CN113862778A - Crucible assembly, crystal pulling furnace and method for pulling monocrystalline silicon rod - Google Patents

Crucible assembly, crystal pulling furnace and method for pulling monocrystalline silicon rod Download PDF

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Publication number
CN113862778A
CN113862778A CN202111165772.7A CN202111165772A CN113862778A CN 113862778 A CN113862778 A CN 113862778A CN 202111165772 A CN202111165772 A CN 202111165772A CN 113862778 A CN113862778 A CN 113862778A
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CN
China
Prior art keywords
melt
crucible assembly
quartz
single crystal
pulling
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Pending
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CN202111165772.7A
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Chinese (zh)
Inventor
衡鹏
张婉婉
李阳
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Xian Eswin Material Technology Co Ltd
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Xian Eswin Material Technology Co Ltd
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Priority to CN202111165772.7A priority Critical patent/CN113862778A/en
Publication of CN113862778A publication Critical patent/CN113862778A/en
Priority to TW111133820A priority patent/TWI808884B/en
Priority to PCT/CN2022/120214 priority patent/WO2023051349A1/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10Crucibles or containers for supporting the melt
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/02Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
    • C30B15/04Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt adding doping materials, e.g. for n-p-junction
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02Elements
    • C30B29/06Silicon

Abstract

The embodiment of the invention discloses a crucible assembly, which comprises: a quartz carrier section for carrying the melt; a quartz substrate portion located outside the quartz carrier portion; and a layer of silicon material located between the quartz substrate portion and the quartz carrier portion, wherein the quartz carrier portion is configured to be fully meltable in the melt during a pulling process of the single crystal silicon rod, and the layer of silicon material has a thickness configured to be at least partially meltable into the melt during the pulling process of the single crystal silicon rod. The silicon material layer of the crucible assembly provided by the embodiment of the invention can be dissolved into the melt, so that the nitrogen concentration in the melt is diluted, and the nitrogen concentration in the pulled silicon single crystal rod tends to be uniform in the axial direction.

Description

Crucible assembly, crystal pulling furnace and method for pulling monocrystalline silicon rod
Technical Field
The invention relates to the field of semiconductor silicon wafer production, in particular to a crucible assembly, a crystal pulling furnace and a method for pulling a single crystal silicon rod.
Background
In the prior art, it is very advantageous to provide a silicon wafer of the type: the silicon wafer has a crystal Defect free Zone (DZ) extending from a front surface, which refers to a surface of the silicon wafer where electronic components are to be formed, into a body and a Zone containing Bulk Micro Defects (BMDs) adjacent to the DZ and further extending into the body. The DZ is important because in order to form an electronic component on a silicon wafer, it is required that no crystal defect exists in the formation region of the electronic component, otherwise, a circuit break or other failure occurs, and the formation of the electronic component in the DZ can avoid the influence of the crystal defect; the BMD has an Intrinsic Gettering (IG) effect on metal impurities, so that the metal impurities in the silicon wafer are kept away from the DZ, thereby preventing adverse effects such as an increase in leakage current and a decrease in film quality of a gate oxide film due to the metal impurities.
In the production of the above-described silicon wafer having a BMD region, it is very advantageous to dope the silicon wafer with nitrogen. For example, in the case where a silicon wafer is doped with nitrogen, the formation of BMDs having nitrogen as a core can be promoted, thereby making the BMDs reach a certain density, making the BMDs effectively function as a metal gettering source, and also making the density distribution of the BMDs favorably influenced, for example, by making the distribution of the BMD density more uniform in the radial direction of the silicon wafer, for example, by making the BMD density higher in a region near the DZ and gradually lower toward the inside of the silicon wafer.
It is noteworthy that the nitrogen concentration in the current nitrogen-doped single crystal silicon rod is not uniform in the axial direction of the entire single crystal silicon rod, but is high with a low head content and a high tail content, which results from the fact that: the segregation coefficient of nitrogen is much less than 1 (about 7X 10)-4) Thus, nitrogen atoms tend to remain in the melt rather than in the single crystal silicon rod, which, as the pulling process continues, decreases, which increases the nitrogen concentration in the melt, resulting in an axis through the single crystal silicon rodThe nitrogen concentration is gradually increased in the upward direction. Non-uniformity of nitrogen concentration in the single crystal silicon rod affects the uniformity of oxygen precipitates or what are known as Bulk Micro Defects (BMDs) in the silicon wafer during subsequent processing.
Disclosure of Invention
In order to solve the above technical problems, embodiments of the present invention are directed to providing a crucible assembly for use in manufacturing a nitrogen-doped single crystal silicon rod using the czochralski method, which solves the problem of non-uniform nitrogen concentration in the nitrogen-doped single crystal silicon rod, and enables effective control of the density distribution of BMDs in a silicon wafer, thereby exerting a good gettering effect.
The technical scheme of the invention is realized as follows:
in a first aspect, embodiments of the present invention provide a crucible assembly, including:
a quartz carrier section for carrying the melt;
a quartz substrate portion located outside the quartz carrier portion; and
a layer of silicon material between the quartz substrate portion and the quartz carrier portion,
wherein the quartz carrier part is arranged to be completely melted in the melt during the pulling process of the single crystal silicon rod, and the thickness of the layer of silicon material is arranged to be at least partially melted into the melt during the pulling process of the single crystal silicon rod.
In a second aspect, embodiments of the present invention provide a crystal pulling furnace comprising a crucible assembly according to the first aspect.
In a third aspect, embodiments of the present invention provide a method for pulling a single crystal silicon rod, the method including:
placing a high purity polycrystalline silicon feedstock into a crucible assembly according to the first aspect, wherein the polycrystalline silicon feedstock is in contact with a quartz carrier;
heating the crucible assembly by a graphite heater to melt the polycrystalline silicon raw material into a melt;
the quartz bearing part of the crucible assembly is melted into the melt along with the process of pulling the monocrystalline silicon rod;
when the quartz carrier part is melted, the silicon material layer is at least partially melted into the melt.
Embodiments of the present invention provide a crucible assembly, a crystal pulling furnace, and a method of pulling a single crystal silicon rod, wherein the crucible assembly includes a silicon material layer between a quartz base portion and a quartz bearing portion, and when a pulling process of the single crystal silicon rod starts, the quartz bearing portion starts to melt into a melt until being completely melted, so that the silicon material layer can come into contact with the melt and undergo a reaction in which the silicon material layer gradually melts into the melt, which dilutes a nitrogen concentration in the melt, thereby making the nitrogen concentration in the pulled single crystal silicon rod uniform in an axial direction.
Drawings
FIG. 1 is a schematic view of a conventional crystal pulling furnace;
FIG. 2 is another schematic view of the conventional crystal pulling furnace of FIG. 1;
FIG. 3 is a schematic view of a crucible assembly according to an embodiment of the present invention;
FIG. 4 is a schematic view of the crucible assembly of FIG. 3 in another state;
FIG. 5 is a schematic view of the crucible assembly of FIG. 3 in another state;
FIG. 6 is a schematic view of the crucible assembly of FIG. 3 in another state;
FIG. 7 is a graph showing the relationship between the concentration of nitrogen within a single crystal silicon rod and the length of the single crystal silicon rod in a nitrogen-doped single crystal silicon rod pulled using a conventional crucible and a nitrogen-doped single crystal silicon rod pulled using a crucible assembly provided by an embodiment of the present invention;
FIG. 8 is a schematic view of a crystal pulling furnace according to an embodiment of the present invention; and
fig. 9 is a flow chart of a method of pulling a single crystal silicon rod according to an embodiment of the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Referring to fig. 1 and 2, one implementation of a conventional crystal pulling furnace is shown. As shown in fig. 1, the crystal pulling furnace 1 includes: a furnace chamber enclosed by the housing 2, a quartz crucible 10 disposed in the furnace chamber, a graphite heater 20, a crucible rotating mechanism 30, and a crucible carrying device 40. The quartz crucible 10 is carried by a crucible carrying device 40, and a crucible rotating mechanism 30 is located below the crucible carrying device 40 for driving the quartz crucible 10 to rotate about its axis in the direction R.
When the crystal pulling furnace 1 is used to pull a single crystal silicon rod, first, a high purity polycrystalline silicon raw material is put into the quartz crucible 10, and the quartz crucible 10 is continuously heated by the graphite heater 20 while the crucible rotating mechanism 40 drives the quartz crucible 10 to rotate in the direction R to melt the polycrystalline silicon raw material contained in the quartz crucible 10 into a molten state, i.e., into a melt S2, wherein the heating temperature is maintained at about one thousand or more degrees celsius, and the gas in the furnace is usually an inert gas to melt the polycrystalline silicon without causing an unnecessary chemical reaction. When the liquid surface temperature of the melt S2 is controlled at the critical point of crystallization by controlling the thermal field provided by the graphite heater 20, the melt S2 grows in the crystal orientation of the single crystal seed crystal S1 as the single crystal seed crystal S1 is raised by pulling the single crystal seed crystal S1 located above the liquid surface upward in the direction T from the liquid surface, growing the single crystal silicon rod S3.
As the crystal pulling process progresses, the melt S2 gradually decreases. As shown in FIG. 2, when the single crystal silicon rod S3 is completely separated from the melt S2 at the end of the pulling process, only a small amount of the melt S2 remains in the quartz crucible 10. As the melt S2 gradually decreases during the crystal pulling process, the concentration of nitrogen in the melt S2 gradually increases, which results in a non-uniform nitrogen content in the single crystal silicon rod S3, which may be the case at a low end.
In order to make the nitrogen content in the single crystal silicon rod S3 uniform, embodiments of the present invention propose a crucible assembly. Referring to fig. 3 to 6, there are shown schematic views of a crucible assembly provided by an embodiment of the present invention in different states. Specifically, referring to fig. 3, an embodiment of the present invention provides a crucible assembly 10' comprising:
a quartz carrier part IE for carrying melt S2;
a quartz base portion DE located outside the quartz carrier portion IE; and
a layer SE of silicon material between said quartz base part DE and said quartz carrier part IE,
wherein the quartz carrier part IE is provided so as to be completely meltable in the melt S2 during the drawing process of the rod S3 of monocrystalline silicon and the layer SE of silicon material is provided with a thickness such as to be at least partially meltable into the melt S2 during the drawing process of the rod S3 of monocrystalline silicon.
Since the crucible assembly provided by the embodiment of the invention includes the silicon material layer between the quartz base portion and the quartz bearing portion, when the pulling process of the single crystal silicon rod is started, the quartz bearing portion starts to be melted into the melt until being completely melted, so that the silicon material layer can be brought into contact with the melt and undergo a reaction in which the silicon material layer is gradually melted into the melt, which dilutes the nitrogen concentration in the melt, thereby making the nitrogen concentration in the pulled single crystal silicon rod tend to be uniform in the axial direction.
For the arrangement of the quartz bearing part, preferably, referring to fig. 3, the thickness of the quartz bearing part IE gradually decreases in the direction from the mouth OP of the crucible assembly to the bottom BO of the crucible assembly. Thus, as the pulling process of the single crystal silicon rod S3 continues, the quartz bearing portion IE tends to be completely melted to enable the layer of silicon material to come into contact with the melt.
For the arrangement of the layer of silicon material, preferably, the thickness of the layer of silicon material gradually increases in the direction from the mouth OP of the crucible assembly to the bottom BO of the crucible assembly, see fig. 3. Thus, as the pulling process of the single crystal silicon rod continues, particularly in the middle and late stages of the pulling process, once the layer of silicon material comes into contact with the melt, a large amount of silicon will be dissolved in the melt, thereby acting to dilute the melt and reduce the nitrogen concentration in the melt present.
For the structure of the quartz bearing part, the quartz substrate part and the silicon material layer, preferably, the quartz bearing part and the quartz substrate part form a closed cavity, and the silicon material layer is filled in the cavity.
In the process of pulling the single crystal silicon rod by using the crucible assembly provided by the embodiment of the invention, the state of the silicon material layer can be changed, preferably, the state of the silicon material layer is in a first time period in the pulling process of the single crystal silicon rod, the silicon material layer is in a solid state, and preferably, the silicon material layer is in a liquid state in a second time period in the pulling process of the single crystal silicon rod, wherein the second time period is later than the first time period.
With reference to fig. 3 to 6, it can be seen that the crucible assembly provided by a preferred embodiment of the present invention has a change in the internal structure during use, and specifically, in the state shown in fig. 3, the pulling process of the nitrogen-doped single crystal silicon rod is just started, the amount of the melt S2 is large and only contacts with the quartz bearing portion IE; as the pulling process of the single crystal silicon rod S3 continues, as shown in fig. 4, a portion of the melt S2 has been transformed into a single crystal silicon rod, so that the level of the melt S2 falls, and at the same time, the quartz bearing portion IE gradually melts in the melt S2 and thus the wall thickness becomes thinner; when the pulling progress of the single crystal silicon rod S3 reached the state shown in fig. 5, the liquid level of the melt S2 had further dropped and the quartz bearing portion IE had completely melted, and the layer SE of silicon material was in direct contact with the melt S2 and started to gradually melt into the melt S2 to dilute the nitrogen concentration in the melt S2; at the final stage of the pulling process of the single crystal silicon rod S3, as shown in fig. 6, the remaining amount of the melt S2 has been small, and the layer SE of silicon material continues to melt to further dilute the nitrogen concentration in the melt S2.
In comparison with a conventional quartz crucible, the nitrogen-doped single crystal silicon rod pulled using the quartz crucible provided by the embodiment of the present invention has a more uniform nitrogen concentration in the axial direction, and specifically, see fig. 7, which shows a graph of the relationship between the nitrogen concentration in the single crystal silicon rod and the length of the single crystal silicon rod in the nitrogen-doped single crystal silicon rod pulled using the crucible assembly provided by the embodiment of the present invention, wherein the solid line represents the case in the single crystal silicon rod pulled using the conventional crucible, and the dotted line represents the case in the single crystal silicon rod pulled using the crucible assembly provided by the embodiment of the present invention. As can be seen by comparison, the nitrogen concentration in the single crystal silicon rod pulled out in the conventional crucible was significantly increased in the length direction of the single crystal silicon rod. However, the nitrogen concentration in the nitrogen-doped single crystal silicon rod pulled by using the crucible assembly provided by the embodiment of the invention has a small increase in the length direction of the single crystal silicon rod, that is, the nitrogen concentration in the axial direction of the single crystal silicon rod is uniform.
Referring to fig. 8, embodiments of the present invention also provide a crystal pulling furnace including a crucible assembly according to embodiments of the present invention.
Referring to fig. 9, an embodiment of the present invention further provides a method for pulling a single crystal silicon rod, where the method includes:
placing a high purity polycrystalline silicon feedstock into a crucible assembly according to an embodiment of the invention, wherein the polycrystalline silicon feedstock is in contact with a quartz carrier;
heating the crucible assembly by a graphite heater to melt the polycrystalline silicon raw material into a melt;
the quartz bearing part of the crucible assembly is melted into the melt along with the process of pulling the monocrystalline silicon rod;
when the quartz carrier part is melted, the silicon material layer is at least partially melted into the melt.
It should be noted that: the technical schemes described in the embodiments of the present invention can be combined arbitrarily without conflict.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (8)

1. A crucible assembly, comprising:
a quartz carrier section for carrying the melt;
a quartz substrate portion located outside the quartz carrier portion; and
a layer of silicon material between the quartz substrate portion and the quartz carrier portion,
wherein the quartz carrier part is arranged to be completely melted in the melt during the pulling process of the single crystal silicon rod, and the thickness of the layer of silicon material is arranged to be at least partially melted into the melt during the pulling process of the single crystal silicon rod.
2. The crucible assembly of claim 1, wherein the thickness of the quartz carrier section gradually decreases in a direction from the mouth of the crucible assembly to the bottom of the crucible assembly.
3. The crucible assembly of claim 2, wherein the layer of silicon material gradually increases in thickness in a direction from the mouth of the crucible assembly to the bottom of the crucible assembly.
4. The crucible assembly of claim 3, wherein the quartz carrier portion and the quartz base portion form an enclosed cavity, the layer of silicon material filling the cavity.
5. The crucible assembly of any one of claims 1-4, wherein the layer of silicon material is in a solid state for a first period of time during a pulling process of a single crystal silicon rod.
6. The crucible assembly of claim 5, wherein the layer of silicon material is in a liquid state during a second period of time of a pulling process of the single crystal silicon rod, wherein the second period of time is later than the first period of time.
7. A crystal pulling furnace, comprising the crucible assembly of claim 1.
8. A method of pulling a single crystal silicon rod, the method comprising:
placing a high purity polycrystalline silicon feedstock into the crucible assembly of any of claims 1 to 6, wherein the polycrystalline silicon feedstock is in contact with a quartz carrier;
heating the crucible assembly by a graphite heater to melt the polycrystalline silicon raw material into a melt;
the quartz bearing part of the crucible assembly is melted into the melt along with the process of pulling the monocrystalline silicon rod;
when the quartz carrier part is melted, the silicon material layer is at least partially melted into the melt.
CN202111165772.7A 2021-09-30 2021-09-30 Crucible assembly, crystal pulling furnace and method for pulling monocrystalline silicon rod Pending CN113862778A (en)

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CN202111165772.7A CN113862778A (en) 2021-09-30 2021-09-30 Crucible assembly, crystal pulling furnace and method for pulling monocrystalline silicon rod
TW111133820A TWI808884B (en) 2021-09-30 2022-09-07 Crucible element, crystal pulling furnace and method for pulling single crystal silicon rod
PCT/CN2022/120214 WO2023051349A1 (en) 2021-09-30 2022-09-21 Crucible assembly, crystal pulling furnace, and method for drawing single crystal silicon rod

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CN202111165772.7A CN113862778A (en) 2021-09-30 2021-09-30 Crucible assembly, crystal pulling furnace and method for pulling monocrystalline silicon rod

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Cited By (2)

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CN114959880A (en) * 2022-05-27 2022-08-30 西安奕斯伟材料科技有限公司 Quartz crucible, crucible assembly and crystal pulling furnace for producing single crystal silicon rods
WO2023051349A1 (en) * 2021-09-30 2023-04-06 西安奕斯伟材料科技有限公司 Crucible assembly, crystal pulling furnace, and method for drawing single crystal silicon rod

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WO2023051349A1 (en) * 2021-09-30 2023-04-06 西安奕斯伟材料科技有限公司 Crucible assembly, crystal pulling furnace, and method for drawing single crystal silicon rod
CN114959880A (en) * 2022-05-27 2022-08-30 西安奕斯伟材料科技有限公司 Quartz crucible, crucible assembly and crystal pulling furnace for producing single crystal silicon rods
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Address after: Room 1-3-029, No. 1888, Xifeng South Road, high tech Zone, Xi'an, Shaanxi 710065

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Address before: 710065 room 1-3-029, No. 1888, Xifeng South Road, high tech Zone, Xi'an City, Shaanxi Province

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