# US 2019/0316271 A1 · Quartz glass crucible and manufacturing method thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0316271 A1 - Document ID: US20190316271A1 - Status: Published application - Kind: A1 - Application number: 16/308,789 - Filed: 2017-08-17 - Published: 2019-10-17 - Earliest claimed: 2016-09-13 - Assignees: Sumco Corporation - Applicants: Sumco Corporation - Inventors: Hiroshi KISHI; Masanori FUKUI - Web page: https://patentgrep.com/patent/US20190316271A1 ## CPC - C30B 15/10: Crucibles or containers for supporting the melt - C03B 19/095: {by centrifuging, e.g. arc discharge in rotating mould (crucibles for crystal pulling in general C30B15/10, C30B35/002)} - C03B 20/00: Processes specially adapted for the production of quartz or fused silica articles {, not otherwise provided for (C03B19/01, C03B19/066, C03B19/106, C03B19/12, C03B19/14, C03B37/00 take precedence)} - C30B 29/06: Silicon - C03B 2201/32: doped with aluminium (C03B2201/36 takes precedence) - C30B: SINGLE-CRYSTAL GROWTH (by using ultra-high pressure, e.g. for the formation of diamonds, B01J3/06); UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL (zone-refining of metals or alloys C22B); PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (casting of metals, casting of other substances by the same processes or devices B22D; working of plastics B29; modifying the physical structure of metals or alloys C21D, C22F); SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (for producing semiconductor devices or parts thereof H10); APPARATUS THEREFOR - C03B: MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES ## Abstract In an exemplary embodiment, a quartz glass crucible 1 includes: a high-aluminum-content layer 14B which is made of quartz glass having a relatively high average aluminum concentration and is provided to form an outer surface 10b of the quartz glass crucible 1; and a low-aluminum-content layer 14A which is made of quartz glass having a lower average aluminum concentration than that of the high-aluminum-content layer 14B and is provided on an inner side of the high-aluminum-content layer 14B, wherein the low-aluminum-content layer 14A includes an opaque layer 11 made of quartz glass containing a large number of minute bubbles, and the high-aluminum-content layer 14B is made of transparent or translucent quartz glass having a lower bubble content than that of the opaque layer 11. The quartz glass crucible is capable of withstanding a single crystal pull-up step undertaken for a very long period of time. ## Claims ### Claim 1 A quartz glass crucible for pulling up a silicon single crystal, comprising: a high-aluminum-content layer which is made of quartz glass having a relatively high average aluminum concentration and is provided to form an outer surface of the quartz glass crucible; and a low-aluminum-content layer which is made of quartz glass having a lower average aluminum concentration than that in the high-aluminum-content layer and is provided on an inner side of the high-aluminum-content layer, wherein the low-aluminum-content layer includes an opaque layer made of quartz glass containing a large number of minute bubbles, and the high-aluminum-content layer is made of transparent or translucent quartz glass having a lower bubble content than does the opaque layer. ### Claim 2 (depends on 1) The quartz glass crucible according to claim 1, further comprising: an inner transparent layer which is provided on an inner side of the opaque layer to form an inner surface of the quartz glass crucible and contains substantially no bubbles; and an outer transparent layer which is provided on an outer side of the opaque layer to form an outer surface of the quartz glass crucible and contains substantially no bubbles, wherein a thickness of the high-aluminum-content layer is thinner than that of the outer transparent layer. ### Claim 3 (depends on 1) The quartz glass crucible according to claim 1, further comprising: a cylindrical straight body portion; a curved bottom portion; and a corner portion which connects the straight body portion to the bottom portion, wherein the high-aluminum-content layer is provided in at least the straight body portion. ### Claim 4 (depends on 1) The quartz glass crucible according to claim 1, wherein the average aluminum concentration in the high-aluminum-content layer is 20 ppm or more, and an average aluminum concentration in the low-aluminum-content layer is less than 20 ppm. ### Claim 5 (depends on 1) The quartz glass crucible according to claim 1, wherein a bubble content in the outer transparent layer is 2.1% or less. ### Claim 6 (depends on 1) The quartz glass crucible according to claim 1, wherein an aluminum concentration distribution in the high-aluminum-content layer is microscopically unevenly distributed. ### Claim 7 (depends on 6) The quartz glass crucible according to claim 6, wherein a part with a high aluminum concentration is present in a mesh form within a region of 1 mm3 in the high-aluminum-content layer. ### Claim 8 (depends on 7) The quartz glass crucible according to claim 7, wherein a high-aluminum-concentration region having an aluminum concentration of 60 ppm or more and a low-aluminum-concentration region having an aluminum concentration of less than 25 ppm coexist within a region of 1 mm2. ### Claim 9 (depends on 8) The quartz glass crucible according to claim 8, wherein an aluminum concentration gradient in a vicinity of a boundary between the high concentration region and the low concentration region is 1 ppm/μm or more and 100 ppm/μm or less. ### Claim 10 (depends on 1) The quartz glass crucible according to claim 1, wherein an average concentration of each of carbon and sulfur in the high-aluminum-content layer is 5 ppm or less. ### Claim 11 (depends on 10) The quartz glass crucible according to claim 10, wherein the bubble content in the high-aluminum-content layer is less than 0.5%. ### Claim 12 A manufacturing method of a quartz glass crucible according to a rotating mold method, the manufacturing method comprising: a step of forming a deposition layer of raw material quartz powder by depositing aluminum-added quartz powder and natural quartz powder in this order on an inner surface of a rotating mold; and a step of subjecting the deposition layer of the raw material quartz powder to arc melting from an inner side of the mold, wherein the step of subjecting the deposition layer of the raw material quartz powder to the arc melting includes a step of forming an inner transparent layer made of quartz glass with substantially no bubbles contained therein by strengthening a degree of decompression through a large number of vent holes provided in the inner surface of the mold at the time of start of the arc melting, a step of forming an opaque layer made of quartz glass containing a large number of minute bubbles by weakening the degree of decompression after forming the inner transparent layer, and a step of forming an outer transparent layer made of quartz glass with substantially no bubbles contained therein by strengthening the degree of decompression again after forming the opaque layer, and in the step of forming the outer transparent layer, the high-aluminum-content layer is formed by melting the aluminum-added quartz powder, and a timing at which the degree of decompression is strengthened again is controlled to form the outer transparent layer so as to cause a thickness of the outer transparent layer to be thicker than that of the high-aluminum-content layer. ### Claim 13 (depends on 12) The manufacturing method of a quartz glass crucible according to claim 12, wherein a thickness of the high-aluminum-content layer is 200 μm or more. ### Claim 14 (depends on 12) The manufacturing method of a quartz glass crucible according to claim 12, wherein an average particle size of the aluminum-added quartz powder is 100 to 400 μm, an aluminum concentration of an top surface of the aluminum-added quartz powder is 60 ppm or more, and an aluminum concentration of a center portion of the aluminum-added quartz powder is less than 25 ppm. ### Claim 15 (depends on 14) The manufacturing method of a quartz glass crucible according to claim 14, further comprising: a step of preparing the aluminum-added quartz powder before filling the mold with the aluminum-added quartz powder, wherein the step of preparing the aluminum-added quartz powder includes a fixing step of fixing aluminum to the natural quartz powder by mixing a solution containing an aluminum compound in the natural quartz powder and thereafter dehydrating and drying the mixture, and a first heat treatment step of allowing the aluminum to penetrate into a surface layer portion of the natural quartz powder by heating the natural quartz powder to which the aluminum is fixed at a temperature of 1000° C. or higher and 1200° C. or lower, at which temperature the natural quartz powder is not sintered. ### Claim 16 (depends on 15) The manufacturing method of a quartz glass crucible according to claim 15, wherein a heating time in the first heat treatment step is two hours or longer and 20 hours or shorter. ### Claim 17 (depends on 15) The manufacturing method of a quartz glass crucible according to claim 15, wherein an aluminum concentration distribution in the high-aluminum-content layer of the quartz glass crucible is measured by secondary ion mass spectrometry, and on the basis of measurement results of the aluminum concentration distribution, a concentration of the solution containing the aluminum compound used for manufacturing a subsequent quartz glass crucible, or a heat treatment time or a heat treatment temperature for the aluminum-added quartz powder is adjusted. ### Claim 18 (depends on 12) The manufacturing method of a quartz glass crucible according to claim 12, further comprising: a step of removing impurities derived from carbon and sulfur adhered to the aluminum-added quartz powder and other manufacturing processes before filling the mold with the aluminum-added quartz powder. ### Claim 19 (depends on 18) The manufacturing method of a quartz glass crucible according to claim 18, wherein the step of removing the impurities includes a second heat treatment step of heating the aluminum-added quartz powder in a chamber in an air atmosphere at normal pressure at 1000° C. or higher and 1200° C. or lower, a first holding step of evacuating an inside of the chamber and holding the aluminum-added quartz powder in a vacuum for a predetermined time, and a second holding step of changing the inside of the chamber to a helium atmosphere at normal pressure and holding the aluminum-added quartz powder in the helium atmosphere at normal pressure for a predetermined time. ### Claim 20 (depends on 19) The manufacturing method of a quartz glass crucible according to claim 19, wherein a heating time in the second heat treatment step is two hours or longer and 20 hours or shorter.