SILICON CARBIDE GEMSTONES

Abstract: Synthetic gemstones having extraordinary brilliance and hardness are formed from large single crystals of relatively low impurity, translucent silicon carbide of a single polytype that are grown in a furnace sublimation system. The crystals are cut into rough gemstones that are thereafter fashioned into finished gemstones. A wide range of colors and shades is available by selective doping of the crystal during growth. A colorless gemstone is produced by growing the crystal undoped in a system substantially free of unwanted impurity atoms.

Description: SILICON CARBIDE GEMSTONES Field of the Invention The invention relateε to synthetic gemstones. More particularly, the invention relates to synthetic gemstones formed of translucent, monocrystalline silicon carbide. Background of the Invention Gemstones Generally; There are a limited number of elements and chemical compoundε that have the physical characteristics to be useful as gemstoneε. The physical characteristics that are generally accepted as being most important are hardnesε, refractive index and color, although thermal stability, chemical εtability and toughness are also considered important in many gemstone applications. To date, the only chemical substances technically considered precious stones are diamond (single crystalline carbon) and corundum (sapphire and ruby [single crystalline aluminum oxide] ) because their hardness when measured on the Mohs scale is approximately 9 or higher. The Mohs εystem is a scale for ranking hardness of a mineral with diamond being the hardest at 10, sapphire at 9, topaz 8 down to the softest mineral, talc, which is 1. Emerald, because it is rare, is accepted as a precious stone even though its hardness is 7.5 while other gems, such as chrysoberyl, topaz and garnet, are usually classified as semiprecious stones because of their lower hardnesε. Hardnesε haε practical value in that it defineε the ability of a gemstone to resist scratching. Refractive index is important because it defines the ability of a gemstone to refract light. When materials with a high refractive index are fashioned into finished gemstones they sparkle and appear brilliant when exposed to light. The characteristic sparkle of a diamond is due mainly to its high refractive index. The color of a gemstone is determined by a variety of factorε, from the impurity atomε that are available to be incorporated into the crystal lattice to the physical and electronic structure of the crystal itself. A ruby, for instance, is simply a sapphire crystal (aluminum oxide) that contains a small concentration of chromium impurity atoms. The thermal and chemical stability of a gemstone can be important during the proceεε of mounting stones into jewelry. In general, it iε beneficial if stones can be heated to high temperatures without changing color or reacting with ambient gases (that mar the surface finish) . The toughness of a gemstone relates to the ability of the gemstone to absorb energy without breaking, chipping or cracking. A gemstone muεt be able to withεtand those impact forces normally encountered during a lifetime of use mounted on a ring or other jewelry item. Hardness, refractive index, color, thermal/chemical stability and toughnesε are all characteriεtics that, in combination, determine the usefulness of a material as a gemεtone. Synthetic Diamond Gemstones: Dating from the 1960s, an effort to produce gem-quality synthetic diamonds was pursued by General Electric Company as evidenced by numerous patents, including U.S. Patent No. 4,042,673. These efforts centered around the use of very high preεεure/high temperature environments for growth of monocrystalline diamonds on seed crystalε. Gem-quality synthetic diamonds generally have not gained commercial acceptance. Synthetic Silicon Carbide Used As Abraεiveε And Semiconductor Materialε; Silicon carbide is rarely found in nature. However, it has been manufactured for more than eighty years, in crystalline form, for abrasive products. Silicon carbide crystalε found in nature and in abrasive productε are black and not translucent because they contain substantial levels of impurity atoms. During the 1960s and 1970s, significant development activities were initiated with the objective of growing large (bulk) crystalε of low impurity εilicon carbide for uεe in the production of εemiconductor devices. Theεe effortε finally reεulted in the commercial availability of relatively low impurity, tranεlucent silicon carbide crystalε in 1990. These silicon carbide crystals are only fabricated and marketed as very thin, green or blue (175μm - 400μm) slices useful for semiconductor devices. Silicon carbide has a very high hardnesε (8.5-9.25 Mohε depending on the polytype [atomic arrangement] and crystallographic direction) and a high refractive index (2.5-2.71 depending on the polytype) . Furthermore, silicon carbide is a very tough material and an extremely stable material that can be heated to more than 2000°F., in air, without suffering damage. Silicon carbide iε a complex material εystem that forms more than 150 different polytypeε, each having different physical and electronic properties. The different polytypes can be claεsified in three basic forms, cubic, rhombohedral and hexagonal. Both the rhombohedral and hexagonal forms can occur in a number of different atomic arrangements that vary according to atomic εtacking εequence. Summary of the Invention The present invention, in one broad aspect, is the discovery that relatively low impurity, translucent, single crystal silicon carbide -- presently used as the material for fabrication of very thin semiconductor devices -- may be grown with desired color and thereafter cut, faceted and polished into synthetic finished gemstones having (i) a hardnesε approaching that of diamond, (ii) excellent toughness, (iii) excellent thermal/chemical stability, and (iv) a high refractive index that renders the εilicon carbide gemstone as brilliant, if not more brilliant, than diamond. According to this aspect of the invention, a single crystal of εilicon carbide, preferably of conεiεtent color, iε grown by an appropriate technique such as the sublimation technique discloεed in U.S. Patent No. Re. 34,861. Instead of εlicing the large cryεtal into many thin εliceε, the cryεtalε εerve as bouleε that are cut into rough εynthetic gemstones having a weight on the order of, for example, 1/4 to 5 caratε. The rough gemstones thereafter are fashioned into finished synthetic silicon carbide gemstones. The faceting and poliεhing techniques are derived from thoεe techniques currently used in connection with the faceting and polishing of colored gemstones such as rubies and sapphire, incorporating certain procedures utilized in connection with diamonds. As mentioned above, preferably the single crystalε of silicon carbide are grown under the same or similar conditions that are used to produce crystalε having the low impurity levelε necessary for semiconductor applications, with it being appreciated, of course, that higher impurity levelε may be permiεεible within accepted rangeε conεiεtent with the need for materialε having εuitable transluσence and other optical properties for gemstone use. Silicon carbide crystals can be grown in a wide range of colorε (including green, blue, red, purple, yellow, and black) and εhadeε within each color by the appropriate selection of dopants (e.g., nitrogen and aluminum) and by varying the net doping densitieε (concentrationε) . Undoped silicon carbide crystals in the hexagonal or rhombohedral forms are colorless and meet, or exceed, the brilliance of diamond. Rough silicon carbide gemstoneε are cut from large single crystals and then fashioned into finished gemεtoneε by a combination of techniques currently employed in connection with conventional colored gemstones and diamonds. The hardness and toughness of silicon carbide permit the stones to be faceted with very sharp edges, thus enhancing the overall appearance and brilliance of the stoneε. Brief Description of the Drawings Some of the objects having been stated, other objects will appear as the description proceeds, when taken in connection with the accompanying drawingε, in which -- Figure 1 iε a pictorial view of a boule compriεing a large εingle cryεtal of one polytype of εilicon carbide. Figure 2 iε an enlarged pictorial view of a rough εynthetic gemεtone cut from the εingle cryεtal of Figure 1. Figure 3 iε an enlarged pictorial view of a finished εynthetic εilicon carbide gemstone fashioned from the rough tone of Figure 2. Detailed Deεcription of the Invention While the present invention will be deεcribed more fully hereinafter with reference to the accompanying drawingε, in which aεpeσtε of the preferred manner of practicing the preεent invention are εhown, it is to be understood at the outset of the description which follows that persons of skill in the appropriate arts may modify the invention herein deεcribed while still achieving the favorable results of this invention. Accordingly, the description which follows iε to be understood as being a broad, teaching disclosure directed to persons of skill in the appropriate arts, and not as limiting upon the present invention. Referring to the drawings, Figure 1 showε a "boule" comprising a large single crystal 11 of silicon carbide that weighs approximately 716 carats and from which approximately 105 five carat rough synthetic gemstones (Figure 2) may be cut. Each five carat rough gemstone, when fashioned into a finished gemstone, will yield an approximate εized gemstone on the order of two carats. Crystal 11 is substantially cylindrical and measures approximately 44mm high and 40mm in diameter. In the preferred manner of practicing the invention, crystal 11 is formed of a single polytype, with a wide enough energy band gap (low enough net electrically active impurity atoms) for example, a hexagonal form such as 6H SiC, and haε a low enough net impurity level to render the cryεtal εufficiently translucent for use as a gemstone. Crystal 11 is grown by an appropriate sublimation or deposition or other growth technique used to grow large (bulk) silicon carbide single crystals, with the preferred method being sublimation growth on a seed crystal. According to this preferred technique, cryεtal 11 is grown by introducing a polished monocrystalline εeed cryεtal of εilicon carbide of a desired polytype into the furnace of a sublimation system along with silicon and carbon containing source gas or powder (source material) . The εource material is heated to a temperature that causeε the source material to create a vapor flux that deposits vaporized Si, Si 2 C, and SiC 2 to the growth surface of the seed crystal. The reproducible growth of a εingle εelected polytype on the εeed cryεtal iε achieved by maintaining a constant flux of Si, Si 2 C and SiC 2 , and by controlling the thermal gradient between the source material and the seed crystal. Crystals grown by sublimation techniques have been used as a material from which very thin slices are taken for use in the production of semiconductor devices. These slices (175μm-400/im) have been green or blue, like the crystal, with the color (and desired electrical properties) achieved by intentionally doping with selected dopants at selected concentrations during the growth process. Undoped (intrinsic) silicon carbide has not been grown commercially. The extremely low electrical conductivity of undoped silicon carbide would give it little or no practical value in the fabrication of semiconductor products. However, it has been found that because the hexagonal and rhombohedral polytypes of silicon carbide have wide energy band gaps (>2.7 electron volts) if they are grown undoped (or, equivalently, with a very low level of impurity atoms or a very low level of electrically active impurity atoms) the crystalε will be colorlesε. In order to grow undoped, colorleεε εilicon carbide εingle cryεtalε, the cryεtal growth system is maintained substantially free of unwanted gaseous or vaporized impurity atomε that would reεult in unintentional doping of the cryεtal aε it growε utilizing low pressure bake-out techniques aε are well known in the art. Preferred polytypes for colorless silicon carbide gemstoneε are 6H and 4H SiC. The εeed for initiating growth of the εingle cryεtal for εuch gemstones is the seed having the same polytype, 6H or 4H SiC respectively. To create crystalε of hexagonal silicon carbide having different colors, one must intentionally add specific impurity atoms. The cubic or 3C form of silicon carbide, because of its more narrow energy band gap, will appear yellow when undoped with impurity atoms. Since a large number of different atomic arrangements of silicon carbide exist (any of which can be doped with a number of different dopants in various combinations and concentrations) it iε possible to produce gemstones in a wide range of colors and shades. With the 6H polytype, the dopants commonly used are nitrogen (n type) and aluminum (p type) in concentrations typically ranging from a low range on the order of 10 15 carrier atoms per cubic centimeter to a high range on the order of 10 J carrier atoms per cubic centimeter. Other dopants such as boron may be used at concentrations sufficient to achieve desired colorε and shades. The table below gives various atomic arrangements and dopants that produce several representative basic colors. Colorless 6H SiC Undoped Colorless 4H SiC Undoped Blue 6H SiC Al-doped Purple 6H SiC High Al-doped Purple 24R SiC N-doped Green 6H SiC N-doped Yellow 3C SiC Undoped Yellow-Green 3C SiC N-doped Red 27R SiC N-doped Light Brown 4H SiC Low N-doped Yellow-Orange 8H SiC N-doped Although the above combinations yield a wide variety of colors, all of the crystals have two very important characteristics in common, (1) high hardnesε and (2) high refractive index. The hardneεε and refractive index of silicon carbide are compared with other gemstone materials, along with a comparison of denεity: Mohs Refractive Denεity Hardneεε Index (SG) Emerald 7.5 1.59 2.5 Corundum (εap & ruby) 9 1.77 3.9 Diamond 10 2.42 3.5 Silicon Carbide (6H) 9 2.69 3.2 Silicon Carbide (4H) 9 2.71 3.2 Cubic Zirconia 7. .5 1.98 4.7 As illustrated by the table above, silicon carbide, when produced in certain atomic arrangements with the controlled introduction of specific dopant atoms, is an excellent colored gemstone material that has physical characteristicε comparing favorably with, or exceeding, thoεe of corundum and emerald. In itε undoped hexagonal and rhombohedral forms, (in particular the hexagonal form which repeatε the same atomic structure every six layers of atoms, i.e., 6H) silicon carbide is the best known candidate to replicate the characteriεtics of diamond. Fashioning the Gemstones Referring back to the drawings, the silicon carbide crystal 11 (Figure 1) of perhaps 716 carats is cut into multiple rough synthetic gemstoneε 12 (one shown in Figure 2) having a selected weight, for example, five carats. The rough gemstone 12 preferably has a cubic or approximately cubic shape. In order to produce a finished gemstone as illustrated in Figure 3, it has been found desirable to fashion the rough gemstone 12 into a finished gemstone according to a novel procesε that iε best εuited to taking advantage of the phyεical characteriεtics of εilicon carbide. This process incorporates faceting techniques that result in precise angles and very sharp edges to take full advantage of the toughness and hardness of the silicon carbide material, while incorporating other techniques more similar to those used on colored stones. A more complete description of the fashioning proceεε will be set forth below following a brief discussion of fashioning, in general, and certain aspects of fashioning colored gemstones such as rubies, sapphires and emeralds. Fashioning In General (Prior Art) Gemstone fashioning includes four techniques: faceting, tumbling, cabbing and carving. Faceting produces flat faces (facets) on gems of many different shapeε. Transparent and highly translucent gems are normally faceted. Less translucent and opaque materials are usually tumbled, cabbed or carved because the optical properties aεsociated with faceting depend on light reflecting from inside the stone. A gem's shape is its outline face up, the position in which it is meant to be seen when it is mounted. Shapes other than round are called fancy. Some popular fancy shapes include the well-known emerald cut, cushion, antique cushion, oval, pear, and marquis. Colored stones (and diamonds over three carats) are generally cut into fancy shapeε because a lapidary can keep more weight of the original gemstone by utilizing a fancy shape, thus improving the weight yield. The precise, standardized faceting seen in diamonds is rare in colored stoneε. One reaεon iε the inability of εome colored stones, becauεe of their lower hardneεε and toughness, to be faceted into sharp angles without breaking or chipping. Another is the difference in what professionals and consumers expect of diamonds versus other εtoneε. "Oriental or native cut" are termε used to describe faceted gems which have distorted shapeε and irregularly placed facetε and are more common on colored stones. The jewelry industry accepts not perfected faceted colored stoneε. Moεt colored stones are faceted just enough to let the light in. Most faceted gems have three main parts: crown, girdle, and pavilion. The crown iε the top part, the girdle iε the narrow εection that formε the boundary between the crown and pavilion; it iε the gem'ε setting edge. The pavilion is the bottom. Colored stoneε uεually have facets on the pavilion and crown. The Fashioning Proceεs In General For Colored Stones (Prior Art) The colored gemstone faceter begins by grinding the rough colored gemstone into the approximate shape and dimensions of the finished stone. This is called preforming. Preforming takes a coarse abrasive. Diamond grit embedded in a nickel-plated copper disc is the best choice for preforming very hard colored stones (corundum, chrysoberyl, spinel and silicon carbide) . Water is the wetting agent in preforming and the rest of the faceting sequence. Lapidaries use various arrangements to keep the wheels wet. Preforming roughε in the girdle outline and the general profile of the crown and pavilion, leaving a froεted εurface all around the stone. Before grinding in the facets, the lapidary needs to mount the colored stone on a dopstick. The procedure is called dopping. The stone iε gently heated, then brought up againεt the end of the dop, which has been dipped into melted dopping wax. Once the preform has set in poεition, it iε set aside to cool. The facets of the colored stone are ground and poliεhed on horizontally spinning wheels called laps. Lapidaries use a serieε of cutting laps with progreεsively finer grit to grind in the facets, gradually εmoothing out their surfaces. Then they do final polishing on a special polishing lap. Polishing laps are made from a variety of materialε. The poliεhing agentε with which theεe are charged are very finely ground powderε, including diamond, corundum, cerium oxide, and tin oxide. To cut and polish consiεtently at the same desired angleε, the faceter attaches the dopstick to a device that holds the stone in position as it meets the lap. The traditional setup used in many colored stone shops is the jamb peg. This has a block mounted on a vertical post. The dopstick fits into one of a series of holes on the side of the block. The position of each hole sets a specific angle (from the girdle plane) at which the facet is cut. Turning the dopstick in the hole places all the facets of a given type at the same angle in their circuit around the stone. The Fashioning Process for Silicon Carbide Gemstones Because the beauty of most diamonds depends on sparkle, brilliance, and fire (not color) , diamond cutters must carefully control the cutting factors that affect these characteristics. It is very difficult to put diamond cuts on colored gemstones. Because the refractive index of εilicon carbide is greater than that of diamond and colored stoneε, according to the present invention the silicon carbide gemstone iε fashioned with precision diamond cuts using diamond hand tools known as .tangs. Tangs allow the cutter to set and adjust the angle of the facet, something the cutter is unable to do with colored stone hand tools which are preset. It is the precision of the diamond hand tools, tangs, that enables the cutter to use the angles and proportions of a diamond, resulting in "sharp edges" on the silicon carbide gemstones of the invention. However, because silicon carbide is not as hard as diamond, traditional colored stone lap wheels are used in the faceting proceεε at rotational speeds lesε than those speeds typically used for diamond wheels, i.e., less than 3000 RPM, and preferably at rotational speedε on the order of 300 RPM. Turning to a more particular description of the silicon carbide fashioning technique of the invention, the silicon carbide rough gemstone is mounted on a dopstick and secured within the top tang. The edge Girdle is cut first on the grinding wheel. This determines the shape of the stone. The Table, the flat top which is the biggest facet on the whole stone, is cut next also using the table tang. The Table is then polished uεing a four- step process of laps (disks, wheels or sciaves) progressing from rough to smooth grit sizeε. Polishing may begin with a 600 grit lap moving to 1200 grit, then to 3000 grit and ending with a ceramic disk having an effective grit size of 0.5 to 1 micron, which is the smoothest. The dop is then transferred to a top tang to cut the top side and make the Crosεwork which consists of 4 Basics (facets) . Then the dop is transferred to a bottom tang and the bottom side is cut into the Crosswork which consistε of 4 Basics (facets) . At this time, the stone is examined by visual inspection to determine its preciεion. After this inεpection, the 4 lap polishing procesε outlined for the Table is repeated for the Basics. The dop is tranεferred to the top tang and the top side Star facets - there are 8 of these cut along with the Upper Girdle Facets (16 facetε) . The dop iε tranεferred to the bottom tang and Lower Girdle Facetε (16 facetε) are cut. The 4 lap polishing process outlined for the Table and Basics is repeated for the remaining Girdle facets. The rough is now a faceted and polished round brilliant gemstone 13 aε εhown in Figure 3. While the invention has been described in connection with certain illustrated embodiments, it will be appreciated that modifications may be made without departing from the true spirit and scope of the invention.

Claims: C L A I M S 1. A synthetic gemstone formed from a single crystal of relatively low impurity, translucent silicon carbide of a single polytype. 2. The synthetic gemstone set forth in claim 1, including a selected dopant at a selected concentration to produce a chosen color and shade for the gemstone. 3. The synthetic gemstone set forth in claim 1, having no dopant or a very low level of dopant sufficient to produce a colorlesε gemεtone. 4. A finished synthetic gemstone fashioned from a rough gemstone cut from a large single crystal of a single polytype of silicon carbide grown from a εeed crystal, said single cryεtal of silicon carbide having a relatively low impurity level that renders the crystal sufficiently translucent for use as a gemstone. 5. The finished gemstone set forth in claim 4, wherein the single crystal forming the gemstone has color, crystalline structure and doping characteristicε selected from the group consisting of: Crystalline Doping Color Structure Characteristics Colorless 6H SiC Undoped Colorless 4H SiC Undoped Blue 6H SiC Al-doped Purple 6H SiC High Al-doped Purple 24R SiC N-doped Green 6H SiC N-doped Yellow 3C SiC Undoped Yellow-Green 3C SiC N-doped Red 27R SiC N-doped Light Brown 4H SiC Low N-doped Yellow-Orange 8H SiC N-doped 6. A method of producing finished gemstones having a Mohs hardnesε of 8.5-9.25, a density(SG) of approximately 3.2, and a brilliance defined primarily by a refractive index of 2.50-2.71, said method comprising the steps of: growing a large single crystal of a single polytype of silicon carbide of a desired color character via selective doping thereof; cutting the single cryεtal into a plurality of rough εynthetic gemεtoneε; and fashioning the rough synthetic gemstones into finished gemstones. 7. The method set forth in claim 6, including the step of growing the εingle crystal of silicon carbide in colorlesε form by growing the crystal undoped or very low doped. 8. The method set forth in claim 7, including the step of growing the single crystal of silicon carbide from a seed crystal in a sublimation syεtem. 9. The method set forth in claim 7, comprising the εtep of growing the εingle cryεtal aε undoped or very low doped 6H SiC with a Mohε hardneεε of approximately 9, a refractive index of approximately 2.69 and a density of approximately 3.2(SG) . 10. The method set forth in claim 7, comprising the step of growing the single crystal as undoped or very low doped 4H SiC with a Mohs hardneεs of approximately 9, a refractive index of approximately 2.71 and a density of approximately 3.2(SG) . 11. The method set forth in claim 6, including the step of doping the single crystal of silicon carbide during its growth to produce a selected color and shade for the finished gemεtone. 12. The method εet forth in claim 11, wherein the color, cryεtalline εtructure and doping characteristics of the single crystal of silicon carbide are selected from the group consisting of: Cryεtalline Doping Color Structure Characteristics Blue 6H SiC Al-doped Purple 6H SiC High Al-doped Purple 24R SiC N-doped Green 6H SiC N-doped Yellow 3C SiC Undoped Yellow-Green 3C SiC N-doped Red 27R SiC N-doped Light Brown 4H SiC Low N-doped Yellow-Orange 8H SiC N-doped 13. The method set forth in claim 6, 7, 8, 9, 10, 11 or 12, wherein the step of fashioning the rough synthetic gemstones into furnished gemstones includes the step of faceting the gemstones with precision diamond cuts. 14. The method set forth in claim 13, wherein the step of faceting the gemstones with precision diamond cuts includes the utilization of diamond hand toolε to achieve εharp edges and the utilization of colored stone lap wheels. 15. A method of producing a finished gemstone of monocrystalline εilicon carbide from a large, tranεlucent single crystal of silicon carbide, comprising the steps of: cutting the single crystal into a plurality of rough synthetic gemstones; and fashioning the rough εynthetic gemstones into finished gemstones. 16. A method of producing a finished, colorless, brilliant gemstone compriεing the steps of: growing a large single crystal of a single polytype of undoped or very low doped silicon carbide in a crystal growth system while maintaining the system substantially free of unwanted gaseous or vaporized impurity atoms; cutting the single crystal into a plurality of rough synthetic gemstones; and fashioning the rough synthetic gemstones into finished gemstones. 17. The method set forth in claim 16, wherein the step of fashioning the rough εynthetic gemεtoneε into finished gemstones includes the step of faceting the gemstones with precision diamond cuts. 18. The method set forth in claim 17, wherein the step of faceting the gemstones with precision diamond cuts includes the utilization of diamond hand toolε to achieve εharp edges. 19. The method set forth in claim 18, wherein the fashioning step includes the use of a colored stone lap wheel. 20. The method set forth in claim 19, including the εtep of operating the colored stone lap wheel at speeds below 3000 RPM. 21. The method set forth in claim 20, including the step of operating the colored stone lap wheel at speeds on the order of 300 RPM.

Inventors: HUNTER CHARLES ERIC, VERBIEST DIRK, HUNTER, CHARLES, ERIC, VERBIEST, DIRK
Applicants: C3 INC, C3, INC.
Application year: 1996
Main classification: C30B29
IPC codes: A44C17, C01B31, C01B33, C30B23, C30B29, C30B33