PATENT DOCUMENT

Publication Number: US-11325860-B2
Application Number: US-201916583204-A
Country: US
Kind Code: B2

Title: Laser-colored sapphire material

Abstract:
A colored sapphire material and methods for coloring sapphire material using lasers are disclosed. The method for coloring the sapphire material may include positioning the sapphire material over an opaque substrate material, exposing the opaque substrate material to a laser beam passing through the sapphire material to impact the substrate material, and inducing a chemical change in a portion of the sapphire material exposed to the laser beam. The method may also include creating a visible color in the portion of the sapphire material as a result of the chemical change. The colored sapphire material may include a first transparent portion, and a second, colored portion substantially surrounded by the first portion. The second, colored portion may have a chemical composition different than that of the first portion.

Claims:
What is claimed is: 
     
       1. A sapphire component, comprising:
 a first portion; and 
 a second portion integrally formed with the first portion and having a chemical composition that is distinct from the first portion, wherein: 
 the second portion is optically contrasted with respect to the first portion. 
 
     
     
       2. The sapphire component of  claim 1 , wherein:
 the first portion is substantially transparent; and 
 the second portion is substantially opaque and defines a visible color distinct from a color of the first portion. 
 
     
     
       3. The sapphire component of  claim 1 , wherein the second portion has an oxygen content that is distinct from an oxygen content of the first portion. 
     
     
       4. The sapphire component of  claim 1 , wherein:
 the first portion defines a primary surface of the sapphire component; and 
 the first and second portions define a secondary surface of the sapphire component. 
 
     
     
       5. The sapphire component of  claim 4 , wherein the second portion extends from the secondary surface and towards the primary surface. 
     
     
       6. The sapphire component of  claim 5 , wherein a chemical composition of the second portion varies between the primary and secondary surfaces. 
     
     
       7. An electronic device, comprising:
 an exterior portion comprising constituent elements; and 
 a colored region formed within the exterior portion and from the constituent elements, the colored region comprising embedded atoms chemically distinct from, and positioned among, the constituent elements. 
 
     
     
       8. The electronic device of  claim 7 , wherein the embedded atoms define a visible color of the colored region. 
     
     
       9. The electronic device of  claim 8 , wherein:
 a chemical characteristic of the embedded atoms varies over a dimension of the colored region; and 
 the visible color changes along the dimension of the colored region based on the chemical characteristic of the embedded atoms. 
 
     
     
       10. The electronic device of  claim 7 , wherein the colored region is visible through the exterior portion.

Description:
CROSS-REFERENCE TO RELATED APPLICATION(S) 
     This application is a divisional patent application of U.S. patent application Ser. No. 15/421,466, filed Feb. 1, 2017, now pending, which is a continuation of U.S. patent application Ser. No. 14/850,535, filed Sep. 10, 2015 and titled “Laser-Colored Sapphire Material,” now U.S. Pat. No. 9,578,768, issued Feb. 21, 2017, the disclosures of which are hereby incorporated by reference in their entireties. 
    
    
     FIELD 
     The disclosure relates generally to sapphire material, and more particularly to laser-colored sapphire material and methods of coloring sapphire material using lasers. 
     BACKGROUND 
     Conventional electronic devices are typically made from durable materials to protect the electronic components of the device. Various portions of the device are thus formed from materials that withstand the everyday wear-and-tear applied to the electronic device. That is, portions of the electronic device may be formed from a material that may withstand constant handling of the electronic device by a user, the transportation and/or packing of the electronic devices and undesired blunt forces (e.g., dropping, sitting on) applied to the electronic device during use. Conventional electronic devices may be formed from metals (e.g., aluminum), reinforced glass, and/or polymers (e.g., plastic, rubber). 
     Alumina (Al 2 O 3 ), one example of which is sapphire typically, is not used to form most portions of electronic devices. As a result of the physical and/or chemical properties of sapphire, certain manufacturing processes used to form portions or components of an electronic device may be difficult and/or expensive to perform on sapphire material. For example, housings for electronic devices typically include designs, text or logos formed right on or in the material forming the housing. The designs, text or logos may be painted directly on a surface of the housing, and the housing may undergo various processes (e.g., heat-setting, coating, and so on) to prevent the paint from being removed. However, over time and normal use of the electronic device, the paint may begin to wear and be removed, as the paint is only applied to a surface of the sapphire material. 
     Laser etching or burning may also be used to form logos on sapphire material. However, these processes typically require the use of difficult and complex intermediate steps, such as ion bombardment of the sapphire material, in order for the etch or burn to be successful on the sapphire material. These complex steps, which are required because of the physical and/or chemical properties of sapphire, increase cost, time and complexity of successfully etching or burning the sapphire. In addition, the visible color of each etched or burned logo onto the sapphire material is typically limited to black, gray or white. 
     SUMMARY 
     A method of coloring a sapphire material. The method comprises positioning the sapphire material over an opaque substrate material, exposing the opaque substrate material to a laser beam passing through the sapphire material to impact the substrate material, and inducing a chemical change in a portion of the sapphire material exposed to the laser beam. The method also comprises creating a visible color in the portion of the sapphire material as a result of the chemical change. 
     A sapphire component comprising a first transparent portion, and a second, colored portion substantially surrounded by the first portion, the second, colored portion comprising a chemical composition different than that of the first portion. 
     An electronic device comprising a housing, a cover glass coupled to the housing for protecting a display positioned within the housing, and an input button positioned through a portion of the housing. The electronic device also comprises a sapphire component forming at least a portion of an external surface of the housing. The sapphire component comprises a first portion, and a second, colored portion positioned adjacent the first portion. The second portion comprises atoms different than atoms of the first portion. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The disclosure will be readily understood by the following detailed description in conjunction with the accompanying drawings, wherein like reference numerals designate like structural elements, and in which: 
         FIG. 1A  depicts a sapphire material, an opaque substrate material and a laser utilized to color a sapphire material. 
         FIG. 1B  depicts the sapphire material, the opaque substrate material and the laser utilized to color the sapphire material of  FIG. 1A  in an assembled position. 
         FIG. 2A  depicts a cross-section view of the sapphire material and the opaque substrate material taken along line  2 - 2  of  FIG. 1B . The sapphire material and the opaque substrate material are shown as being initially exposed to a laser beam used to color the sapphire material. 
         FIG. 2B  depicts an enlarged portion  2 B- 2 B of the sapphire material and the opaque substrate material of  FIG. 2A . 
         FIG. 2C  depicts a cross-section view of the sapphire material and the opaque substrate material taken along line  2 - 2  of  FIG. 1B . The sapphire material and the opaque substrate material are shown after being exposed to the laser beam used to color the sapphire material. 
         FIG. 2D  depicts an enlarged portion  2 D- 2 D of the sapphire material and the opaque substrate material of  FIG. 2C . 
         FIG. 2E  depicts an enlarged portion  2 E- 2 E of the sapphire material and the opaque substrate material of  FIG. 2C . 
         FIG. 2F  depicts a cross-section view of the sapphire material and the opaque substrate material taken along line  2 - 2  of  FIG. 1B . The sapphire material and the opaque substrate material are shown as being exposed to a laser beam used to color the sapphire material two distinct colors. 
         FIG. 2G  depicts an enlarged portion  2 G- 2 G of the sapphire material and the opaque substrate material of  FIG. 2F . 
         FIG. 3A  depicts an enlarged front, cross-section view of a portion of sapphire material and opaque substrate material of  FIG. 2A  prior to being exposed to the laser. 
         FIG. 3B  depicts an enlarged front, cross-section view of a portion of sapphire material and opaque substrate material of  FIG. 2A  after being exposed to the laser. 
         FIG. 4  depicts a top view of a portion of a sapphire material having a visible colored portion formed therein. 
         FIG. 5A  depicts a first cross-section view of the sapphire material of  FIG. 4 , showing a first option for a colored region formed in the sapphire material. 
         FIG. 5B  depicts an alternative cross-section view of the sapphire material of  FIG. 4 , showing a second option for a colored region formed in the sapphire material. 
         FIG. 6  depicts a flow chart of an example process for coloring a sapphire material. 
         FIG. 7A  depicts a front view of an electronic device including a sapphire material having a visible colored portion. 
         FIG. 7B  depicts a back view of the electronic device of  FIG. 7A  including a sapphire material having a visible colored portion. 
     
    
    
     DETAILED DESCRIPTION 
     Reference will now be made in detail to representative embodiments illustrated in the accompanying drawings. It should be understood that the following descriptions are not intended to limit the embodiments to one preferred embodiment. To the contrary, it is intended to cover alternatives, modifications, and equivalents as can be included within the spirit and scope of the described embodiments as defined by the appended claims. 
     The following disclosure relates generally to sapphire materials, and more particularly, to laser-colored sapphire material and methods of coloring sapphire material using lasers. 
     In a particular embodiment, process or method for coloring sapphire material includes positioning sapphire material over an opaque substrate material, typically a metal or metal alloy, and subsequently exposing the opaque substrate material to a laser through the sapphire material to induce a chemical change in the exposed portion of the sapphire material. The chemical change in the sapphire material results in a change in visible color through a portion of the sapphire material that is exposed to the laser. Specifically, the formation of a color within the sapphire material is a result of an exchange of ions and/or atoms between the opaque substrate material and the sapphire material, and/or the embedding of ions and/or atoms from the opaque substrate material into the crystal lattice of the sapphire material. 
     Further, the visible color portion is permanently formed in the sapphire material, and is not easily removed. Additionally, the visible color varies the operational parameters and/or characteristics of the laser beam and/or the material composition of the opaque substrate material. As a result, the sapphire material can includes distinct and different visible colored portions, and even multiple colored regions within the same sapphire material. 
     As discussed herein, the chemical change experienced by the sapphire material may refer to a variety of chemical, compositional and/or physical changes experienced by the sapphire material. In non-limiting examples discussed herein, the chemical change experienced by the sapphire material may refer to an exchange of ions and/or atoms between the opaque substrate material and the sapphire material, or embedding ions and/or atoms released from the opaque substrate material into the crystal lattice of the sapphire material. In additional non-limiting examples, the chemical change may refer to the change or alteration of the structure of the sapphire material with respect to the atoms forming the sapphire material, the compositional structure of the sapphire material and/or the physical structure of the sapphire material. In a further non-limiting example, the chemical change may refer to the change and/or alteration in the material change of the sapphire material, where the changed sapphire material may be materially and/or compositionally distinct from pure sapphire (e.g., Alumina (Al 2 O 3 )). 
     These and other embodiments are discussed below with reference to  FIGS. 1A-7B . However, those skilled in the art will readily appreciate that the detailed description given herein with respect to these Figures is for explanatory purposes only and should not be construed as limiting. 
       FIGS. 1A and 1B  show illustrative perspective views of components utilized to color a sapphire material. One component may be a sapphire material  100 . Sapphire material  100 , as shown in  FIGS. 1A and 1B , can be naturally occurring or a wafer of artificially grown corundum to be further processed (e.g., colored, and/or polished) and used in an electronic device, as discussed herein. The artificially grown corundum used to form sapphire material  100  is grown using any conventional growth process including, but not limited to: hydrothermal growth; vertical horizontal gradient freezing (“VHGF”); edge-defined film-fed growth (“EFG”); horizontal moving growth (e.g., Bridgman growth); and Kyropoulos growth. Additionally, naturally occurring corundum can also form sapphire material  100 , and are processed similar to the artificially grown corundum in preparation for forming sapphire material  100 . Sapphire material  100  can be utilized as a variety of components of many distinct electronic devices. In non-limiting examples, and discussed in detail herein, sapphire material  100  can be used to form cover glass, buttons, housings or enclosures, and the like for electronic devices. 
     Sapphire material  100  has a top surface  102  and a bottom surface  104  positioned opposite top surface  102 . As shown in  FIG. 1A , sidewall  106  are substantially perpendicular to top surface  102  and bottom surface  104 , respectively. Sapphire material  100  has a plurality of plane orientations for the surfaces (e.g., top surface  102 , bottom surface  104 ) of sapphire material  100 . Each of the surfaces of sapphire material  100  may be in alignment with a crystallographic plane orientation determined by the formation of sapphire material  100 . In the non-limiting example shown in  FIGS. 1A and 1B , top surface  102  has an A-plane crystallographic orientation, while sidewall  106  has a C-plane crystallographic orientation. 
     Corundum (e.g., sapphire) is an anisotropic material. The crystallographic orientations of the surfaces of components made from sapphire (e.g., sapphire material  100 ) affect the physical properties and/or material characteristics (e.g., strength, ductility, elasticity, and so on) of the component. Further, the crystallographic orientation of the various surfaces are dependent on the growing processes used for creating sapphire material  100  and/or the additional processes used to form sapphire material  100 . For example, sapphire material  100  may be grown using an EFG growth process. In the growth process, a seed crystal may include a plane orientation that may allow for specific, desired planes (e.g., C-plane, A-plane) to be utilized in components formed from the resulting sapphire. By knowing the orientation of the seed crystal used in the EFG growth process, and ultimately knowing the crystallographic orientation of the grown sapphire, manufacturers can cut the sapphire in a specific direction to form sapphire material  100  and subsequent components from sapphire material  100  with surfaces having specific plane crystallographic orientations, or substantially desirable plane crystallographic orientations. 
       FIGS. 1A and 1B  also depict an opaque substrate material  108 . Opaque substrate material  108  can be formed from any substantially rigid material that may support sapphire material  100  during a coloring process and impart color to sapphire material  100  as a result of the processes discussed herein. In non-limiting examples, opaque substrate material  108  is formed from metal or metal alloys including, but not limited to, stainless steel, aluminum, titanium, copper, iron, cobalt, chromium, tungsten, brass, nickel-carbon, sterling silver, and so on. In additional non-limiting examples, opaque substrate material  108  is formed from nonmetals or compounds including, but not limited to, carbon, phosphorus, sulfur and so on. As discussed herein, the material composition of opaque substrate material  108  substantially affect the visible color formed on/within sapphire material  100  during a coloring process. 
     Opaque substrate material  108  includes a top surface  110  and a bottom surface  112  positioned opposite top surface  110 ; top surface  110  is connected to bottom surface  112  by one of more sidewalls. As shown in  FIG. 1B , bottom surface  104  of sapphire material  100  contacts top surface  110  of opaque substrate material  108  when a process of coloring sapphire material  100  is performed. That is, sapphire material  100  is disposed, placed or positioned over, on, or otherwise adjacent to opaque substrate material  108  when performing a process for coloring a portion of sapphire material  100 . As a result of sapphire material  100  being positioned over and/or on top of opaque substrate material  108 , an interface  118  is formed between the bottom surface  104  of sapphire material  100  and top surface  110  of opaque substrate material  108 . In the non-limiting example shown in  FIG. 1B , no intermediate layer is positioned between and/or separate sapphire material  100 , and opaque substrate material  108 . Additionally, sapphire material  100  and opaque substrate material  108  typically abut one another such that no space or gap exists between the, when sapphire material  100  undergoes a coloring processes, as discussed herein. In another non-limiting example, an intermediate layer and/or a gap is present between sapphire material  100 , and opaque substrate material  108  during the coloring processes discussed herein. 
     A laser  120  is also shown in  FIGS. 1A and 1B . Laser  120  is positioned above sapphire material  100 , and emits a laser beam  122  toward sapphire material  100  and opaque substrate material  108  (see,  FIG. 1B ) during a process for coloring sapphire material  100 . As discussed in detail herein, laser beam  122  of laser  120  passes through transparent sapphire material  100  and contacts top surface  110  of opaque substrate material  108 . Laser beam  122  of laser  120  passes through sapphire material  100  because of sapphire material&#39;s  100  transparent properties and/or as a result of the operational parameters (for example, pulse width, frequency, and so on) of laser beam  122 . Laser beam  122  of laser  120  contacting top surface  110  of opaque substrate material  108  induces a chemical change in sapphire material  100 . As discussed herein, when laser beam  122  contacts opaque substrate material  108 , ions and/or atoms of opaque substrate material  108  may be excited, and subsequently exchanged with or implanted between the ions and/or atoms of sapphire material  100 . The laser-induced chemical change in sapphire material  100  results in the creation of a visible color in a portion of sapphire material  100  exposed to laser beam  122 . Although shown as converging toward sapphire material  100 , it is understood that the depicted shape of laser beam  122  of laser  120  is arbitrary. As such, all features formed in sapphire material  100  by laser beam  122 , as discussed herein, can be formed independent of the depicted shape or geometry of laser beam  122 . 
     Laser  120  may be any suitable laser that may pass through sapphire material  100 , contact opaque substrate material  108  and/or cause a chemical change in sapphire material  100  and/or opaque substrate material  108 , resulting in the formation of visible color in sapphire material  100 . In a non-limiting example laser  120  may be an infrared (IR) laser that may emit an IR laser beam (e.g., laser beam  122 ) toward and/or through sapphire material  100 . As discussed herein, the operational parameters and/or characteristics (e.g., frequency, wavelength, pulse width and so on) of laser  120  and/or emitted laser beam  122  may substantially affect the visible color formed on/within sapphire material  100  during a coloring process. 
       FIGS. 2A-2G  show cross-section side views of sapphire material  100 , opaque substrate material  108  and laser beam  122  of  FIG. 1B  during a process of coloring sapphire material  100 . As discussed herein, sapphire material  100  is disposed, placed or positioned over and/or on opaque substrate material  108  when coloring sapphire material  100 . As shown in  FIGS. 2A-2G , sapphire material  100  is positioned directly over and/or contacts opaque substrate material  108 . Interface  118  is the point, plane and/or region between bottom surface  104  of sapphire material  100  and top surface  110  of opaque substrate material  108 . Interface  118  can be the point of contact between sapphire material  100  and opaque substrate material. Additionally discussed herein and shown in the embodiments of  FIGS. 2A-2G , no intermediate layer, component substrate and/or substance is positioned between sapphire material  100  and opaque substrate material  108 , nor is there a gap between sapphire material  100  and opaque substrate material  108 . 
       FIGS. 2A and 2B  shows sapphire material  100  and opaque substrate material  108  being initially exposed to laser beam  122  of laser  120 .  FIG. 2B  shows an enlarged portion  2 B- 2 B of  FIG. 2A . In a non-limiting example, laser beam  122  passes completely through sapphire material  100 . Laser beam  122  passes through sapphire material  100  without substantially affecting the majority of the portion of sapphire material  100  exposed to laser beam  122 . The operational parameters and/or characteristics of laser beam  122  and/or the transparent properties of sapphire material  100  allow laser beam  122  to pass through sapphire material  100  without affecting the majority of the portion of sapphire material  100  exposed to laser beam  122 . However, and as discussed in detail herein, the bottom surface  104  of sapphire material  100 , and an internal portion of sapphire material  100  surrounding bottom surface  104  are affected (e.g., undergo an chemical, compositional, ionic and/or atomic change) as a result of being exposed to laser beam  122 . 
     Laser beam  122  of laser  120  passes completely through sapphire material  100  and may contact opaque substrate material  108 . In a non-limiting example shown in  FIGS. 2A and 2B , laser beam  122  contacts top surface  110  of opaque substrate material  108 , and as a result, interface  118  formed between sapphire material  100  and opaque substrate material  108  may be exposed to laser beam  122 . In the non-limiting example where opaque substrate material  108  is formed from a metal or metal alloy material, laser beam  122  cannot substantially pass through opaque substrate material  108  like sapphire material  100 , although laser beam  122  may melt, ablate and/or penetrate at least a portion of opaque substrate material  108 . Further, laser beam  122  contacts, reflect from and/or is absorbed by top surface  110  of opaque substrate material  108 . The interaction between laser beam  122  and opaque substrate material  108  may result in a chemical change in opaque substrate material  108  and/or sapphire material  100 . 
     Enlarged portion  2 B- 2 B shown in  FIG. 2B  depicts the chemical, material, compositional ionic and/or atomic change that may occur during the initial exposure of interface  118  to laser beam  122 . In a non-limiting example shown in  FIG. 2B , exposing opaque substrate material  108  to laser beam  122  may excite atoms  124   a ,  124   b  of opaque substrate material  108 . That is, exposing opaque substrate material  108  to and/or allowing laser beam  122  to pass through sapphire material  100  and contact, reflect and/or be absorbed by opaque substrate material  108  results in atoms  124   a ,  124   b  of opaque substrate material  108  being excited. As shown in insert  FIG. 2B , surface atoms  124   a , forming top surface  110  of opaque substrate material  108 , are altered from a steady-state to an excited state when exposed and/or directly contacted by laser beam  122 . Laser beam  122  may diffuse on top surface  110  of opaque substrate material  108 , as shown in  FIG. 2B , or alternatively, may continue to pass through at least a portion of opaque substrate material  108 . 
     A region of excited atoms  124   b  extends into at least a portion of opaque substrate material  108 . Still with reference to  FIG. 2B , atoms  124   b  positioned below excited surface atoms  124   a  are also be excited by laser beam  122  during the process of coloring sapphire material  100 . In the non-limiting example, laser beam  122  may be absorbed by and/or into opaque substrate material  108 , and as such, transfer energy to excite subsurface atoms  124   b  and surface atoms  124   a . During the initial exposure to laser beam  122 , as shown in  FIG. 2B , the number of excited atoms  124   b  positioned below excited surface atoms  124   a  decreases as the distance from top surface  110  of opaque substrate material  108  increases. 
     All atoms of opaque substrate material  108  may not be excited. Rather, atoms  126  of portions of opaque substrate material  108  not exposed to laser beam  122  may remain in a steady state. Additionally, atoms  126  positioned a substantial distance below top surface  110  of opaque substrate material  108  that are not impacted by laser beam  122  may also be unaltered and/or may remain in a steady state. 
     Although discussed herein as contacting, reflecting and/or absorbing laser beam  122 , opaque substrate material  108  can be affected by laser beam  122  in various other ways. In a non-limiting example, laser beam  122  excites atoms  124   a ,  124   b  of opaque substrate material  108 , and in the process also ablates, melts, burns, or etches a portion of opaque substrate material  108  when the material is exposed to laser beam  122 . These various processes that opaque substrate material  108  may undergo when exposed to laser beam  122 , and the exciting of atoms  124   a ,  124   b  may result in any or some chemical, ionic, atomic and/or compositional change in opaque substrate material  108 . These various processes, and the resulting chemical, ionic, atomic and/or compositional change achieved in opaque substrate material  108 , may color sapphire material  100 , as discussed herein. 
     The term “atoms,” as used herein, refers to the particles of matter that make up the material of opaque substrate material  108 . Atoms may generally, and indiscriminately, refer to the atoms that make-up and/or form the entire material of opaque substrate material  108 . In a non-limiting example where opaque substrate material  108  is formed from stainless steel, atoms may be used as a general description, and may refer to the atoms of all elements (e.g., chromium, iron, and so on) of the stainless steel indiscriminately. As such, and as described herein, excited atoms  124   a ,  124   b  may be any atoms associated with any of the various elements that form stainless steel. In another non-limiting example, the atoms  124   a ,  124   b  excited in opaque substrate material  108  and transferred to sapphire material  100 , as described below, may be multiple atoms of different elements that form the material (e.g., stainless steel) of opaque substrate material  108 . 
     In an additional non-limiting example, the term atoms may be used to describe the specific elemental atom forming a compound material formed from multiple elements. In the additional non-limiting example above, opaque substrate material  108  may be formed from stainless steel. Excited atoms  124   a ,  124   b  may only refer elemental atoms associated with a single element (e.g., iron) that forms a portion of the stainless steel. The distinct, elemental atoms forming the compound material may be distinctly or separately excited based on the operational parameters and/or characteristics of laser  120  and/or laser beam  122 . Additionally, and as discussed herein, the excited atoms of each distinct element forming the component material may affect the visible color created on sapphire material  100 . 
       FIGS. 2C-2E  shows sapphire material  100  and opaque substrate material  108  after the initial exposure to laser beam  122  of laser  120 . In the non-limiting example shown in  FIG. 2C , after the initial exposure, laser beam  122  moves in a direction (D), passes through distinct portions of sapphire material  100  and may be exposed to distinct portions bottom surface  104  of sapphire material  100  and top surface  110  of opaque substrate material  108  at interface  118 . Laser beam  122  is moved in a desired direction and/or in a desired pattern to form a design (e.g., logo, graphic, glyph and so on) out of visible color within sapphire material  100 , as discussed herein. 
     Also shown in  FIG. 2C , a portion  128  of sapphire material  100  that was exposed to laser beam  122  has undergone a laser-induced chemical, compositional and/or atomic change. In a non-limiting example, chemically changed portion  128  of sapphire material  100  is a portion of sapphire material  100  positioned adjacent interface  118  and exposed to laser beam  122 . Additionally, laser beam  122  has passed through chemically changed portion  128  of sapphire material  100  to impact opaque substrate material  108 . As shown in  FIG. 2C , chemically changed portion  128  of sapphire material  100  begins adjacent interface  118  and/or at bottom surface  104  of sapphire material  100  and may extend partially into or through sapphire material  100 . As discussed herein, the depth to which chemically changed portion  128  extends into sapphire material  100  depends, at least partially, on the operational parameters and/or characteristics of laser  120  and/or laser beam  122 . Additionally as shown in  FIG. 2C  and discussed herein, distinct portions of sapphire material  100  surrounding chemically changed portion  128  may be substantially unaffected by laser beam  122 , may be chemically and/or compositionally distinct from chemically changed portion  128 , and/or may remain substantially transparent. 
     The chemical, compositional and/or atomic change that occurs in chemically changed portion  128  as a result of exciting and transferring atoms  124   a ,  124   b  from opaque substrate material  108  to sapphire material  100  results in a visible color region  130  being formed in sapphire material  100 . As shown in  FIG. 2C , visible color region  130  of sapphire material  100  has a distinct color from the color (e.g., clear) of the remaining portions of sapphire material  100 . In a non-limiting example, the remaining portions of sapphire material are clear and substantially transparent, while visible color region  130  may include various colors within the visible light spectrum. Additionally, and as similarly discussed herein, with respect to chemically changed portion  128 , visible color region  130  is formed only in and/or through a portion of sapphire material  100 . Visible color region  130  is substantially visible through the unaffected, transparent portion of sapphire material  100  positioned between visible color region  130  and top surface  102  of sapphire material  100 . 
     As discussed herein, a portion  132  of opaque substrate material  108  may also undergo a laser-induced chemical, compositional and/or atomic change. In a non-limiting example shown in  FIG. 2C , and as previously discussed herein with respect to  FIG. 2B , opaque substrate material  108  may undergo various processes (e.g., ablation, melting, burning, etc.) as a result of being exposed to laser beam  122 , which may result in the formation of chemically changed portion  132  in opaque substrate material  108 . As discussed herein, the laser-induced chemically changed portion  132  of opaque substrate material  108  forms laser-induced chemically changed portion  128  of sapphire material  100  and/or creates visible color region  130  in chemically changed portion  128  of sapphire material  100 . 
     Enlarged portion shown in  FIG. 2D  depicts a non-limiting example of chemically changed portion  128  of sapphire material  100 . In the non-limiting example shown in  FIG. 2D , chemically changed portion  128  includes visible color region  130  formed in chemically, compositionally and/or atomically altered sapphire material  100 . Additionally, chemically changed portion  128  includes a chemically, compositionally and/or atomically altered part of sapphire material  100  positioned adjacent bottom surface  104 , and extending partially into or through sapphire material  100 . In the non-limiting example, chemically changed portion  128 , of altered portions of sapphire material  100  are altered on an atomic level. That is, and similar to the configuration shown in  FIG. 2B , altering sapphire material  100  at bottom surface  104  and within an internal portion of sapphire material  100  to form chemically changed portion  128  occurs by altering and/or exciting surface atoms  134   a  and distinct atoms  134   b  positioned adjacent surface atoms  134   a . The alteration or exciting of atoms  134   a ,  134   b  of sapphire material  100  to form chemically changed portion  128  in sapphire material  100  creates visible color in visible color region  130  of sapphire material  100 . In the non-limiting example, the exciting of atoms  134   a ,  134   b  of sapphire material  100  in chemically changed portion  128  alters the chemical, compositional and/or atomic properties in chemically changed portion  128  of sapphire material  100 . Additionally, and as discussed herein, exciting of atoms  134   a ,  134   b  of sapphire material  100  in chemically changed portion  128  and the resulting alteration of the chemical, compositional and/or atomic properties in chemically changed portion  128  of sapphire material  100  allows exited atoms  124   a ,  124   b  of opaque substrate material  108  to be transferred to sapphire material  100  to create visible color in sapphire material  100 . 
     Similar to configuration shown in  FIG. 2B , the number of excited atoms  134   b  positioned adjacent surface atoms  134   a  of sapphire material  100  decreases as the distance from bottom surface  104  of sapphire material  100  increases. As shown in  FIG. 2D , the greater the distance from bottom surface  104  of sapphire material  100 , the less likely it is that the atoms making up sapphire material  100  are excited. Rather the atoms  136  maintain a steady state, and as a result, maintain transparency. Additionally, the atoms forming sapphire material  100  positioned directly adjacent top surface  102  and the atoms positioned within an interior portion or depth of sapphire material  100  also remain as steady state atoms  136 . As such, the number of excited atoms  134   a ,  134   b  of sapphire material  100  increases when moving from top surface  102  to bottom surface  104  of sapphire material  100 . Further, the lowest concentration (e.g., none) of excited atoms  134   a ,  134  are positioned adjacent top surface  102 , and the highest concentration of excited atoms  134   a ,  134   b  are positioned adjacent bottom surface  104 . 
     Also similarly discussed herein with respect to opaque substrate material  108  in  FIG. 2B , not all atoms of sapphire material  100  are altered from a steady state to an excited state. In the non-limiting example shown in  FIG. 2D , atoms  136  of portions of sapphire material  100  surrounding chemically changed portion  128  and atoms  134   a ,  134   b  may remain in a steady state. Unaltered or affected atoms  136  may be positioned between chemically changed portion  128  creating first color region  130  in sapphire material  100 , and top surface  102  of sapphire material, as discussed herein. Additionally, it is understood that atoms  136  not exposed to laser beam  122 , and surrounding chemically changed portion  128  creating first color region  130  in sapphire material  100  may also be unaltered and/or may remain in a steady state. The portions of sapphire material  100  that are not exposed to laser beam  122  may have steady state atoms  136  positioned entirely through sapphire material  100  (e.g., from bottom surface  104 /interface  118  to top surface  102 ). Unaltered or unaffected, steady state atoms  136  may maintain transparency in those portions for sapphire material  100 . 
     The exposure to laser beam  122  and subsequent modification (e.g., melting, burning ablating, etc.), if any, of opaque substrate material  108  aids in the inducing and/or forming chemically changed portion  128 , and ultimately, the creation of visible color region  130  in sapphire material  100 . As shown in  FIG. 2D , during the chemical change in sapphire material  100 , at least a portion of excited atoms  124   a ,  124   b  of opaque substrate material  108  are transferred, enter and/or are embedded in sapphire material  100 . Excited atoms  124   a ,  124   b  may be embedded and scattered within sapphire material  100 , amongst the excited atoms  134   a ,  134   b  of sapphire material  100 . The number of excited atoms  124   a ,  124   b  of opaque substrate material  108  that may be embedded into sapphire material  100  may decrease as the distance from bottom surface  104  of sapphire material  100  increases. 
     Additional changes in sapphire structure  100  may also aid in inducing and/or forming chemically changed portion  128 , and ultimately, the creation of visible color region  130  in sapphire material  100 . That is, the sapphire material&#39;s  100  exposure to laser beam  122 , and/or the effects laser beam  122  has on opaque substrate material  108  may result in chemical, compositional and/or atomic changes in sapphire structure that may aid in inducing or forming chemically changed portion  128  formed in sapphire material  100 . Turning to  FIG. 2E , a non-limiting example of an additional change to sapphire material  100  is shown. Distinct from FIG.  2 D,  FIG. 2E  shows atoms  138  of sapphire material  100  that are elemental oxygen forming sapphire material  100 . In the non-limiting example, the number of oxygen atoms  138  in sapphire material  100  changes in chemically changed portion  128 . That is, oxygen atoms  138  may be transferred from sapphire material  100  to the atmosphere and/or to opaque substrate material  108 , as shown in  FIG. 2E , which may result in the chemical change or alteration of sapphire material  100 . By releasing or removing oxygen from sapphire material  100 , the chemical and/or compositional characteristics of sapphire material  100  may be altered or changed. This alteration of the amount of oxygen in sapphire material  100  may also aid in the creation and/or influence the creation of visible color region  130  of sapphire material  100 . 
     Although shown in two distinct illustrations, the embedding of excited atoms  124   a ,  124   b  of opaque substrate material  108 , as depicted in  FIG. 2D , and altering of the oxygen of sapphire material  100 , as depicted in  FIG. 2E , may not be mutually exclusive. The laser-induced chemical change formed in the portion  128  of sapphire material  100  may occur as a result of embedding exited atoms  124   a ,  124   b  of opaque substrate material  108  in sapphire material  100 , as a result of altering the amount of oxygen in portion  128  of sapphire material  100 , or a combination of the two. In the non-limiting example involving both processes, the oxygen atoms of sapphire material  100  may be replaced by excited atoms  124   a ,  124   b  of opaque substrate material. 
     The laser-induced chemical change in portion  128  of sapphire material  100  results in a visible color being formed in visible color region  130  of sapphire material  100 . In the non-limiting example shown in  FIGS. 2D and 2E , as a result of the chemical, atomic and/or compositional change in portion  128  of sapphire material  100 , visible color region  130  may be formed in sapphire material  100 , such that a user or viewer of sapphire material  100  may see distinct, the visible color region in sapphire material  100 . As discussed herein, visible color region  130  formed in laser-induced chemically changed portion  128  of sapphire material  100  may be a different color than the remaining, unaffected portion of sapphire material. Additionally, visible color region  130  may alter the optical transparency of chemically changed portion  128  of sapphire material  100 . For example, chemically changed portion  128  may be substantially translucent or opaque. As discussed herein, even where chemically changed portion  128  is translucent or opaque, visible color region  130  may still be seen through unaffected, transparent portions of sapphire material  100  positioned adjacent and/or in-line with visible color region  130  and/or chemically changed portion  128 . Visible color region  130  may be any color or light that is included within the visible color spectrum. 
     As discussed herein, created visible color region  130  of sapphire material  100  may be dependent on a material composition of opaque substrate material  108 . In a non-limiting example, where opaque substrate material  108  is formed from zinc, visible color region  130  formed on sapphire material  100  using the process discussed herein may be white. In another non-limiting example, where opaque substrate material  108  is formed from stainless steel, visible color region  130  formed on sapphire material  100  may be blue. 
     In other non-limiting examples, and separate from or in conjunction with the material composition of opaque substrate material  108 , created visible color region  130  of sapphire material  100  may be dependent on operational parameters or characteristics of laser  120  and/or laser beam  122 . Operational parameters or characteristics of laser  120  and/or laser beam  122  may include, but are not limited to, laser frequency, laser wavelength, laser pulse length, laser beam exposure size and the like. Where the operational parameters or characteristics of laser  120  and/or laser beam  122  are altered, the laser-induced chemical change in sapphire material  100  may also be altered. This may result in a distinct and/or varied visible color being formed in sapphire material  100 . 
     As shown in  FIG. 2F  and corresponding enlarged portion shown in  FIG. 2G , operational parameters or characteristics of laser  120  and/or laser beam  122  may be adjusted to form distinct visible colors within sapphire material  100 . For example, the operational parameters or characteristics (e.g., frequency, pulse width, and so on) of laser  120  and/or laser beam  122  are altered, and a distinct portion of opaque substrate material  108  may be exposed to laser beam  122 . As similarly discussed herein with respect to laser-induced chemically changed portion  128  as shown in  FIG. 2C , exposure to laser beam  122  having the altered operational parameters or characteristics induces a distinct chemical change in portion  142  of sapphire material  100 , which results in creating a distinct visible color region  140  in distinct chemically changed portion  142  of sapphire material  100 . Visible color region  140  can be distinct from both the visible color in chemically changed portion  128  and the unaffected, transparent portion of sapphire material  100 . 
     Enlarged portion shown in  FIG. 2G  further depicts the distinction in chemically changed portions  128 ,  142  and/or the visible color regions  130 ,  140  formed therein. As similarly discussed herein with respect to laser-induced chemically changed portion  128  as shown in  FIGS. 2D and 2E , chemically changed portion  142  extends into sapphire material  100 , where the chemical, atomic and/or compositional change (e.g., number of exited atoms  134   b ) varies or decreases as the distance from interface  118  increases. Additionally, and as discussed herein with respect to  FIGS. 2D and 2E , the number of transferred and embedded atoms  124  from opaque substrate material  108  also decreases as the distance extending into sapphire material  100  from interface  118  increases. 
     As shown in  FIG. 2G , distinct, chemically changed portion  142  also differs from chemically changed portion  128  as a result in the alteration in the operational parameters and/or characteristics of laser  120  and/or laser beam  122 . In the non-limiting example, chemically changed portion  142  does not extend into or is not formed within sapphire material  100  as deep as chemically changed portion  128 . That is, the laser-induced chemical change in portion  128  occupies or takes up more space or depth within sapphire material  100 , than the distinct laser-induced chemical change in portion  142 . As discussed in detail herein, the distinct chemical change formed in portion  142  results in a distinct visible color region  140  formed in sapphire material  100 . 
     Sapphire material  100  may be affected by the various processes for coloring sapphire material  100  in distinct ways. In a non-limiting example, the exposure to laser beam  122  and/or the laser-induced chemical change formed in sapphire material  100  may result in altering or changing the physical characteristics of sapphire material  100 .  FIGS. 3A and 3B  show an enlarged portion of sapphire material  100  and opaque substrate material  108 , as shown in  FIGS. 2B, 2D, 2E and 2G . 
       FIG. 3A  shows a portion of sapphire material  100  and opaque substrate material  108  prior to being exposed to laser beam  122 . In the non-limiting example shown in  FIG. 3A , sapphire material  100  includes material defects, such as a crack  144  and a void or gap  146  formed on bottom surface  104 . Crack  144  and/or gap  146  may be formed due to normal wear-and-tear (e.g., transportation) of sapphire material  100  and/or because bottom surface  102  of sapphire material  100  includes a crystallographic plane orientation that is substantially brittle and susceptible to cracking or chipping. Additionally, crack  144  and/or gap  146  may be formed when performing initial processes (e.g., polishing, cutting, planning and so on) on sapphire material  100  prior to performing the coloring process. Material defects, such as crack  144  and gap  146 , negatively affect sapphire material  100 . For example, cracks  144  and gap  146  make the material susceptible to damage and/or weaken the material. 
       FIG. 3B  shows a portion of sapphire material  100  and opaque substrate material  108  after being exposed to laser beam  122 , where sapphire material  100  and opaque substrate material  108  have undergone a chemical, atomic and/or compositional change, as discussed herein with respect to  FIG. 2C . In the non-limiting example shown in  FIG. 3B , exposure to laser beam  122  and the inducing of the chemical, atomic and/or compositional change alters or changes the physical and/or material characteristics of sapphire material  100  by filling crack  144  and gap  146  (shown in phantom). In the non-limiting example, the exposure to laser beam  122 , and the subsequent effects of laser beam  122  on opaque substrate material  108  heats or provides heat via laser beam  122  to bottom surface  104  of sapphire material  100 . This heat melts, reflows and/or anneals the portion of sapphire material  100  including crack  144  and gap  146  to eliminate the material defects. Additionally, the laser-induced chemical change that occurs in both sapphire material  100  and opaque substrate material  108  cures the material defects in sapphire material  100 . That is, and as discussed herein with respect to  FIG. 2C , as excited atoms of opaque substrate material  108  are transferred and embedded in sapphire material  100  and/or as atoms associated with oxygen in sapphire material  100  are altered or removed, crack  144  and gap  146  are substantially filled by the transferring of atoms between the two components. 
       FIG. 4  depicts a top view of sapphire material  100  having a visible color region  130 . As shown in  FIG. 4 , visible color region  130  is seen when looking at top surface  102  of sapphire material  100 . In a non-limiting example, visible color region  130  may be seen through the transparent, unaltered portion of sapphire material  100  that is positioned above visible color region  130  and does not undergo the laser-induced chemical change, as discussed herein. Visible color region  130  created on or in sapphire material  100  may be created as a design (e.g., logo, graphic, glyph and so on). As discussed herein, sapphire material  100 , having a design formed from visible color region  130 , and the process detailed above, may be utilized in an electronic device in a variety of components and uses. 
       FIGS. 5A and 5B  depict cross-section views of sapphire material  100  of  FIG. 4 , taken along line  5 - 5  and showing two different version of a colored pattern or portion of sapphire material.  FIG. 5A  shows sapphire material  100  having visible color region  130  formed on bottom surface  104  of sapphire material  100 . When sapphire material  100  having visible color region  130  formed on bottom surface  104  forms a component of an electronic device, as discussed herein, visible color region  130  is formed on an interior surface of the component formed from sapphire material  100 . As such, visible color region  130  is not exposed and is seen through the unaltered, transparent portion of sapphire material  100 , as discussed herein. 
     In another non-limiting example shown in  FIG. 5B , visible color region  130  is formed on top surface  102  of sapphire material  100 . To form visible color region  130  on top surface  102 , sapphire material  100  is positioned over opaque substrate material  108  in a “flipped” orientation when performing the process of coloring sapphire material  100 , as discussed herein with respect to  FIGS. 2A-2G . In the non-limiting example, top surface  102  of sapphire material  100  and top surface  110  of opaque substrate material  108  contact and/or are positioned adjacent each other to form interface  118  as discussed herein. Once visible color region  130  is formed on top surface  102  of sapphire material  100 , sapphire material  100  can be flipped so visible color region  130  is exposed and/or directly seen when viewing sapphire material  100 , as shown in  FIG. 5B . 
     When sapphire material  100  having visible color region  130  formed on top surface  102  forms a component of an electronic device, visible color region  130  is formed on an exterior surface of the component formed from sapphire material  100 . As such, visible color region  130  may be exposed and may be directly visible to a user of the electronic device having sapphire material  100  with visible color region  130  formed on top surface  102 . 
       FIG. 6  depicts an example process for coloring a sapphire material. Specifically,  FIG. 6  is a flowchart depicting one example process  200  for coloring a portion of a sapphire material, such that the colored portion of the sapphire material is of a distinct color and/or transparency than the remaining portions of the sapphire material. In some cases, the colored sapphire material may be utilized in an electronic device, as discussed below with respect to  FIGS. 7A and 7B . 
     In operation  202 , sapphire material is positioned over an opaque substrate material. Sapphire material is disposed, placed or positioned over the opaque substrate material to form an interface between two contacting surfaces of the sapphire material and the opaque substrate material. In a non-limiting example, no gap or intermediate layer is positioned between the sapphire material and the opaque substrate material. In another non-limiting example, a gap and/or at least one intermediate layer may be positioned between and contact each of the sapphire material and the opaque substrate material. 
     In operation  204 , the opaque substrate material is exposed to a laser beam. The laser beam passes through the sapphire material to contact the opaque substrate material. In exposing the opaque substrate material, atoms in a portion of the opaque substrate material are altered from a steady state to an excited state. 
     In operation  206 , a chemical change is induced in a portion of the sapphire material exposed to the laser beam. Specifically, portions of the sapphire material positioned adjacent the opaque substrate material that is exposed to the laser beam undergo a laser-induced chemical change. The inducing of the chemical change in the portion of the sapphire material includes transferring a portion of the excited atoms of the opaque substrate material, and subsequently embedding the excited atoms of the opaque substrate material at least partially through the sapphire material. Additionally, the inducing of the chemical change in the portion of the sapphire material includes altering the sapphire material at a surface of the sapphire material contacting the opaque substrate material, and altering at least an internal portion of the sapphire material positioned adjacent the altered surface of the sapphire material. The inducing of the chemical change in the portion of the sapphire material also includes, altering the amount of oxygen in the portion of the sapphire material including the chemical change, altering the surface atoms of the sapphire material, and/or changing the physical characteristics and/or the chemical composition of the sapphire material exposed to the laser beam. 
     In operation  208 , a visible color is created in the portion of the sapphire material as a result of the chemical change. That is, a visible color, which may be viewed through the remaining unaffected, transparent portions of the sapphire material, is formed or created in the laser-induced, chemically-changed portion of the sapphire material. The visible color that is created on the sapphire material is a color within the visible color spectrum. Additionally, the visible color created in the sapphire material is dependent upon the material composition of the opaque substrate material and/or the operational parameters and/or characteristics (e.g., laser frequency, laser wavelength, laser pulse length, and so on) of the laser beam. 
     Turning to  FIGS. 7A and 7B , a front and back view of one example of an electronic device  300  that may utilize sapphire material  100  including visible color region  130  is shown. In the illustrated embodiment, electronic device  300  is implemented as a smart telephone. Other embodiments can implement electronic device  300  differently, such as, for example, as a laptop or desktop computer, a tablet computing device, a gaming device, a display, a digital music player, a wearable computing device or display, a health monitoring device, and so on. 
     Electronic device  300  includes a housing  302  at least partially surrounding a display  304 , a cover glass  306  substantially covering display  304  and one or more buttons  308  or input devices (see,  FIG. 7A ). Housing  302  can form an outer surface or partial outer surface and protective case for the internal components of the electronic device  300 , and may at least partially surround display  304  positioned within an internal cavity formed by housing  302 . Housing  302  can be formed of one or more components operably connected together, such as a front piece and a back piece (see,  FIG. 7B ). Alternatively, housing  302  can be formed of a single piece operably connected to display  304 . 
     Display  304  can be implemented with any suitable technology, including, but not limited to, a multi-touch sensing touchscreen that uses liquid crystal display (LCD) technology, light emitting diode (LED) technology, organic light-emitting display (OLED) technology, organic electroluminescence (OEL) technology, or another type of display technology. Display  304  may be positioned within an internal cavity of housing  302  and may be substantially protected on almost all sides by housing  302 . 
     Cover glass  306  may be formed integral with and/or may be coupled to housing  302  to substantially cover and protect display  304 . Cover glass may cover at least a portion of the front surface of electronic device  300 . When a user interacts with display  304  of electronic device  300 , the user may touch or contact cover glass  306 . 
     Button  308  can take the form of a home button, which may be a mechanical button, a soft button (e.g., a button that does not physically move but still accepts inputs), an icon or image on a display, and so on. Further, in some embodiments, button  308  can be integrated as part of cover glass  306  of the electronic device  300 . 
     Electronic device  300  can utilize sapphire material  100  having visible color region  130  to form at least a portion of an external surface of housing  302 . That is, sapphire material  100  is utilized as a variety of components in electronic device  300 , and the component formed from sapphire material  100  may form at least a portion of the external surface and/or a portion of housing  302  of electronic device  300 . In a non-limiting example shown in  FIG. 7A , sapphire material  100  is utilized to form cover glass  306  for protecting display  304 . In another non-limiting example shown in  FIG. 7A , sapphire material  100  is utilized to form button  308  or at least an external layer of button  308  of electronic device  300 . In both, non-limiting examples shown in  FIG. 7A , sapphire material  100  utilized in electronic device  300  includes visible color region  130  formed therein as a design, in a similar fashion or process of that discussed herein with respect to  FIGS. 2A-2C . 
     In another non-limiting example shown in  FIG. 7B , a portion of housing  302  is formed from sapphire material  100  including visible color region  130  formed as a design (e.g., logo, glyphs, and the like). In the non-limiting example, sapphire material  100  including visible color region  130  forms at least a portion of an exposed surface of housing  302 . 
     The foregoing description, for purposes of explanation, used specific nomenclature to provide a thorough understanding of the described embodiments. However, it will be apparent to one skilled in the art that the specific details are not required in order to practice the described embodiments. Thus, the foregoing descriptions of the specific embodiments described herein are presented for purposes of illustration and description. They are not targeted to be exhaustive or to limit the embodiments to the precise forms disclosed. It will be apparent to one of ordinary skill in the art that many modifications and variations are possible in view of the above teachings.

Metadata:
Filing Date: 20190925
Publication Date: 20220510
Grant Date: 20220510
Priority Date: 20150910
Inventors: LI, MICHAEL M.
FAGAN, CHRISTOPHER R.
PRASAD, ANUBHAV
Assignee: APPLE INC
CPC Classifications: [{"code": "B01J19/121", "inventive": true, "first": true, "tree": "[]"}, {"code": "B23K2103/54", "inventive": false, "first": false, "tree": "[]"}, {"code": "C01F7/021", "inventive": true, "first": false, "tree": "[]"}, {"code": "B23K26/50", "inventive": true, "first": false, "tree": "[]"}, {"code": "B01J2219/0879", "inventive": false, "first": false, "tree": "[]"}, {"code": "B23K26/50", "inventive": true, "first": false, "tree": "[]"}, {"code": "B01J2219/12", "inventive": false, "first": false, "tree": "[]"}, {"code": "B01J2219/0879", "inventive": false, "first": false, "tree": "[]"}, {"code": "B01J19/121", "inventive": true, "first": false, "tree": "[]"}, {"code": "B23K2103/54", "inventive": false, "first": false, "tree": "[]"}, {"code": "C03C23/0025", "inventive": true, "first": true, "tree": "[]"}, {"code": "B23K26/50", "inventive": true, "first": false, "tree": "[]"}, {"code": "B01J19/121", "inventive": true, "first": false, "tree": "[]"}, {"code": "B23K2103/54", "inventive": false, "first": false, "tree": "[]"}, {"code": "B01J2219/0879", "inventive": false, "first": false, "tree": "[]"}, {"code": "B01J2219/12", "inventive": false, "first": false, "tree": "[]"}, {"code": "C01F7/021", "inventive": true, "first": false, "tree": "[]"}, {"code": "C03C23/0025", "inventive": true, "first": true, "tree": "[]"}]
Family ID: 58017450