WO2014055134A1 - Procédé de revêtement optique, appareil et produit correspondants - Google Patents

Procédé de revêtement optique, appareil et produit correspondants Download PDF

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Publication number
WO2014055134A1
WO2014055134A1 PCT/US2013/043415 US2013043415W WO2014055134A1 WO 2014055134 A1 WO2014055134 A1 WO 2014055134A1 US 2013043415 W US2013043415 W US 2013043415W WO 2014055134 A1 WO2014055134 A1 WO 2014055134A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
substrate
dome
vacuum chamber
substrate carrier
Prior art date
Application number
PCT/US2013/043415
Other languages
English (en)
Inventor
Christopher Morton Lee
Xiao-feng LU
Michael Xu Ouyang
Junhong Zhang
Original Assignee
Corning Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/690,904 external-priority patent/US20140113083A1/en
Priority claimed from US13/690,829 external-priority patent/US20130135741A1/en
Application filed by Corning Incorporated filed Critical Corning Incorporated
Priority to CN201380060386.9A priority Critical patent/CN105143500B/zh
Publication of WO2014055134A1 publication Critical patent/WO2014055134A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/50—Substrate holders
    • C23C14/505—Substrate holders for rotation of the substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/542—Controlling the film thickness or evaporation rate
    • C23C14/545—Controlling the film thickness or evaporation rate using measurement on deposited material
    • C23C14/547—Controlling the film thickness or evaporation rate using measurement on deposited material using optical methods
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
    • C23C16/4581—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber characterised by material of construction or surface finish of the means for supporting the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
    • C23C16/4582—Rigid and flat substrates, e.g. plates or discs
    • C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
    • C23C16/4584—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally the substrate being rotated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
    • C23C16/4582—Rigid and flat substrates, e.g. plates or discs
    • C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
    • C23C16/4585—Devices at or outside the perimeter of the substrate support, e.g. clamping rings, shrouds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process

Definitions

  • 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.
  • 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.
  • 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.
  • AR antireflective
  • an AR coating is 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.
  • ETC easy-to-clean
  • 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.
  • 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.
  • the adhesive material may include acrylic adhesives, rubber adhesives, and/or silicone adhesives.
  • 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.
  • 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.
  • the substrate carrier may 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.
  • the positions of the plurality of pins are adjustable to accommodate substrates of different shapes and dimensions.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • Figure 1A is a schematic drawing of a coating apparatus 100 according to one or more embodiments described herein;
  • Figure IB schematically depicts an enlarged view of glass plate 116 and illustrates the opening 116a for receiving a quartz monitor
  • Figure 1C schematically depicts an enlarged view of the glass plate with the quartz monitor received within the opening and an optical fiber, both of which are used to measure and control the deposition of the optical coating materials onto glass substrates attached to a substrate carrier;
  • Figure 2 is a drawing representing a top-down view through a section of the dome of the coating apparatus of Figure 1 A illustrating a plurality of substrate carriers magnetically attached to the dome;
  • Figure 3A schematically depicts an oblique bottom-up side view of a segment of the dome of the coating apparatus of Figure 1A with a plurality of substrate carriers magnetically attached to the dome;
  • Figure 3B schematically depicts a frame that supports the dome segments 110a; frame 160 having an outer lip/rim 161 as is also illustrated in Figure 3 A, an inner rim (not numbered) at opening 164 to which the rotation shaft 117 can be attached (not illustrated) and a plurality of spokes 162 that are sufficiently wide to accommodate the side edges of the dome segments as is illustrated at 168;
  • Figure 4 A schematically depicts a non-magnetic substrate carrier 130 having a plurality of elements 134 for magnetically attaching the carrier to dome 110 and for holding a glass substrate/article 140 during the coating process;
  • Figure 4B is a side view of Figure 4A illustrating a glass substrate 140 resting on pins 136 that extend into the substrate carrier base 130 for a distance from the substrate carrier surface 130a, a plurality of magnets 134 that extend from the surface 130a of the substrate carrier 130 and through the substrate for a distance beyond the base 130b, a side stopper 150 extending from the base of carrier 130 to a distance from glass article 140's top face 140a;
  • Figure 4C is a bottom view of a substrate carrier base 131 depicting magnets 134 positioned outside of a perimeter 142 of the substrate retention area 141 ;
  • Figure 5 schematically depicts one of the pins 138a and 138b against which a glass substrate 140 is held by the force exerted against it by a spring loaded adjustable pin 138a, and a shaped edge 141 that is in contact with the pin, in this case a chamfered edge;
  • Figure 6 illustrates substrate carriers 130 attached to dome 110 such that the retractable pin 138 A, is positioned perpendicular to the rotation direction, that is, closer to opening at the top T of the dome 110 than the pins 138b also illustrated in Figure 6;
  • Figure 7 a-c is a schematic representation of the fluorinated silane grafting reaction with glass or an oxide AR coating
  • Figure 8 illustrates the AR optical coating layers that would underlie the ETC coating to provide a barrier to isolate glass surface chemistry and contamination, and further to provide a lower activation energy site for fluorinated silanes to chemically bond to the AR optical coating with maximum coating density as well as crosslinking over the coated surface in order to maximize abrasion reliability (durability);
  • Figure 9 is an illustration of AR-ETC coated GRIN lenses 208 for use with optical fibers 206 and some of their uses;
  • Figure 10 is a comparison of abrasion testing data for a glass article having a PVD 8- lOnm ETC on 6 layer ARC (IN ⁇ Os/SiCh) coating and a glass article having only a spray coated ETC coating;
  • Figure 11 is a comparison of the abrasion reliability of a glass article having a 6 layer PVD IAD-EB AR coating and an 8-10nm thermal deposited ETC coating on top of the AR coating relative to a glass article having PVD AR coating deposited in a first conventional coater and an ETC deposited in a second conventional coater;
  • Figure 12 is a graph of % Reflectance versus wavelength for glass articles coated with an AR coating and an ETC coating after 6K, 7K, 8K and 9K wipes;
  • Figure 13 is a graph of % Transmission versus wavelength for glass articles with an AR coating and an ETC coating after 6K, 7K, 8K and 9K wipes;
  • Figure 14 is a graph of Reflectance % versus wavelength and illustrating the effect of the numbers of AR coating layers/periods reflectance versus glass without an AR coating;
  • Figure 15 illustrates an adjustable magnetic carrier 130a that is substantially similar to the carrier 130 illustrated in Figure 4 A and enables the use of a single carrier for different size substrates;
  • Figure 16A illustrates a prior art dome carrier 300 having a plurality of openings 302 for placements of the lenses that are to be coated;
  • Figure 16B illustrates a lens 304 that has slipped off one carrier 300 shoulder 306 inside opening 302, the lens 304 being in a position to be broken as the carrier 300 cools;
  • Figure 17A is an illustration of an embodiment of the coating apparatus having a shadow mask covering a selected area of the dome to improve the uniformity of the optical coating;
  • Figure 17B is a graph of the Water Contact Angle versus Abrasion Cycles illustrating the improvement that is obtained using the mask as illustrated in Figure 17 A;
  • Figure 18 is a simulation of the reflectance (y-axis) as a function of wavelength (x- axis) for a glass substrate coated with a 6 layer AR coating (IN ⁇ Os/SiCh) and an ETC coating with the AR coating having a thickness variation of 2%;
  • Figure 19 graphically depicts the reflectance (y-axis) as a function of wavelength for a plurality of actual samples coated with a 6 layer AR coating (IN ⁇ Os/SiCh) and an ETC coating;
  • Figure 20A schematically depicts a retention surface 131a of a substrate carrier having a layer of adhesive material 143 disposed thereon;
  • Figure 20B schematically depicts a cross section of a substrate carrier with a polymer film 144 and adhesive layer 143 positioned on the substrate carrier base;
  • Figure 21 A schematically depicts a vertical cross section of one embodiment of a coating apparatus
  • Figure 21B schematically depicts a horizontal cross section of the coating apparatus of Figure 21 A.
  • Figure 22 graphically depicts variations in coating thickness as a function of the relative positioning of the coating source and the substrate being coated.
  • FIG. 1A One embodiment of a coating apparatus is schematically depicted in Figure 1A.
  • the coating apparatus generally includes a vacuum chamber with a magnetic dome positioned therein.
  • the coating apparatus also includes an e-beam source, a thermal evaporation source and a plasma source. Glass substrates to be coated can by magnetically attached to an underside of the dome and coated with an optical coating and an ETC coating using the e- beam source and the thermal evaporation source, respectively.
  • the plasma source may be used to densify the deposited optical coating materials.
  • the plasma source may be used to densify the deposited optical coating materials.
  • the terms “process” and “method” may be used interchangeably.
  • 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.
  • 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 A 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.
  • 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 Figures 10, 11, and 17B.
  • the ETC coating can be considered as part of the optical coating during design and, as such, the ETC coating will not change the desired optical performance.
  • the glass articles described herein are shadow free across the optically coated surface of the glass.
  • a particular example of an in-situ process is a box coater schematically depicted in Figure 1A.
  • the box coater is equipped with an electron beam (e-beam) source for optical coatings, a thermal evaporation source for the ETC coating material, and an ion beam or a plasma source for surface cleaning before coating and optical coating impaction during coating to increase the density of the coating and the smoothness of the coating surface.
  • e-beam electron beam
  • 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: Zr0 2 , Hf0 2 , Ta 2 0 5 , Nb 2 0 5 , Ti0 2 , Y 2 0 3 , Si 3 N 4 , SrTi0 3 , W0 3 ; an exemplary median index material having an index of refraction n greater than or equal to 1.5 and less than 1.7 is A1 2 0 3 ; and an exemplary low index materials having an index of refraction n greater than or equal to 1.3 and less than or equal to 1.6) include: Si0 2 , MgF 2 , YF 3 , YbF 3 .
  • the optical coating stack that is deposited on a substrate comprises at least one material/layer to provide a specified optical function.
  • a high and a low index material can be used to design a complex optical filter (including AR coatings), for example, Hf0 2 as the high index material and Si0 2 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), ln 2 0 3 , and similar binary and ternary oxide compounds.
  • 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.
  • 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, alumino silicate glass, borosilicate glass, aluminoborosilicate glass and soda lime glass.
  • the glass articles have a thickness in the range of 0.2mm to 1.5mm, 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 tablet computer, or larger.
  • optical coatings referred to herein include antireflection coatings (AR coatings), band-pass filter coatings, edge neutral mirror coatings and beam splitters, multi-layer high- reflectance coatings and edge filters as described in H. Angus Macleod, "Thin Film Optical Filters", 3 rd 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.
  • the PVD method i.e., ion-assisted, e-beam deposition
  • 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 .
  • One pair of HL 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.
  • index refers to the index of refraction of the material.
  • 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 Si0 2 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 Zr0 2 , Hf0 2 , Ta 2 0 5 , Nb 2 0 5 , Ti0 2 , Y 2 0 3 , Si 3 N 4 , SrTi0 3 , and W0 3 ; 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 Si0 2 , MgF 2 , YF 3 , and YbF 3 ; 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 A1 2 0 3 or another suitable medium refractive index material.
  • 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.
  • 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 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.
  • PVD physical vapor deposition
  • CVD/PECVD chemical vapor deposition
  • ALD atomic layer deposition
  • 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 Si0 2 .
  • the fluorocarbons have a carbon chain length in the range of greater than or equal to 3nm and less than or equal to 50nm.
  • the fluorocarbons can be obtained commercially from vendors including, without limitation, Dow-Corning (for example fluorocarbons 2604 and 2634), 3M Company (for example ECC-1000 and 4000), Daikin Corporation, Canon, Don (South Korea), Ceko (South Korea), Cotec-GmbH (for example DURALON UltraTec) and Evonik.
  • Dow-Corning for example fluorocarbons 2604 and 2634
  • 3M Company for example ECC-1000 and 4000
  • Daikin Corporation Canon, Don (South Korea), Ceko (South Korea), Cotec-GmbH (for example DURALON UltraTec) and Evonik.
  • FIG. 1A schematically depicts a coating apparatus 100 and various operating elements of the apparatus according to one or more embodiments disclosed herein. Coordinate axes are provided for reference.
  • x is from side-to-side (i.e., left to right)
  • y is from front-to-back (i.e., in and out of the page)
  • z is from bottom-to -top.
  • the coating apparatus 100 generally comprises a vacuum chamber 102 having therein a rotatable dome 110 with lip 161 (depicted in Figure 3 A) that is part of a frame 160 (further illustrated in Figure 3B) that supports dome 110.
  • the dome includes a plurality of substrate carriers 130 magnetically attached to an underside of the dome as illustrated in Figure 2.
  • a plasma source 118 is located in the vacuum chamber 102 below the dome 110 and is generally oriented to emit ions or plasma upwards, towards the underside of the dome 110.
  • the plasma source is used to densify the optical coating materials as they are deposited and/or after deposition thereby increasing the hardness of the finished optical coating.
  • the ions or plasma emitted from the plasma source impact the coating during deposition and/or after a coating layer has been applied resulting in a densification of the deposited material. Densifying the deposited optical coating improves the abrasion resistance of the optical coating.
  • the deposited optical coating will have at least double the abrasion reliability or abrasion resistance of an optical coating deposited without the use of a plasma source.
  • the plasma source 118 may be used in conjunction with a neutralizer 121, as described in more detail herein with respect to FIG. 21A.
  • 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 125 a, 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.
  • Figure 1A depicts a single e-beam source 120, it should be understood that a plurality of e-beam sources can be used to minimize the time to change from one coating material to another, for example, changing from Nb 2 0 5 to Si0 2 and back again, as required to deposit the required number of individual layers of material for the optical coating.
  • the coating apparatus may comprise greater than or equal to 2 e-beam sources and less than or equal to 6 e-beam sources. When a plurality of e-beam sources are used, each e-beam source may be directed to a separate container (i.e., the boats 126, described further herein) holding the material to be coated.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the dome 1 10 is made of a light weight material that is magnetic or contains a magnetic material, for example and without limitation, aluminum containing iron or another suitable magnetic material.
  • the dome 110 can be rotated either clockwise or counter-clockwise.
  • an opening 164 (depicted in Figure 3B) and a transparent glass plate 116 is placed on the underside of the dome to cover the opening.
  • the transparent glass plate 116 may include an opening 116a as depicted in the enlarged view of the transparent glass plate 116 depicted in Figure IB.
  • a quartz monitor 114 is received in and passes through the transparent glass plate 116.
  • An optical fiber 112 is positioned above the transparent glass plate 1 16, as illustrated.
  • the quartz monitor 114 controls the deposition rate of the optical materials by feedback to the e-beam power supply so that the deposition rate of the coating material is kept substantially constant.
  • the optical fiber 112 is positioned above the transparent glass plate 116 to protect it from the deposition materials within the vacuum chamber 102.
  • FIG 1C is an enlargement of the circled area of the transparent glass plate 116 of Figure 1A showing the relative orientations of the optical fiber 112, the quartz monitor 114 and the transparent glass plate 116.
  • the quartz monitor 114 is positioned in the middle of the transparent glass plate 116 and passes through the opening 116a.
  • the optical fiber 112 is positioned to the side of the quartz monitor 114. Light transmitted from the optical fiber 112 passes through the transparent glass plate 116 and is reflected back as the surface of the transparent glass plate is coated.
  • the arrows adjacent to %R schematically depict the reflectance of light from the surface 116b of the transparent glass plate as the transparent glass plate is being coated. The reflectance increases with the thickness of the coatings applied to surface 116b of the transparent glass plate.
  • the light reflected from the surface 116b of the transparent glass plate is directed back to an optical sensor (not shown) coupled to a controller (not shown) of the e-beam source.
  • the output of the optical sensor (which is indicative of the thickness of the applied optical coating and/or the ETC coating) is utilized by the controller to determine the deposited thickness of the coatings.
  • the reflected light can be used to control the deposited thickness of an individual layer, a coating period, and the entire optical coating as well as the deposited thickness of the ETC coating.
  • 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.
  • 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.
  • Figure 2 schematically depicts a segment 110a of dome 110. As shown in Figure 2, a plurality of substrate carriers 130 are magnetically attached to the dome 110. The substrate carriers 130 are utilized to secure glass substrates for coating in the coating apparatus 100.
  • Figure 3 A is a drawing illustrating an oblique bottom-up side view of a segment 110a of the dome 110 showing the lip 161 with a plurality of substrate carriers 130 magnetically attached to the dome 110.
  • Figure 3B is an illustration of the frame 160 that is used to support a plurality of segments 110a.
  • the frame 160 has an outer lip 161 (as depicted in Figure 3 A), an inner rim (not numbered) adjacent to opening 164 to which the vacuum shielded rotation shaft 117 can be attached (not illustrated) and a plurality of spokes 162 extending radially outward from the inner rim.
  • the spokes 162 are sufficiently wide to accommodate the side edges of the dome segments as is illustrated at 168.
  • Figure 17A is a simplified illustration of an alternative embodiment of a coating apparatus for depositing an optical coating and an ETC coating on a substrate.
  • the coating apparatus includes a shadow mask 127 covering a selected area of the dome to improve the uniformity of the optical coating deposited on the substrate.
  • the support for adjustably supporting the shadow mask 127 is not depicted in Figure 17 A.
  • the plasma source is an ion source 118a.
  • the ion source 118a and the e-beam source 120 used to evaporate the optical coating materials are located on different sides of the vacuum chamber, the ion source is not shielded by the shadow mask, thereby improving the efficacy of the ion source 118a in hardening the deposited optical coating materials.
  • the ion source is used to densify the optical coating material to near bulk density thereby increasing the hardness of the optical coating and improving the abrasion reliability/abrasion resistance of the optical coating.
  • FIG 21 A schematically depicts another alternative embodiment of a coating apparatus 500 for depositing an optical coating and an ETC coating on a substrate.
  • a cross section of the coating apparatus 500 is schematically depicted in Figure 2 IB.
  • the coating apparatus 500 includes a vacuum chamber 102 with a rotatable dome 110 comprising a magnetic material, as described with respect to Figure 1.
  • the rotating dome is coupled to a vacuum shielded rotation shaft 117 which is disposed in a vacuum seal bearing 119 to facilitate rotation of the dome in the vacuum chamber.
  • the dome also includes a transparent glass plate 116 with a quartz monitor 114 and an optical fiber 112 which, collectively, are used to monitor and control the deposition rate of coatings applied to substrates attached to the dome, as described above with respect to Figures 1 A-1C.
  • 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.
  • 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.
  • 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.
  • the first optical coating material is different from the second optical coating material.
  • 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.
  • 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.
  • 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 Figure 21 A), wherein the first shadow mask 125 is positioned between at least one of the e-beam sources and the rotatable dome, and a retracted position (not depicted), wherein the first shadow mask is not positioned between the rotatable dome and either e-beam source.
  • the first shadow mask 125 may comprise a first portion 180 which is coupled to an actuator 175, such as an electric motor or the like, which rotates the first shadow mask 125 from the extended position to the retracted position.
  • the first shadow mask 125 may include a second portion 181 pivotally attached to the first portion 180. The second portion 181 may fold towards the first portion 180 as the first shadow mask is rotated to the retracted position (i.e., as the first shadow mask is rotated downward, in a clockwise direction in Figure 21 A).
  • the first shadow mask 125 is positioned between the e-beam source 120a and the underside of the dome 110 (not shown) when the first shadow mask 125 is in the extended position.
  • the second shadow mask 129 is fixedly positioned between the e-beam source 120b and the underside of the dome 110 (not shown).
  • the first shadow mask 125 can be extended or retracted depending on the type of optical coating materials being deposited. For example, when Nb 2 0 5 is deposited, the first shadow mask 125 may be in a retracted position. However, when Si0 2 is deposited, the first shadow mask 125 may be in the extended position.
  • the shadow masks are utilized to promote thickness uniformity in the deposited optical coating irrespective of the position of the substrate on the dome.
  • the deposited thickness of the coating materials evaporated from a point source 400 generally varies according to the relationship Cos n (9)/R 2 where n is material and process parameter dependent and R is the distance between the evaporation source and the substrate 140 being coated, and ⁇ is the angle between the vertical normal 402 to the point source and a normal 404 to the surface of the substrate 140 being coated, as schematically depicted in Figure 22. Accordingly, the position of the plasma source, the position of the e- beam source, and the shape and diameter of the dome will each affect the thickness of the coating deposited on the substrate.
  • the contour curves 410 depicted in Figure 22 schematically depict the thickness of the material deposited for a given distance R from the point source 400. Each discrete location on a particular curve will have approximately the same thickness of deposited material.
  • the uniformity masks positioned on the interior of the vacuum chamber are appropriately shaped and positioned to provide uniform coating thicknesses for substrates positioned on different areas of the dome by providing a mask which intermittently obscures the substrates from the coating materials as the substrates are rotated in the vacuum chamber on the dome..
  • 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.
  • 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.
  • a plasma source such as an ion-beam source.
  • the plasma source 118 is located in the vacuum chamber 102 below the dome 110 and is generally oriented to emit ions or plasma upwards, towards the underside of the dome 110 thereby densifying and/or hardening the optical coating applied to the substrates attached to the underside of the dome.
  • the plasma source is vertically oriented and positioned within the vacuum chamber 102 such that the plasma source 118 is located radially outward from an axis of rotation 171 of the rotatable dome 110 and the plasma emitted from the plasma source 118 is incident on the underside of the rotatable dome 110 from at least the center of the dome to at least an outer edge 172 of the rotatable dome.
  • the plasma source 1 18 is positioned such that a distance S between the axis of rotation 171 of the rotatable dome 110 and the plasma source 118 is greater than a distance S' between the plasma source 118 and a projected perimeter 173 (i.e., the perimeter of the cylinder circumscribed by the rotation of the rotatable dome 110). Moreover, the path between the plasma source 118 and the underside of the dome 110 is unobstructed (such as by a shadow mask or the like) which increases the amount of plasma incident on the underside of the dome 110.
  • the coating apparatus 500 may also include a neutralizer 121 positioned to project an electron cloud into the path of the plasma emitted from the plasma source 118.
  • the plasma emitted from the plasma source 118 may include charged ions (such as Ar +1 ions, 0 +1 ions, and/or 0 +2 ions) which are accelerated towards the substrate by an anode.
  • the neutralizer 121 is used to direct an electron cloud into the path of the plasma emitted from the plasma source 118.
  • the neutralizer 121 includes an electron emitter, such as a hot filament and/or high flux/high rate electron emission device.
  • the electron emitter may include a hollow cathode. The electron cloud emitted from the neutralizer interacts with the charged ions of the plasma, thereby neutralizing the charge (e.g., Ar ions ⁇ Ar°, 0 +1 ions ⁇ C"2, etc.
  • the substrate carrier 130 for carrying a single size substrate is schematically depicted.
  • the substrate carrier 130 has a non-magnetic substrate carrier base 131, a retention surface 131a for releasably affixing a substrate to be coated, an underside 131b positioned opposite the retention surface 131a, and a plurality of magnets 134 for magnetically attaching the carrier to the dome 110 and for off-setting the substrate carrier a distance from the dome.
  • a substrate may be releasably affixed to the retention surface 131a of the substrate carrier.
  • the substrate carrier 130 also includes a plurality of pins 136 for supporting a surface of a substrate 140 (illustrated in Figure 4B) and a spring system 132.
  • the spring system 132 generally includes a retractable pin 138a that is held in place by a spring 133 (schematically depicted as an arrow) that biases the retractable pin 138a in the direction indicated by the arrow, and a plurality of fixed pins 138b.
  • Pins 138a and 138b are used to hold a substrate 140 (indicated by dashed line) in place on the substrate carrier 130 while the glass substrate is being coated. Specifically, when a substrate 140 is positioned on the retention surface 131a of the substrate carrier 130, a portion of an edge of the substrate abuts pins 138b and the spring system 132 is arranged to bias pin 138a into contact with an opposing edge of the substrate, thereby releasably retaining the substrate between the pins 138a, 138b.
  • pins 138a, 138b are arranged on the substrate carrier base 131 such that no portion of the pin extends above the surface of the substrate thereby promoting coating thickness uniformity across the coated surface of the glass substrate.
  • FIG. 4B is a side view of Figure 4A illustrating a substrate 140 supported on pins 136 that extend into the nonmagnetic substrate carrier base 131 for a distance from the retention surface 131a, a plurality of magnets 134 that extend from below the retention surface 131a of the substrate carrier 130 and through the substrate for a distance beyond the underside 131b, a side stopper 150 extending from the nonmagnetic substrate carrier base 131 to a distance from a top surface 140a of the substrate 140 releasably affixed on the retention surface 131a.
  • the side stopper 150 orients the glass substrate on the nonmagnetic substrate carrier base 131 without affecting the application of the coatings thereby preventing "shadows" on the surface of the glass substrate.
  • the top surface 140a of the glass substrate is the surface that will be coated with the optical coating and the easy-to-clean coating.
  • the side stoppers 150 are sized such that the side stoppers do not extend above the top surface 140a of the substrate 140 releasably affixed on the retention surface 131a.
  • the top of side stopper 150 will be in the range of 2-3mm below the top surface 140a of the substrate 140.
  • the opening (not numbered) in the middle of the substrate carrier reduces the weight of the carrier.
  • Figures 4A and 4B show one particular arrangement of the magnets 134 in the substrate carrier base 131 , it should be understood that other arrangements are contemplated.
  • the magnets 134 may be arranged in the substrate carrier base 131 to minimize the affect that the magnetic field of the magnets has on the coating process, such as repelling ions and/or particulate matter deposited on the substrate.
  • the substrate carrier base 131 has a substrate retention area 141 (schematically depicted in dashed lines) on the substrate retention surface opposite the underside 131b.
  • the area of the substrate retention area 141 is less than the area of the substrate retention surface and the magnets 134 are positioned on the underside of the 131b of the substrate carrier base 131 outside of a perimeter 142 of the substrate retention area 141. Locating the magnets 134 outside of the perimeter 142 of the substrate retention area 141 mitigates the effect the magnetic field of each magnet 134 has on the coating process.
  • the magnets may be appropriately sized to accommodate the size and weight of the substrate(s) retained on the substrate retention surface. For example, larger magnets may be used in conjunction with substrate carrier bases sized to hold larger substrates whereas smaller magnets may be used in conjunction with substrate carrier bases sized to hold smaller substrates.
  • the adjustable substrate carrier 130a has a non-magnetic substrate carrier base 131 which includes a plurality of magnets 134 for attaching the adjustable substrate carrier to the dome of the coating apparatus as described above.
  • the adjustable substrate carrier 130a also includes one or more mechanisms or adhesion aids for releasably affixing one or more substrates to the substrate carrier 130a or, more specifically, to the retention surface 131a of the substrate carrier.
  • the mechanism or adhesion aid includes a plurality of pins 136 extending from the retention surface 131 a of the substrate carrier for supporting a surface of a glass substrate releasably affixed on the adjustable substrate carrier 130a.
  • the mechanism or adhesion aid may include a housing 138aa that is positioned proximate an edge of the adjustable substrate carrier 130a and houses a retractable pin 138a (depicted partially extended from the housing).
  • the housing 138aa includes a spring (not shown) positioned in the housing 138aa. The spring bias the retractable pin 138a outward from the housing 138aa.
  • the adjustable substrate carrier 130a may optionally include side stoppers 150a (not illustrated in Figure 15) for orienting a glass substrate on the adjustable substrate carrier 130a.
  • the adjustable substrate carrier 130a further includes a plurality of moveable pins 139 for holding an edge of the glass substrate.
  • the moveable pins 139 are positioned in tracks 137 to facilitate adjustably positioning the moveable pins 139 relative to the adjustable substrate carrier 130a.
  • the moveable pins 139, in combination with the retractable pin 138a enable the use of a single carrier for different size substrates.
  • the substrate or substrates may be held by the pins, and any optional side stoppers 150a in the same manner as described above with respect to Figures 4 A and 4B so that a shadow free coating is formed on the substrate.
  • the magnets 134 may be positioned outside of the perimeter of the substrate retention described above with respect to Figure 4C.
  • the substrate carrier 130 utilizes a layer of adhesive material 143 disposed on the retention surface 131a in the substrate retention area to releasably receive substrates to be coated.
  • the adhesive material 143 generally comprises a pressure sensitive contact adhesive. Suitable materials may include, without limitation, acrylic adhesives, rubber adhesives, silicone adhesives, and/or similar pressure sensitive adhesives.
  • the substrates may be held to the retention surface 131a using a static charge, such as when a statically charged film is positioned on the retention surface 131a and acts as an adhesive material.
  • a static charge such as when a statically charged film is positioned on the retention surface 131a and acts as an adhesive material.
  • These materials permit the substrate to be firmly attached to the substrate carrier 130b, and specifically to the retention surface 131a, during coating but also permit the substrate to be readily removed from the substrate carrier 130b after coating is complete.
  • the magnets 134 may be positioned outside of the perimeter of the substrate retention described above with respect to Figure 4C.
  • use of a layer of adhesive material 143 on the retention surfaces enables one size of substrate carrier to be used for substrates of different sizes and/or shapes and also allows for multiple substrates to be attached to a single substrate carrier.
  • the adhesive material 143 is positioned on a polymer film 144 which, in turn, is adhered to the retention surface 131a of the substrate carrier base 131.
  • the polymer film may be a thermoplastic polymer film such as a polyethylene film or a polyester polymer film.
  • the polymer film may be a polymer film capable of being statically charged.
  • a separate adhesive material 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. The use of these magnetic carriers is an improvement over dome carriers that are used in the coating of optical elements such as lenses.
  • Figure 16A illustrates a conventional dome carrier 300 having a plurality of openings 302 for positioning lenses that are to be coated. When the lenses are coated they are inserted into an opening in the carrier.
  • this conventional design it is difficult to uniformly coat both the inside and outside of the dome. It is also difficult to keep the coating material away from surfaces of the lenses that are not to be coated.
  • the part being coated can move with respect to the opening in the dome as the dome heats up, resulting in breakage as the dome cools after coating.
  • Figure 16B illustrates a lens 304 that has slipped off one support shoulder 306 inside an opening 302 of the dome carrier. As is easily seen, if the carrier cools faster than the lens 304, the contraction of the carrier can cause the lens to break.
  • the substrate carrier is off-set a distance from the dome by the magnets that hold the carrier to the dome, heat transfer is minimized and breakage does not occur as the dome cools.
  • only one side of the glass article being coated is subjected to the coating materials due to the proximity of the carrier/substrate combination to interior surface of the dome. As a result the difficulties mentioned above in conventional dome carriers can be avoided.
  • FIG. 5 a cross section of one embodiment of the pins 138a, 138b against which a glass substrate is held by the force exerted against it by the retractable pin 138a is schematically depicted.
  • These pins may be utilized in the substrate carriers schematically depicted in Figures 4 A and 15.
  • the glass substrate has a shaped edge which fits between the head 138h of pins 138a and 138b and the remainder of the body of the pin.
  • the edge of the glass substrate may be chamfered as illustrated at 141, rounded, bull nosed or otherwise contoured.
  • the top 140a of the glass substrate is 2-3mm below the top of the pin 138a or 138b.
  • reference numeral 140b indicates the bottom surface of the substrate 140.
  • a substrate 140 is loaded onto the substrate carrier 130 and the combination of the substrate 140 and the substrate carrier 130 is magnetically attached to the underside of dome 110.
  • the retractable pin 138a is positioned perpendicular to the rotation direction of the dome 110 as indicated by the arrow; that is, the pin is closer to the opening at the top T of the dome 110 than the fixed pins 138b.
  • the optical coating is uniformly deposited over the entire surface of the glass substrate 140 to form a "shadowless” or "shadow free” coated substrate 140.
  • the top surface 140a of glass substrate 140 is less than 1mm below head 138h of pin 138a
  • the top of side stoppers 150 are not lower than the top surface 140a; then the deposition of the optical coating will be non-uniform in the areas where these elements and other elements holding the substrate are located. As a result, the optical coating will be thinner near these elements and thicker as one moves away from them. The result is a non-uniform optical deposition or "shadow" that can be noticed by a user of the articles. Such shadows can be avoided using the apparatus and methods described in this disclosure. Such shadows can also be avoided utilizing the substrate carriers which do not include any elements which project beyond the top surface of the substrate positioned on the carrier, such as the substrate carriers which utilize a layer of adhesive material to releasably affix the substrates to the substrate retention surface as depicted in Figure 20A.
  • the materials for applying the optical coating to the glass substrate are loaded into separate boats 126 (i.e., separate source containers) of the optical coating carrier 124.
  • the optical coating is composed of alternating layers of high and low refractive index materials or alternating layers of high and middle refractive index materials.
  • Exemplary high index materials having an index of refraction n greater than or equal to 1.7 and less than or equal to 3.0 are: Zr0 2 , Hf0 2 , Ta 2 0 5 , Nb 2 0 5 , Ti0 2 , Y 2 0 3 , S1 3 N 4 , SrTiC"3, WO 3 ; an exemplary medium index material having an index of refraction n greater than or equal to 1.5 and less than 1.7 is AI2O3; and an exemplary low index materials having an index of refraction n greater than or equal to 1.3 and less than or equal to 1.6) are: Si0 2 , MgF 2 , YF 3 , YbF 3 .
  • medium refractive index material may be used to form the low refractive index layer L.
  • the low index material may be selected from Si0 2 , MgF 2 , YF 3 , YbF 3 and A1 2 0 3 .
  • the optical coating materials are 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 Si0 2 .
  • the material for applying the easy-to-clean (ETC) coating is loaded in to the at least one thermal evaporation source 128.
  • the fluorocarbons have a carbon chain length in the range of greater than or equal to 3nm and less than or equal to 50nm.
  • the vacuum chamber 102 is sealed and evacuated to a pressure less than or equal to 10 ⁇ 4 Torr.
  • the dome 1 10 is then rotated in the vacuum chamber by rotating the vacuum shielded rotation shaft 1 17.
  • the plasma source 1 18 is then activated to direct ions and/or plasma towards the glass substrates positioned on the underside of the dome 1 10 to densify the optical coating materials as they are applied to the glass substrate.
  • the optical coating and ETC coating are sequentially applied to the glass substrate.
  • the optical coating is first applied by vaporizing the optical materials positioned in the boats 126 of the optical coating carrier 124.
  • 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 surface of the glass substrates as the glass substrates are rotated with the dome 1 10.
  • the rotation of the dome 1 10 in conjunction with the shadow mask 125 and the orientation of the glass substrates 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.
  • 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 1 14 and the optical fiber 1 12 are utilized to monitor the thicknesses of the deposited materials and thereby control the deposition of the optical coating, as described herein.
  • optical coating ceases and the ETC coating is applied over the optical coating by thermal evaporation as the glass substrate rotates with the dome 110.
  • 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 by condensation.
  • the rotation of the dome 110 in conjunction with the orientation of the glass substrates on the substrate carriers 130 facilitates uniformly coating the ETC materials onto the glass substrate.
  • 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.
  • Figures 7 (a)-(c) are a schematic representation of the fluorinated silane grafting reactions with glass or an oxide optical coating (i.e., the reaction between the ETC coating material and the glass or an oxide optical coating).
  • Figure 7c illustrates that, when fluorocarbon trichloro silane is grafted to the glass, the silane silicon atom can be either (1) triply bonded (three Si-0 bonds) to the glass substrate or the surface of a multilayer oxide coating on the substrate or (2) doubly bonded to a glass substrate and have one Si-O-Si bond to an adjacent RpSi moiety.
  • the ETC coating process time is very short and can be used to provide an ETC coating having a thickness in a range from greater than or equal to 3nm and less than or equal to 50nm over the freshly applied optical coating without breaking vacuum (i.e., without exposing the optical coating to ambient atmosphere).
  • the ETC material is evaporated from a single source.
  • the ETC material may also be simultaneously evaporated from a plurality of sources.
  • 2-5 separate ETC material sources may be advantageous.
  • the use of a plurality of sources containing the ETC material results in a more uniform ETC coating and can enhance coating durability.
  • an Si0 2 layer is generally applied as a capping layer for optical coatings.
  • the Si0 2 layer is generally deposited as part of the optical coating prior to the deposition of the ETC coating.
  • This Si0 2 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.
  • 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 bond between the ETC silicon atom and surface oxygen atom, and release alcohol or acid once exposed to air.
  • the ETC coating material typically contains 1-2 fluorinated groups and 2-3 reactive groups such as CH 3 0- 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 Figure 7(c), to create a strongly bonded ETC coating.
  • the PVD deposited Si0 2 surface is pristine and has a reactive surface.
  • the binding reaction has a much lower activation energy, as is illustrated in Figure 8, than on a glass that has a complicated surface chemistry, has an environmental contaminant on it or, has a water layer on the glass surface.
  • the glass substrate 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.
  • 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%.
  • the surface of the coating is wiped with a soft brush or an iso propyl 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.
  • 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 n 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 n 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.
  • 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.
  • 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 Si0 2 .
  • the capping layer may be applied on over one or a plurality of periods and may have a thickness in the range greater than or equal to 20nm and less than or equal to 200nm.
  • the optical coating may have a thickness in the range from greater than or equal to lOOnm to less than or equal to 2000nm.
  • greater thicknesses are possible depending on the intended use of the coated article.
  • the optical coating thickness can be in the range of lOOnm to 2000nm.
  • the optical coating thickness can be in the range of 400nm to 1200nm or even in the range from 400nm to 1500nm.
  • 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 5nm and less than or equal to 200nm.
  • 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 5nm and less than or equal to lOOnm.
  • the coated glass articles exhibit an improved resistance to abrasion to 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 10kg normal load.
  • the abraded area is 10mm x 10mm.
  • the frequency of abrasion is 60Hz and the travel distance of the steel wool is 50mm.
  • the abrasion testing is performed at a relative humidity RH ⁇ 40%.
  • 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.
  • the coated glass articles have a surface scratch length of less than 2mm following 8000 abrasion cycles.
  • 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.
  • 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.
  • 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 mean that the optical coating is uniformly deposited over the entire coated surface of the glass substrate.
  • 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%.
  • the variation 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%.
  • 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%.
  • 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, A1N, TCO materials, such as ITO and SnO x , Ge and the like), and absorbing materials (Si x , SiO x N y , Ti , AlSiO x , CrO x , and the like).
  • metals e.g., Cr, Ag, Au, W, Ti and the like
  • semiconductors e.g., Si, A1N, TCO materials, such as ITO and SnO x , Ge and the like
  • absorbing materials Si x , SiO x N y , Ti , AlSiO x , CrO x , 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 40mm x 60mm to approximately 180mm x 320mm, depending on 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 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.
  • 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.
  • the ETC material can be coated on selected regions to avoid contamination to other locations of substrate.
  • a 4-layer Si02/Nb20 5 /Si02/Nb20 5 / substrate AR optical coating was deposited on sixty (60) pieces of GorillaTM Glass (commercially available from Corning Incorporated) with dimension (Length, Width, Thickness) of approximately 115mm L x 60mm W x 0.7mm T.
  • the coating was deposited using the methods described herein.
  • the AR coating had a thickness of approximately 600nm.
  • 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 5nm to 20nm (OptoolTM fluoro coating, Daikin Industries was used as an exemplary species).
  • the deposition of the AR and ETC coating was carried out in a single chamber coating apparatus as illustrated in Figure 1A. After the AR coating was deposited the AR coating source material was shut off and the ETC material was thermally evaporated and deposited on the AR coated glass. The coating process was 73 minutes including parts loading/unloading.
  • Example 2 the same fluoro-coating used in Example 1 was coated on a GRIN- lens for optical connectors, as is illustrated in Figure 9, for use on optical fibers 206 used in laptop computers.
  • Numeral 200 and arrow point to of a selective region of the GRIN lenses 208 for placing an ETC coating on top of an 850nm AR coating to provide particle and wear resistance.
  • Numeral 202 illustrates connecting an optical fiber to a laptop or tablet device
  • numeral 204 illustrates the use of a coated fiber optic to connect a laptop to a media dock.
  • Figure 10 is abrasion testing data on a glass article having an 8-10nm thermally deposited on a ETC coating on a 6 layer AR coating consisting of substrate/(Nb205/Si02)3, ETC/6L-AR coating, versus a glass sample with only the spray coated ETC coating.
  • the glass was 0.7mm thick Corning code 2319 glass which is commercially available, chemically tempered (ion-exchanged) glass.
  • the abrasion testing was carried out under following conditions: grade 0000# steel wool, 10kg load on 10mm x 10mm area, 60Hz, 50mm travel distance, RH ⁇ 40%. A water contact angle greater than 75 degrees is the criterion for judging coating failure.
  • Figure 11 is a comparison of the abrasion durability of a (1) a glass article with a 6 layer PVD IAD-EB AR coating and an 8-10nm thermally deposited ETC coating on top of the AR coating (indicated by numeral 220 and the diamond data marker), versus a commercially available glass article (indicated by numeral 222 and the square data marker) having a PVD-AR coating deposited by a first commercial coater apparatus and an ETC deposited in a second chamber by a commercial process such as dipping or spraying. Both coatings were deposited on samples of the same chemically tempered (ion-exchanged) 0.7mm thick Corning Code 2319 glass. Glass article 220 was coated according to the methods described herein.
  • the commercially available glass article was coated by a commercial coating vendor.
  • the abrasion durability was carried out at a relative humidity of 40%.
  • At the point indicated by arrow 224 only short, shallow scratches, less than 2mm long, appeared after 8,000 cycles.
  • long scratches, greater than 5mm long appeared after only 200 wipes.
  • the test results indicate that the abrasion durability of AR coating-ETC glasses coated as described herein is at least 10 times greater than the durability of commercially available products.
  • Figure 17B graphically depicts the Water Contact Angle versus Abrasion Cycles illustrating the improvement that is obtained using a coating apparatus configured as depicted in Figure 17 A.
  • the water contact angle results can be compared to those of Figures 10 and 11.
  • the data in Figure 17B show that, after 10,000 abrasion cycles, all the substrates illustrated in Figure 17B have a water contact angle of greater than 110°, and substantially all of the substrates had a water contact angle of 112° or higher.
  • the data of Figures 10 and 11 indicate that the water contact angles were less than 100° after 10,000 abrasion cycles.
  • the data in Figure 17B indicates that for substrates that have been subjected to 12,000 abrasion cycles, the water contact angles of the substrates is greater than 106°.
  • Figure 12 is a graph of % Reflectance versus wavelength, where Reflectance means the percentage of light reflected from the surface of the coated glass article coated with an AR coating and ETC coating as described herein.
  • Reflectance means the percentage of light reflected from the surface of the coated glass article coated with an AR coating and ETC coating as described herein.
  • a new (unabraded or unwiped) article was used for each wiping test.
  • the abrasion/wiping was carried out under following conditions: grade 0000# steel wool, 10kg load on 10mm x 10mm area, 60Hz, 50mm travel distance, RH ⁇ 40%. Reflectance was measured after 6K, 7K, 8K and 9K abrasions.
  • the graph indicates that new articles and articles wiped up to 8K wipes have substantially the same reflectance. After 8K wipes the reflectance increases.
  • Figure 13 is a graph of % Transmission versus wavelength. The testing was performed on coated glass articles coated with an AR coating and ETC coating as described herein. A new (unabraded or unwiped) article was used for each wiping test. The transmission test used the same articles as the reflectance test. The graph indicates that new articles and articles wiped up to 8K wipes have substantially similar transmissions, the transmission being the range of 95-96%. After 8K wipes the transmission falls to approximate 92% over the entire wavelength range. This transmission decrease is believed due to slight abrasion of the glass surface as a result of a large number of wipes. In the graph the letter “A” means “After wiping" and the letter “B” means “Before wiping" (zero wipes). The letter “K” means "kilo" or "thousand".
  • Figure 14 is a graph of Reflectance % versus wavelength illustrating the effect of the numbers of AR coating layers/periods on reflectance relative to glass without an AR coating.
  • Curve 240 represents uncoated ion-exchanged glass, Corning Code 2319.
  • Curve 244 is a 2-layer, or 1-period, coating consisting of Si0 2 /Nb 2 0 3 .
  • Curves 246 and 248 are 4-layer (2 periods) and 6-layer (3 periods) coatings consisting of Si0 2 /Nb 2 0 3 layer pairs.
  • Curve 242 is a 1-layer coating of Nb 2 0 3 . The data indicates that increasing the AR coating stack number (layers/periods) will broaden the utility of the AR coating spectral range and will also decrease the Refiectance %.
  • Figure 18 is a computer simulation of the refiectance (y-axis) as a function of wavelength (x-axis) for a glass substrates coated with a 6 layer AR coating (Nb 2 0 5 /Si0 2 ) and an ETC coating.
  • the AR coating was simulated with a thickness variation of 2%.
  • the resultant refiectance profile simulates the reflectance of a 6 layer AR coating (Nb 2 0 5 /Si0 2 ) and an ETC coating where the ETC coating has a thickness variation of
  • Figure 19 graphically depicts the refiectance (y-axis) as a function of wavelength for a plurality of actual samples coated with a 6 layer AR coating (Nb 2 05/Si0 2 ) and an ETC coating using the methods and apparatuses described herein.
  • the reflectance profile of the actual samples is similar to the refiectance profile of the simulated samples, thus indicating that the samples coated using the methods described have an optical coating in which the thickness variation of the optical coating across the coated substrate (i.e., from the first edge to second edge of the optical coating) is less than 3%.
  • the AR/ETC coating described herein can be utilized in many commercial articles.
  • the resulting coating can be used to make televisions, cell phones, electronic tablets, and 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.

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Abstract

Cette invention porte sur un procédé amélioré pour la fabrication d'articles en verre portant un revêtement optique et un revêtement facile à nettoyer, sur un appareil pour le procédé et sur un produit fabriqué à l'aide du procédé. En particulier, l'invention porte sur un procédé dans lequel l'application du revêtement optique et l'application du revêtement facile à nettoyer peuvent être effectuées séquentiellement à l'aide d'un seul appareil. L'utilisation de l'association de l'appareil de revêtement et du support de substrat décrits dans la présente invention a pour résultat un article en verre ayant à la fois un revêtement optique et un revêtement facile à nettoyer qui ont une meilleure durabilité de la résistance à la rayure et une meilleure performance optique et de plus les articles ainsi obtenus sont « exempts d'ombre ».
PCT/US2013/043415 2012-10-04 2013-05-30 Procédé de revêtement optique, appareil et produit correspondants WO2014055134A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018089580A1 (fr) * 2016-11-09 2018-05-17 Corning Incorporated Articles en verre revêtus et leurs procédés de production

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EP1630261A2 (fr) * 2004-08-20 2006-03-01 JDS Uniphase Corporation Support de substrat pour un appareil de dépôt en phase vapeur
JP2006055731A (ja) * 2004-08-19 2006-03-02 Showa Shinku:Kk 真空装置
JP2009299129A (ja) * 2008-06-13 2009-12-24 Toshiba Corp 真空蒸着装置及びこの装置の電子ビーム照射方法

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JP2006055731A (ja) * 2004-08-19 2006-03-02 Showa Shinku:Kk 真空装置
EP1630261A2 (fr) * 2004-08-20 2006-03-01 JDS Uniphase Corporation Support de substrat pour un appareil de dépôt en phase vapeur
JP2009299129A (ja) * 2008-06-13 2009-12-24 Toshiba Corp 真空蒸着装置及びこの装置の電子ビーム照射方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018089580A1 (fr) * 2016-11-09 2018-05-17 Corning Incorporated Articles en verre revêtus et leurs procédés de production
US11827558B2 (en) 2016-11-09 2023-11-28 Corning Incorporated Coated glass articles and processes for producing the same

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