CN110029395A - CCZ continuous crystal-pulling crucible and coating process - Google Patents

CCZ continuous crystal-pulling crucible and coating process Download PDF

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Publication number
CN110029395A
CN110029395A CN201910312944.5A CN201910312944A CN110029395A CN 110029395 A CN110029395 A CN 110029395A CN 201910312944 A CN201910312944 A CN 201910312944A CN 110029395 A CN110029395 A CN 110029395A
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China
Prior art keywords
crucible
ccz
pulling
inner ring
continuous crystal
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Pending
Application number
CN201910312944.5A
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Chinese (zh)
Inventor
李德建
王会敏
何京辉
王东
颜超
路鹏
刘钦
李增卫
何志国
陈阳
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Gtat Intellectual Property Co Ltd
Xingtai Jinglong Electronic Material Co Ltd
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Gtat Intellectual Property Co Ltd
Xingtai Jinglong Electronic Material Co Ltd
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Application filed by Gtat Intellectual Property Co Ltd, Xingtai Jinglong Electronic Material Co Ltd filed Critical Gtat Intellectual Property Co Ltd
Priority to CN201910312944.5A priority Critical patent/CN110029395A/en
Publication of CN110029395A publication Critical patent/CN110029395A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5007Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing
    • C04B41/501Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing containing carbon in the anion, e.g. carbonates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
    • 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
    • C30B15/002Continuous growth
    • 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
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02Elements
    • C30B29/06Silicon

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The present invention provides a kind of CCZ continuous crystal-pulling crucible and coating processes, belong to semiconductor material preparation technical field, including outer crucible and crucible inner ring, outer crucible is for accommodating silicon material to be melted;Crucible inner ring is set in outer crucible, lower end offsets with outer crucible inner wall, its internal growing space formed for crystal growth, forms the charging space for accommodating silicon material between outside and outer crucible, crucible inner ring is equipped with the material hole for entering growing space for the silicon material of melting.CCZ continuous crystal-pulling crucible provided by the invention and coating process are able to extend pot life, improve monocrystalline silicon quality.

Description

CCZ continuous crystal-pulling crucible and coating process
Technical field
The invention belongs to technical field of semiconductor material preparation, are to be related to a kind of CCZ continuous crystal-pulling earthenware more specifically The coating process of crucible and the crucible.
Background technique
Currently, monocrystalline pull-rod technology is from multiple charging crystal pulling (RCZ) to continuous crystal-pulling (CCZ) transition.CCZ can have Effect reduces time, crucible cost and the energy consumption of monocrystalline pull-rod, and CCZ output crystal bar resistivity is more uniform, distribution is narrower, Quality is higher.The silica crucible for the high-quality that CCZ also needs the service life to reach 500 hours, and existing vertical pulling method crucible and more The service life and quality of the crucible of secondary charging crystal pulling are not able to satisfy the demand of continuous crystal-pulling, it is therefore desirable to crucible into Row is further to be improved.
Summary of the invention
The purpose of the present invention is to provide a kind of CCZ continuous crystal-pulling crucible, with solve existing crucible life it is short, cannot be very The technical problems such as continuous crystal-pulling technology, monocrystalline silicon is of poor quality are adapted to well.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of CCZ continuous crystal-pulling crucible is provided, comprising:
Outer crucible, for accommodating silicon material to be melted;
Crucible inner ring is set in the outer crucible, and lower end offsets with the outer crucible inner wall, and internal formed is used for The growing space of crystal growth forms the charging space for accommodating silicon material, the crucible between outside and the outer crucible Inner ring is equipped with the material hole for entering the growing space for the silicon material of melting.
Further, the bottom of the outer crucible is recessed arcwall face, the lower end of the crucible inner ring and the arc Face offsets, and the crucible inner ring and the outer crucible are coaxial.
Further, the radian of the arcwall face is R100-R500.
Further, the bottom of the outer crucible and the intersection of its side wall are arc transiting surface.
Further, the radian of the arc transiting surface is R80-R150.
Further, the outer crucible with a thickness of 10mm-15mm, the thickness of the crucible inner ring 8mm-15mm it Between.
Further, the height of the crucible inner ring is lower than the height of the outer crucible, difference in height 5mm-15mm.
Further, the inner wall of the outer crucible and the inside and outside wall of the crucible inner ring are evenly coated with coating respectively.
Further, the material of the coating is barium element, or including at least the compound of barium element, crucible surface Coating amount is 2g/ ㎡ -10g/ ㎡.
Another object of the present invention is to provide a kind of coating processes of crucible, comprising:
Cleaning, cleans crucible, carries out configuration cleaning solution using hydrofluoric acid and nitric acid, proportion 1:5 to 2:1 it Between;
Drying, dries the crucible after cleaning;
Spraying carries out coating to crucible surface using chemical agent, and the chemical agent is barium element, or is at least wrapped The compound of baric element, coating crucible surface amount are 2g/ ㎡ -10g/ ㎡.
The beneficial effect of CCZ continuous crystal-pulling crucible provided by the invention is: compared with prior art, CCZ of the present invention connects Continuous crystal pulling crucible, has outer crucible and crucible inner ring, is charging space between outer crucible and crucible inner ring, is in crucible inner ring Crystal growth space, silicon material melt in charging space, enter in crucible inner ring through the material hole in crucible inner ring, carry out crystal Growth, melt and crystal pulling carry out simultaneously, and charging space and growing space separate, and it is empty that the silicon material being just added will not enter growth Between, thus the growing space melt of crystal uniformly, temperature, can make that resistivity is more uniform, distribution is more concentrated Crystal bar;Also it can reduce and avoid the impurity in melt to enter growing space, reduce the defect of monocrystalline silicon, improve monocrystalline silicon Quality, therefore have both that minority carrier life time is high, dislocation density is low and the advantages such as inexpensive.
Meanwhile coating plays the role of extension to the CCZ continuous crystal-pulling service life, reasonable quantity for spray can extend crucible in high temperature Time during crystal pulling, extend pot life to greatest extent.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, embodiment or the prior art will be retouched below Attached drawing needed in stating is briefly described, it should be apparent that, the accompanying drawings in the following description is only of the invention one A little embodiments for those of ordinary skill in the art without creative efforts, can also be according to this A little attached drawings obtain other attached drawings.
Fig. 1 is the structural schematic diagram of crucible provided in an embodiment of the present invention.
Wherein, marked in the figure:
1- outer crucible;2- crucible inner ring;3- material hole;The growing space 4-;5- charging space.
Specific embodiment
In order to which technical problems, technical solutions and advantages to be solved are more clearly understood, tie below Accompanying drawings and embodiments are closed, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only Only to explain the present invention, it is not intended to limit the present invention.
Referring to Fig. 1, existing be illustrated CCZ continuous crystal-pulling crucible provided by the invention.The CCZ continuous crystal-pulling earthenware Crucible, including outer crucible 1 and crucible inner ring 2, outer crucible 1 is for accommodating silicon material to be melted;Crucible inner ring 2 is set to outer crucible 1 Interior, lower end offsets with 1 inner wall of outer crucible, internal to form the growing space 4 for being used for crystal growth, it is external with outer crucible 1 it Between form the charging space 5 for accommodating silicon material, crucible inner ring 2, which is equipped with, enters the logical of growing space 4 for the silicon material of melting Expect hole 3.
CCZ continuous crystal-pulling crucible provided by the invention, compared with prior art, the space 5 that feeds is in outer crucible 1 and crucible It is crystal growth space 4 in crucible inner ring 2, silicon material melts in charging space 5, through the logical material in crucible inner ring 2 between inner ring 2 Hole 3 enters in crucible inner ring 2, carries out crystal growth, and melt and crystal pulling carry out simultaneously, and charging space 5 and growing space 4 every It opens, the silicon material being just added will not enter growing space 4, therefore 4 melt of growing space of crystal is uniform, temperature, can make Make that resistivity is more uniform, the crystal bar more concentrated of distribution;Also it can reduce and avoid the impurity in melt to enter growing space 4, the defect of monocrystalline silicon is reduced, the quality of monocrystalline silicon is improved, therefore has both that minority carrier life time is high, dislocation density is low and inexpensive etc. Advantage.
Wherein, the charging space 5 between outer crucible 1 and crucible inner ring 2, which can satisfy, holds wanting for 50-200kg silicon material It asks.
Wherein, to avoid the impurity in melt from entering growing space 4, material hole 3 is provided with the lower end of crucible inner ring 2, this Sample makes melt enter growing space 4 from bottom, conducive to the temperature and purity for keeping melt.Wherein, the shape of material hole 3 can be with For circle, ellipse, regular polygon etc., the quantity of material hole 3 can be one, two, three etc., and multiple material holes 3 are in earthenware The lower end of crucible inner ring 2 is simultaneously circumferentially uniformly distributed.
Referring to Fig. 1, a kind of specific embodiment as CCZ continuous crystal-pulling crucible provided by the invention, outer crucible 1 Bottom be recessed arcwall face, lower end and the arcwall face of crucible inner ring 2 offset, and crucible inner ring 2 and outer crucible 1 are coaxial.
Referring to Fig. 1, a kind of specific embodiment as CCZ continuous crystal-pulling crucible provided by the invention, the arc The radian in face is R100-R500.For example, radian can be the numerical value such as 120,130,200,300,400, namely 100 to 500 Between any value, no longer enumerated here.
Refering to fig. 1, a kind of specific embodiment as CCZ continuous crystal-pulling crucible provided by the invention, the outer crucible 1 bottom and the intersection of its side wall are arc transiting surface.
Referring to Fig. 1, a kind of specific embodiment as CCZ continuous crystal-pulling crucible provided by the invention, the arc The radian of transition face is R80-R150.Radian is chosen as any between 90,100,110,120,140 etc. namely 80 to 150 Numerical value.Among the above, the design of 1 bottom radian of outer crucible, 1 bottom and side wall intersection radian of outer crucible, it is therefore an objective to reduce solid Silicon material washes away crucible, extends the service life of crucible.
Referring to Fig. 1, a kind of specific embodiment as CCZ continuous crystal-pulling crucible provided by the invention, outer crucible 1 With a thickness of 10mm-15mm.For example, with a thickness of 11mm, 12mm, 13mm, 14mm etc..The thickness of crucible inner ring is in 8mm-15mm Between.
Referring to Fig. 1, a kind of specific embodiment as CCZ continuous crystal-pulling crucible provided by the invention, crucible inner ring 2 height is lower than the height of outer crucible 1, difference in height 5mm-15mm.
Referring to Fig. 1, a kind of specific embodiment as CCZ continuous crystal-pulling crucible provided by the invention, outer crucible 1 Inner wall and crucible inner ring inside and outside wall respectively uniformly be coated with coating.Crucible coating layer is uniform, and stable quantity for spray connects CCZ The continuous crystal pulling service life plays the role of extension, and reasonable quantity for spray can extend crucible and use time, maximum during high temperature crystal pulling Limit extends pot life, can meet crucible using the time in 250h or more.
Refering to fig. 1, a kind of specific embodiment as CCZ continuous crystal-pulling crucible provided by the invention, the coating Material is barium element, or including at least the compound of barium element, and purity reaches 99.999% or more.For example, compound is Barium carbonate and saturation barium hydroxide, coating crucible surface amount are 2g/ ㎡ -10g/ ㎡.
The present invention also provides a kind of coating processes of crucible, comprising:
Cleaning, cleans crucible, carries out configuration cleaning solution using hydrofluoric acid and nitric acid, proportion 1:5 to 2:1 it Between;
Drying, dries the crucible after cleaning;
Spraying carries out coating to crucible surface using chemical agent, and the chemical agent is barium element, or is at least wrapped The compound of baric element, coating crucible surface amount are 2g/ ㎡ -10g/ ㎡.
It is cleaned before coating, keeps the cleaning of crucible, prevent impurity from retaining inside crucible, crucible coating layer packet Control containing the quantity for spray to crucible chemical agent is kept uniformly, and quantity for spray is between 2g/ ㎡ -10g/ ㎡, stable spraying Amount plays the role of extension to the CCZ continuous crystal-pulling service life, and reasonable quantity for spray can extend crucible time during high temperature crystal pulling, Extend pot life 50h or more to greatest extent, crucible can be met using the time in 250h or more.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (10)

1.CCZ continuous crystal-pulling crucible characterized by comprising
Outer crucible, for accommodating silicon material to be melted;
Crucible inner ring is set in the outer crucible, and lower end offsets with the outer crucible inner wall, internal to be formed for crystal life Long growing space, it is external to form the charging space for accommodating silicon material between the outer crucible, in the crucible inner ring Enter the material hole of the growing space equipped with the silicon material for melting.
2. CCZ continuous crystal-pulling crucible as described in claim 1, which is characterized in that the bottom of the outer crucible is recessed arc Shape face, lower end and the arcwall face of the crucible inner ring offset, and the crucible inner ring and the outer crucible are coaxial.
3. CCZ continuous crystal-pulling crucible as claimed in claim 2, which is characterized in that the radian of the arcwall face is R100- R500。
4. CCZ continuous crystal-pulling crucible as claimed in claim 2, which is characterized in that the bottom of the outer crucible and its side wall Intersection is arc transiting surface.
5. CCZ continuous crystal-pulling crucible as claimed in claim 4, which is characterized in that the radian of the arc transiting surface is R80- R150。
6. CCZ continuous crystal-pulling crucible as described in claim 1, which is characterized in that the outer crucible with a thickness of 10mm- 15mm, the thickness of the crucible inner ring is between 8mm-15mm.
7. CCZ continuous crystal-pulling crucible as described in claim 1, which is characterized in that the height of the crucible inner ring is lower than described The height of outer crucible, difference in height 5mm-15mm.
8. CCZ continuous crystal-pulling crucible as described in claim 1, which is characterized in that the inner wall of the outer crucible and the crucible The inside and outside wall of inner ring is evenly coated with coating respectively.
9. CCZ continuous crystal-pulling crucible as claimed in claim 8, which is characterized in that the material of the coating is barium element, or Including at least the compound of barium element, coating crucible surface amount is 2g/ ㎡ -10g/ ㎡.
10. such as the coating process of the described in any item crucibles of claim 1-9 characterized by comprising
Cleaning, cleans crucible, carries out configuration cleaning solution using hydrofluoric acid and nitric acid, proportion is in 1:5 between 2:1;
Drying, dries the crucible after cleaning;
Spraying carries out coating to crucible surface using chemical agent, and the chemical agent is barium element, or includes at least barium member The compound of element, coating crucible surface amount are 2g/ ㎡ -10g/ ㎡.
CN201910312944.5A 2019-04-18 2019-04-18 CCZ continuous crystal-pulling crucible and coating process Pending CN110029395A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1065105A (en) * 1991-03-21 1992-10-07 北京有色金属研究总院 The double crucible that the preparation semiconductor monocrystal is used
CN1160779A (en) * 1996-01-12 1997-10-01 三菱麻铁里亚尔硅材料株式会社 Single crystal fulling apparatus
CN101855179A (en) * 2007-09-07 2010-10-06 莫门蒂夫性能材料股份有限公司 Quartz glass crucibles and the method for handling surface of quartz glass crucible
CN102363899A (en) * 2011-06-30 2012-02-29 常州天合光能有限公司 Quartz crucible used for continuous material charging
CN102995108A (en) * 2012-11-27 2013-03-27 无锡市蓝德光电科技有限公司 Continuous charging silicon single crystal furnace
CN103502513A (en) * 2012-01-13 2014-01-08 信越石英株式会社 Silica vessel for pulling monocrystalline silicon and method for producing same
CN104342750A (en) * 2013-08-08 2015-02-11 徐州协鑫太阳能材料有限公司 Quartz crucible and preparation method thereof
CN210104124U (en) * 2019-04-18 2020-02-21 邢台晶龙电子材料有限公司 CCZ continuous crystal pulling crucible

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1065105A (en) * 1991-03-21 1992-10-07 北京有色金属研究总院 The double crucible that the preparation semiconductor monocrystal is used
CN1160779A (en) * 1996-01-12 1997-10-01 三菱麻铁里亚尔硅材料株式会社 Single crystal fulling apparatus
CN101855179A (en) * 2007-09-07 2010-10-06 莫门蒂夫性能材料股份有限公司 Quartz glass crucibles and the method for handling surface of quartz glass crucible
CN102363899A (en) * 2011-06-30 2012-02-29 常州天合光能有限公司 Quartz crucible used for continuous material charging
CN103502513A (en) * 2012-01-13 2014-01-08 信越石英株式会社 Silica vessel for pulling monocrystalline silicon and method for producing same
CN102995108A (en) * 2012-11-27 2013-03-27 无锡市蓝德光电科技有限公司 Continuous charging silicon single crystal furnace
CN104342750A (en) * 2013-08-08 2015-02-11 徐州协鑫太阳能材料有限公司 Quartz crucible and preparation method thereof
CN210104124U (en) * 2019-04-18 2020-02-21 邢台晶龙电子材料有限公司 CCZ continuous crystal pulling crucible

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