PATENT DOCUMENT

Publication Number: US-11921259-B2
Application Number: US-202016843137-A
Country: US
Kind Code: B2

Title: Oleophobic coatings for glass structures in electronic devices

Abstract:
An electronic device includes electrical components in a housing. The components may include optical components such as a display. Protective structures may be used to protect the optical components. The protective structures may include one or more protective transparent layers such as layers of glass or crystalline material such as sapphire. The protective transparent layers may be coated with an oleophobic coating. To enhance coating durability, catalyst may be used to help bond the oleophobic coating. An adhesion promotion layer such as a silicon oxide layer may be deposited on the transparent protective layer. A catalyst layer such as a layer of sodium fluoride may be deposited on the adhesion promotion layer. The oleophobic material may be evaporated or otherwise deposited on the catalyst layer. Heat and moisture may help the oleophobic material form chemical bonds with the adhesion promotion layer, thereby forming a durable oleophobic coating.

Claims:
What is claimed is: 
     
       1. A method, comprising:
 depositing an adhesion promotion layer onto a protective transparent layer; 
 depositing a catalyst layer onto the adhesion promotion layer; 
 depositing oleophobic material onto the catalyst layer; and 
 curing the oleophobic material to form an oleophobic coating layer that is chemically bonded to the protective transparent layer. 
 
     
     
       2. The method defined in  claim 1  wherein depositing the adhesion promotion layer comprises depositing a silicon oxide layer onto the protective transparent layer. 
     
     
       3. The method defined in  claim 2  wherein depositing the catalyst layer comprises depositing a layer of sodium fluoride onto the adhesion promotion layer. 
     
     
       4. The method defined in  claim 3  wherein depositing the oleophobic material comprises depositing fluoropolymer. 
     
     
       5. The method defined in  claim 4  wherein depositing the fluoropolymer comprises evaporating perfluoropolyether. 
     
     
       6. The method defined in  claim 5  wherein depositing the silicon oxide layer comprises depositing the silicon oxide layer by evaporation and wherein depositing the layer of sodium fluoride comprises depositing the layer of sodium fluoride by evaporation. 
     
     
       7. The method defined in  claim 5  wherein the curing comprises exposure of the oleophobic material to moisture. 
     
     
       8. The method defined in  claim 7  wherein the curing comprises exposure of the oleophobic material to a temperature of at least 100° C. to form Si—O—Si chemical bonds. 
     
     
       9. The method defined in  claim 8  further comprising spraying the oleophobic material with water to remove sodium. 
     
     
       10. A method of forming an oleophobic coating on a transparent protective layer for an electronic device, comprising:
 cleaning the transparent protective layer; 
 evaporating a layer of silicon oxide onto a surface of the cleaned transparent protective layer; 
 evaporating a catalyst layer onto the layer of silicon oxide; and 
 depositing fluoropolymer onto the catalyst layer. 
 
     
     
       11. The method defined in  claim 10  wherein evaporating the catalyst layer comprises evaporating a sodium fluoride catalyst layer onto the layer of silicon oxide. 
     
     
       12. The method defined in  claim 11  wherein depositing the fluoropolymer comprises evaporating perfluoropolyether onto the catalyst layer. 
     
     
       13. The method defined in  claim 12  further comprising curing the deposited fluoropolymer in the presence of the sodium fluoride catalyst layer to chemically bond the oleophobic coating to the transparent protective layer. 
     
     
       14. The method defined in  claim 13  wherein the fluoropolymer comprises a silane coupling group.

Description:
This application claims the benefit of provisional patent application No. 62/835,371, filed Apr. 17, 2019, which is hereby incorporated by reference herein in its entirety. 
    
    
     BACKGROUND 
     This relates generally to coatings, and, more particularly, to coatings for glass structures in electronic devices. 
     Electronic devices such as cellular telephones, computers, watches, and other devices may contain layers of glass or other transparent material. For example, electronic devices may have displays and camera windows that are covered with protective layers of transparent material. 
     The inclusion of transparent protective layers may help prevent damage to electrical components such as display and camera components, but such layers may pick up fingerprints. To provide a transparent protective layer with anti-smudge properties, an oleophobic coating layer can be added to the outer surface of the protective layer. Oleophobic coating layers help reduce smudging from finger contact, but can be vulnerable to scratching. 
     SUMMARY 
     An electronic device may include a housing. Electrical components may be mounted in within an interior region of the housing. The electrical components may include optical components such as a display, optical sensors, and/or other components that emit and/or detect light. 
     Protective structures may be used to protect the optical components. The protective structures may include one or more protective transparent layers. Protective transparent layers may be formed from glass or crystalline materials such as sapphire. 
     To prevent fingerprint smudging, the protective transparent layers may be coated with an oleophobic coating. To enhance coating durability, catalyst may be used to help bond the oleophobic coating. During coating formation, an adhesion promotion layer such as a silicon oxide layer may be deposited on the transparent protective layer. A catalyst layer such as a layer of sodium fluoride may be deposited on the adhesion promotion layer. The oleophobic material may be evaporated or otherwise deposited on the catalyst layer. Heat and moisture may be applied while the evaporated oleophobic material is in the presence of the catalyst layer to help the oleophobic material form chemical bonds with the adhesion promotion layer. This forms a durable transparent oleophobic coating. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG.  1    is a perspective view of an illustrative electronic device of the type that may include a transparent protective layer with a coating in accordance with an embodiment. 
         FIG.  2    is a cross-sectional side view of a portion of an electronic device with an electrical component covered with a transparent protective layer with a coating in accordance with an embodiment. 
         FIG.  3    is a diagram showing how an oleophobic coating layer may be formed in accordance with an embodiment. 
         FIG.  4    is a schematic diagram of an illustrative oleophobic material in accordance with an embodiment. 
         FIG.  5    is a chemical diagram showing how oleophobic material may bond to an adhesion layer in accordance with an embodiment. 
         FIG.  6    is a flow chart of illustrative operations associated with forming an oleophobic coating in accordance with an embodiment. 
     
    
    
     DETAILED DESCRIPTION 
     Electronic devices and other items may be provided with optical components. These optical components may include displays and optical sensors. For example, an electronic device may include a display on a front face of the device. The display may have an array of pixels for displaying images for a user. To protect the pixel array from damage, the display may be covered with a transparent protective layer such as a layer of glass, sapphire, or other transparent material that serves as a display cover layer. Other portions of electronic devices may also include transparent protective structures. For example, a transparent protective layer may form a camera window. Transparent protective layers may also overlap status indicator lights, proximity sensors, ambient light sensors, and other optical components. If desired, layers of glass, crystalline material such as sapphire, or other transparent material may be used in forming electronic device housing structures (e.g., a rear housing wall, sidewall structures, etc.). 
     To prevent smudging from fingerprints, a transparent protective layer or other structure formed from glass, sapphire, or other crystalline materials in an electronic device may be covered with an oleophobic coating. The oleophobic coating may be formed from a fluoropolymer or other material that has oleophobic properties. To ensure that the oleophobic coating is durable, the oleophobic coating may be applied using a catalyst that promotes bonding between the oleophobic coating and an adhesion layer on the surface of the transparent protective layer. 
     In general, any electronic device structures may be covered with oleophobic coatings. These structures may include structures formed from glass, sapphire or other crystalline materials, transparent ceramic, polymer, and/or other materials. The oleophobic coatings may include one or more thin-film layers. These layer(s) may include dielectric materials (e.g., polymer, inorganic dielectrics such as oxides, carbides, nitrides, etc.), metals, and/or semiconductors. Illustrative arrangements in which thin-film layers are used for forming an oleophobic coating on a transparent protective layer such as a layer of glass or a layer of crystalline material such as sapphire may sometimes be described herein as an example. The transparent protective layer may cover a display, may serve as a camera window, or may overlap other optical components. 
     An illustrative electronic device of the type that may include transparent protective structures is shown in  FIG.  1   . Electronic device  10  may be a computing device such as a laptop computer, a computer monitor containing an embedded computer, a tablet computer, a cellular telephone, a media player, or other handheld or portable electronic device, a smaller device such as a wristwatch device (e.g., a wristwatch with a wrist strap), a pendant device, a headphone or earpiece device, a device embedded in eyeglasses or other equipment worn on a user&#39;s head, or other wearable or miniature device, a television, a computer display that does not contain an embedded computer, a gaming device, a navigation device, an embedded system such as a system in which electronic equipment with a display is mounted in a kiosk or automobile, equipment that implements the functionality of two or more of these devices, or other electronic equipment. In the illustrative configuration of  FIG.  1   , device  10  is a portable device such as a cellular telephone, media player, tablet computer, wrist device, or other portable computing device. Other configurations may be used for device  10  if desired. The example of  FIG.  1    is merely illustrative. 
     In the example of  FIG.  1   , device  10  includes a display such as display  14 . Display  14  may be a touch screen display that incorporates a layer of conductive capacitive touch sensor electrodes or other touch sensor components (e.g., resistive touch sensor components, acoustic touch sensor components, force-based touch sensor components, light-based touch sensor components, etc.) or may be a display that is not touch-sensitive. Capacitive touch screen electrodes may be formed from an array of indium tin oxide pads or other transparent conductive structures. 
     Display  14  may include an array of pixels formed from liquid crystal display (LCD) components, an array of electrophoretic pixels, an array of plasma pixels, an array of organic light-emitting diode pixels or other light-emitting diodes such as light-emitting diodes formed from crystalline semiconductor dies, an array of electrowetting pixels, or pixels based on other display technologies. For example, display  14  may be an organic light-emitting diode display or a liquid crystal display. 
     Device  10  may have a housing such as housing  12 . Housing  12 , which may sometimes be referred to as an enclosure or case, may be formed of plastic, glass, ceramics, fiber composites, metal (e.g., stainless steel, aluminum, titanium, gold, etc.), other suitable materials, or a combination of any two or more of these materials. Housing  12  may be formed using a unibody configuration in which some or all of housing  12  is machined or molded as a single structure or may be formed using multiple structures (e.g., an internal frame structure, one or more structures that form exterior housing surfaces, etc.). Electrical components (e.g., a pixel array for display  14 , optical sensors, other optical components, integrated circuits, a battery, etc.) may be mounted in an interior region within housing  12 . 
     Housing  12  or structures coupled to housing  12  may include one or more transparent portions. For example, a portion of housing  12  may be formed from a layer of transparent material such as glass or a layer of transparent material such as sapphire or other crystalline material that serves as a display cover layer. The display cover layer may cover and protect the pixels of display  14  and other overlapped optical components (e.g., a proximity sensor, ambient light sensor, camera flash, three-dimensional sensor, time-of-flight sensor, digital image sensor, etc.). Display  14  and the transparent protective layer that overlaps display  14  (and, if desired, that overlaps other optical components such as optical sensors) may be formed on front face F of device  10  or other portion of device  10 . 
     Other structures in device  10  may also be formed from transparent material. For example, portions of housing  12  on rear face R and/or portions of housing  12  forming a sidewall W that extends between the portion of housing  12  on front face F and the portion of housing  12  on rear face R may be formed from glass or crystalline material such as sapphire. Transparent structures in device  10  such as glass or sapphire portions of housing  12  may include planar layers and transparent members with non-planar shapes such as shapes with curved cross-sectional profiles, transparent layers with bends along the peripheral edges of device  10 , glass window structures for cameras and other optical components, and/or other glass members with planar and/or curved shapes. 
       FIG.  2    is a cross-sectional side view of a portion of an illustrative device such as device  10  of  FIG.  1    that contains transparent structures. As shown in  FIG.  2   , device  10  may have optical components such as component  18  mounted within interior region  16  of device  10 . Component  18  may be a display (e.g., a pixel array), a proximity sensor that emits and detects light, an image sensor (e.g., a visible light and/or an infrared camera), a three-dimensional image sensor, an ambient light sensor, a status indicator light, a camera flash, and/or other component that emits and/or detects light. Component  18  may be formed in an interior region within device  10  (e.g., in interior region  16  inside housing  12  of  FIG.  1   ). Housing  12  may include, for example, rear wall structures, sidewalls, and/or front housing wall portions (e.g., a display cover layer for a display). Transparent portions of housing  12  (e.g., a display cover layer), camera window structures, and other transparent protective structures in device  10  are illustrated as transparent protective layer (structure)  20  of  FIG.  2   . 
     As shown in  FIG.  2   , transparent protective layer  20  may be covered by an adhesion promotion layer such as adhesion promotion layer  22 . Layer  22  may, for example, be a thin-film layer such as a silicon oxide thin-film layer. Oleophobic coating  24  may be formed from a polymer layer that is chemically bonded to layer  22 . The use of silicon oxide in forming layer  22  may help layer  22  adhere well to transparent protective layer  20  and may promote adhesion of oleophobic coating  24  to layer  22  (and thereby layer  20 ). Oleophobic layer  24  may be an oleophobic polymer layer such as a fluoropolymer layer. 
     Transparent protective layer  20  may have a thickness of at least 100 μm, at least 0.5 mm, at least 1 mm, at least 2 mm, less than 4 mm, less than 3 mm, or other suitable thickness. Adhesion promotion layer  22  may have a thickness of about 2-10 nm, 5 nm, 5-10 nm, at least 0.005 μm, at least 0.01 μm, at least 0.05 μm, less than 0.3 μm, less than 0.1 μm, or other suitable thickness. Oleophobic layer  24  may have a thickness of 2-100 nm, at least 0.005 μm, at least 0.01 μm, at least 0.1 μm, at least 1 μm, less than 5 μm, less than 2 μm, less than 0.7 μm, less than 0.3 μm, or other suitable thickness. 
     Oleophobic coating  24  may help resist fingerprints as a user touches the outer surface of device  10 , thereby preventing smudges on protective transparent layer  20 .  FIG.  3    illustrates a process for forming oleophobic layer  24 . At the top of  FIG.  3   , substrate  20  is shown after a cleaning process has been performed on upper (outermost) surface  28 . After surface  28  is cleaned, adhesion promotion layer  22  may be deposited as shown in the second-from-top portion of  FIG.  3   . Catalyst layer  26  may then be formed on layer  22  as shown in the third-from-top portion of  FIG.  3   . With an illustrative arrangement, layer  20  is glass or a crystalline material such as sapphire. Adhesion promotion layer  22  is a thin-film dielectric layer such as a layer of silicon oxide that promotes polymer adhesion to layer  20 . Catalyst layer  26  is a material that catalyzes bond formation between oleophobic coating  24  and adhesion promotion layer  22 . As shown at the bottom of  FIG.  3   , the presence of catalyst layer  26  helps promote bond formation and enhances adhesion of oleophobic coating  24  to adhesion promotion layer  22 , thereby helping to attach oleophobic coating  24  to layer  22  and underlying transparent protective layer  20 . With an illustrative configuration, oleophobic layer  26  is a fluoropolymer and layer  26  is sodium fluoride. 
       FIG.  4    is a schematic diagram of oleophobic polymer material for forming layer  24 . As shown in  FIG.  4   , oleophobic material  36  may include oleophobic polymer chain  30  and a coupling group such as coupling group  34  (e.g., a silane coupling group). Coupling group  34  is formed at the end of polymer chain  30  and helps attach oleophobic polymer material  32  to transparent protective layer  20 . Oleophobic polymer chain  30  may be a fluoropolymer chain. Initially, coupling group  34  has oxygen atoms terminated by methyl groups. In the presence of moisture and heat and exposure to the surface of layer  22  and in the presence of sodium fluoride or other catalyst  26  on layer  22 , the methyl groups are replaced by hydroxyl groups and begin to bond with hydroxyl groups from layer  22 . Eventually, water (a pair of hydrogen atoms and an oxygen atom) is released from each OH—OH group, forming Si—O—Si chemical bonding as shown in  FIG.  5   . In this way, the silane coupling group (and thereby polymer chain  30  of oleophobic material  36 ) are chemically bonded to adhesion promotion layer  22 , as shown in  FIG.  5   . In particular, most or all of the silicon atoms from coupling group  34  are bonded by respective oxygen atoms to corresponding silicon atoms in silicon oxide adhesion promotion layer  22 , which chemically bonds oleophobic material  36  to the material of layer  22 . As a result, oleophobic coating  24  is securely attached to adhesion promotion layer  22  and will be more resistant to wear than oleophobic coatings that are formed on layer  22  in the absence of catalyst layer  26 . 
     Illustrative operations involved in forming oleophobic coating  24  are shown in  FIG.  6   . 
     During the operations of block  40 , transparent protective layer  20  is cleaned. For example, a glass layer or a layer of crystalline material such as sapphire is mechanically and chemically cleaned followed by surface treatment (e.g., ion beam surface treatment) to activate surface free radicals. 
     After cleaning, adhesion promotion layer  22  may be formed the outer surface of layer  20  (and may optionally be cleaned and/or exposed to surface treatment). For example, during the operations of block  42 , a layer of silicon oxide may be deposited on the surface of layer  20  by evaporation in a vacuum chamber. The silicon oxide layer may have a thickness of 5-10 nm, at least 1 nm, less than 50 nm, or other suitable thickness. 
     During the operations of block  44 , catalyst layer  26  may be deposited on the exposed surface of layer  22 . For example, a layer of sodium fluoride (NaF) of 0.5 nm to 2 nm in thickness or other suitable thickness (e.g., at least 0.1 nm, at least 0.5 nm, at least 1 nm, less than 10 nm, less than 5 nm, etc.) may be evaporated onto layer  22 . E-beam evaporation may be used for forming layer  22  and depositing catalyst layer  26  (as an example). 
     During the operations of bock  46 , oleophobic material  36  (e.g., a fluoropolymer such as perfluoropolyether (PFPE)) may be heated in a crucible in a vacuum chamber to evaporate material  36  onto the catalyst-coated surface of layer  22 . The vacuum chamber may have a pressure of about 2.5*10 −2  Pa and contains residual moisture. Due to heating from the deposition processes, the temperature of layer  20  and the thin-film structures on layer  20  are raised to about 20-100° C. (e.g., 70° C., 50-100° C., etc.). As described in connection with  FIG.  5   , the application of heat and moisture causes hydroxyl groups to form on coupling groups  34  and, in the presence of catalyst  26 , initiates formation of Si—O—Si bonds between material  36  and adhesion promotion layer  22  as shown in  FIG.  5   . 
     Complete bond formation occurs during curing and final processing operations (block  48 ). The coating layer can be cured 1) at room temperature (e.g., over a period of 5 days), 2) at an elevated temperature produced in the vacuum chamber and/or produced by using a heating tool to raise the temperature of the coating to 140° C. (or at least 100° C., at least 120° C., or other temperature less than 200° C.) for 0.5-24 h, or 3) at 65° C. for 4 h at 90% humidity, or may be cured using other suitable curing arrangements. The curing process in the presence of catalyst from layer  26  completes the formation of a full or nearly full set of Si—O—Si bonds between material  36  and layer  22  and thereby forms a robust chemically bonded oleophobic layer (layer  24  of  FIG.  2   ) on adhesion promotion layer  22 . 
     During curing (e.g., partway through a curing process such as after 5-50 hours of curing), excess catalyst material may be removed. For example, water may be sprayed on the layer of material  36  on layer  22  (e.g., with a mild detergent while polishing off excess portions of material  36  with a cloth pad). This helps remove sodium from catalyst layer  26  and thereby prevents the sodium from reacting with carbon and oxygen to form haze-producing materials (e.g., to help prevent formation of Na 2 CO 3 , which might make the oleophobic coating hazy). Adhesion promotion layer  22  may be free of bulk sodium doping (e.g., layer  22  may be a bulk-sodium-doping-free silicon oxide layer and may therefore contain less than 0.1% sodium by weight, less than 0.01% sodium by weight, and/or other suitable amount of sodium by weight) to help reduce cosmetic defects that might arise when using sodium catalyst in layer  22  instead of layer  26 . The spraying and polishing process will generally remove most sodium from layer  26  and will prevent haze in layer  24 . In some situations (e.g., when no cleaning operations are performed), a residual amount of sodium may be present after layer  24  is formed. For example, the ratio of Na/Si at the interface between coating  24  and layer  22  may be 0.02-0.5, at least 0.01, less than 0.8, or other suitable amount). 
     The foregoing is merely illustrative and various modifications can be made to the described embodiments. The foregoing embodiments may be implemented individually or in any combination.

Metadata:
Filing Date: 20200408
Publication Date: 20240305
Grant Date: 20240305
Priority Date: 20190417
Inventors: MITTAL, MANISH
LIU, FENG
ISHIZEKI, KENJI
ROGERS, MATTHEW S.
MATSUYUKI, NAOTO
OETTING, WOLF
Assignee: APPLE INC
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Family ID: 72832275