimize the scratch resistance of the optical film structure. For example, Si3N4 and/or AlN may comprise at least 50% by weight of the materials utilized in the optical film structure 120. Si3N4 and/or AlN may optionally comprise 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more or 75% by weight or more of the materials utilized in the optical film structure 120. Additionally or alternatively, the oxygen content may be modified to tune the hardness, and/or dopants and alloys may be used to modify the lubricity of the optical film structure 120.
The materials selected for the optical film structure may impart ion diffusion barrier properties. In one or more embodiments, the optical film structure may provide a diffusion barrier against the diffusion of sodium ions and/or potassium ions from the substrate 110 into other films or layers disposed on the substrate (e.g., the optical film structure itself or any transparent conductive oxide layers, anti-reflection layers or other such layers).
In one more embodiments, the optical film structure may include AlN having a small grain polycrystalline structure. In one or more specific embodiments, the optical film structure may include AlN having an amorphous and/or microcrystalline structure. Without being bound by theory, it is believed the inclusion of at least some amorphous structure in the optical film structure imparts isotropic mechanical properties that may prevent cracks from forming in the optical film structure and/or dissipates energy from a crack or crack-causing force.
In the embodiment illustrated in FIG. 2, an article 200 includes an optical film structure 220 disposed on one of the opposing major surfaces 112, 114 of the substrate 110. The optical film structure 220 shown in FIG. 2 includes a surface 221, a first layer 222 and a second layer 224. The first layer 222 includes a first sub-layer 226 and a second sub-layer 228 (with a second sub-layer surface 229) such that the first sub-layer 226 is disposed between the substrate 110 and the second sub-layer 228. In one or more embodiments, the first layer 222 may include an aluminum-containing oxide, an aluminum-containing oxy-nitride, AlN or combinations thereof and the second layer 224 may include a transparent dielectric material such as SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof. In one or more specific embodiments, the first layer 222 may include Al2O3, AlN, AlOxNy, SiAlN, SiuAlvOxNy or combinations thereof. In one variant, the first sub-layer 226 may include Al2O3. In another variant, the first sub-layer may include AlOxNy. In yet another variant, the second sub-layer 228 includes AlN. In one embodiment, the optical film structure 220 comprises a first layer 222 including a first sub-layer 226 comprising Al2O3 and a second sub-layer 228 including AlN, and a second layer 224 including a transparent dielectric material (e.g., SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof). In another embodiment, the optical film structure 220 comprises a first layer 222 with a first sub-layer 226 including AlOxNy and a second sub-layer 228 including AlN, and a second layer 224 including a transparent dielectric material (e.g., SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof). The hardness of the second layer may be in the range from about 7 GPa to about 10 GPa, as measured by the Berkovich Indenter Hardness Test. In embodiments in which Al2O3 is utilized in the second layer 224, the nitrogen and oxygen gas concentrations can be modified to form Al2O3, AlOxNy and/or AlN to form the layers of the optical film structure.
In one or more specific embodiments, the second sub-layer 228 can include AlN, AlOxNy, SiAlN, SiuAlvOxNy or combinations thereof, and is thicker or substantially thicker than the first sub-layer 226 and/or the second layer 224. In one or more embodiments, the second sub-layer 228 has a thickness that is greater or substantially greater than the combined thickness of the first sub-layer 226 and the second layer 224. In one variant, the second sub-layer 228 may have a thickness of 1 μm or greater. For example, the second sub-layer 228 may have a thickness in the range from about 1 μm to about 3 μm or more specifically from about 2 μm to about 3 μm. Specific embodiments may include a second sub-layer 228 having a thickness of about 1.1 μm or greater, about 1.2 μm or greater, about 1.3 μm or greater, about 1.4 μm or greater, about 1.5 μm or greater, about 1.6 μm or greater, about 1.7 μm or greater, about 1.8 μm or greater, about 1.9 μm or greater, about 2 μm or greater, about 2.1 μm or greater, about 2.2 μm or greater, about 2.3 μm or greater, about 2.4 μm or greater, about 2.5 μm or greater, about 2.6 μm or greater, about 2.7 μm or greater, about 2.8 μm or greater, about 2.9 μm or greater, or about 3 μm or greater. In embodiments in which the second sub-layer 228 includes AlN, the thickness of the second sub-layer may be about 2 μm or greater. For example, the second sub-layer may have a thickness of about 2.2 μm or greater, about 2.3 μm or greater, about 2.4 μm or greater, about 2.5 μm or greater, about 2.6 μm or greater, about 2.7 μm or greater, about 2.8 μm or greater, about 2.9 μm or greater, or about 3 μm or greater. Exemplary thicknesses of the 1st sub-layer 226 and the second layer 224 are illustrated in the examples herein and can be modified to provide the optical properties described herein.
In some embodiments, the second layer 224 may have a thickness that is less than about 200 nm (e.g., in the range from about 1 nm to about 200 nm, from about 10 nm to about 200 nm, from about 20 nm to about 200 nm, from about 40 nm to about 200 nm, from about 50 nm to about 200 nm, from about 60 nm to about 200 nm, from about 1 nm to about 180 nm, from about 1 nm to about 160 nm, from about 1 nm to about 140 nm, from about 1 nm to about 120 nm, from about 1 nm to about 100 nm, or from about 10 nm to about 150 nm). In some instances, the second layer 224 may be the outermost layer in the optical film structure and, in some cases, may be the outermost layer in the articles described herein (and thus, forms the front face 101 of the article). In some instances, the second layer 224 reduces light scattering after the front face 101 is subjected to abrasion and reduces the visibility of any abrasion damage. Without being bound by theory, the second layer 224 may include a low refractive index material as described more fully below, which reduces the light scattering and thus reduces scratch or damage visibility. In some embodiments, the second layer 224 may have a reduced hardness, as compared to the other layers in the optical film structure and may suppress some of the damage modes, such as frictive cracking, that may be associated with single contact event or multiple contact event scratch damage.
In some embodiments, the use of a thicker second sub-layer 228 (e.g., having a thickness greater than about 5 μm, or greater than about 10 μm) provides enhanced optical properties. For example, in some instances, the use of a thicker sub-layer 228 reduces or eliminates angular metamerism. Angular metamerism results in perceived color change in transmittance or reflectance, when the viewing angle is at an oblique incidence. In some designs of the optical film, the reflectance spectrum or transmittance spectrum include oscillations over the visible spectrum. Under certain conditions, these oscillations move when the viewing angle changes from normal incidence to an oblique incidence. When the line width of the illuminant is narrow (e.g., the line width of a spectral component in a F02 illuminant), this movement in the oscillations are more readily perceived as a change in color (in transmittance or reflectance) (and thus angular metamerism is present). When the line width of the illuminant is wider (e.g., the line width of a spectral component in a D65 illuminant), the movement in the oscillations are not as readily or are not perceived as a change in color (in transmittance or reflectance) (and thus angular metamerism is reduced or eliminated). Without being bound by theory, it is believed that use of a thicker second sub-layer at least reduces or may even eliminate angular metamerisms under all or specific illuminants. Such illuminants include standard illuminants as determined by the CIE, such as A illuminants (representing tungsten-filament lighting), B illuminants (daylight simulating illuminants), C illuminants (daylight simulating illuminants), D series illuminants (representing natural daylight), and F series illuminants (representing various types of fluorescent lighting). In specific embodiments, the use of a thicker second sub-layer may reduce or eliminate angular metamerism under F02 illuminants. The angular metamerism may be reduced or even eliminated through the use of thicker second sub-layers when the viewing angle is at an oblique incidence in the range from about 0 degrees to about 80 degrees, from about 0 degrees to about 75 degrees, from about 0 degrees to about 70 degrees, from about 0 degrees to about 65 degrees, from about 0 degrees to about 60 degrees, from about 0 degrees to about 55 degrees, from about 0 degrees to about 50 degrees, from about 0 degrees to about 45 degrees, from about 0 degrees to about 40 degrees, from about 0 degrees to about 35 degrees, from about 0 degrees to about 30 degrees, from about 0 degrees to about 25 degrees, from about 0 degrees to about 20 degrees, from about 0 degrees to about 15 degrees, from about 5 degrees to about 80 degrees, from about 5 degrees to about 80 degrees, from about 5 degrees to about 70 degrees, from about 5 degrees to about 65 degrees, from about 5 degrees to about 60 degrees, from about 5 degrees to about 55 degrees, from about 5 degrees to about 50 degrees, from about 5 degrees to about 45 degrees, from about 5 degrees to about 40 degrees, from about 5 degrees to about 35 degrees, from about 5 degrees to about 30 degrees, from about 5 degrees to about 25 degrees, from about 5 degrees to about 20 degrees, from about 5 degrees to about 15 degrees, and all ranges and sub-ranges therebetween, from normal incidence. The optical film may exhibit reduced angular metamerism all the oblique incidence angles in the range from about 0 degrees to about 80 degrees from normal incidence.
The refractive index of the first sub-layer 226 may be in the range from about 1.45 to about 1.8. In one or more specific embodiments, the refractive index of the first sub-layer 226 may be in the range from about 1.6 to about 1.75. For example, the refractive index of the first sub-layer 226 may include 1.45, 1.46, 1.47, 1.48, 1.49, 1.5, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70, 1.71, 1.72, 1.73, 1.74, 1.76, 1.77, 1.78, 1.79, 1.8 and all ranges and sub-ranges therebetween, which may be present at locations along the first sub-layer. The refractive index of the second sub-layer 228 may be in the range from about 1.8 to about 2.2. In one or more embodiments, the refractive index of the second sub-layer may be from about 2.0 to about 2.15. For example, the refractive index of the second sublayer 228 may include 1.8, 1.82, 1.84, 1.86, 1.88, 1.90, 1.92, 1.94, 1.96, 1.98, 1.99, 2.0, 2.02, 2.04, 2.06, 2.08, 2.1, 2.12, 2.14, 2.15, 2.16, 2.18, 2.2 and all ranges or sub-ranges therebetween, which may be present at locations along the second sub-layer. The refractive index of the second layer 224 may be in the range from about 1.4 to about 1.6 (e.g., about 1.46±0.03). In specific embodiments, the second layer 224 may have a refractive index in the range from about 1.45 to about 1.55. For example, the refractive index of the second layer 224 may include 1.4, 1.42, 1.44, 1.46, 1.48, 1.50, 1.52, 1.54, 1.56, 1.58, 1.6 and all ranges and sub-ranges therebetween, which may be present at locations along the second layer.
FIG. 7 generally illustrates the optical properties of the optical film structure 220 illustrated in FIG. 2. In the graph, the thickness values on the x-axis illustrate the thickness of the optical film structure 220 in a direction moving away from the substrate 110. The refractive index values of the optical film structure 220 are provided on the y-axis to illustrate the changes in refractive index along the thickness of the optical film structure. The graph of FIG. 7 does not take into account the refractive indices of the substrate 110 (or any other layer between the substrate 110 and the optical film structure 220) or air (or any other layer disposed on the optical film structure 220). The interface between the substrate 110 and the first sub-layer 226 is indicated by reference number 600, the interface between the first sub-layer 226 and the second sub-layer 228 is indicated by reference number 610, the interface between the second sub-layer 228 and the second layer 224 is indicated by reference number 620 and the interface between the second layer 224 and air is indicated by reference number 630. As shown in FIG. 7, the refractive index of the first sub-layer 226 and the second layer 224 are less than the refractive index of the second sub-layer 228. In one particular embodiment, the first sub-layer 226 has a refractive index of about 1.75, the second sub-layer has a refractive index of about 2.1 and the second layer 224 has a refractive index of about 1.5. In FIG. 7, the second sub-layer 228 has a greater thickness than the first sub-layer 226 and the second layer 224.
In the embodiment illustrated in FIG. 3, the article 300 includes an optical film structure 320 disposed on one of the opposing major surfaces 112, 114 of the substrate 110. The optical film structure 320 shown in FIG. 3 includes a first layer 322 and a second layer 324. The first layer 322 includes a first sub-layer 326, a second sub-layer 328 and a third sub-layer 330. In the embodiment shown in FIG. 3, in the first layer 320, the second sub-layer 328 between is between the first sub-layer 326 and the third sub-layer 330. The first sub-layer 326 is disposed between the substrate 110 and the second sub-layer 328 while the third sub-layer 330 is disposed between the second sub-layer 328 and the second layer 324. In one or more embodiments, the first layer 322 may include an aluminum-containing oxide, an aluminum-containing oxy-nitride, AlN or combinations thereof and may further include a transparent dielectric material (e.g., SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof). In one or more specific embodiments, the first layer 322 may include Al2O3, AlN, AlOxNy or combinations thereof, and may further include a transparent dielectric material (e.g., SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof). The second layer 324 may include a transparent dielectric material (e.g., SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof). In one variant, the first sub-layer 326 may include AlN, the second sub-layer 328 may include SiO2 and the third sub-layer 330 may include AlN. In another variant, the first sub-layer 326 may include AlN, the second sub-layer 328 may include Al2O3 and the third sub-layer 330 may include AlN. In embodiments in which Al2O3 is utilized in the second sub-layer 328 and the second layer 324, the nitrogen and oxygen gas concentrations can be modified to form either Al2O3 or AlN to form the layers of the optical film structure.
In one or more specific embodiments, the first sub-layer 326 and the third sub-layer 330 may each have a thickness or may have a combined thickness that is greater or substantially greater than the thickness of either the second sub-layer 328 or the second layer 324. In one or more embodiments, the first sub-layer 326 and the third sub-layer 330 may each have a thickness or may have a combined thickness that is greater or substantially greater than the combined thickness of the second sub-layer 328 and the second layer 324. In one variant, the first sub-layer 326 and/or the third sub-layer 330 may have a thickness each or combined of about 1 μm or greater. For example, the first sub-layer 326 and/or the third sub-layer 330 may have a thickness each or combined of about 1.1 μm or greater, about 1.2 μm or greater, about 1.3 μm or greater, about 1.4 μm or greater, about 1.5 μm or greater, about 1.6 μm or greater, about 1.7 μm or greater, about 1.8 μm or greater, about 1.9 μm or greater, or about 2 μm or greater. In embodiments in which the first sub-layer 326 and/or the third sub-layer 330 include AlN, the thickness of these sub-layers 326, 328 may be about 2 μm or greater each or in combination. For example, the first sub-layer 326 and/or the third sub-layer 328 may each or combined have a thickness of about 2.1 μm or greater, about 2.2 μm or greater, about 2.3 μm or greater, about 2.4 μm or greater, about 2.5 μm or greater, about 2.6 μm or greater, about 2.7 μm or greater, about 2.8 μm or greater, about 2.9 μm or greater, or about 3 μm or greater. In one or more embodiments, the first sub-layer 326 may have the same or different thickness as the third sub-layer 330. The first sub-layer 326 may have a thickness that is greater than or less than the thickness of the third sub-layer 330. In one or more embodiments, the thicknesses of the second sub-layer 328 and the second layer 324 are the same. In one or more alternative embodiments, the optical film structure 320 has a thickness regime of thick/thin/thick/thin wherein the first and third sub-layers 326, 330 are thick and the second-sub-layer 328 and the second layer 324 are thin relative to the first and third sub-layers 326, 330.
The refractive index of the first sub-layer 326 may be in the range from about 1.7 to about 2.1. For example, the refractive index of the first sub-layer 326 may include 1.70, 1.72, 1.74, 1.76, 1.78, 1.80, 1.82, 1.84, 1.86, 1.88, 1.90, 1.92, 1.94, 1.96, 1.98, 2.0, 2.1 and all ranges and sub-ranges therebetween. In one or more alternative embodiments, the refractive index is related to an increase in hardness of the first sub-layer 326. The refractive index of the third sub-layer 330 may be in the range from about 1.7 to about 2.1. In one or more embodiments, the refractive index of the third sub-layer 330 may be in the range from about 2.0 to about 2.1. For example, the refractive index of the third sub-layer 330 may include 1.70, 1.72, 1.74, 1.76, 1.78, 1.80, 1.82, 1.84, 1.86, 1.88, 1.90, 1.92, 1.94, 1.96, 1.98, 2.0, 2.1 and all ranges and sub-ranges therebetween. In one or more alternative embodiments, the refractive index is related to an increase in hardness of the first sub-layer 326. The refractive index of the second sub-layer 328 may be in the range from about 1.45 to about 1.8. In one or more embodiments, the refractive index of the second sub-layer 328 may be in the range from about 1.65 to about 1.75. For example, the refractive index of the second sub-layer 328 may be 1.45, 1.46, 1.48, 1.50, 1.52, 1.54, 1.56, 1.58, 1.60, 1.62, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70, 1.71, 1.72, 1.73, 1.74, 1.75, 1.76, 1.78, 1.8 and all ranges and sub-ranges therebetween. The refractive index of the second layer 324 may be in the range from about 1.45 to about 1.8. In one or more embodiments, the refractive index of the second sub-layer 328 may be in the range from about 1.45 to about 1.55. For example, the refractive index of the second sub-layer 328 may be 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.58, 1.60, 1.62, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70, 1.71, 1.72, 1.73, 1.74, 1.75, 1.76, 1.78, 1.8 and all ranges and sub-ranges therebetween
FIG. 8 generally illustrates the optical properties of the optical film structure 320 illustrated in FIG. 3. In the graph, the thickness values on the x-axis illustrate the thickness of the optical film structure 320 in a direction moving away from the substrate 110. The refractive index values of the optical film structure 320 are provided on the y-axis to illustrate the changes in refractive index along the thickness of the optical film structure. In FIG. 8, the graph does not take into account the refractive indices of the substrate 110 (or any other layer between the substrate 110 and the optical film structure 320) or air (or any other layer disposed on the optical film structure 320). The interface between the substrate 110 and the first sub-layer 326 is indicated by reference number 700, the interface between the first sub-layer 326 and the second sub-layer 328 is indicated by reference number 710, the interface between the second sub-layer 328 and the third sub-layer 330 is indicated by reference number 720, the interface between the third sub-layer 330 and the second layer 324 is indicated by reference number 730 and the interface between the second layer 324 and air is indicated by reference number 740. As shown in FIG. 8, the refractive index of the first sub-layer 326 and the third sub-layer 330 are greater than the refractive index of the second sub-layer 328 and the refractive index of the second layer 324. In the embodiment illustrated in FIG. 8, the refractive indices of the first sub-layer 326 and the third sub-layer 330 are shown as equal to each other and the refractive indices of the second sub-layer 328 and the second layer 324 are shown as equal to each other. In one or more alternative embodiments, the refractive index of the first sub-layer 326 may be different from the refractive index of the third sub-layer 330 and the refractive index of the second sub-layer 328 may be different from the refractive index of the second layer 324. In FIG. 8, the thickness of the first and third sub-layers 326, 330 are shown as being greater than the thickness of the second sub-layer 328 and the second layer 324. In addition, the thickness of the third sub-layer 330 is shown as greater than the thickness of the first sub-layer 324; however, it may be possible for the first sub-layer 324 to have a greater thickness than the third sub-layer 330.
In the embodiment illustrated in FIG. 4, the article 400 includes an optical film structure 420 disposed on one of the opposing major surfaces 112, 114 of the substrate 110. The optical film structure 420 shown in FIG. 4 includes a first layer 422 and a second layer 424. The first layer 422 includes a silicon-containing oxide, a silicon-containing oxy-nitride, silicon nitride, an aluminum-containing oxide, an aluminum-containing oxy-nitride (e.g., AlOxNy and SiuAlvOxNy), aluminum-containing nitride (e.g., AlN and AlxSiyN) or combinations thereof. The second layer 424 may include a transparent dielectric material (e.g., SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof).
The first layer 422 may include at least one of an oxygen content gradient, a nitrogen content gradient, a silicon content gradient and aluminum content gradient and various combinations thereof. As used herein, the term “gradient” refers to a variation in atomic % of an element in the composition of a layer. The variation in atomic % of an element may occur among a plurality of sub-layers of a layer. In some instances, up to 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120 or even 130 sub-layers having a different atomic % of an element from one another may be utilized to form a layer having a gradient. In a layer that includes an oxygen gradient, the amount of oxygen (atomic %) in the composition of the layer at or near the interface between the layer and the substrate 110 may differ from the amount of oxygen (atomic %) in the composition of the layer at or near the interface between the layer and another layer (e.g., the first layer and the second layer) and other areas therebetween.
In one or more embodiments, the composition gradient may include a silicon/aluminum composition gradient, where the atomic % of silicon and aluminum change along the thickness of the first layer independently of one another or in relation to one another. In other embodiments, the compositional gradient may include an oxygen/nitrogen composition gradient, where the atomic % of oxygen and nitrogen change along the thickness of the first layer independently of one another or in relation to one another. In one or more embodiments, the ratio of oxygen to nitrogen at or near the interface between the substrate 110 and the first layer 422 may be greater than the ratio of oxygen to nitrogen at or near the interface between the first layer 422 and the second layer 424. For example, there may be very little or no nitrogen present in the first layer 422 at or near the interface between the substrate 110 and the first layer 422 and/or there may be very little or no oxygen present in the first layer 422 at or near the interface between the first layer 422 and the second layer 424. In one or more embodiments, the ratio of silicon to aluminum at or near the interface between the substrate 110 and the first layer 422 may be greater than the ratio of silicon to aluminum at or near the interface between the first layer 422 and the second layer 424. For example, there may be very little or no aluminum present in the first layer 422 at or near the interface between the substrate 110 and the first layer 422 and/or there may be very little or no silicon present in the first layer 422 at or near the interface between the first layer 422 and the second layer 424.
In one or more embodiments, the oxygen content gradient and/or the nitrogen content gradient may be controlled by the flow rate of oxygen gas and/or nitrogen gas introduced into the deposition process (i.e., into the deposition chamber in which the optical film structure is being deposited onto the substrate). To increase the oxygen or nitrogen content, the flow rate of oxygen or nitrogen is increased. In some embodiments, the aluminum and/or silicon gradient may be controlled by controlling the power directed at the aluminum and/or silicon source materials (e.g., where sputtering is used to form the optical film structure, the power directed at the aluminum and/or silicon sputtering targets is controlled). To increase the aluminum or silicon content, the power directed to the aluminum and/or silicon source materials is increased.
The oxygen and/or silicon content in the first layer 422 may decreases along the thickness t of the first layer 422 moving along the thickness t moving away from the substrate 110, as illustrated in FIG. 6A. The oxygen content and/or silicon content gradient may extend along the entire thickness t of the first layer 422. In another variant, the oxygen content and/or silicon content gradient may extend along a portion of the thickness t of the first layer 422, while the remaining portion of the first layer 422 may not include an oxygen content and/or silicon content gradient, and thus may have a constant oxygen and/or silicon content (which may include no oxygen and/or silicon). For example, the oxygen content and/or silicon content gradient may continue until the interface between the optical film structure and the substrate 110 or any other layer between the substrate 110 and the layer containing the oxygen content and/or silicon content gradient, such as an interlayer, which will be discussed below in greater detail. Alternatively, the oxygen content and/or silicon content gradient may stop at a distance from the substrate 110 or an interlayer disposed between the substrate 110 and the first layer 422. In one or more embodiments, the oxygen content and/or silicon content of the first layer 422 may be the greatest near the interface between the optical film structure 420 and the substrate 110 and the least near the interface between the first layer 422 and the second layer 424. In one or more embodiments, the composition of the first layer 422 may depend on the oxygen content and/or silicon content of the first layer 422. For example, the first layer 422 may include the highest oxygen content and/or silicon content in a region of the first layer 422 adjacent to the substrate 110. The first layer 422 may include the lowest oxygen content and/or silicon content in a region of the first layer 422 adjacent to the second layer 424, such as the embodiment shown in FIG. 5.
In one or more specific embodiments, the region of the first layer 422 adjacent to the substrate 110 may include the highest oxygen content and no nitrogen content (i.e. y=0). In one such specific embodiment, the region of the first layer 422 adjacent to the substrate 110 may include Al2O3, SiO2 or a combination thereof.
In one or more embodiments, the first layer 422 may include an aluminum content gradient and/or a nitrogen content gradient. The aluminum content and/or nitrogen content in the first layer 422 increase along the thickness t of the first layer 422 moving along the thickness t moving away from the substrate 110, as illustrated in FIG. 6B. The aluminum content and/or nitrogen content gradient may extend along the entire thickness t of the first layer 422. In another variant, the aluminum content and/or nitrogen content gradient may extend along a portion of the thickness t of the first layer 422, while the remaining portion of the first layer 422 may not include an aluminum content and/or nitrogen content gradient, and thus may have a constant aluminum content and/or nitrogen content (which may include no aluminum and/or nitrogen). For example, the aluminum content and/or nitrogen content gradient may continue until the interface between the optical film structure and the substrate 110 or any other layer between the substrate 110 and the layer containing the aluminum content and/or nitrogen content gradient, such as the interlayer, which will be discussed below in greater detail. Alternatively, the aluminum content and/or nitrogen content gradient may stop at a distance from the substrate 110 or an interlayer disposed between the substrate 110 and the first layer 422. In one or more embodiments, the aluminum content and/or nitrogen content of the first layer 422 may be the lowest near the interface between the optical film structure 420 and the substrate 110 and the greatest near the interface between the first layer 422 and the second layer 424. FIG. 6B illustrates the relative aluminum content and/or nitrogen content of the first layer 424. In one or more embodiments, the first layer 422 includes a silicon oxide, a silicon oxynitrides, silicon nitride, aluminum-containing oxide, an aluminum-containing oxy-nitride (e.g., AlOxNy and SiuAlvOxNy) or aluminum-containing nitride (e.g., AlN and AlxSiyN) depending on the silicon content, oxygen content, aluminum content and/or nitrogen content of the first layer 422. For example, the first layer 422 may include the lowest silicon content and/or oxygen content in a region of the first layer 422 adjacent to the second layer 424, as shown in FIG. 6A. As also shown in FIG. 6A, the first layer 422 may include the highest silicon content and/or oxygen content in a region of the first layer 422 adjacent to the substrate 110. FIG. 4A illustrates an embodiment in which the first layer 422 includes a silicon gradient, an aluminum gradient, an oxygen gradient and a nitrogen gradient. In FIG. 4A, the silicon and oxygen contents decrease with thickness in a direction moving away from the substrate 110 and the aluminum and nitrogen contents increase with thickness in a direction moving away from the substrate 110. The relative amounts of each of silicon, aluminum, oxygen and nitrogen are shown in FIG. 4A; however, it should be noted that the changes in the contents of silicon, aluminum, oxygen and nitrogen may not be linear or consistent and mixtures of SiO2, SiOxNy, SiuAlvOxNy, AlxSiyN and AlN may be present at various thicknesses of the first layer 422.
Between the region adjacent to the substrate 110 and the region adjacent to the second layer 424, the first layer 422 may include AlOxNy, where x and y are dependent on the amount of nitrogen present and may change as the nitrogen content increases along thickness t in a direction moving away from the substrate 110. Moreover, between the region adjacent to the substrate 110 and the region adjacent to the second layer 424, the first layer 422 may include SiuAlvOxNy (where (u+v)=1 and (x+y)=1) or SiOxNy where x and y are dependent on the amount of nitrogen and/or aluminum present and change as the nitrogen content and/or aluminum content increases along thickness t in a direction moving away from the substrate 110.
In another embodiment, the first layer includes SiuAlvOxNy and/or SiOxNy where, in at least one region of the first layer 422 along thickness t, x or y may equal zero. In one or more specific embodiments, the region of the first layer 422 adjacent to the substrate 110 may include no nitrogen content and the highest oxygen content (i.e. y=0). In one such specific embodiment, the region of the first layer 422 adjacent to the substrate 110 may include SiO2. In another specific embodiment, the region of the first layer 422 adjacent to the second layer 424 may include the highest nitrogen content and/or highest aluminum content and the lowest oxygen content and/or lowest silicon content. In such embodiments, the region of the first layer 422 adjacent to the second layer 424 may include AlN, Si3N4 or AlxSiyN.
In one or more embodiments, the first layer 422 includes SiO2 adjacent to the substrate 110 or may be rich in silicon and/or oxygen and may be deficient or lack aluminum and/or nitrogen. In one or more embodiments, the first layer 422 includes AlN adjacent to the second layer 424 or may be rich in aluminum and/or nitrogen and may be deficient or lack silicon and/or oxygen.
In another embodiment, the first layer includes AlOxNy, where, in at least one region of the first layer 422 along thickness t, y may equal zero. In one or more specific embodiments, the region of the first layer 422 adjacent to the substrate 110 may include the highest oxygen content and no nitrogen content (i.e. y=0). In one such specific embodiment, the region of the first layer 422 adjacent to substrate 110 may include Al2O3.
In one or more embodiments, the composition of layer 422 may tuned to minimize the variation on the reflectance color points as the viewing angle is changed from normal incidence (i.e., 0 degrees) to oblique incidence. In such embodiments, the composition of layer 422 is graded such that the composition near the interface between the first layer 422 and the second layer 424, the first layer comprises AlN, AlxSiyN, Si3N4, SiuAlvOxNy (where x<0.1) or AlOxNy (where x<0.1).
In one or more specific embodiments, the first layer 422 has a thickness that is greater or substantially greater than the thickness of the second layer 424. In one variant, the first layer 422 has a thickness of 1 μm or greater. For example, the first layer 422 may have a thickness of 1.1 μm or greater, 1.2 μm or greater, 1.3 μm or greater, 1.4 μm or greater, 1.5 μm or greater, 1.6 μm or greater, 1.7 μm or greater, 1.8 μm or greater, 1.9 μm or greater, 2 μm or greater, 2.1 μm or greater, 2.2 μm or greater, 2.3 μm or greater, 2.4 μm or greater, 2.5 μm or greater, 2.6 μm or greater, 2.7 μm or greater, 2.8 μm or greater, 2.9 μm or greater, or 3 μm or greater.
In the embodiment shown in FIG. 4, the refractive index of the first layer 422 may be in the range from about 1.6 to about 2.1. For example, the refractive index of the first layer 422 may include 1.6, 1.62, 1.64, 1.66, 1.68, 1.70, 1.72, 1.74, 1.76, 1.78, 1.80, 1.82, 1.84, 1.86, 1.88, 1.90, 1.92, 1.94, 1.96, 1.98, 2.0, 2.1 and all ranges and sub-ranges therebetween. The refractive index of the second layer 424 may be in the range from about 1.45 to about 1.55. For example, the refractive index of the second layer 424 may include 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55 and all ranges and sub-ranges therebetween. As will be discussed below in greater detail, the first layer 422 of the optical film structure 420 may have a refractive index gradient.
In embodiments in which Al2O3 is utilized in the second layer 424, the nitrogen and oxygen gas concentrations can be modified to form any of Al2O3, AlOxNy and/or AlN to form the layers of the optical film structure.
In one or more alternative embodiments, the optical film structure 420 may not include a second layer 424 and may only include the first layer 422.
FIG. 9 generally illustrates the optical properties of the optical film structure 420 illustrated in FIG. 4. In the graph, the thickness values on the x-axis illustrate the thickness of the optical film structure 420 in a direction moving away from the substrate 110. The refractive index values of the optical film structure 420 are provided on the y-axis to illustrate the changes in refractive index along the thickness of the optical film structure. In FIG. 9, the graph does not take into account the refractive indices of the substrate 110 (or any other layer between the substrate 110 and the optical film structure 420) or air (or any other layer disposed on the optical film structure 420). The interface between the substrate 110 and the first layer 422 is indicated by reference number 800, the interface between the first layer 422 and the second layer 424 is indicated by reference number 810, the interface between the second layer 424 and air is indicated by reference number 820. As shown in FIG. 9, the refractive index of the first layer 422 increases along the thickness moving away from the substrate 110 (or the substrate-first layer interface 800). In one or more embodiments, the refractive index changes with the changes in oxygen content in the first layer 422. In FIG. 9, the refractive index of the first layer 422 is greater than the refractive index of the second layer 424 for a greater portion of the first layer 422. In other words, a larger portion of the first layer 422 has a higher refractive index than the second layer 424. In FIG. 9, the thickness of the first layer 422 is shown as being greater than the thickness of the second layer 424.
FIG. 5 illustrates a article 500 that includes an optical film structure 520 disposed on one of the opposing major surfaces 112, 114 of the substrate 110. The optical film structure 520 shown in FIG. 5 includes a first layer 522 and a second layer 524. The first layer 522 includes a silicon-containing oxide, a silicon-containing oxynitrides, silicon nitride, an aluminum-containing oxide, an aluminum-containing oxy-nitride (e.g., AlOxNy and SiuAlvOxNy), an aluminum-containing nitride (e.g., AlN and AlxSiyN), or combinations thereof. The second layer 524 may include a transparent dielectric material (e.g., SiO2, GeO2, Al2O3, Nb2O5, TiO2, Y2O3 and other similar materials and combinations thereof), or a combination thereof. The first layer 522 includes a first sub-layer 526 and a second sub-layer 528. The first sub-layer 526 may include an oxygen content gradient, a nitrogen content gradient, a silicon content gradient and aluminum content gradient and various combinations thereof, as described with reference to optical film structure 420.
In one or more embodiments, the first sub-layer 526 includes a silicon-containing oxide, a silicon-containing oxynitrides, silicon nitride, an aluminum-containing oxide, an aluminum-containing oxy-nitride (e.g., AlOxNy and SiuAlvOxNy), aluminum-containing nitride (e.g., AlN and AlxSiyN), and/or combinations thereof depending on the oxygen content, silicon content, nitrogen content and/or aluminum content of the first sub-layer 526. In a specific embodiment, the first sub-layer 526 may be free of AlN and/or Si3N4. In other words, the first sub-layer 526 of one or more specific embodiments includes oxygen throughout the thickness t, but the amount of oxygen varies along the thickness t. The second sub-layer 528 may include AlN and/or Si3N4. In one or more embodiments, the second sub-layer 528 may be free of any intentionally included oxygen. Accordingly, in one or more embodiments, the oxygen content gradient of the first layer 522 may extend only along the thickness t of the first sub-layer 526, while the second sub-layer 528 may be free of oxygen.
FIG. 5A illustrates an embodiment in which the first sub-layer 526 includes a silicon gradient, an aluminum gradient, an oxygen gradient and a nitrogen gradient. In FIG. 5A, the silicon and oxygen contents decrease with thickness in a direction moving away from the substrate 110 and the aluminum and nitrogen contents increase with thickness in a direction moving away from the substrate 110. The relative amounts of each of silicon, aluminum, oxygen and nitrogen are shown; however, it should be noted that the changes in the contents of silicon, aluminum, oxygen and nitrogen may not be linear or consistent and mixtures of SiO2, SiONy, SiuAlvOxNy, AlxSiyN and AlN may be present at various thicknesses of the first sub-layer 526. In one or more embodiments, the first sub-layer may not include AlN and may include only SiO2, SiONy, SiuAlvOxNy, and/or AlxSiyN, and the second sub-layer may include AlN.
In one or more embodiments, the decrease or increase in oxygen, silicon, aluminum and/or nitrogen content along thickness t of the first layer 422, or first sub-layer 526 in a direction moving away from the substrate 110 may be constant. In one or more alternative embodiments, the decrease or increase in oxygen, silicon, aluminum and/or nitrogen is not constant. In such embodiments in which the decrease or increase in oxygen, silicon, aluminum and/or nitrogen is not constant, it will be understood that the oxygen, silicon, aluminum and/or nitrogen will either decrease or remain constant along portions of the thickness t in the direction moving away from the substrate 110; however the respective oxygen, silicon, aluminum and/or nitrogen content of the first layer 422, or first sub-layer 526 will decrease or increase, as a general trend, along the thickness t in the direction moving away from the substrate 110. For example, the layers of the optical film structures with an oxygen content gradient disclosed herein do not include an increase in oxygen content along the thickness t in a direction moving away from the substrate 110. The oxygen content gradient of embodiments in which the oxygen content either decreases or remains constant along portions of the thickness t of the first layer 422, or first sub-layer 526, may be referred to as “step-wise” oxygen content gradients or may be described as having an oxygen content that decreases step-wise, along the thickness to of the first layer 422, or first sub-layer 526. In one or more specific embodiments, the oxygen content may decrease at a slower rate along the thickness of the first layer 422, or first sub-layer 526 closer to the substrate 110 and decrease at a faster rate along the thickness of the first layer 422, or first sub-layer 526 closer to the second layer 424 or second sub-layer 528. In other words, the rate at which the oxygen content decreases along the thickness of the first layer 422, or first sub-layer 526 may increase in a direction moving away from the substrate 110. Accordingly, the oxygen content gradient may increase linearly or non-linearly along the thickness t in a direction moving away from the substrate. These types of gradients (i.e., stepwise, constant, faster/slower rates, linear and non-linear) are equally applicable to silicon content gradients, aluminum gradients, and nitrogen gradients described herein where the silicon content, aluminum content and/or nitrogen content increases and decreases along the thickness of the first layer 422, or first sub-layer 526.
In one or more embodiments, the second sub-layer 528 has a thickness that is tuned to optimize the hardness of the optical film structure. In one or more specific embodiments, the thickness of the second sub-layer 528 may be tuned in relation to the first sub-layer 526. In one or more specific embodiments, the second sub-layer 528 is thicker or substantially thicker than either of the first sub-layer 526 or the second layer 524. In one or more embodiments, the second sub-layer 528 has a thickness that is greater or substantially greater than the combined thickness of the first sub-layer 526 and the second layer 524. In one variant, the second sub-layer 528 may have a thickness of 1 μm or greater. For example, the second sub-layer 528 may have a thickness in the range from about 1 μm to about 3 μm or more specifically from about 2 μm to about 3 μm. Specific embodiments of the second sub-layer 528 may have a thickness of about 1.1 μm or greater, about 1.2 μm or greater, about 1.3 μm or greater, about 1.4 μm or greater, about 1.5 μm or greater, about 1.6 μm or greater, about 1.7 μm or greater, about 1.8 μm or greater, about 1.9 μm or greater, about 2 μm or greater, about 2.1 μm or greater, about 2.2 μm or greater, about 2.3 μm or greater, about 2.4 μm or greater, about 2.5 μm or greater, about 2.6 μm or greater, about 2.7 μm or greater, about 2.8 μm or greater, about 2.9 μm or greater, or about 3 μm or greater. In embodiments in which the second sub-layer 528 includes AlN, the thickness of the second sub-layer may be 2 μm or greater. For example, the second sub-layer 528 may have a thickness of about 2.2 μm or greater, about 2.3 μm or greater, about 2.4 μm or greater, about 2.5 μm or greater, about 2.6 μm or greater, about 2.7 μm or greater, about 2.8 μm or greater, about 2.9 μm or greater, or about 3 μm or greater.
The refractive index of the first sub-layer 526 may be in the range from about 1.6 to about 2.1. For example, the refractive index of the first sub-layer 326 may include 1.6, 1.62, 1.64, 1.66, 1.68, 1.70, 1.72, 1.74, 1.76, 1.78, 1.80, 1.82, 1.84, 1.86, 1.88, 1.90, 1.92, 1.94, 1.96, 1.98, 2.0, 2.1 and all ranges and sub-ranges therebetween. The refractive index of the second sub-layer 528 may be in the range from about 2.0 to about 2.1. For example, the refractive index of the second sub-layer may include 2.0, 2.01, 2.02, 2.03, 2.04, 2.05, 2.06, 2.07, 2.08, 2.09, 2.1 and all ranges and sub-ranges therebetween. The refractive index of the second layer 524 may be in the range from about 1.45 to about 1.55. For example, the refractive index of the second layer 524 may include 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55 and all ranges and sub-ranges therebetween. As will be discussed below in greater detail, the first layer 522 of the optical film structure 520 may have a refractive index gradient.
In embodiments in which Al2O3 is utilized in the second layer 524, the nitrogen and oxygen gas concentrations can be modified to form any of Al2O3, AlOxNy and/or AlN to form the layers of the optical film structure.
FIG. 10A generally illustrates the optical properties of the optical film structure 520 illustrated in FIG. 5. In the graph, the thickness values on the x-axis illustrate the thickness of the optical film structure 520 in a direction moving away from the substrate 110. The refractive index values of the optical film structure 520 are provided on the y-axis to illustrate the changes in refractive index along the thickness of the optical film structure. In FIG. 10A, the graph does not take into account the refractive indices of the substrate 110 (or any other layer between the substrate 110 and the optical film structure 520) or air (or any other layer disposed on the optical film structure 520). The interface between the substrate 110 and the first sub-layer 526 is indicated by reference number 900, the interface between the first sub-layer 526 and the second sub-layer 528 is indicated by reference number 910, the interface between the second sub-layer 528 and the second layer 524 is indicated by reference number 920 and the interface between the second layer 524 and air is indicated by reference number 930. As shown in FIG. 10A, the refractive index of the first sub-layer 526 increases along the thickness of the first sub-layer 526 in a direction moving away from the substrate 110 (or the substrate-first sub-layer 526 interface 900). In one or more alternative embodiments, the refractive index of the first sub-layer 526 changes with the change in oxygen content in the first sub-layer 526. In addition, the first sub-layer 526 has a refractive index that is greater than the refractive index of the second layer 524 along a majority of the thickness of the first sub-layer 526. The second sub-layer has a refractive index that is greater than the refractive index of the second layer 524 along the entire thickness of the second sub-layer. In FIG. 10A, the thickness of the first and second sub-layers 526, 528 are shown as being greater than the thickness of the second layer 524. In addition, the thickness of the first and second sub-layers 526, 528 are shown as about equal; however in some embodiments one of the first and second sub-layers 526, 528 may have a greater thickness than the other of the first and second sub-layers.
FIG. 10B generally illustrates the optical properties of an alternative embodiment of the optical film structure shown in FIG. 5. In the embodiment shown in FIG. 10B, the second-sub-layer 528 has the same refractive index as the second layer 524. In one or more embodiments, the second sub-layer 528 may be compositionally similar or identical to at least a portion of the second layer 524. In the graph shown in FIG. 10B, the thickness values on the x-axis illustrate the thickness of the optical film structure 520 in a direction moving away from the substrate 110. The refractive index values of the optical film structure 520 are provided on the y-axis to illustrate the changes in refractive index along the thickness of the optical film structure. In FIG. 10B, the graph does not take into account the refractive indices of the substrate 110 (or any other layer between the substrate 110 and the optical film structure 520) or air (or any other layer disposed on the optical film structure 520). The interface between the substrate 110 and the first sub-layer 526 is indicated by reference number 1000, the interface between the first sub-layer 526 and the second sub-layer 528 is indicated by reference number 1010, the interface between the second sub-layer 528 and the second layer 524 is indicated by reference number 1020 and the interface between the second layer 524 and air is indicated by reference number 1030. As shown in FIG. 10AB, the refractive index of the first sub-layer 526 increases along the thickness of the first sub-layer 526 in a direction moving away from the substrate 110 (or the substrate-first sub-layer 526 interface 900). In one or more alternative embodiments, the refractive index of the first sub-layer 526 changes with the change in oxygen content in the first sub-layer 526. In addition, the first sub-layer 526 has a refractive index that is less than the refractive index of the second layer 524 along at least a portion of the thickness of the first sub-layer 526. The second sub-layer has a refractive index that is the same as the refractive index of the second layer 524 along the entire thickness of the second sub-layer. In FIG. 10B, the thickness of the first and second sub-layers 526, 528 are shown as being greater than the thickness of the second layer 524; however, the thicknesses of the first sub-layer 526, the second sub-layer 528 and the second layer 524 may be equal or may be thicker or thinner with respect to one another as needed to provide the desired scratch resistance and optical properties. In addition, the thickness of the first and second sub-layers 526, 528 are shown as about equal; however in some embodiments one of the first and second sub-layers 526, 528 may have a greater thickness than the other of the first and second sub-layers.
In the embodiments shown in FIGS. 4 and 5, the first layer 422, 522 of the optical film structure may have a refractive index gradient. The refractive index gradient may be related to the oxygen and/or nitrogen content gradient in the first layer 422, 522 or may be caused by a compositional gradient in the first layer 422, 522. The first layer 222, 322 shown in FIGS. 2 and 3 may also have a refractive index gradient. In such embodiments, the refractive index of the first layer of the optical film structure may increase along the thickness t in a direction moving away from the substrate 110. For example, the refractive index gradient may be in the range from about 1.45 to about 2.2 or, more specifically, in the range from about 1.7 to about 2.1. In embodiments utilizing an oxygen content gradient, the oxygen content may be adjusted to optimize optical properties along the visible spectrum. Similarly, in embodiments utilizing a nitrogen content gradient, the nitrogen content may be adjusted to optimize optical properties along the visible spectrum.
In one or more embodiments, the first layer 222, 322, 422, 522 is free of silicon or is free of aluminum. In one or more specific embodiments, the first layer 222, 322, 422, 522 includes AlN or Si3N4, however an oxide is disposed between the AlN or Si3N4 in the first layer 222, 322, 422, 522 and the substrate 110. The oxide may be selected to adjust the optical properties such that the article exhibits an average transmittance of about 85% or greater over the visible spectrum, as otherwise described herein. In one or more embodiments, the oxide may be selected to adjust the optical properties such that the article exhibits a total reflectivity that is the same or less than the total reflectivity of the substrate 110 without the optical film structures described herein over the visible spectrum. In one or more embodiments, the oxide may be selected to adjust the optical properties such that the article exhibits the color shift values described herein for a transmittance color, reflectance color or both transmittance color and reflectance color.
In one or more embodiments, the optical film structures described herein are free of nanostructures or intentionally added nanostructures, such as particulates. Intentionally added nanostructures are particulates that are purposely introduced into the optical film structure for the properties of such nanostructures (e.g., to increase surface area of the optical film structure or any of the layers therein, to provide anti-glare properties etc.). In one or more embodiments, the optical film structures described herein are free of porous layers or layers with intentionally added porosity. Intentionally added porosity includes treating the optical film structure to provide or increase porosity or including a pore forming material into the optical film structure to provide or increase porosity. In one or more embodiments, the second layer 224, 324, 424, 524 excludes aluminum or aluminum oxy-nitrides.
In one or more embodiments, the optical film structures described herein may include a modifier to enhance or suppress one or more properties. In one or more specific embodiments, the modifiers can be incorporated into the optical film structure to enhance the conductivity of the optical film structure. In such embodiments, the optical film structure may be modified or doped with Mg and/or Ca to control conductivity. Other modifiers dopants such as Si and/or Ge may be incorporated into the optical film structures described herein, and specifically into layers of the optical film structures comprising AlN. In one or more embodiments, the use of Si and/or Ge modifiers or dopants allow refractive index control, without having to alter the oxygen or nitrogen content of a given layer of the optical film structures described herein. In other words, the use of Si and/or Ge allows refractive index control of a given layer within the optical film structure without having to change oxygen or nitrogen content. Moreover, Si may also enhance the hardness of AlN when used in small amounts (i.e., to provide AlNxSiy where y<0.1, and x+y=1). Boron may also be alloyed with any material disclosed herein as appropriate. For example, AlN may be alloyed with boron to provide AlxByN, where x+y=1. The incorporation of small amounts of boron may provide improved lubricity to specific layers within the optical film structure or to the optical film structure, as a whole. The incorporation of boron could also provide increased hardness to specific layers within the optical film structure or to the optical film structure, as a whole. Layers of the optical film structures described herein that include nitrogen or a nitride may optionally include a carbon modifier or dopant. In one or more embodiments, the carbon modifier or dopant may be used as an alloy to form carbides within the optical film structure. Alternatively, the optical film structure may be free of modifiers or dopants or may be free of intentionally added modifiers or dopants.
In one or more alternative embodiments, a modifier or dopant including hexagonal BN can be incorporated into the optical film structure to improve the optical properties of the optical film structure. For example, hexagonal BN may be incorporated into the optical film structure to increase the refractive index of one or more layers of the optical film structure. The layers of the optical film structure that are modified or doped in this manner may include AlN, Si3N4, SiONy, SiuAlvOxNy, AlxSiyN or AlOxNy.
Optionally, a modifier including hexagonal BN, Ag, Cr and/or other large atoms may be incorporated into the optical film structure to improve the mechanical properties of the optical film structure. Specifically, the use of modifiers including hexagonal BN, Ag, Cr and/or other large atoms may be incorporated into the optical film structure to manage the stress in the optical film structure. Without being bound by theory, the doping of the AlN, Si3N4, SiONy, SiuAlvOxNy, AlxSiyN or AlOxNy layers with certain atoms may allow the film to relax and have less stress. Relaxed films tend not to flake apart when subjected to a force, such as a single event scratch, which prevents scratch damage and also prevents optical damage. Example atoms include silver (Ag), Yttrium (Y), Indium (In) and Tin (Sn), and other elements of row 5 on the periodic table. Additionally the use of phosphorous as a dopant may also provide a relaxation effect to the optical film structure. Relaxed films also resist being pulled apart by the forces that occur during the sliding contact event that cause scratches. Accordingly, the inclusion of certain atoms into the optical film structure allows the film to have the desired hardness, without the undesirable tension or compression. As such the inclusion of certain atoms provides an additional degree of freedom for tuning the optical properties of the optical film structure.
In one or more embodiments, a hexagonal BN modifier may be incorporated into the optical film structure to impart lubricity to the optical film structure. The hexagonal BN may have a sheet-like structure that is similar to graphene.
In one or more embodiments, the optical film structure may have a coefficient of friction that is less than the coefficient of friction of other optical film structures that include AlN, Si3N4, SiONy, SiuAlvOxNy, AlxSiyN or AlOxNy but do not incorporate a hexagonal BN modifier into the optical film structure. For example, when measured using a silicon carbide sphere counter surface, the optical film structure comprising AlN, Si3N4, SiONy, SiuAlvOxNy, AlxSiyN or AlOxNy and incorporating a hexagonal BN modifier may have a coefficient of friction of less than about 0.3. In one or more embodiment, the coefficient of friction may be about 0.28 or less, about 0.26 or less, about 0.24 or less, about 0.22 or less, about 0.20 or less, about 0.18 or less, about 0.16 or less, about 0.14 or less, about 0.12 or less or about 0.1 or less.
In one or more embodiments, the modifier may be incorporated into a layer of the optical film structure comprising AlN, Si3N4, SiOxNy, AlxSiyN or AlOxNy. For example, in the embodiment shown in FIG. 2, the modifier may be incorporated into a second sub-layer 226 including AlN or AlOxNy. In the embodiment shown in FIG. 3, the first sub-layer 326 and/or the third sub-layer 330 may incorporate a modifier. In the embodiment shown in FIG. 4, the first layer 422 may incorporate a modifier. In the embodiment shown in FIG. 5, the first sub-layer 526 or the second sub-layer 528 may incorporate a modifier.
In one or more embodiments, a modifier comprising fluorine may be incorporated into the second layers 224, 324, 424, 524 disclosed herein. In such embodiments, the fluorine modifier decreases the coefficient of friction of the second layer and thus the optical film structure. A fluorine modifier may be incorporated into other layers of the optical film structures. In one or more embodiments, the second layers disclosed herein comprise SiO2 and a modifier comprising fluorine.
The optical film structure of one or more embodiments may include or exhibit a sensing function or include or exhibit one or more properties enabling sensing. As used herein, sensing may include optical sensing, electrical sensing, magnetic sensing, mechanical sensing or a combination thereof. The sensing function may include capacitive sensing, resistive sensing, inductive sensing, surface acoustic wave sensing, photoelectric sensing, or other known sensing functions. In one or more embodiments, a portion of the optical film structure (e.g., a single or select layer(s)) may exhibit such sensing function or one or more properties enabling sensing. In one embodiment, the optical film structure or portion thereof may exhibit piezoelectric properties, pyro-electric properties or a combination thereof. In some embodiments, the optical film structure may exhibit piezoelectric properties but be essentially free of pyro-electric properties and vice versa. One or more piezoelectric layers within the optical film structure may comprise crystalline or polycrystalline material, and may also exhibit the hardness described herein and/or a low optical absorption (and/or high optical transparency). In some embodiments, the piezoelectric properties may be present in one or more aluminum nitride or oxygen-doped aluminum nitride layers within the optical film structure. In some embodiments, such optical film structures may sense a magnitude of force or pressure, sense acoustic signals, and/or sense acceleration. Such embodiments may be described as having an optical film structure including a sensor or sensor layer. The optical film structure may include or may be used with one or more electrically conducting layers, transparent conductor layers (i.e. optically transparent and electrically conducting layers) and/or optical waveguiding layers to perform such sensing functions. The optical film structure may be coupled to a signal detector, electrode, or signal processor in order to capture, store, or interpret the output of the sensing function.
In one or more embodiments, the optical film structures described herein exclude infrared reflecting layers or material. The optical film structures may also exclude layers or materials that have optical properties that are specifically tuned to the infrared region.
As shown in FIG. 1, the substrate 110 includes opposing minor surfaces 116, 118. In one or more embodiments, the article 100 may include a wrapped film (not shown) that may be disposed on the opposing minor surfaces 116, 118 and/or the opposing major surfaces 112, 114. In such embodiments, the wrapped film may be disposed between the substrate 110 and the optical film structure 120, 220, 320, 420, 520. Alternatively, the wrapped film may form all or part of the first layer 222, 322, 422, 522. In a specific embodiment, the wrapped film may form all or part of the first sub-layer 226, 326, 526. The wrapped film may include Al2O3. The wrapped film may provide nucleation layer(s) for the first sub-layers 226, 326, 526 and first layer 424 disclosed herein. The nucleation layer may effect on the atomic arrangements of atoms in the first few atomic layers of the first sub-layers 226, 326, and 526 or first layer 424 (i.e. the nucleation layers that are less than 10 nm from the interface between the first sub-layers 226, 326, 526 or first layer 424 and the wrapped film.
The articles disclosed herein may include additional films or layers disposed thereon. For example, the articles may include an anti-reflective film and/or a passivation film. Exemplary anti-reflective films may include single layers or multiple layers (e.g., 4 layer films, 6 layer films etc.). Where anti-reflective films with multiple layers are utilized, the layers may include different refractive indices and may include layers with high refractive indices (H) and low refractive indices (L) where “high” and “low” are with respect to one another and within known ranges for anti-reflective films. The layers may be arranged so that high and low refractive index layers alternate. In one or more embodiments, an interlayer may be disposed between the substrate 110 and the optical film structures described herein. In a specific embodiment, the interlayer may include a film or layers of organic materials, inorganic materials or a combination thereof for maintaining the average flexural strength of the article. The interlayer may be a composite of several layers which may have the same composition or different compositions from one another. In one or more specific embodiments, the interlayer includes a polymer. Exemplary polymers include polyimides, polysiloxanes, polyethersulfones, polysulfones, polyethyletherketones, parylenes, polytetrafluoroethanes, and the like. The interlayer may also include diamond-like carbon. The interlayer may have average strain-to-failure, fracture toughness or modulus properties that prevent cracks originating in the optical film structure from bridging into the substrate. In one or more embodiments, the interlayer may form the first sub-layer of the optical film structures described herein. In such embodiments, the first sub-layer comprising the interlayer may have a thickness of about 300 nm. It will be understood that the other layers of the optical film structure may have thicknesses that are greater than 300 nm such that the optical film structure, as a whole, has a thickness as otherwise described herein. Where an interlayer is included as a separate layer between the optical film structure or as part of the optical film structure, the optical film structure (and/or any of the layers therein) may be tuned to modify the optical properties of the structure.
The optical film structures described herein may be disposed on the substrate 110 using vacuum deposition techniques, for example, chemical vapor deposition (e.g., plasma enhanced chemical vapor deposition), physical vapor deposition (e.g., reactive or nonreactive sputtering or laser ablation), thermal or e-beam evaporation and/or atomic layer deposition. The processing conditions for disposing the optical film structures disclosed herein may be modified to tune the mechanical properties of the optical film structure or the mechanical properties of one or more specific layers of the optical film structure. For example, in one or more embodiments, the optical film structure is deposited at an elevated pressure to reduce the stress within the optical film structure. Exemplary elevated pressures include pressures in the range from about 0.5 mTorr to about 50 mTorr (e.g., about 1 mTorr). In one or more embodiments, the elevated pressure includes 10 mTorr. In one or more embodiments, the layers of the optical film structure including AlN are disposed at a high pressure. In specific embodiments, other layers of the optical film structure, for example, those not including AlN may be disposed at low pressure. Examples of low pressure include pressure in the range from about 2 mTorr to about 20 mTorr.
The articles disclosed herein may include articles with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, and the like), architectural articles, transportation articles (e.g., automotive, trains, aircraft, sea craft, etc.), appliance articles, or any article that requires some transparency, scratch-resistance, abrasion resistance or a combination thereof.
A second aspect of the disclosure pertains to a method of forming the articles described herein. In one or more embodiments, the method includes providing an substrate, which may be a strengthened glass substrate, a non-strengthened glass substrate, a strengthened glass ceramic substrate or a non-strengthened glass ceramic substrate, as described herein, having opposing major surfaces, and disposing an optical film structure on one of the opposing major surfaces of the substrate. In one or more embodiments, the optical film structure is disposed on the substrate at a pressure in the range of about 0.5 mTorr to about 20 mTorr to provide an optical film structure having lower stress than an optical film structure that is deposited at a lower pressure. In one or more specific embodiments, the optical film structure is disposed at a pressure of about 3 mTorr. The pressures that may be utilized may vary. Please note that these are examples, and their exact value can change from depending on the reactor utilized, the reactor engineering (e.g., the reactor shape, dimensions, carrier gasses, throughput etc.). The deposition temperature may be in the range from about 100° C. to about 200° C. The method may include flowing any one or more of the process gases: N2, O2 and argon. The flow rate of oxygen may be increased to form lower refractive index layers.
In one or more embodiments, the optical film structure may be disposed on the substrate via a vacuum deposition technique. Exemplary vacuum deposition techniques include chemical vapor deposition, plasma-enhanced chemical vapor deposition, physical vapor deposition such as sputtering, reactive sputtering, thermal evaporation and atomic layer deposition.
In one or more embodiments, the method includes modifying one or more properties of the optical film structure. The one or more properties may include conductivity, lubricity, stress, refractive index, hardness, thickness, deposition rate, and film reactivity with the environment, and combinations thereof. Modification of one or more of the conductive, lubricity, stress, and refractive index properties may include incorporation of one or more modifiers, as described herein, into the optical film structure. In one or more embodiments, the method includes increasing the conductivity of the optical film structure. In a specific embodiment, increasing the conductivity of the optical film structure includes doping the optical film structure with a modifier or dopant, which may include Mg, Ca or a combination thereof. The method according to one or more embodiments may include increasing the lubricity of the optical film structure. In one or more specific embodiments, increasing the lubricity of the optical film structure includes incorporating BN into the optical film structure. In one or more embodiments, the method includes reducing the stress in the optical film structure. In such embodiments, reducing the stress includes incorporating one or more of BN, Ag, Cr or a combination thereof into the optical film structure.
In one or more embodiments, the method includes introducing oxygen into the optical film structure. The introduction of oxygen may modify the refractive index of the optical film structure. In one or more embodiments, the method may include creating an oxygen content gradient in the optical film structure, as otherwise described herein.
EXAMPLES
Various embodiments will be further clarified by the following examples.
It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the disclosure.
Examples 1-8
In the following examples, three-layer optical film structures were designed and the transmittance of the samples was evaluated across the visible spectrum using various models. Ellipsometry was used to characterize the refractive index and extinction coefficient of each layer in the three-layer optical film structures. The refractive index and extinction coefficient information of each of the layers was used in known modeling tools (e.g., thin film designing codes) to determine the optical behavior of the optical film structures described in Examples 1-8. The foregoing characterization and modeling can be used with 2-layer, 4-layer or other layer configurations of the optical film structures described herein.
The optical film structure from which the refractive index and extinction coefficient information were measured and used in Examples 1-8 was formed using an ion beam sputtering process on a strengthened glass substrate having width and length dimensions of about 2′′ by 2′′. The glass substrate included an alkali aluminoborosilicate glass having a composition that includes about 65 mol % SiO2, about 14 mol % Al2O3; about 5 mol % B2O3; about 14 mol % Na2O; about 2.5 mol % MgO and about 0.1 mol % SnO2. The glass substrate was strengthened to exhibit a CS of at least about 700 MPa and a DOL of at least about 40 μm. The CS and DOL were formed by immersing the glass substrate in a molten salt bath having a temperature of about 400-430° C. for about four to about eight hours. The thicknesses of the respective layers of the optical film structure were controlled by deposition time. The deposition temperature was maintained at about 200° C. and the pressure was maintained at 6.7×10−6 Torr. Each of the layers of the optical film structure was sputtered from an appropriate target (e.g., Ge target to form germanium-containing oxides, Si target to form silicon-containing oxides or Al target to form aluminum-containing oxides, nitrides or oxynitrides) in the presence of argon flowed at a rate of about 75 sccm, with DC power supplied at about 4 kW. The ion beam was generated at a power in the range from about 180 W to about 800 W using a mixture of oxygen (flowed at a rate of about 2 sccm), nitrogen (flowed at a rate of about 50 sccm) and argon (flowed at a rate of about 25 sccm) gases. For example, when forming Al2O3, the ion beam was generated at a power of about 600 W, when forming AlOxNy, the ion beam was generated at a power of about 180 W, and when forming SiO2, the ion beam was generated at a power of about 800 W. Al2O3 was formed at a rate of about 3 Å/second, AlOxNy was formed at a rate of about 1.6 Å/second and SiO2 was formed at a rate of about 5 Å/second.
In known structures, designs with the lowest reflectivity still showed a variation on the reflectance color points as the viewing angle was changed from normal incidence (i.e., 0 degrees) to oblique incidence. Accordingly, the low-reflectivity regions (and not necessarily the lowest reflectivity regions) have a reduced color, (i.e., the low-reflectivity regions are closer to the (a*, b*) origin), achieved through variation of the thicknesses and dispersion of the two impedance-matching layers of the design.
In Example 1, the impedance-matching layers of an optical film structure include Al2O3 and SiO2 layers surrounding a layer having a high refractive index and a relatively high hardness (e.g., AlOxNy, where x≧0). Specifically, in Example 1, samples having an optical film structure including a first sub-layer of Al2O3, a second sub-layer of AlOxNy and a second layer of SiO2, were prepared and the refractive index and extinction coefficient values of each layer was measured using ellipsometry. The thicknesses of the Al2O3 and SiO2 layers were varied using modeling, as described above, based on the measured refractive index and extinction coefficient values. The thickness of the AlOxNy layer was constant. For each thickness of the SiO2 and Al2O3 layers, the color coordinates in the (L*, a*, b*) colorimetry system of the samples according to Example 1 were predicted. FIG. 11 shows a contour plot of the optical film structure color performance, in transmission, according to Example 1, in which the conditions for a* is zero and b* is zero. Additionally, the distance or color shift between the color coordinates of the optical film structure from the origin (or coordinates (0,0) gives a measure of nearness to a truly unbiased, white (or colorless) transparency.
For the contour plot shown in FIG. 11, the AlOxNy thickness is held constant at 1850 nm and the thicknesses of the SiO2 and Al2O3 layers are varied from 0 to 160 nm and 0 to 800 nm, respectively, using modeling as described above. Dispersion functions that were fit to experimental measurements of the refractive index and extinction coefficients of layers including the three materials were utilized.
The contour plot shown in FIG. 11 is limited to contours near zero, to provide data regarding the sensitivity of the low-color solution (a*, b*) (0, 0) to the design parameters (i.e., the SiO2 layer and Al2O3 layer thicknesses). Other contours levels were suppressed for clarity.
The results indicate that there are coincident solutions in the regions where the solid, thinnest contour line (where a*=0.0) and the dashed, thickest contour line (where b*=0.0) intersect or nearly intersect. The inclusion of SiO2, Al2O3, and AlOxNy layers having the thicknesses at these intersections in FIG. 11 would provide an optical film structure having a colorless transmittance. Such optical film structures are shown in Table 1.







TABLE 1







Optical Film Structures having colorless


transmittance from FIG. 11.











SiO2
AlOxNy
Al2O3
















Optical Film Structure 1
40 nm
1850 nm
500 nm



Optical Film Structure 2
52 nm
1850 nm
440 nm



Optical Film Structure 3
62 nm
1850 nm
450 nm



Optical Film Structure 4
30 nm
1850 nm
350 nm



Optical Film Structure 5
75 nm
1850 nm
330 nm



Optical Film Structure 6
35 nm
1850 nm
160 nm










In Example 2, the refractive index and extinction coefficient values measured in Example 1 were utilized. The thicknesses of Al2O3 and SiO2 layers were varied using modeling, as described above, based on the measured refractive index and extinction coefficient values; however, the thickness of the AlOxNy layer was constant at about 2000 nm. For each modeled thickness of the SiO2 and Al2O3 layers, the color coordinates in the (L*, a*, b*) colorimetry system of the samples according to Example 2 were predicted. In relation to Example 1, the thickness of the AlOxNy layer was increased to 2000 nm to show the dependence of the contours on the thickness of the AlOxNy layer. FIG. 12 is a contour plot of the optical film structure color performance, in transmission, according to Example 2.
The inclusion of SiO2, Al2O3, and AlOxNy layers having the thicknesses at these intersections in FIG. 12 would provide an optical film structure having a colorless transmittance. Such optical film structures are shown in Table 2.







TABLE 2







Optical Film Structures having colorless


transmittance from FIG. 12.











SiO2
AlOxNy
Al2O3
















Optical Film Structure 7
43 nm
2000 nm
500 nm



Optical Film Structure 8
67 nm
2000 nm
490 nm



Optical Film Structure 9
62 nm
2000 nm
450 nm



Optical Film Structure 10
35 nm
2000 nm
350 nm



Optical Film Structure 11
63 nm
2000 nm
300 nm



Optical Film Structure 12
75 nm
2000 nm
380 nm










In Example 3, the refractive index and extinction coefficient values measured in Example 1 were utilized. The thicknesses of Al2O3 and SiO2 layers were varied using modeling, as described above, based on the measured refractive index and extinction coefficient values; however, the thickness of the AlOxNy layer was constant at about 2250 nm. FIG. 13 is a contour plot of the optical film structure color performance, in transmission, according to Example 3, in which the AlOxNy layer has a constant thickness of 2250 nm.
The inclusion of SiO2, Al2O3, and AlOxNy layers having the thicknesses at these intersections in FIG. 13 would provide an optical film structure having a colorless transmittance. Such optical film structures are shown in Table 3.







TABLE 3







Optical Film Structures having colorless


transmittance from FIG. 13.











SiO2
AlOxNy
Al2O3
















Optical Film Structure 13
48 nm
2250 nm
495 nm



Optical Film Structure 14
65 nm
2250 nm
490 nm



Optical Film Structure 15
60 nm
2250 nm
310 nm



Optical Film Structure 16
37 nm
2250 nm
350 nm



Optical Film Structure 17
72 nm
2250 nm
320 nm










In Example 4, the refractive index and extinction coefficient values measured in Example 1 were utilized. The thicknesses of Al2O3 and SiO2 layers were varied using modeling, as described above, based on the measured refractive index and extinction coefficient values; however, the thickness of the AlOxNy layer was constant at about 2500 nm. FIG. 14 is a contour plot of the optical film structure color performance, in transmission, according to Example 4, in which the AlOxNy layer has a constant thickness of 2500 nm.
The inclusion of SiO2, Al2O3, and AlOxNy layers having the thicknesses at these intersections in FIG. 14 would provide an optical film structure having a colorless transmittance. Such optical film structures are shown in Table 4.







TABLE 4







Optical Film Structures having colorless


transmittance from FIG. 14.











SiO2
AlOxNy
Al2O3
















Optical Film Structure 18
53 nm
2500 nm
490 nm



Optical Film Structure 19
60 nm
2500 nm
490 nm



Optical Film Structure 20
38 nm
2500 nm
240 nm



Optical Film Structure 21
68 nm
2500 nm
325 nm










In Example 5, the refractive index and extinction coefficient values measured in Example 1 were utilized. The thicknesses of Al2O3 and SiO2 layers were varied using modeling, as described above, based on the measured refractive index and extinction coefficient values; however, the thickness of the AlOxNy layer was constant at about 2750 nm. FIG. 15 is a contour plot of the optical film structure color performance, in transmission, according to Example 5, in which the AlOxNy layer has a constant thickness of 2750 nm.
The inclusion of SiO2, Al2O3, and AlOxNy layers having the thicknesses at these intersections in FIG. 15 would provide an optical film structure having a colorless transmittance. Such optical film structures are shown in Table 5.







TABLE 5







Optical Film Structures having colorless


transmittance from FIG. 15.











SiO2
AlOxNy
Al2O3
















Optical Film Structure 22
42 nm
2750 nm
340 nm



Optical Film Structure 23
65 nm
2750 nm
330 nm










In Example 6, the refractive index and extinction coefficient values measured in Example 1 were utilized. The thicknesses of Al2O3 and SiO2 layers were varied using modeling, as described above, based on the measured refractive index and extinction coefficient values; however, the thickness of the AlOxNy layer was constant at about 3000 nm. FIG. 16 is a contour plot of the optical film structure color performance, in transmission, according to Example 6, in which the AlOxNy layer has a constant thickness of 3000 nm.
The inclusion of SiO2, Al2O3, and AlOxNy layers having the thicknesses at these intersections in FIG. 16 would provide an optical film structure having a colorless transmittance. Such optical film structures are shown in Table 6.







TABLE 6







Optical Film Structures having colorless


transmittance from FIG. 16.











SiO2
AlOxNy
Al2O3
















Optical Film Structure 24
42 nm
3000 nm
340 nm



Optical Film Structure 25
61 nm
3000 nm
320 nm










In Example 7, the refractive index and extinction coefficient values measured in Example 1 were utilized. The thicknesses of Al2O3 and SiO2 layers were varied using modeling, as described above, based on the measured refractive index and extinction coefficient values; however the thickness of the AlOxNy layer was constant at about 3250 nm. FIG. 17 is a contour plot of the optical film structure color performance, in transmission, according to Example 7, in which the AlOxNy layer has a constant thickness of 3250 nm.
The inclusion of SiO2, Al2O3, and AlOxNy layers having the thicknesses at this intersection in FIG. 17 would provide an optical film structure having a colorless transmittance. Such optical film structure is shown in Table 7.







TABLE 7







Optical Film Structure having colorless


transmittance from FIG. 17.











SiO2
AlOxNy
Al2O3
















Optical Film Structure 26
55 nm
3250 nm
330 nm










In Example 8, the refractive index and extinction coefficient values measured in Example 1 were utilized. The thicknesses of Al2O3 and SiO2 layers were varied using modeling, as described above, based on the measured refractive index and extinction coefficient values; however the thickness of the AlOxNy layer was constant at about 3500 nm. FIG. 18 is a contour plot of the optical film structure color performance, in transmission, according to Example 8, in which the AlOxNy layer has a constant thickness of 3250 nm.
The inclusion of SiO2, Al2O3, and AlOxNy layers having the thicknesses at these intersections in FIG. 18 would provide an optical film structure having a near colorless (but not completely colorless) transmittance. Such optical film structure is shown in Table 8.







TABLE 8







Optical Film Structure having near colorless


transmittance from FIG. 18.











SiO2
AlOxNy
Al2O3
















Optical Film Structure 27
55 nm
3500 nm
340 nm










As shown in FIGS. 11-18, for thicker layers of AlOxNy within an optical film structure (e.g., thickness of about 3500 nm), the b* surface in parameter space no longer crosses zero for this region of the parameter space (i.e., the b* surface parameter space no longer intersects the a* parameter space where b*=zero and a*=zero. Accordingly, with thicker AlOxNy layers, there are fewer options to tune the other layers (e.g., the SiO2 and Al2O3 layers) to achieve a colorless or near colorless transmittance.
As stated otherwise herein, the distance or color shift of a particular color point (a*, b*) (transmitted or reflected) from the origin (0, 0) in the (L, a*, b*) colorimetry system is given by the Euclidean distance, d=√(a*2+b*2). The contour plots shown in FIGS. 19A, 20A, 21A, 22A, 23A, 24A, 25A and 26A illustrate luminosity, L* over the same range of the design space for the samples according to Examples 1-8, respectively. FIGS. 19B, 19C, 20B, 20C, 21B, 21C, 22B, 22C, 23B, 23C, 24B, 24C, 25B, 25C, 26B and 26C show plots of the samples of Examples 1-8, respectively, with false color indicating the value of d, the distance or color shift from the origin as a function of the SiO2 and Al2O3 thicknesses on both a linear (FIGS. 19B, 20B, 21B, 22B, 23B, 24B, 25B and 26B) and logarithmic (FIGS. 19C, 20C, 21C, 22C, 23C, 24C, 25C and 26C) scales. The distance or color shift from the color origin (clear/white) is plotted as a function of the design parameters.
FIGS. 19A, 20A, 21A, 22A, 23A, 24A, 25A and 26A illustrate the transmittance or luminosity, with greater luminosity representing greater transmittance. The dark areas in FIGS. 19B, 19C, 20B, 20C, 21B, 21C, 22B, 22C, 23B, 23C, 24B, 24C, 25B, 25C, 26B and 26C illustrate the thicknesses of the SiO2, Al2O3 and AlOxNy layers at which the distance from the origin (0,0) in the L*a*b* color space is the least. When luminosity and distance, d, are compared, the suitable thicknesses of the SiO2, Al2O3 and AlOxNy can be obtained so that transmittance is maximized, while the distance, d (and the transmittance color) is minimized. For example, in FIGS. 19A and 19B, an optical film structure with a SiO2 layer having a thickness of 35 nm, an Al2O3 layer having a thickness of 200 nm, and a AlOxNy layer having a thickness of 1850 nm may have colorless transmittance based on FIG. 19B; however, such an optical film structure may have luminosity of between 95% and 96%. Likewise, selecting a SiO2 layer having a thickness of 90 nm, an Al2O3 layer having a thickness of 100 nm, and an AlOxNy layer having a thickness of 1850 may provide luminosity of 99%; however such an optical film structure may have a distance, d or color shift of greater than 2 or 3 and thus would not have colorless transmittance.
Referring to FIGS. 19C, 20C, 21C, 22C, 23C, 24C, 25C and 26C, the darker areas illustrate thicknesses for the layers of the optical film structure design that are less sensitive to variations. Accordingly, these Figures may be used to select thicknesses of the layers of the optical film structure that may be able to withstand manufacturing variances and still achieve the desired colorless transmittance.
Example 9
One sample each of Example 9 and Comparative Example 9A were formed using a sputtering method. Each sample was made by providing the same substrates utilized in Examples 1-8 and having length and width dimensions of 50 mm each. Example 9 included a layer comprising SiuAlvOxNy, wherein the u, v, x and y varied along the thickness of the layer to provide an oxygen content gradient, a silicon content gradient, an aluminum content gradient and a nitrogen content gradient. Comparative Example 9A included an AlN layer. The layer including SiuAlvOxNy of Example 9 had a thickness of about 260 nm, as measured by profilometry, and was formed via sputtering process using silicon and aluminum targets and nitrogen and oxygen gases. The AlN layer (without a gradient) had a thickness of about 250 nm, as measured by profilometry. The layer without the gradient of Comparative Example 9A was formed in a similar manner as the layer of Example 9; however, only an aluminum target was utilized and only nitrogen gas was utilized. The total deposition time to form the respective layers of Example 9 and Comparative Example 9A was about 6 hours.
FIG. 27 illustrates the reflectivity % of the layer of Example 9 including a SiuAlvOxNy gradient and the layer of Comparative Example 9A without such a gradient. The layer of Example 9 exhibits a flat reflectance spectra (or transmittance spectra) over the visible spectrum, when compared to the layer without the gradient of Comparative Example 9A. In other words, the layer of Example 9 shows a decrease in the amplitude of the oscillations in reflectivity % relative to the homogeneous layer of Comparative Example 9A. As shown in FIG. 27, the reflectivity of the layer of Example 9 over the visible spectrum is substantially constant or does not vary by more than about 20%. In other words the layer of Example 9 has an average reflectivity of about 16% and the maximum (e.g., 18%) and a minimum (e.g., 14%) are less than about 20% of the average reflectivity of 16%. For comparison, the reflectivity % of the AlN layer of Comparative Example 9A shows oscillations such that the reflectivity % over the visible spectrum varies from as low as about 8% to as high as about 27%.
Example 10
One sample each of Example 10 and Comparative Example 10A were formed using a sputtering method. Each sample was made by providing the same substrates utilized in Examples 1-8 and having length and width dimensions of 50 mm each. Example 10 included a layer with 121 sub-layers comprising SiuAlvOxNy, wherein the u, v, x and y varied along the thickness of the layer to provide an oxygen content gradient, a silicon content gradient, an aluminum content gradient and a nitrogen content gradient. The 121 sub-layers of the SiuAlvOxNy layer were formed onto one side of a glass substrate. The layer was formed by first sputtering a silicon target at a pressure of about 3 mTorr in the presence of argon flowed at a rate of about 20 sccm, nitrogen flowed at a rate of 40 sccm and oxygen flowed at a rate of 2 sccm. RF power was supplied at 4 W, at least initially for three minutes. After the first three minutes, DC power was then generated to sputter aluminum from an aluminum target starting 50 W. DC power was in 20 W increments every three minutes thereafter until 300 W. While the DC power was being increased, the RF power, argon gas flow rate, nitrogen gas flow rate and oxygen gas flow rate were constant. After reaching 300 W DC power, the RF power was decreased from 400 W to 0 W in successive steps and DC power continued to increase at 20 W increments for three minutes between each increase until 480 W DC power was generated. Thereafter, then in successive steps, the oxygen gas flow rate was decreased from 2 sccm to 0.25 sccm oxygen, in about 0.2 sccm increments, with a final decrease of 0.05 sccm. After the oxygen flow rate was decreased to 0.25 sccm, the deposition process continued for an additional 3 hours and only AlN was being formed in the layer. In other words, the sub-layers formed when oxygen was flowed at 0.25 sccm comprised AlN. During the entire deposition process, the flow rates of nitrogen and argon were constant and the pressure was constant. No cleaning steps were performed during the deposition or between any changes in flow rates, RF power or DC power.
Comparative Example 10A included a single AlOxNy layer. The layer including SiuAlvOxNy of Example 10 had the same thickness as the single layer of AlOxNy of comparative Example 10A. Example 10 was formed by sputtering using silicon and aluminum targets and nitrogen and oxygen gases. Comparative Example 10A (without a gradient) was formed in a similar manner as the layer of Example 10; however, only an aluminum target was utilized and oxygen and nitrogen gas was utilized.
FIG. 28 illustrates the transmittance % of the layer of Example 10 including a SiuAlvOxNy gradient and the layer of Comparative Example 10A without such a gradient. The layer of Example 10 exhibits a flat transmittance spectrum over the visible spectrum, when compared to the layer without the gradient of Comparative Example 10A. In other words, the layer of Example 10 shows a decrease in the amplitude of the oscillations in transmittance % relative to the homogeneous layer of Comparative Example 10A. As shown in FIG. 28, the transmittance of the layer of Example 10 over the visible spectrum is substantially constant or does not vary by more than about 4%. For comparison, the transmittance % of the AlOxNy layer of Comparative Example 10A shows oscillations in such that the transmittance % over the visible spectrum varies from as low as about 78% to as high as about 93%. The gradient layer of Example 10 also exhibited scratch resistance as otherwise described herein.
Without being bound by theory, it is believed that the amplitude of the oscillations in reflectivity % of the optical film structures described herein, and of the layers including an aluminum content, silicon content, nitrogen content and/or oxygen content gradients (e.g., first layer 422 and/or first sub-layer 526 and/or the layers of Example 9 and Example 10) may be decreased to about zero when the oxygen content is decrease linearly along the thickness of a layer.
Example 11
In the following example, a three-layer optical film structure disposed on a glass substrate was designed. The transmittance and reflectance of the optical film structure and glass substrate were evaluated across the visible spectrum using various models, in the same manner as Examples 1-8. Ellipsometry was again used to characterize the refractive index and extinction coefficient of each layer in the three-layer optical film structure. The refractive index and extinction coefficient information of each of the layers was used in known modeling tools (e.g., thin film designing codes) to determine the optical behavior of the optical film structure and substrate.
The optical film structure was formed in the same manner as Examples 1-8, using the same substrates as used in Examples 1-8.
In Example 11, the impedance-matching layers of the optical film structure included Al2O3 and SiO2 layers surrounding a layer having a high refractive index and a relatively high hardness. Specifically, the optical film structure included a first sub-layer of Al2O3, a second sub-layer of AlOxNy and a second layer of SiO2. The thicknesses of the Al2O3 and SiO2 layers were varied using modeling, as described above, based on the measured refractive index and extinction coefficient values. The thickness of the AlOxNy layer was constant at 2 μm. For each thickness of the SiO2 and Al2O3 layers, the L*a*b* color coordinates of the samples were predicted.
FIG. 29A shows a contour plot of the a* reflectance color performance of the optical film structure and substrate, according to Example 11. In the contour plot, a value of zero indicates the reflectance of the optical film structure and substrate combination is without color. The suitable thicknesses for the SiO2 layer and the Al2O3 layer include the thicknesses along the contours between the solid R, a*=0.5 line and the dashed R, a*=−0.5 line or in some instances, between two dashed R, a*=0 lines. When SiO2 and Al2O3 layers having these thicknesses are combined with the 2 μm AlOxNy layer, the optical film and substrate would exhibit a* values in the range from about −0.5 to about 0.5, which would in turn limit the distance or color shift between the color coordinates of the optical film and substrate and the color coordinates (a*=0, b*=0). For Al2O3 thicknesses between 0 nm and 500 nm, examples of appropriate SiO2 layer thicknesses include from about 0 nm to about 60 nm, with more specific thicknesses for the Al2O3 and/or SiO2 layers falling between the solid R, a*=0.5 line and the dashed R, a*=−0.5 line. In one or more embodiments, for Al2O3 thicknesses between 0 nm and 500 nm, suitable thicknesses for the SiO2 layer can also include thicknesses in the range from about 0 nm to about 150 nm; however, using a thickness that falls within a wider range of layer thicknesses between the solid R, a*=0.5 line and the dashed R, a*=−0.5 line provides more flexibility in manufacturing (i.e., minor variations in thickness will not dramatically affect a* values). To this end, thicknesses of SiO2 between 0 nm and 60 nm and Al2O3 layer thicknesses between 0 nm and 200 nm may provide greater tolerance to optical film thickness variations, while providing optical film and substrate combinations that exhibit a* values in the range from about −0.5 to about 0.5, and color coordinates with minimized distance or color shift from the color coordinates (a*=0, b*=0).
FIG. 29B shows a contour plot of the a* reflectance color performance of the optical film structure and underlying substrate, according to Example 11, with the contours showing the difference between the combination of the optical film structure and substrate and the bare substrate (without the optical film structure). In the contour plot, the value of zero for the plotted quantities means the combination of the optical film structure and substrate has the same color coordinates as the bare substrate. As shown in FIG. 29B, the contours shift to accommodate the substrate. Accordingly, the thicknesses of the SiO2 and Al2O3 layers between the solid R, a*=0.5 line and the dashed R, a*=−0.5 line or in some instances, between two dashed R, a*-0.5 lines, are modified from those shown in FIG. 29A. When SiO2 and Al2O3 layers having these thicknesses are combined with the 2 μm AlOxNy layer, the optical film and substrate combination would exhibit a* values in the range from about −0.5 to about 0.5, which would in turn limit the distance or color shift between the color coordinates of the optical film and substrate combination and the color coordinates of the bare substrate (without the optical film). For Al2O3 thicknesses between 0 nm and 500 nm, examples of appropriate SiO2 layer thicknesses include from about 0 nm to about 60 nm, with more specific thicknesses for the Al2O3 and/SiO2 layers falling between the solid R, a*=0.5 line and the dashed R, a*=−0.5 line. In one or more embodiments, for Al2O3 thicknesses between 0 nm and 500 nm, suitable thicknesses for the SiO2 layer can also include thicknesses in the range from about 0 nm to about 140 nm; however, using a thickness that falls within a wider range of layer thicknesses between the solid R, a*=0.5 line and the dashed R, a*=−0.5 line provides more flexibility in manufacturing (i.e., minor variations in thickness will not dramatically affect a* values). To this end, use of a SiO2 layer having a thickness in the range from about 0 nm to about 60 nm and a Al2O3 layer having a thickness in the range from about 0 nm to about 200 nm may provide greater tolerance to optical film thickness variations, while providing optical film and substrate combinations that exhibit a* values in the range from about −0.5 to about 0.5. The use of such SiO2 and Al2O3 layers and a 2 μm-thick AlOxNy layer in the optical film would provide, when combined with the substrate, an article exhibiting color coordinates that are close in distance or color shift (e.g., <2) from the color coordinates (a*=0, b*=0).
FIG. 29C shows a contour plot b* reflectance color performance of the optical film structure and substrate, according to Example 11. In the contour plot, a value of zero indicates the optical film structure and substrate combination is without color. The suitable thicknesses for the SiO2 layer and the Al2O3 layer includes the thicknesses along the contours between the solid R, b*=0.5 line and the dashed R, b*=−0.5 line or in some instances, between two dashed R, b*=−0.5 lines. When SiO2 and Al2O3 layers having these thicknesses are combined with the 2 μm AlOxNy layer, the optical film and substrate combination would exhibit b* values in the range from about −0.5 to about 0.5, which would in turn limit the distance or color shift from the color coordinates (a*=0, b*=0). For Al2O3 layer thicknesses between 0 nm to about 500 nm, examples of appropriate SiO2 layer thicknesses include from about 0 to about 40 nm, or from about 170 nm to about 175 nm, with more specific thicknesses for the Al2O3 and SiO2 layers falling between the solid R, b*=0.5 line and the dashed R, b*=−0.5 line. An SiO2 layer having a thickness of about 175 nm may be used and may provide an optical film and substrate combination with improved b* reflectance color performance; however, any deviations from this thickness may result in changes to b* values.
FIG. 29D shows a contour plot of the b* reflectance color performance of the optical film structure and substrate, according to Example 11. The contours in the contour plot show the difference between the combination of the optical film structure and substrate and the bare substrate (without the optical film structure). In the contour plot, the value of zero for the plotted quantities means the combination of the optical film structure and substrate has the same color coordinates as the bare substrate. As shown in FIG. 29D, the contours shift to accommodate the substrate. Accordingly, the thicknesses of the SiO2 and Al2O3 layers between the solid R, b*=0.5 line and the dashed R, b*=−0.5 line or in some instances, between two dashed R, b*=−0.5 lines, are modified from those shown in FIG. 29C. When SiO2 and Al2O3 layers having these thicknesses are combined with the 2 μm AlOxNy layer, the optical film and substrate combination would exhibit b* values in the range from about −0.5 to about 0.5, which would in turn limit the distance or color shift between the color coordinates of the optical film and substrate combination and the color coordinates of the bare substrate (without an optical film). For Al2O3 layer thicknesses between 0 nm to about 500 nm, examples of suitable thicknesses for the SiO2 layer include from 0 nm to about 30 nm, or from about 170 nm to about 175 nm, with more specific thicknesses for both Al2O3 and SiO2 falling between the solid R, b*=0.5 line and the dashed R, b*=−0.5 line. The thicknesses and thickness ranges for the Al2O3 layer did not change significantly in FIG. 29D, as compared to FIG. 29C.
FIG. 29E shows the thicknesses of the SiO2 and Al2O3 layers at which the distance or color shift of the reflectance color coordinates of the article (including the optical film and the substrate) and the color coordinates (a*=0, b*=0) are less than about 1, less than about 0.5, less than about 0.2 and less than about 0.1. FIG. 29E shows that an optical film with a SiO2 layer having a thickness in the range from about 0 nm to about 50 nm and a Al2O3 layer having a thickness in the range from about 0 nm to about 180 nm, with more specific thicknesses for the Al2O3 and/or SiO2 layers falling between the solid d=0.1 line and the dashed d=1.0 line, when combined with a 2 μm thick AlOxNy layer, will exhibit color coordinates, in reflection, having a distance or color shift from the color coordinates (a*=0, b*=0) of less than about 1. In another example, the combination of a SiO2 layer having a thickness in the range from about 0 nm to about 50 nm, a Al2O3 layer having a thickness in the range from about 0 nm to about 500 nm, a 2 μm-thick AlOxNy layer and the glass substrate, would also exhibit desired reflectance color performance. In another example, the combination of a SiO2 layer having a thickness from about 75 nm to about 100 nm, an Al2O3 layer having a from about 250 nm to about 500 nm, a 2 μm-thick AlOxNy layer and the glass substrate, would also exhibit desired reflectance color performance; although these thickness ranges for the SiO2 and Al2O3 layers allow for lower tolerances in thickness variation, the transmittance of the optical film and substrate combination was found to be improved over some other thicknesses.
FIG. 29F shows the thicknesses of the SiO2 and Al2O3 layers at which the distance or color shift of the color coordinates of the article and the color coordinates of the substrate are less than about 1, less than about 0.5, less than about 0.2 and less than about 0.1. FIG. 29F shows that the combination of a glass substrate and an optical film a 2 μm-thick AlOxNy layer, a SiO2 layer having a thickness in the range from about 0 nm to about 30 nm or 35 nm and a Al2O3 layer having a thickness in the range from about 0 nm to about 170 nm (with more specific thicknesses for both Al2O3 and SiO2 falling between the solid d=0.1 line and the dashed d=1.0 line), would exhibit color coordinates, in reflection, having a distance or color shift from the color coordinates of the substrate of less than about 1. Another example includes a substrate and optical film with a 2 μm-thick AlOxNy layer, a SiO2 layer having a thickness from about 30 nm to about 40 nm and an Al2O3 layer having a thickness from about 260 nm to about 290 nm. Yet another example includes a substrate and optical film with a 2 μm-thick AlOxNy layer, a SiO2 layer having a thickness from about 20 nm to about 40 nm and an Al2O3 layer having a thickness from about 420 nm to about 450 nm.
FIG. 30A shows a contour plot of the a* transmittance color performance of an optical film structure and substrate, according to Example 11. In the contour plot, a value of zero indicates the optical film structure and substrate combination is without color. The suitable thicknesses for the SiO2 layer and the Al2O3 layer includes the thicknesses along the contours between the solid T, a*=0.5 line and the dashed T, a*=−0.5 line or in some instances, between two dashed T, a*=−0.5 lines, which, when combined with the 2 μm AlOxNy layer in the optical film, would provide a* values in the range from about −0.5 to about 0.5. When SiO2 and Al2O3 layers having these thicknesses are combined with the 2 μm AlOxNy layer, the optical film would exhibit a* values in the range from about −0.5 to about 0.5, which would in turn limit the distance or color shift between the color coordinates of the optical film and substrate and the color coordinates (a*=0, b*=0). For Al2O3 layer thicknesses between 0 nm to about 500 nm, examples of suitable thicknesses for the SiO2 layer include from about 0 nm to about 160 nm, with more specific thicknesses for both Al2O3 and SiO2 falling between the solid T, a*=0.5 line and the dashed T, a*=−0.5 line. Examples of thicknesses that may not provide the desired a* transmittance include an SiO2 layer having a thickness from about 65 nm to about 105 nm in combination with an Al2O3 layer having a thickness from about 10 nm to about 120 nm, an SiO2 layer having a thickness from about 20 nm to about 140 nm in combination with an Al2O3 layer having a thickness from about 185 nm to about 275 nm, or an SiO2 layer having a thickness from about 0 nm to about 125 nm in combination with an Al2O3 layer having a thickness from about 350 nm to about 420 nm, as these thickness ranges and combinations fall between two dashed T, 0.5 lines.
FIG. 30B shows a contour plot of the a* transmittance color performance of the optical film structure and substrate, according to Example 11. The contours show the difference between the combination of the optical film structure and substrate and the bare substrate (without the optical film structure). In the contour plot, the value of zero for the plotted quantities means the combination of the optical film structure and substrate has the same color coordinates as the bare substrate. As shown in FIG. 30B, the contours shift to accommodate the substrate. Accordingly, the thicknesses of the SiO2 and Al2O3 layers between the solid T, a*=0.5 line and the dashed T, a*=−0.5 line or in some instances, between two dashed T, a*=−0.5 lines, are modified from those shown in FIG. 30A. When SiO2 and Al2O3 layers having these thicknesses are combined with the 2 μm AlOxNy layer, the optical film and substrate would exhibit a* values in the range from about −0.5 to about 0.5, which would in turn limit the distance or color shift of the color coordinates of the optical film and substrate from the color coordinates of the bare substrate (without an optical film). For Al2O3 layer thicknesses between 0 nm to about 500 nm, examples of suitable thicknesses for the SiO2 layer include from about 0 nm to about 160 nm, with more specific thicknesses for the Al2O3 and/or SiO2 layers falling between the solid T, a*=0.5 line and the dashed T, a*=−0.5 line. Examples of thicknesses that may not provide the desired a* transmittance include an SiO2 layer having a thickness from about 65 nm to about 105 nm in combination with an Al2O3 layer having a thickness from about 0 nm to about 120 nm, an SiO2 layer having a thickness from about 20 nm to about 120 nm in combination with an Al2O3 layer having a thickness from about 190 nm to about 275 nm, or an SiO2 layer having a thickness from about 0 nm to about 125 nm in combination with an Al2O3 layer having a thickness from about 330 nm to about 420, as these thickness ranges and combinations fall between two dashed T, a*=−0.5 lines.
FIG. 30C shows a contour plot of the b* transmittance color performance of the optical film structure and substrate, according to Example 11. In the contour plot, a value of zero indicates the optical film structure and substrate combination is without color. The suitable thicknesses for the SiO2 layer and the Al2O3 layer includes the thicknesses along the contours between the solid T, b*=0.5 line and the dashed T, b*=−0.5 line or in some instances, between two dashed T, b*=−0.5 lines. When SiO2 and Al2O3 layers having these thicknesses are combined with the 2 μm AlOxNy layer, the optical film and substrate combination would exhibit b* values in the range from about −0.5 to about 0.5, which would in turn limit the distance or color shift between the color coordinates of the optical film structure and substrate and the color coordinates (a*=0, b*=0). For Al2O3 layer thicknesses between 0 nm to about 500 nm, examples of suitable thicknesses for the SiO2 layer include from about 0 nm to about 90 nm, with more specific thicknesses for the Al2O3 and/or SiO2 layers falling between the solid T, b*=0.5 line and the dashed T, b*=−0.5 line. Examples of thicknesses that may not provide the desired b* transmittance include an SiO2 layer having a thickness from about 20 nm to about 80 nm in combination with an Al2O3 layer having a thickness from about 0 nm to about 250 nm, an SiO2 layer having a thickness from about 20 nm to about 80 nm in combination with an Al2O3 layer having a thickness from about 260 nm to about 500 nm, or an SiO2 layer having a thickness from about 0 nm to about 25 nm in combination with an Al2O3 layer having a thickness from about 80 nm to about 150 nm, from about 220 nm to about 290 nm or from about 380 nm to about 440 nm, as these thickness ranges and combinations fall between two dashed T, b*=−0.5 lines or between two solid T, b*=0.5 lines.
FIG. 30D shows a contour plot of the b* reflectance color performance of the optical film structure and substrate, according to Example 11. The contours show the difference between the combination of the optical film structure and substrate and the bare substrate (without the optical film structure). In the contour plot, the value of zero for the plotted quantities means the combination of the optical film structure and substrate has the same color coordinates as the bare substrate. As shown in FIG. 30D, the contours shift to accommodate the substrate. Accordingly, the thicknesses of the SiO2 and Al2O3 layers between the solid T, b*=0.5 line and the dashed T, b*=−0.5 line or in some instances, between two dashed T, b*-0.5 lines, are modified from those shown in FIG. 30C. When SiO2 and Al2O3 layers having these thicknesses are combined with the 2 μm AlOxNy layer, the optical film would exhibit b* values in the range from about −0.5 to about 0.5, which would in turn limit the distance or color shift between the color coordinates of the optical film and substrate combination and the color coordinates of the bare substrate (without an optical film). For Al2O3 layer thicknesses between 0 nm to about 500 nm, examples of suitable thicknesses for the SiO2 layer include from about 0 nm to about 40 nm, from about 70 nm to about 100 nm or from about 160 nm to about 175 nm, with more specific thicknesses for the Al2O3 and/or SiO2 layers falling between the solid T, b*=0.5 line and the dashed T, b*=−0.5 line. Examples of thicknesses that may not provide the desired b* transmittance include an SiO2 layer having a thickness from about 0 nm to about 80 nm in combination with an Al2O3 layer having a thickness from about 0 nm to about 500 nm, an SiO2 layer having a thickness from about 80 nm to about 170 nm in combination with an Al2O3 layer having a thickness from about 0 nm to about 500, an SiO2 layer having a thickness from about 0 nm to about 25 nm in combination with an Al2O3 layer having a thickness from about 100 nm to about 130 nm, or from about 230 nm to about 290 nm, or from about 390 nm to about 420 nm, as some of these thickness ranges and combinations fall between two dashed T, b*=−0.5 lines or between two solid T, b*=0.5 lines.
FIG. 30E shows the thicknesses of the SiO2 and Al2O3 layers at which the distance or color shift of the reflectance color coordinates of the article (including the optical film and the substrate) and the color coordinates (a*=0, b*=0) are less than about 1, less than about 0.5, less than about 0.2 and less than about 0.1. FIG. 30E shows that an optical film in which there are very few thicknesses for either the SiO2 layer and the Al2O3 layer at which, when combined with a 2 nm thick AlOxNy layer, will exhibit color coordinates, in transmittance, having a distance or color shift from the color coordinates (a*=0, b*=0) of greater than about 1. For example, an optical film with a SiO2 layer having a thickness in the range from about 0 nm to about 50 nm and a Al2O3 layer having a thickness in the range from about 0 nm to about 500 nm (with more specific thicknesses for the Al2O3 and/or SiO2 layers falling between the solid d=0.1 line and the dashed d=1.0 line), when combined with a 2 nm thick AlOxNy layer, will exhibit color coordinates, in transmittance, having a distance or color shift from the color coordinates (a*=0, b*=0) of less than about 1. In another example, the SiO2 layer thickness can be from about 0 nm to about 50 nm and the Al2O3 layer thickness can be from about 0 nm to about 220 nm, with more specific thicknesses for the Al2O3 and/or SiO2 layers falling between the solid d=0.1 line and the dashed d=1.0 line. In another example, the SiO2 layer thickness can be from about 60 nm to about 100 nm, and the Al2O3 layer thickness can be from about 100 nm to about 500 nm, with more specific thicknesses for the Al2O3 and/or SiO2 layers falling between the solid d=0.1 line and the dashed d=1.0 line.
FIG. 30F shows the thicknesses of the SiO2 and Al2O3 layers at which the distance or color shift of the color coordinates of the article and the color coordinates of the substrate are less than about 1, less than about 0.5, less than about 0.2 and less than about 0.1. FIG. 30F shows that a substrate and an optical film with a 2-nm-thick AlOxNy layer, a SiO2 layer having a thickness in the range from about 0 nm to about 50 nm and a Al2O3 layer having a thickness in the range from about 0 nm to about 200 nm (with more specific thicknesses for the Al2O3 and/or SiO2 layers falling between the solid d=0.1 line and the dashed d=1.0 line), would exhibit color coordinates, in transmittance, having a distance or color shift from the color coordinates of the bare substrate of less than about 1. In another example, the SiO2 layer thickness can be from about 70 nm to about 100 nm, and the Al2O3 layer thickness can be from about 100 nm to about 500 nm, with more specific thicknesses for the Al2O3 and/or SiO2 layers falling between the solid d=0.1 line and the dashed d=1.0 line.
In FIGS. 29A-29F and 30A-30F, contour lines of a* and b* in the range from −0.5 to 0.5 and d of 0.1, 0.2, 0.5 and 1 were utilized to illustrate various design parameters to achieve the optical properties described herein. It should be noted that contour lines with greater ranges can be used (e.g., a* or b* in the range from about −1 to about 1 or from about −2 to about 2, or d=1.5, 2, 2.5 etc.) depending on illuminant of interest and/or observer preferences (i.e., some observers find greater variations in a*, b*, the combination of a* and b* and greater distances d to be acceptable).
Example 12
Example 12A was formed using an aluminosilicate glass substrate that was chemically strengthened and exhibited a compressive stress in the range from about 700 MPa to about 900 MPa and a depth of compressive stress layer in the range from about 40 about 40 μm to about 50 μm. Example 12A included an optical film structure including a first sub-layer of Al2O3 having a thickness of about 115 nm disposed on the substrate, a second sub-layer of AlOxNy having a thickness of about 2000 nm disposed on the first sub-layer, and a second layer of SiO2 having a thickness of about 32 nm disposed on the second sub-layer. Comparative Example 12B included the same substrate as Example 12A but was uncoated. Comparative Example 12C included the same substrate as Example 12A with a hydrophobic, low-friction fluorosilane coating having a thickness of about 10 nm disposed on the substrate. Comparative Examples 12D-12F included the same substrate as Example 12A with a single layer of either SiuAlvOxNy having a thickness of 186 nm (12D) or 478 nm (12E) or AlOxNy with a thickness of about 294 nm (12F).
The coatings on Example 12A, and Comparative Examples 12D-F were formed using reactive DC sputtering or combined reactive DC and RF sputtering from metallic targets. It should be noted that layers of AlOxNy can often be substituted for the layers of SiuAlvOxNy layers and can be formed using the same or a similar process used to form such layers. Both SiuAlvOxNy, and AlOxNy layers can be made which exhibited a refractive index at 550 nm of about 1.95-2.05 and a measured hardness greater than 15 GPa measured using the Berkovich Indentation Hardness Test along an indentation depth of about 100 nm or greater.
Table 9 shows scattered light intensity (CCBTDF, 1/steradian) and transmission haze (with 8 mm aperture) after subjecting the samples to the Taber Test. Table 9 also shows the average scattered light intensity value and haze value of Example 12A, and Comparative Examples 12B-F, as a baseline. Lower scattered light intensity and lower haze correlates to less visible scratches and less visible damage after the abrasion test. Example 12A exhibited the lowest scattered light intensity and haze after the Taber Test indicating superior resistance to multiple contact event damage.







TABLE 9







Scattered Light Intensity and Haze Measurements


for Example 12A and Comparative Examples 12B-12F.










Scattered light intensity -
Range of



Avg. +/− Std. Dev.
Transmission



(CCBTDF, 1/steradian)
Haze













Examples
At 20 degrees
With 8 mm




aperture


Comparative Example 12B - IX
0.021 +/− 0.004
0.1-0.4


glass (no coating)


Comparative Example 12C - IX
0.022 +/− 0.015
0.25-0.35


Glass + hydrophobic, low-


friction fluorosilane coating


Comp. Ex. 12D - IX Glass + 1L
0.03 +/− 0.01
0.8


SiuAlvOxNy 186 nm


Comp. Ex. 12E - IX Glass + 1L
0.018 +/− 0.001
0.3


SiuAlvOxNy 478 nm


Comp. Ex. 12F - IX Glass + 1L
0.174 +/− 0.04 
5.1


AlOxNy 294 nm


Example 12A 3L SRC
 0.002 +/− 0.0001
0.05


Al2O3/AlON/SiO2


Average of non-abraded
0.002 +/− 0.001
 0-0.2


regions of Examples 12A and


Comparative Examples 12B-12F









It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the invention.

## Claims

1. A transparent article comprising:
a substrate having opposing major surfaces; and
an optical film structure disposed on a first major surface of the substrate forming a front face,
wherein the article comprises
a maximum hardness of about 12 GPa or greater, as measured on the front face by a Berkovich Indenter Hardness Test along an indentation depth from about 200 nm to about 600 nm, and
either one or both of:
article transmittance color coordinates in the (L*, a*, b*) colorimetry system at normal incidence exhibiting a color shift of less than about 2 from a reference point as measured at the front face, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the transmittance color coordinates of the substrate, and
article reflectance color coordinates in the (L*, a*, b*) colorimetry system at normal incidence exhibiting a color shift of less than about 2 from a reference point as measured at the front face, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the reflectance color coordinates of the substrate,
wherein, when the reference point is the color coordinates of the substrate, the color shift is defined by √(a*article−a*substrate)2+(b*article−b*substrate)2), and
wherein, when the reference point is the color coordinates (a*=0, b*=0), the color shift is defined by √(a*article)2+(b*article)2),


wherein the article comprises an average transmittance of 85% or more, over the visible spectrum as measured at the front face.

2. The transparent article of claim 1, wherein the article comprises an average transmittance of 87% or more, over the visible spectrum as measured at the front face.

3. The transparent article of claim 1, further comprising a scratch resistance such that, when the front face is scratched with a Berkovich indenter using a load of 160 mN at a speed of 10 μm/seconds for at least a length of 100 μm along the front face of the article, a scratch having a scratch depth of less than 250 nm is formed.

4. The transparent article of claim 1, further comprising a scratch resistance such that, when the front face is scratched with a Berkovich indenter using a load of 160 mN at a speed of 10 μm/seconds for at least a length of 100 μm along the front face of the article, a scratch having a scratch width of less than 10 μm is formed.

5. The transparent article of claim 1, wherein the article comprises a maximum hardness of about 16 GPa or greater, as measured on the front face by a Berkovich Indenter Hardness Test along the indentation depth.

6. The transparent article of claim 1, wherein the optical film structure comprises one of a silicon-containing oxide, a silicon-containing oxy-nitride, silicon nitride, aluminum nitride, an aluminum-containing oxy-nitride, an aluminum-containing oxide, silicon aluminum oxy-nitride or a combination thereof.

7. The transparent article of claim 1, wherein the optical film structure comprises at least two layers, wherein a first layer is disposed between the substrate and a second layer.

8. The transparent article of claim 7, wherein the first layer comprises at least one of silicon-containing oxide, a silicon-containing oxy-nitride, silicon nitride, aluminum nitride, an aluminum-containing oxy-nitride, an aluminum-containing oxide, and silicon aluminum oxy-nitride, and wherein the second layer comprises at least one of SiO2, GeO2, and Al2O3.

9. The transparent article of claim 7, wherein the first layer comprises Al2O3, AlN, AIOXNy or combinations thereof.

10. The transparent article of claim 7, wherein the first layer comprises a first sub-layer comprising Al2O3 and a second sub-layer comprising AlN and, wherein the first sub-layer is disposed between the substrate and the second sub-layer.

11. The transparent article of claim 7, wherein the first layer comprises a first sub-layer comprising AlOxNy and a second sub-layer comprising AlN and, wherein the first sub-layer is disposed between the substrate and the second sub-layer.

12. The transparent article of claim 7, wherein the first layer further comprises SiO2.

13. The transparent article of claim 1, wherein the optical film structure comprises a first layer and a second layer, wherein the first layer has a thickness greater than the thickness of the second layer.

14. The transparent article of claim 13, wherein the optical film structure has a thickness of 1 μm or greater.

15. The transparent article of claim 1, wherein the optical film structure comprises a compositional gradient comprising any one or more of an oxygen content gradient, a nitrogen content gradient, a silicon content gradient and an aluminum content gradient.

16. The transparent article of claim 1, wherein the substrate comprises a crystalline substrate.

17. The transparent article of claim 1, further comprising an interlayer disposed between the optical film structure and the substrate, wherein the interlayer comprises a polymer.

18. An article comprising:
a substrate having opposing major surfaces; and
an optical film structure disposed on a first major surface of the substrate forming a front face, the optical film structure comprising a first layer having a thickness of at least about 1 μm and comprising an aluminum-containing nitride, an aluminum-containing oxy-nitride, an aluminum-containing oxide or a combination thereof, and a second layer disposed on the first layer,
wherein the article comprises a maximum hardness of 12 GPa or greater as measured on the front face by the Berkovich Indenter Hardness Test along an indentation depth from about 200 nm to about 600 nm, and wherein the article comprises an average transmittance of 85% or more over the visible spectrum, wherein the article comprises at least one of:
article transmittance color coordinates in the (L*, a*, b*) colorimetry system at normal incidence comprising a color shift of less than about 2 from a reference point as measured at the front face, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the transmittance color coordinates of the substrate, and
article reflectance color coordinates in the (L*, a*, b*) colorimetry system at normal incidence comprising a color shift of less than about 2 from a reference point as measured at the front face, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the reflectance color coordinates of the substrate, and
wherein, when the reference point is the color coordinates of the substrate, the color shift is defined by √((a*article−a*substrate)2+(b*article−b*substrate)2), and
wherein, when the reference point is the color coordinates (a*=0, b*=0), the color shift is defined by √((a*article)2+(b*article)2).

19. The article of claim 18, wherein the first layer comprises a first sub-layer, a second sub-layer and a third sub-layer, wherein the second sub-layer is disposed between the first sub-layer and the third sub-layer, and wherein the first and third sub-layers comprise AlN and the second sub-layer comprises SiO2.

20. The article of claim 18, wherein the second layer comprises SiO2, GeO2, Al2O3, and a combination thereof.

21. The article of claim 18, wherein the optical film structure further comprises a modifier selected from BN, Ag, Cr and combinations thereof.

22. The article of claim 21, wherein the optical film structure comprises a coefficient of friction of less than 0.3, when measured against a silicon carbide sphere counter surface.

23. The article of claim 18, wherein the article comprises a maximum hardness of about 16 GPa or greater, as measured on the front face by a Berkovich Indenter Hardness Test along an indentation depth in the range from about 200 nm to about 600 nm.

24. The article of claim 18, wherein the article comprises a maximum hardness of about 16 GPa or greater, as measured on the front face by a Berkovich Indenter Hardness Test along the indentation depth.

25. The article of claim 18, wherein the optical film structure comprises a sensor layer.

26. A transparent article comprising:
a substrate having opposing major surfaces; and
an optical film structure disposed on a first major surface of the substrate forming a front face,
wherein the article comprises a maximum hardness of 12 GPa or greater as measured on the front face by the Berkovich Indenter Hardness Test along an indentation depth from about 200 nm to about 600 nm or greater, and
wherein the article comprises either one or both of:
article transmittance color coordinates in the (L*, a*, b*) colorimetry system at normal incidence exhibiting a color shift of less than about 2 from a reference point as measured at the front face, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the transmittance color coordinates of the substrate, and
article reflectance color coordinates in the (L*, a*, b*) colorimetry system at normal incidence exhibiting a color shift of less than about 2 from a reference point as measured at the front face, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the reflectance color coordinates of the substrate,
wherein, when the reference point is the color coordinates of the substrate, the color shift is defined by √((a*articie−a*substrate)2+(b*article−b*substrate)2), and
wherein, when the reference point is the color coordinates (a*=0, b*=0), the color shift is defined by √(a*article)2+(b*article)2), and

wherein the article comprises an abrasion resistance comprising any one or more of:
about 5% haze or less, as measured using a hazemeter having an aperture, wherein the aperture has a diameter of about 8 mm, and
a scattered light intensity of about 0.1 (in units of 1/steradian) or less, at a polar scattering angle in the range from about 15 degrees to about 60 degrees, as measured at normal incidence in transmission using an imaging sphere for scatter measurements, with a 2 mm aperture at 600 nm wavelength,
wherein the abrasion resistance is measured after a 500-cycle abrasion on the front face using a Taber Test, and

wherein the article comprises an average transmittance of 85% or more, over the visible spectrum as measured at the front face.

27. The transparent article of claim 26, wherein the abrasion resistance comprises about 1% haze or less.

28. The transparent article of claim 26, wherein the abrasion resistance comprises a scattered light intensity of about 0.05 (in units of 1/steradian) or less, at a polar scattering angle of about 40 degrees or less.

29. The transparent article of claim 26, wherein the abrasion resistance comprises a scattered light intensity of about 0.1 (in units of 1/steradian) or less, at a polar scattering angle of about 20 degrees or less.

30. A consumer electronic article comprising the transparent article of claim 1.

31. The consumer electronic article of claim 30, further comprising a mobile phone, a tablet, a computer, or a navigation system.

32. A consumer electronic article comprising the transparent article of claim 18.

33. The consumer electronic article of claim 32, further comprising a mobile phone, a tablet, a computer, or a navigation system.

34. A consumer electronic article comprising the transparent article of claim 26.

35. The consumer electronic article of claim 34, further comprising a mobile phone, a tablet, a computer, or a navigation system.