This disclosure is directed to a process for making glass articles having an optical coating and an easy-to-clean (ETC) coating thereon, an apparatus for performing the process and an article made using the process. In particular, the disclosure is directed to a process in which the application of the optical coating and the ETC coating can be sequentially carried out using the same apparatus.
Glass, and in particular chemically strengthened glass, has become the material of choice for the view screen of many, if not most, consumer electronic products. For example, chemically strengthened glass is particularly favored for “touch” screen products whether they be small items, such as cell phones, music players, eBook readers and electronic notepads, or larger items, such as computers, automatic teller machines, airport self-check-in machines and other similar electronic items. Many of these items require the application of antireflective (“AR”) coatings on the glass in order to reduce the reflection of visible light from the glass and thereby improve contrast and readability, for example, when the device is used in direct sunlight. However, some of the drawbacks of an AR coating are its sensitivity to surface contamination and its poor anti-scratch durability, that is, the AR coating becomes easily scratched during use, for example, by a wiping cloth or the dirt and grime on a user's finger. Fingerprints and stains are very noticeable on an AR coated surface and are not always easily removed. As a result, it is highly desirable that the glass surface of any touch device be easy to clean which is achieved by applying an easy-to-clean (ETC) coating to the glass surface.
The current processes for making glass articles having both antireflection and ETC coatings require that the coating be applied using different equipment, and consequently separate manufacturing runs. The basic procedure is to apply the antireflection (“AR”) coating to a glass article using, for example, a chemical vapor (“CVD”) or physical vapor deposition (“PVD”) method. In conventional processes, an optically coated article, for example, one with an AR coating, will be transferred from the optical coating apparatus to another apparatus to apply the ETC coating on top of the AR coating. While these processes can produce articles that have both an AR and an ETC coating, they require separate runs and have higher yield losses due to the extra handling that is required. This may result in poor reliability of the final product due to contamination arising from the extra handling between the AR coating and ETC coating procedures. For example, using the conventional 2-step coating process of ETC over an optical coating results in an article that is easily scratched in touch screen applications. In addition, while the AR coated surface can be cleaned before applying the ETC coating, this involves additional steps in the manufacturing process. All the additional steps increase the product costs. Consequently, alternative methods and apparatuses are needed by which both coatings can be applied using the same basic procedure and equipment, thus reducing manufacturing costs. Advantages of the process disclosed herein and the resulting products are set forth in the following paragraphs and claims.
In one or more embodiments, the disclosure provides a substrate carrier for holding a substrate during a coating process. The substrate carrier may include a substrate carrier base comprising a retention surface, an underside, and a substrate retention area disposed on the retention surface. The substrate retention area may have an area less than an area of the retention surface. The substrate carrier may also include a plurality of magnets coupled to the underside of the substrate carrier base and positioned outside of a perimeter of the substrate retention area. In one or more embodiments, the adhesive material may be positioned over the retention surface in the substrate retention area for releasably affixing at least one substrate to be coated to the retention surface. The adhesive material may include a pressure sensitive adhesive. In one variant, the adhesive material may include acrylic adhesives, rubber adhesives, and/or silicone adhesives. Optionally, a polymer film may be positioned between the retention surface and the adhesive material.
The substrate carrier may include a plurality of pins for supporting a substrate positioned on the retention surface. Optionally, the substrate carrier may include a spring system comprising a retractable pin held in place by a spring which biases the retractable pin into contact with the substrate when the substrate is positioned on the retention surface, and a plurality of side stoppers extending from the substrate carrier base for a distance such that, when the substrate is positioned on the plurality of pins, tops of the plurality of side stoppers are below a top surface of the substrate. In one variant, the substrate carrier may be a housing with a retractable pin disposed in the housing, wherein the retractable pin is held in place by a spring, the retractable pin being outwardly biased from the housing and into contact with the substrate when the substrate is positioned on the retention surface and a plurality of movable pins for holding an edge of the substrate when the substrate is positioned on the retention surface. In another variant, the positions of the plurality of pins are adjustable to accommodate substrates of different shapes and dimensions.
In yet another embodiment, the disclosure provides a coating apparatus for coating a substrate. The coating apparatus may include a vacuum chamber and a rotatable dome positioned in the vacuum chamber and comprising a magnetic material. A plasma source may be positioned within the vacuum chamber and substantially vertically oriented to direct plasma onto an underside of the rotatable dome, wherein the plasma source is positioned below the rotatable dome and radially outward from an axis of rotation of the rotatable dome such that the plasma emitted from the plasma source is incident on the underside of the rotatable dome from at least an outer edge of the rotatable dome to at least a center of the rotatable dome. In one or more embodiments, the distance between the axis of rotation of the rotatable dome and the plasma source is greater than a distance between a projected perimeter of the rotatable dome and the plasma source. The coating apparatus may include at least one thermal evaporation source positioned in the vacuum chamber.
The coating apparatus may optionally include at least one e-beam source positioned in the vacuum chamber and oriented to direct an electron beam onto coating source materials positioned in the vacuum chamber. The coating apparatus may include a second e-beam source in the vacuum chamber. The second e-beam source may be oriented to direct a second electron beam onto coating source materials positioned in the vacuum chamber.
In another option, the coating apparatus may include at least one shadow mask adjustably positionable within the vacuum chamber. The shadow mask may be adjustable from an extended position, wherein the at least one shadow mask is positioned between the at least one e-beam source and the rotatable dome, and a retracted position, wherein the at least one shadow mask is not positioned between the at least one e-beam source and the rotatable dome. In one or more embodiments, a second shadow mask may be included. In such embodiments, the second shadow mask may be positioned between the second e-beam source and the rotatable dome.
The coating apparatus may include a rotatable dome that includes an opening at a top center of the rotatable dome, a transparent glass plate covering the opening of the rotatable dome, and a monitor positioned in an opening in the transparent glass plate for monitoring a deposition rate of coating material deposited in the vacuum chamber. An optical fiber may be positioned above the transparent glass plate, wherein the optical fiber collects light reflected from the transparent glass plate as the transparent glass plate is coated to determine a change in reflectance of the transparent glass plate and thereby a thickness of coatings applied to the transparent glass plate.
In yet another embodiment, the disclosure provides a coating apparatus for coating a substrate. The coating apparatus may include a vacuum chamber and a rotatable dome positioned in the vacuum chamber. The rotatable dome may be constructed from a magnetic material. The apparatus may also include at least one substrate carrier for attachment to the rotatable dome. The at least one substrate carrier may include a substrate carrier base comprising a retention surface, an underside, and a substrate retention area disposed on the retention surface. A plurality of magnets may be coupled to the underside of the substrate carrier base and positioned outside of a perimeter of the substrate retention area. An adhesive material may be positioned over the retention surface in the substrate retention area for releasably affixing at least one substrate to be coated. The coating apparatus may include a plasma source positioned within the vacuum chamber and substantially vertically oriented to direct plasma onto an underside of the rotatable dome, wherein the plasma source is positioned below the rotatable dome and radially outward from an axis of rotation of the rotatable dome such that the plasma emitted from the plasma source is incident on the underside of the rotatable dome from at least an outer edge of the rotatable dome to at least a center of the rotatable dome. In one variant, the distance between the axis of rotation of the rotatable dome and the plasma source is greater than a distance between a projected perimeter of the rotatable dome and the plasma source. The coating apparatus may include a first e-beam source positioned in the vacuum chamber and oriented to direct a first electron beam onto a first coating source material positioned in the vacuum chamber and a second e-beam source positioned in the vacuum chamber and oriented to direct a second electron beam onto a second coating source material positioned in the vacuum chamber. The first coating source material may exhibit a high refractive index and the second coating source material may exhibit a low refractive index or a medium refractive index. The coating apparatus may include at least one shadow mask adjustably positionable within the vacuum chamber. The shadow mask may be adjustable from an extended position, wherein the at least one shadow mask is positioned between at least one of the first e-beam source and the second e-beam source and the rotatable dome and a retracted position, wherein the at least one shadow mask is not positioned between either the first e-beam source or the second e-beam source and the rotatable dome.
Additional features and advantages of the methods described herein will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments 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 describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments and are incorporated into and constitute a part of this specification. The drawings illustrate the various embodiments described herein, and together with the descriptions, serve to explain the principles and operations of the claimed subject matter.
Reference will now be made in detail to embodiments of glass articles coated with optical coatings and easy-to-clean coatings and methods and apparatuses for forming the same, 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. One embodiment of a coating apparatus is schematically depicted in
Herein the terms “process” and “method” may be used interchangeably. Also herein the terms “shadowless” and “shadow free” mean that the optical coating is uniformly deposited over the entire surface of the glass substrate such that, when the glass article with the coating deposited using the methods and apparatuses described herein is viewed, the shadow that is observed on glass articles having optical coating prepared using conventional optical coating methods and apparatuses is not observed. The shadow observed on conventionally coated glass articles arises when areas of the substrate being coated shield the surface of the substrate from the deposition of the optical coating materials. These shadows are frequently observed adjacent to elements that are used to hold the substrate being coated in place during the coating process or are on the substrate carrier for transport of the carrier and the elements being coated into and out of the coater.
The terms “glass article” and “glass substrate” are used herein interchangeably and generally refer to any glass item coated using the methods and apparatuses described herein.
The present disclosure is directed to a process in which both an optical coating, for example an AR coating, comprising alternating layers of high refractive index and low refractive index materials, and an ETC coating, for example a perfluoroalkylsilane coating, can be applied to a glass substrate in sequential steps (i.e., first applying the optical coating and then applying the ETC coating over the optical coating) using substantially the same procedure without exposing the article to air or ambient atmosphere at any time during the application of the optical coating and the ETC coating. A reliable ETC coating provides lubrication to surface(s) of glass, transparent conductive coatings (TCC), and optical coatings. In addition, the abrasion resistance of glass and optical coatings will be more than 10 times better than the conventional coating process or 100-1000 times better than an AR coating without an ETC coating by using an in-situ, one-step process in which the coatings are sequentially applied, as graphically depicted in
A particular example of an in-situ process is a box coater, as schematically depicted in
The optical coating is composed of high and median or low refractive index materials. Exemplary high index materials having an index of refraction greater than or equal to 1.7 and less than or equal to 3.0 include: ZrO2, HfO2, Ta2O5, Nb2O5, TiO2, Y2O3, Si3N4, SrTiO3, and WO3; an exemplary median index material having an index of refraction greater than or equal to 1.5 and less than 1.7 is Al2O3; and exemplary low index materials having an index of refraction greater than or equal to 1.3 and less than or equal to 1.6) include: SiO2, MgF2, YF3, and YbF3. The optical coating stack that is deposited on a substrate comprises at least one material/layer to provide a specified optical function. In most cases, a high and a low index material can be used to design a complex optical filter (including AR coatings), for example, HfO2 as the high index material and SiO2 as the low index material. TCC (two-component coating) materials suitable for use in the coatings include ITO (indium tin oxide), AZO (Al doped zinc oxide), IZO (Zn stabilized indium oxides), In2O3, and similar binary and ternary oxide compounds.
In embodiments, the optical coatings are applied to glass substrates using PVD coating (sputtered or IAD-EB coated optical coating with thermal evaporation of the ETC coating). PVD is a “cold” process in which the substrate temperature is under 100° C. As a result, there is no degradation of the strength of a chemically strengthened or tempered glass substrate to which the coatings are applied.
In the embodiments described herein, the glass used to make the shadow free, optical and ETC coated glass articles described herein may be an ion-exchanged or non-ion-exchanged glass. Exemplary glasses include silica glass, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass and soda lime glass. The glass articles have a thickness in the range of 0.2 mm to 1.5 mm, and a length and width suitable for the intended purpose. Thus the length and width of the glass article can range from that of a cell phone to a tablet computer, or larger.
The optical coatings referred to herein include antireflection coatings (AR coatings), band-pass filter coatings, edge neutral mirror coatings, beam splitters, multi-layer high-reflectance coatings and edge filters, as described in H. Angus Macleod, “Thin Film Optical Filters”, 3rd edition, Institute of Physics Publishing, Bristol and Philadelphia, 2001. Applications using such optical coatings include displays, camera lenses, telecommunications components, instruments, medical devices, photochromic and electrochromic devices, photovoltaic devices, and other elements and devices.
Alternating layers of high and low refractive index materials can be used to form optical coatings, such as antireflective or anti-glare for ultraviolet (“UV”), visible (“VIS”) and infrared (“IR”) applications. The optical coatings can be deposited using a variety of methods. Herein the PVD method (i.e., ion-assisted, e-beam deposition) for depositing the optical coatings is used as an exemplary method. The optical coatings comprise at least one layer of a high index material H and at least one layer of low index material L. Multilayer coatings consist of a plurality of alternating high and low index layers, for example, HL, HL, HL . . . , etc., or LH, LH, LH . . . , etc. One pair of HL layers (or LH layers) is referred to as a “period” or a “coating period.” A medium index material M can be used in place of a low index material in all or some of the low index layers. The term “index,” as used herein, refers to the index of refraction of the material. In a multilayer coating, the number of periods can range widely depending on the function of the intended product. For example, for AR coatings, the number of periods can be in the range of greater than or equal to 2 and less than or equal to 20. An optional final capping layer of SiO2 can also be deposited on top of the AR coating as a final layer. Various techniques may be used to deposit the ETC material on top of the optical coating without exposing the optical coating to the ambient atmosphere including, without limitation, thermal evaporation, chemical vapor deposition (CVD) or atomic layer deposition (ALD).
The optical coatings deposited on the glass substrates described herein may be multilayer optical coatings comprising at least one period of a high refractive index material and a low refractive index material. The high refractive index material may be selected from ZrO2, HfO2, Ta2O5, Nb2O5, TiO2, Y2O3, Si3N4, SrTiO3, and WO3; however, it should be understood that other suitable high refractive index materials may be used. The low refractive index material may be selected from the group consisting of SiO2, MgF2, YF3, and YbF3; however, it should be understood that other suitable low refractive index materials may be used. In some embodiments, the low refractive index material may be replaced with a medium refractive index material, such as Al2O3 or another suitable medium refractive index material.
In one embodiment, the present disclosure is directed to a process in which, in a first step, a multilayer optical coating is deposited on a glass substrate followed by a second step in which the ETC coating is thermally evaporated and deposited in the same chamber as the optical coating. In another embodiment, a multilayer optical coating is deposited on a glass substrate in one chamber followed by the thermal evaporation and deposition of the ETC coating on top of the multilayer coating in a second chamber, with the provision that the transfer of the multilayer coated substrate from the first chamber to the second chamber is carried out inline in a manner such that the substrate is not exposed to air between the application of the multilayer coating and the ETC coating. The coating techniques utilized may include, without limitation PVD, CVD/PECVD, and ALD coating techniques. Depending on the size of the chamber or chambers and the size of the substrates being coated, one or a plurality of substrates can simultaneously be coated within a single chamber.
The multilayer optical coatings are typically oxide coatings in which the high index coating is a lanthanide series oxide, such as La, Nb, Y, Gd or other lanthanide metals, and the low index coating is SiO2. The ETC materials may be, for example, fluorinated silanes, typically alkyl perfluorocarbon silanes having the formula (R:
The coating apparatus further comprises an e-beam source 120 located below the dome 110 and an e-beam reflector 122 for directing the e-beam from the e-beam source toward the optical coating material being applied to the glass substrate to thereby vaporize the optical material. A shadow mask 125 for enabling uniform coating across the dome is located below the dome 110. The shape and position of the shadow mask 125 are adjustable such that the shadow mask is “tunable” to achieve a desired coating uniformity. The shadow mask 125 is positioned on a support 125a such that the position of the shadow mask 125 can be adjusted vertically along the support 125a, as indicated by the dashed double headed arrow. The position of the shadow mask 125 on the support 125a can be adjusted as needed to prevent the shadow mask from shielding the glass substrates located on the underside of the dome 110 from the ions or plasma emitted from the plasma source 118 as the optical coating is applied. While
The coating apparatus 100 further comprises an optical coating carrier 124 having a plurality of boats 126 which contain the optical coating material. The boats 126 are separate source containers used to contain the different materials used to deposit the optical coating layer. The optical coating carrier 124 is positioned in the vacuum chamber 102 such that an e-beam emitted from the e-beam source 120 can be reflected by the e-beam reflector 122 onto the optical coating material contained in the boats 126, thereby vaporizing the optical coating material. The boats 126 contain different optical coating materials so that only one type of coating material (e.g., either a high refractive index, low refractive index, or medium refractive index material), is applied at one time. After the proper thickness of one coating material is reached, the lid (not depicted) of the corresponding boat is closed and a lid to another boat containing a different coating material to be applied is opened. In this manner, the high refractive index material, low refractive index material, or medium refractive index material can be applied in an alternating manner to form an optical coating material having the desired optical properties.
The coating apparatus 100 also comprises at least one thermal evaporation source 128 for evaporating the ETC coating material to facilitate depositing the coating material onto glass substrates retained on the underside of the dome 110. The at least one thermal evaporation source 128 is positioned in the vacuum chamber 102 below the dome 110. In one or more embodiments, the ETC coating may be provided in the vacuum chamber 102 via steel wool-filled copper crucible (not shown) or a porous ceramic-filled copper crucible (not shown). The use of steel wool provides for uniform heating of the ETC material and increases the evaporation surface area. The use of steel wool also provides for a more controlled deposition rate of the ETC coating on a substrate.
Still referring to
The top of the dome 110 is attached to a vacuum shielded rotation shaft 117 indicated by the dashed parallel lines. The vacuum shielded rotation shaft 117 has a vacuum seal bearing 119 attached to the vacuum shielded rotation shaft for rotating the vacuum shielded rotation shaft 117 and dome 110. Accordingly, it should be understood that the vacuum shielded rotation shaft 117 is vacuum sealed to the top of the dome 110. The vacuum shielded rotation shaft 117 is driven by an external motor (not illustrated) located external to the vacuum chamber 102. In an embodiment, the dome 110 may be rotated at a rotation frequency in the range from about 20 rpm to about 120 rpm. In another embodiment, the rotation frequency is in the range from about 40 rpm to about 83 rpm.
The coating apparatus 500 also includes an optical coating carrier 124 having a plurality of boats 126 which contain optical coating materials. The boats 126 are separate source containers used to contain the different materials used to deposit the optical coating layer on substrates affixed on the underside of the dome 110. The boats 126 contain different optical coating materials so that only one type of coating material (e.g., either a high refractive index, low refractive index, or medium refractive index material) is applied at a time. In this embodiment, the coating apparatus 500 includes a first e-beam source 120a, a second e-beam source 120b, and an e-beam reflector 122. The first e-beam source 120a, the second e-beam source 120b, and the e-beam reflector 122 are arranged such that electron beams emitted from the respective sources are directed onto the e-beam reflector 122 and redirected from the e-beam reflector 122 onto a single optical coating material contained in a boat 126 located on the optical coating carrier 124 to co-evaporate the optical coating material. It has been found that the use of multiple e-beam sources used to co-evaporate a single optical coating material enhances the thickness uniformity of the resultant coating deposited on a substrate. Additionally or alternatively, the first e-beam source 120a emits a first electron beam onto the e-beam reflector 122, such that the first electron beam is redirected to a first optical coating material contained in the boat 126, and the second e-beam source 120b emits a second electron beam onto the e-beam reflector 122, such that the second electron beam is redirected to a second optical coating material contained in a different boat 126. In one or more embodiments, the first optical coating material is different from the second optical coating material. In embodiments, the first optical coating material includes a high refractive index material and the second optical coating material includes a low or medium refractive index material. In embodiments, more than one reflector may be utilized such that one reflector (not shown) redirects the first electron beam and a second reflector (not shown) redirects the second electron beam.
In this embodiment, the coating apparatus 500 further comprises a first shadow mask 125, which is adjustably positionable in the vacuum chamber 102, and a second shadow mask 129, which has a fixed position within the vacuum chamber 102. The first shadow mask is adjustable between an extended position (depicted in
In the cross section of the coating apparatus 500 schematically depicted in
In addition, the coating apparatus 500 also includes at least one thermal evaporation source 128 for evaporating the ETC coating material to facilitate depositing the coating material onto substrates affixed on the underside of the dome 110. The at least one thermal evaporation source 128 is positioned in the vacuum chamber 102 below the dome 110. In embodiments, liquid ETC coating material is placed in a copper crucible filled with steel wool or a porous ceramic material. The crucible is heated by the thermal evaporation source 128 to evaporate the ETC coating material which, in turn, is deposited on substrates located on the underside of the rotatable dome 110.
The coating apparatus 500 also contains a plasma source, such as an ion-beam source. As described above with reference to
Referring now to
While
Referring now to
Referring now to
Referring now to the cross section of the substrate carrier 130b depicted in
In some embodiments, the polymer film 144 may be capable of being statically charged. In these embodiments, a separate adhesive material 143 is not needed as the statically charged film acts as the adhesive for releasably retaining the substrates on the retention surface 131a. Suitable static films include, without limitation, Visqueen film manufactured by British Polyethylene Industries Limited.
The substrate carriers 130, 130a, 130b have non-magnetic substrate carrier bases 131 and a plurality of magnets 134 for holding the carriers to the dome 110 and for off-setting the carrier a distance from the dome 110. The use of these magnetic carriers is an improvement over dome carriers that are used in the coating of optical elements, such as lenses. For example,
Referring now to
Referring now to
Referring again to
Once the coating materials are loaded, the vacuum chamber 102 is sealed and evacuated to a pressure less than or equal to 10−4 Torr. The dome 110 is then rotated in the vacuum chamber 102 by rotating the vacuum shielded rotation shaft 117. The plasma source 118 is then activated to direct ions and/or plasma towards the glass substrates 140 positioned on the underside of the dome 110 to densify the optical coating materials as they are applied to the glass substrate 140. Thereafter, the optical coating and ETC coating are sequentially applied to the glass substrate 140. The optical coating is first applied by vaporizing the optical materials positioned in the boats 126 of the optical coating carrier 124. Specifically, the e-beam source 120 is energized and emits a stream of electrons which are directed onto the boats 126 of the optical coating carrier 124 by the e-beam reflector 122. The vaporized material is deposited on the surfaces of the glass substrates 140 as the glass substrates 140 are rotated with the dome 110. The rotation of the dome 110, in conjunction with the shadow mask 125 and the orientation of the glass substrates 140 on the substrate carriers 130, allows the optical coating materials to be uniformly coated onto the glass substrate carriers, thereby avoiding “shadows” on the coated surface of the glass substrate 140. As described hereinabove, the e-beam source 120 is utilized to sequentially deposit layers of high refractive index material and low refractive index material or medium refractive index material to achieve an optical coating having the desired optical properties. The quartz monitor 114 and the optical fiber 112 are utilized to monitor the thicknesses of the deposited materials and thereby control the deposition of the optical coating, as described herein.
Once the optical coating has been applied to the glass substrate 140 to the desired thickness using the desired coating material(s), optical coating ceases and the ETC coating is applied over the optical coating by thermal evaporation as the glass substrate 140 rotates with the dome 110. Specifically, the ETC material positioned in the at least one thermal evaporation source 128 is heated, thereby vaporizing the ETC material in the vacuum chamber 102. The vaporized ETC material is deposited on the glass substrate 140 by condensation. The rotation of the dome 110, in conjunction with the orientation of the glass substrates 140 on the substrate carriers 130, facilitates uniformly coating the ETC materials onto the glass substrate 140. The quartz monitor 114 and the optical fiber 112 are utilized to monitor the thicknesses of the deposited materials and thereby control the deposition of the ETC coating, as described herein.
In the embodiments described herein, an SiO2 layer is generally applied as a capping layer for optical coatings. The SiO2 layer is generally deposited as part of the optical coating prior to the deposition of the ETC coating. This SiO2 layer provides a dense surface for grafting and crosslinking of silicon atoms of the ETC coating as these layers were deposited at high vacuum (10−4-10−6 Torr) without the presence of free OH. Free OH, for example a thin layer of water on the glass or AR surface, is detrimental during ETC material deposition, because the OH prevents the silicon atoms in the ETC material from bonding with the oxygen atoms of metal oxide or silicon oxide surfaces, that is, the optical coating surface. When the vacuum in the deposition apparatus is broken, that is, the apparatus is opened to the atmosphere, air from the environment, which contains water vapor, is admitted, and the silicon atoms of the ETC coating react with the optical coating surface to create at least one chemical bonds between the ETC silicon atom and surface oxygen atom and release alcohol or acid once exposed to air. Since the ETC coating material typically contains 1-2 fluorinated groups and 2-3 reactive groups, such as CH3O— groups, the ETC coating is capable of bonding to 2-3 oxygen atoms at the optical coating surface, or crosslinking with another coating molecule, as shown in
Thus, once the ETC coating has been applied over the optical coating, the glass substrate 140 with the optical coating and the ETC coating is removed from the chamber and allowed to cure in air. If allowed to cure simply by sitting at room temperature (approximately 18-25° C., Relative Humidity (RH) 40%), the curing will take 1-3 days. Elevated temperatures may be utilized to expedite curing. For example, in one embodiment, the ETC coated article may be heated to a temperature of 80-100° C. for a time period from about 10 minutes to about 30 minutes at a RH in the range of greater than 50% and less than 100%. Typically, the relative humidity is in the range of 50-85%.
Once the ETC coating has been cured, the surface of the coating is wiped with a soft brush or an isopropyl alcohol wipe to remove any ETC material that has not bonded to the optical coating.
The methods and apparatuses described herein may be used to produced coated glass articles, such as coated glass substrates, which have both an optical coating (such as an AR coating or a similar optically functional coating) and an ETC coating positioned over the optical coating. Utilizing the methods and apparatuses described herein, the coated glass articles are generally shadow free across the optically coated surface of the glass article. In embodiments, the optical coating applied to the glass article may have a plurality of periods consisting of a layer of high refractive index material H having an index of refraction greater than or equal to 1.7 and less than or equal to 3.0, and a layer of low refractive index material L having an index of refraction greater than or equal to 1.3 and less than or equal to 1.6. The layer of high refractive index material may be the first layer of each period, and the layer of low refractive index material L may be the second layer of each period. Alternatively, the layer of low refractive index material may be the first layer of each period, and the layer of high refractive index material H may be the second layer of each period. In some embodiments, the number of coating periods in the optical coating may be greater than or equal to 2 and less than or equal to 1000. The optical coating may further include a capping layer of SiO2. The capping layer may be applied on over one or a plurality of periods and may have a thickness in the range of greater than or equal to 20 nm and less than or equal to 200 nm. In the embodiments described herein, the optical coating may have a thickness in the range from greater than or equal to 100 nm to less than or equal to 2000 nm. However, greater thicknesses are possible depending on the intended use of the coated article. For example, in some embodiments, the optical coating thickness can be in the range of 100 nm to 2000 nm. In some other embodiments, the optical coating thickness can be in the range of 400 nm to 1200 nm or even in the range from 400 nm to 1500 nm.
The thickness of each of the layers of high refractive index material and low refractive index material may be in a range from greater than or equal to 5 nm and less than or equal to 200 nm. The thickness of each of the layers of high refractive index material and low refractive index material may be in a range from greater than or equal to 5 nm and less than or equal to 100 nm. As will be described further herein, the coated glass articles exhibit an improved resistance to abrasion from the specific coating methods and techniques utilized herein. The degradation of the coatings applied to the glass article may be assessed by the water contact angle following exposure of the glass coating to abrasion testing. The abrasion testing was carried out by rubbing grade 0000# steel wool across the coated surface of the glass substrate under a 10 kg normal load. The abraded area is 10 mm×10 mm. The frequency of abrasion is 60 Hz, and the travel distance of the steel wool is 50 mm. The abrasion testing is performed at a relative humidity RH<40%. In the embodiments described herein, glass articles have a water contact angle of at least 75° after 6,000 abrasion cycles. In some embodiments, the glass articles have a water contact angle of at least 105° after 6,000 abrasion cycles. In still other embodiments, the glass articles have a water contact angle of greater than 90° after 10,600 abrasion cycles.
The resistance of the glass article to abrasion and degradation may also be assessed by the length of scratches present on the glass article following abrasion testing. In embodiments described herein, the coated glass articles have a surface scratch length of less than 2 mm following 8000 abrasion cycles.
Moreover, the resistance of the glass article to abrasion and degradation may also be assessed by the change in the reflectance and/or transmittance of the glass article following abrasion testing, as will be described in more detail herein. In some embodiments, a % Reflectance of the glass article after at least 8,000 abrasion/wiping cycles is substantially the same as the % Reflectance of an unabraded/unwiped glass article. In some embodiments, the % Transmission of the glass article after at least 8,000 abrasion/wiping cycles is substantially the same as the % Transmission of an unabraded/unwiped glass article.
The deposition methods described herein may be used to produce a shadow free optical coating. This means that the optical coating is uniformly deposited over the entire coated surface of the glass substrate. In embodiments of the coated glass substrates described herein, the variation in a thickness of the optical coating from a first edge of the optical coating to second edge of the optical coating of the glass substrate is less than 4%. For example, in some embodiments, the variation in the thickness of the optical coating from a first edge of the optical coating to second edge of the optical coating of the glass substrate is less than or equal to 3%. In some other embodiments the variation in the thickness of the optical coating from a first edge of the optical coating to second edge of the optical coating of the glass substrate is less than or equal to 2%. In still other embodiments, the variation in the thickness of the optical coating from a first edge of the optical coating to second edge of the optical coating of the glass substrate is less than or equal to 1%.
The coating apparatus 500, the substrate carrier 130 and/or the methods described herein may be utilized to form other coatings on glass substrates or other substrates (e.g., plastic substrates). Such other coatings may include optical decorative coatings or protective coatings, which may include, without limitation, non-absorbing and absorbing materials. Exemplary decorative coating can be formed by either transparent dielectrics or absorbing materials. Such materials include metals (e.g., Cr, Ag, Au, W, Ti and the like), semiconductors (e.g., Si, AlN, TCO materials, such as ITO and SnOx, Ge and the like), and absorbing materials (SiNx, SiOxNy, TiN, AlSiOx, and the like).
Ion-assisted electron-beam deposition provides a unique advantage for coating small and medium size glass substrates, for example, those having facial dimensions in the range of approximately 40 mm×60 mm to approximately 180 mm×320 mm, depending on the chamber size. Ion-assisted coating process provides a freshly deposited optical coating on the glass surface that has low surface activation energy with regard to the subsequent application of the ETC coating since there is no surface contamination (water or other environmental) that might impact the ETC coating performance and reliability. The application of the ETC coating directly after completion of the optical coating improves crosslinking between two fluorocarbon functional groups, improves wear resistance, and improves contact angle performance (higher oleophobic and hydrophobic contact angles) following thousands of abrasion cycles applied to the coating. In addition, ion-assisted e-beam coating greatly reduces coating cycle time to enhance coater utilization and throughput. Further, no post deposition heat treatment or UV curing of the ETC coating is required due to lower activation energy of the optical coating surface which makes the process compatible with post ETC processes in which heating is not permitted. Using the Ion-assisted e-beam PVD processes described herein, the ETC material can be coated on selected regions to avoid contamination to other locations of the substrate.
A 4-layer SiO2/Nb2O5/SiO2/Nb2O5/substrate AR optical coating was deposited on sixty (60) pieces of Gorilla™ Glass (commercially available from Corning Incorporated) with dimensions (Length, Width, Thickness) of approximately 115 mm L×60 mm W×0.7 mm T. The coating was deposited using the methods described herein. The AR coating had a thickness of approximately 600 nm. After deposition of the AR coating, an ETC coating was applied on top of the AR coating by thermal evaporation using perfluoroalkyl trichlorosilanes having a carbon chain length in the range of 5 nm to 20 nm (Optool™ fluoro coating, Daikin Industries was used as an exemplary species). The deposition of the AR and ETC coatings was carried out in a single chamber coating apparatus as illustrated in
In this Example, the same fluoro-coating used in Example 1 was coated on a GRIN-lens for optical connectors, as is illustrated in
The data in
The AR/ETC coating described herein can be utilized in many commercial articles. For example, the resulting coating can be used to make televisions, cell phones, electronic tablets, book readers and other devices readable in sunlight. The AR/EC coatings also have utility in antireflection beamsplitters, prisms, mirrors and laser products; optical fibers and components for telecommunication; optical coatings for use in biological and medical applications; and for anti-microbial surfaces.
It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover the modifications and variations of the various embodiments described herein provided such modification and variations come within the scope of the appended claims and their equivalents.
This application is a divisional application and claims the benefit of priority to U.S. Non-Provisional application Ser. No. 13/906,065 filed on May 30, 2013 (now U.S. Pat. No. 10,077,207) and is a continuation-in-part of U.S. Non-Provisional patent application Ser. No. 13/690,829 filed Nov. 30, 2012 (now abandoned) entitled “Optical Coating Method, Apparatus and Product”, which claims the priority of U.S. Provisional Application No. 61/709,423 entitled “Optical Coating Method, Apparatus and Product” filed Oct. 4, 2012, the contents of which are relied upon and incorporated herein by reference in its entirety. Further, this application is a continuation-in-part of U.S. Non-Provisional patent application Ser. No. 13/690,904 filed Nov. 30, 2012 (now abandoned) entitled “Process for Making of Glass Articles with Optical and Easy-To-Clean Coatings”, which claims the priority of U.S. Provisional Application No. 61/565,024 entitled “Process for Making of Glass Articles With Optical and Easy-To-Clean Coatings” filed Nov. 30, 2011, the contents of which are relied upon and incorporated herein by reference in its entirety.
Number | Name | Date | Kind |
---|---|---|---|
2338234 | Dimmick | Jan 1944 | A |
4817559 | Ciparisso | Apr 1989 | A |
4851095 | Scobey et al. | Jul 1989 | A |
5026469 | Kunkel et al. | Jun 1991 | A |
5105310 | Dickey | Apr 1992 | A |
5106346 | Locher et al. | Apr 1992 | A |
5328768 | Goodwin | Jul 1994 | A |
5342665 | Krawitz | Aug 1994 | A |
5352294 | White et al. | Oct 1994 | A |
5699189 | Murphy | Dec 1997 | A |
5759643 | Miyashita et al. | Jun 1998 | A |
5783299 | Miyashita et al. | Jul 1998 | A |
5800918 | Chartier et al. | Sep 1998 | A |
6119626 | Miyazawa et al. | Sep 2000 | A |
6264751 | Kamura et al. | Jul 2001 | B1 |
6296793 | Anthes et al. | Oct 2001 | B1 |
6383565 | Monaghan | May 2002 | B1 |
6405465 | Dwyer et al. | Jun 2002 | B2 |
6592659 | Terrazas et al. | Jul 2003 | B1 |
6749750 | Barbera-Fuillem et al. | Jun 2004 | B2 |
6863965 | Fujinawa et al. | Mar 2005 | B2 |
6929822 | Kono | Aug 2005 | B2 |
7070849 | Mori et al. | Jul 2006 | B2 |
7294731 | Flynn | Nov 2007 | B1 |
7508567 | Clark | Mar 2009 | B1 |
7578877 | Giessler et al. | Aug 2009 | B2 |
7604358 | Ninomiya et al. | Oct 2009 | B2 |
7692855 | Arrouy et al. | Apr 2010 | B2 |
7790004 | Seddon | Sep 2010 | B2 |
7889284 | Nemeth et al. | Feb 2011 | B1 |
7967961 | Dogi et al. | Jun 2011 | B2 |
8211544 | Itami et al. | Jul 2012 | B2 |
8318245 | Roisin et al. | Nov 2012 | B2 |
8475595 | Pei | Jul 2013 | B2 |
8817376 | Lee et al. | Aug 2014 | B2 |
20010022652 | Van Schaik et al. | Sep 2001 | A1 |
20010033893 | Anthes et al. | Oct 2001 | A1 |
20020050453 | Monaghan | May 2002 | A1 |
20020060848 | Mitsuishi et al. | May 2002 | A1 |
20030003227 | Kono | Jan 2003 | A1 |
20030116872 | Klemm et al. | Jun 2003 | A1 |
20030165698 | Vaneeckhoutte et al. | Sep 2003 | A1 |
20030180544 | Murphy | Sep 2003 | A1 |
20030234460 | Hayashi et al. | Dec 2003 | A1 |
20040043260 | Nadaud et al. | Mar 2004 | A1 |
20040076750 | Boulineau et al. | Apr 2004 | A1 |
20040142185 | Takushima | Jul 2004 | A1 |
20040182701 | Miyamura | Sep 2004 | A1 |
20050008778 | Utsugi et al. | Jan 2005 | A1 |
20050158910 | Jiang et al. | Jul 2005 | A1 |
20060049044 | Seddon | Mar 2006 | A1 |
20060118408 | Myli et al. | Jun 2006 | A1 |
20060158738 | Nakamura et al. | Jul 2006 | A1 |
20060181774 | Ojima et al. | Aug 2006 | A1 |
20060269663 | Mori | Nov 2006 | A1 |
20070104891 | Fournand | May 2007 | A1 |
20070184183 | Chu et al. | Aug 2007 | A1 |
20070190342 | Teng | Aug 2007 | A1 |
20080002260 | Arrouy et al. | Jan 2008 | A1 |
20080007849 | Meschenmoser et al. | Jan 2008 | A1 |
20080050600 | Fan et al. | Feb 2008 | A1 |
20080095999 | Yoshihara et al. | Apr 2008 | A1 |
20080121335 | Kiuchi et al. | May 2008 | A1 |
20080187766 | Heider et al. | Aug 2008 | A1 |
20080206470 | Thomas et al. | Aug 2008 | A1 |
20080213473 | Roisin et al. | Sep 2008 | A1 |
20080025999 | O'Brien | Oct 2008 | A1 |
20080250955 | O'Brien | Oct 2008 | A1 |
20090098309 | Brody et al. | Apr 2009 | A1 |
20090104385 | Reymond et al. | Apr 2009 | A1 |
20090197048 | Amin | Aug 2009 | A1 |
20090208728 | Itami et al. | Aug 2009 | A1 |
20090216035 | Itami et al. | Aug 2009 | A1 |
20090226610 | Koenig et al. | Sep 2009 | A1 |
20090257022 | Abe et al. | Oct 2009 | A1 |
20100053547 | Baude et al. | Mar 2010 | A1 |
20100062217 | Kurematsu | Mar 2010 | A1 |
20100173149 | Hung | Jul 2010 | A1 |
20100238557 | Tomoda | Sep 2010 | A1 |
20100304086 | Carre et al. | Dec 2010 | A1 |
20110097511 | Shiono | Apr 2011 | A1 |
20110100806 | Sugawara | May 2011 | A1 |
20110198219 | Ohmi et al. | Aug 2011 | A1 |
20110232749 | Lienhart et al. | Sep 2011 | A1 |
20110305874 | Thoumazet et al. | Dec 2011 | A1 |
20120009429 | Shmueli et al. | Jan 2012 | A1 |
20120013845 | Conte et al. | Jan 2012 | A1 |
20120109591 | Thompson et al. | May 2012 | A1 |
20120162095 | Liang et al. | Jun 2012 | A1 |
20120275026 | Zhou et al. | Nov 2012 | A1 |
20130025503 | Park et al. | Jan 2013 | A1 |
20140113083 | Lee et al. | Apr 2014 | A1 |
Number | Date | Country |
---|---|---|
2082094 | Oct 1996 | CA |
1737191 | Feb 2006 | CN |
1737192 | Feb 2006 | CN |
1244165 | Mar 2006 | CN |
101501045 | Aug 2009 | CN |
101939266 | Jan 2011 | CN |
101512389 | Mar 2011 | CN |
614957 | Sep 1994 | EP |
1136973 | Sep 2001 | EP |
1255129 | Nov 2002 | EP |
0933377 | Nov 2004 | EP |
1630261 | Mar 2006 | EP |
1328579 | Mar 2012 | EP |
50003454 | Jan 1975 | JP |
5843402 | Mar 1983 | JP |
03-044607 | Feb 1991 | JP |
6029332 | Apr 1994 | JP |
07145481 | Jun 1995 | JP |
10036142 | Feb 1998 | JP |
200180941 | Mar 2001 | JP |
2003-014904 | Jan 2003 | JP |
2004-250784 | Sep 2004 | JP |
2006-057185 | Mar 2006 | JP |
2006055731 | Mar 2006 | JP |
2006171204 | Jun 2006 | JP |
2007240707 | Sep 2007 | JP |
20081869 | Jan 2008 | JP |
04147518 | Sep 2008 | JP |
2009-541808 | Nov 2009 | JP |
2009299129 | Dec 2009 | JP |
2011-510904 | Apr 2011 | JP |
2011202190 | Oct 2011 | JP |
578004 | Mar 2004 | TW |
200415679 | Aug 2004 | TW |
200420979 | Oct 2004 | TW |
201109459 | Mar 2011 | TW |
201137137 | Nov 2011 | TW |
2011060047 | May 2001 | WO |
2006025336 | Mar 2006 | WO |
2006107083 | Oct 2006 | WO |
2009043122 | Apr 2009 | WO |
2012064989 | May 2012 | WO |
2012137744 | Oct 2012 | WO |
2012176990 | Dec 2012 | WO |
2013099824 | Jul 2013 | WO |
2013121984 | Aug 2013 | WO |
2013121985 | Aug 2013 | WO |
2013121986 | Aug 2013 | WO |
Entry |
---|
Machine Translation of JP2018162776 Office Action dated Jul. 31, 2019, Japan Patent Office, 4 pgs. |
Calottes R Willy, Practical Design and Production of Optical Thin Films; Mercel Dekker 1966, pp. 115-121. |
Choy et al.; Handbook of Nanostructured Materials and Nanotechnology, vol. 1: Synthesis and Processing. Academic Press; 2000. p. 533. |
CN201280068319.7 Office Action dated Jan. 27, 2016. |
CN201280068398.1 Office Action dated Feb. 1, 2016. |
EP12798577.8 Search Report dated Apr. 12, 2016. |
Fuchs, et al, “Wetting & Surface Properties of (Modified) Fluoro-Silanised Glass”; Collioids and Surfaces A: Physicochem Eng. Aspects 307 (2007) 7-15. |
International Search Report and Written Opinion of the International Searching Authority; PCT/US2012/067370; dated Jul. 10, 2013; 10 pages. |
International Search Report and Written Opinion of the International Searching Authority; PCT/US2012/067383; dated Jul. 8, 2013, 11 pages. |
International Search Report and Written Opinion of the International Searching Authority; PCT/US2013/043415; dated Oct. 23, 2013. |
JP2014544942 Office Action dated Nov. 15, 2016, Japan Patent Office. |
Kondo et al; ““Durable Anti-Smudge Materials for Display Terminals””;http://www.findarticles.com/p/articles/mi qa5322/is 200906/ai n3212753 l/. |
MacLeod, “Thin Film Optical Filters”, 3rd Edition, Institute of Physics Publishing. Beistol and Philadelphia, 2001. |
Martinet et al; “Deposition of SI02 and TI02 Thin Films By Plasma Enchanced Chemical Vapor Deposition for Antireflection Coating”; Journal of Non-Crystalling Solids 216 (1997) 77-82. |
Taiwan Office Action 101145139 dated Jun. 23, 2016, 5 pgs. |
TW102119804 Search Report dated Jan. 25, 2017, Taiwan Patent Office. |
TW105137761 Search Report dated Jul. 25, 2017, Taiwan Patent Office. |
English Translation of JP2014544939 Office Action dated Dec. 27, 2016, Japan Patent Office. |
Machine translation JP2001080941. |
Machine Translation of CN 1244165C, 21 pages. |
Machine Translation of EP0614957, 10 pages. |
Machine Translation of JP2006055731, 15 pages. |
Machine Translation of JP2009299129, 10 pages. |
Machine Translation of JP6029332, 12 pages. |
Machine translation WO2012176990. |
Number | Date | Country | |
---|---|---|---|
20190010083 A1 | Jan 2019 | US |
Number | Date | Country | |
---|---|---|---|
61709423 | Oct 2012 | US | |
61565024 | Nov 2011 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13906065 | May 2013 | US |
Child | 16128048 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13690829 | Nov 2012 | US |
Child | 13906065 | US | |
Parent | 13690904 | Nov 2012 | US |
Child | 13690829 | US |