CN115323481A - Eccentric Czochralski silicon single crystal furnace and crystal pulling process thereof - Google Patents

Eccentric Czochralski silicon single crystal furnace and crystal pulling process thereof Download PDF

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Publication number
CN115323481A
CN115323481A CN202210922506.2A CN202210922506A CN115323481A CN 115323481 A CN115323481 A CN 115323481A CN 202210922506 A CN202210922506 A CN 202210922506A CN 115323481 A CN115323481 A CN 115323481A
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China
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crucible
central line
seed rod
single crystal
eccentric
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CN202210922506.2A
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Chinese (zh)
Inventor
张波
赵彩霞
杨旭彪
杨飞飞
梁玲
吕涛
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Shanxi Luan Solar Energy Technology Co Ltd
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Shanxi Luan Solar Energy Technology Co Ltd
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Priority to CN202210922506.2A priority Critical patent/CN115323481A/en
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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
    • C30B15/30Mechanisms for rotating or moving either the melt or the crystal
    • 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
    • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention relates to the field of solar cell production, in particular to an eccentric czochralski silicon single crystal furnace, which comprises a furnace body, a crucible and a seed crystal rod, wherein the crucible is arranged in the furnace body, molten silicon liquid is filled in the crucible, and the crucible rotates by self-rotation deviating from the central line of a crucible shaft; the seed rod is arranged in the furnace body, the seed rod rotates along the central line of the self axis in a self-rotation manner, and the seed rod is opposite to the crucible in the self axial direction and can be lifted. The self-rotation of the crucible deviated from the central line of the crucible shaft is equivalent to the increase of the caliber of the crucible, so that the separation effect on impurities is greater than that of a non-eccentric crucible.

Description

Eccentric Czochralski silicon single crystal furnace and crystal pulling process thereof
Technical Field
The invention relates to the field of solar cell production, in particular to the field of a czochralski silicon single crystal furnace.
Background
Solar cells are devices that directly convert light energy into electrical energy by the photoelectric or photochemical effect. At present, crystalline silicon solar cells working under the photovoltaic effect are the mainstream, and the crystalline silicon solar cells are divided into single crystalline silicon solar cells and polycrystalline silicon solar cells.
The power generation efficiency of the monocrystalline silicon solar cell is higher than that of a polycrystalline silicon solar cell, and the monocrystalline silicon solar cell is more and more widely applied. The quality of the monocrystalline silicon wafer determines the quality of the monocrystalline silicon solar cell, and therefore, the improvement of the quality of the monocrystalline silicon wafer is of great importance. The monocrystalline silicon piece is formed by peeling and cutting a monocrystalline silicon rod, and in the process of drawing the monocrystalline silicon rod, main primary defects can be named as: crystal Originated defects (COPs), flow Pattern Defects (FPDs), or Laser Scattering Tomography Defects (LSTDs). The formation of crystal originated defects, which are mainly caused by the supersaturation degree of vacancies and self-interstitial silicon atoms, can be reduced by reducing impurities in the molten silicon and maintaining the uniformity of the internal temperature of the molten silicon. Further, the formation of void-type defects generally proceeds through two processes, first, aggregation nucleation of a small number of vacancies, and then formation of a core to absorb a large number of vacancies to form void-type defects. The temperature interval Tn for fast nucleation of void defects is approximately 1040-1120 ℃, and the process mainly determines the size of the defects. When the temperature of the silicon single crystal rod is lower than Tn, the hollow type defects start to grow, and the temperature is reduced in the process, so that the density of the defects is mainly increased, and the sizes of the defects do not change too much. Therefore, in order to reduce the size and increase the density of defects in the produced single crystal silicon rod, it is necessary to make the single crystal silicon rod pass through the temperature range of defect nucleation as quickly as possible and reach the temperature range of defect growth.
One limitation on the removal of impurities from molten silicon has been reached, and further elimination of impurities from molten silicon is often cost prohibitive.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: further reducing impurities in the monocrystalline silicon battery piece, and further eliminating crystal primary defects in the monocrystalline silicon crystallization process.
The technical scheme adopted by the invention is as follows: an eccentric Czochralski silicon single crystal furnace comprises a furnace body, a crucible and a seed rod, wherein the crucible is arranged in the furnace body, molten silicon liquid is filled in the crucible, and the crucible rotates by self-rotation deviating from the central line of a crucible shaft; the seed rod is arranged in the furnace body, the seed rod rotates along the central line of the self axis in a self-rotation manner, and the seed rod is opposite to the crucible in the self axial direction and can be lifted.
The rotating central line of the crucible is superposed with the rotating central line of the seed rod.
The czochralski silicon single crystal furnace also comprises an air inlet pipe and a shunting baffle, wherein the shunting baffle is a fence-shaped annular plate fixed on the cover body, and the air inlet pipe is positioned above the shunting baffle.
The crucible is arranged on an output shaft of the first motor, the bottom of the crucible is stably fixed on the output shaft of the first motor through the support frame, and the central line of the output shaft of the first motor is not overlapped with the central line of the crucible shaft.
The czochralski silicon single crystal furnace also comprises a cover body and a lifting device, wherein the seed rod is positioned in the cover body and is connected with the lifting device through a connecting rope.
The lifting device comprises a plurality of studs, a gear and a second motor, the studs are meshed with the periphery of the gear, the projections of the studs on the same horizontal plane are positioned on a circle, the upper end of one stud in the studs is installed on an output shaft of a third motor, the upper ends of other studs are directly fixed to the top of the inner side of the furnace body, a base of the third motor is fixed to the top of the inner side of the furnace body, the third motor drives the gear to rotate when rotating, the gear rises or falls in the rotating process, the gear drives the third motor to rise or fall in the rising or falling process, and the output shaft of the third motor is connected with a seed rod, so that the seed rod rotates along the axis of the seed rod, and the seed rod can rise or fall relative to the crucible along the axial direction of the seed rod.
A process for pulling crystal in an eccentric Czochralski silicon single crystal furnace comprises the steps of slowly lifting a seed rod with a silicon rod, crystallizing the seed crystal or the lower part of a silicon wafer in molten silicon, descending the seed rod by 2-3 cm within 1-2 seconds after the seed rod slowly rises by 1-2 cm, then ascending by 2-3 cm within 1-2 seconds, and then slowly rising by 1-2 cm within 1-2 seconds to recrystallize the bottom of the silicon rod which just finishes crystallization, thereby reducing primary defects.
When the crucible rotates in a self-rotation way deviating from the central line of the crucible shaft, the lower part of the seed crystal or the silicon wafer in the molten silicon liquid is crystallized, and the rotating central line of the crucible deviates from the central line of the crucible shaft, so that impurities are positioned on the wall of the crucible farthest from the rotating central line of the crucible, and the impurities at the corresponding position of the lower part of the seed crystal or the silicon wafer in the molten silicon liquid are reduced.
The invention has the beneficial effects that: the eccentric czochralski silicon single crystal furnace crucible deviates from the central line of the crucible shaft and rotates in an autorotation way, and molten silicon liquid in the crucible rotates along with the crucible; those skilled in the art know that the larger the diameter of the crucible, the better the impurity separation effect, but the higher the cost, including heating input and heat dissipation loss, etc.; the self-rotation of the crucible deviated from the central line of the crucible shaft is equivalent to the increase of the caliber of the crucible, so that the separation effect on impurities is greater than that of a non-eccentric crucible. In addition, due to the surface tension action of the crucible wall, the surface tension can pull impurities to be transferred to the crucible wall deviated from the rotation center, and therefore, the impurities on the crystalline silicon rod can be effectively reduced through the autorotation of the crucible deviated from the central line of the crucible shaft.
In addition, when the bottom of the seed rod is crystallized, the prior art is usually direct crystallization layer by layer, and the monocrystalline silicon has more vacancies and forms more serious cavity defects after being cooled. In this patent, after the first crystallization is accomplished to seed rod lower part, can slowly descend and immerse in the molten silicon liquid, the monocrystalline silicon that just crystallized can be in semicrystalline and half dissolved state, when promoting again and leave the molten silicon liquid, can carry out the secondary crystallization, and the secondary crystallization is crystallized in the cladding of outer primary crystallization, and partial vacancy can be eliminated, and then has reduced cavity type defect.
Drawings
FIG. 1 is a schematic view showing the structure of an eccentric Czochralski silicon single crystal furnace of the present invention;
FIG. 2 is a schematic view of the lifting device of the present invention;
the device comprises a lifting device 1, a lifting device 2, a flow dividing baffle plate 3, an air inlet pipe 4, a cover body 5, a crucible 6, molten silicon liquid 7, a support frame 8, a crucible shaft center line 9, a crucible rotating center line and a seed rod rotating center line 10, a seed rod and a silicon rod in crystallization 11, a stud 12, a gear 13, a second motor 14 and a connecting rope.
Detailed Description
Embodiments of the present invention will be described in further detail with reference to the drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example" or "some examples" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this description, a schematic representation of the above terms does not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "connected" and "connected" are to be interpreted broadly, e.g., as being fixed or detachable or integrally connected; may be a mechanical connection; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. Also, in the description of the present invention, unless otherwise specified, "a plurality", and "a plurality" mean two or more, and "several", and "several groups" mean one or more.
As shown in figure 1, the eccentric czochralski silicon single crystal furnace comprises a furnace body, a crucible 5 and a seed rod 10, wherein the crucible 5 is arranged in the furnace body, molten silicon liquid is filled in the crucible 5, and the crucible 5 rotates in a self-rotation way deviating from the central line 8 of the crucible axis; the seed rod 10 is arranged in the furnace body, the seed rod 10 rotates along the central line of the self axis, and the seed rod 10 can be lifted relative to the crucible 5 along the self axis. The rotating central line of the crucible is superposed with the rotating central line of the seed rod.
In one embodiment, the czochralski silicon single crystal furnace further comprises an air inlet pipe and a flow dividing baffle plate, wherein the flow dividing baffle plate is a fence-shaped annular plate fixed on the cover body, and the air inlet pipe is positioned above the flow dividing baffle plate.
In one embodiment, there are a plurality of air inlet pipes 3, such as 3, 4, 5, 6, the air inlet pipes 3 are bent at right angles in the furnace body, the outlets of the air inlet pipes 3 face the flow dividing baffle 2, the flow dividing baffle 2 is annular, and the outer edge of the flow dividing baffle 2 is fixed on the cover 4. The reposition of redundant personnel baffle 2 can make the cooling gas that intake pipe 3 got into concentrate on the periphery of seed rod and crystal to from the top down cooling, the crystal on upper strata has the primary cooling, and the influence is little that cooling gas aligns, and during the lower floor, cooling gas has been heated by upper silicon stick, and the effectual monocrystalline silicon of avoiding produces the defect of the cavity type of great size, influences the quality of monocrystalline silicon.
In one embodiment, the crucible is arranged on an output shaft of the first motor, the bottom of the crucible is stably fixed on the output shaft of the first motor through the support frame, and the center line of the output shaft of the first motor is not coincident with the center line of the crucible shaft. The output shaft of the first motor rotates to drive the crucible bottom 5 to rotate eccentrically. The eccentric rotation here means that the crucible rotates by rotating on its own from the center line of the crucible axis.
In one embodiment, the czochralski silicon single crystal furnace further comprises a cover body and a lifting device, wherein the seed rod is positioned in the cover body and is connected with the lifting device through a connecting rope.
In one embodiment, the lifting device comprises a plurality of studs, a gear and a second motor, the studs are meshed with the periphery of the gear, in the embodiment, the number of the studs is four, the projections of the four studs on the same horizontal plane are located on a circle, the upper end of one stud in the four studs is installed on an output shaft of a third motor, the upper ends of other studs are directly fixed on the top of the inner side of the furnace body, a base of the third motor is fixed on the top of the inner side of the furnace body, the third motor drives the gear to rotate when rotating, the gear rises or falls in the rotating process, the gear drives the third motor to rise or fall in the rising or falling process, and the output shaft of the third motor is connected with the seed rod, so that the seed rod can rotate along the axis of the seed rod, and can rise or fall relative to the crucible along the axial direction of the seed rod. The third motor is a stepping rotating motor.
The lifting device in this embodiment realizes the up-and-down stepping lifting under the action of the third motor. And simultaneously drives the second motor to carry out stepping lifting.
In one embodiment, the seed rod slowly rises with the silicon rod, the seed crystal or the lower part of the silicon wafer in the molten silicon is crystallized, after the seed rod slowly rises for 1-2 cm, the seed rod descends for 2-3 cm within 1-2 seconds, then ascends for 2-3 cm within 1-2 seconds, and then slowly rises for 1-2 cm within 1-2 seconds, so that the bottom of the silicon rod which just completes crystallization is recrystallized, and the primary defects are reduced. The slow rise is 1-2 cm in 1-2 seconds.
When the bottom of the seed crystal rod (the bottom of the silicon rod) is crystallized, the prior art is usually direct crystallization layer by layer, and the monocrystalline silicon has more vacancies and forms more serious cavity defects after being cooled. In the embodiment, after the primary crystallization is completed at the lower part of the seed rod, the seed rod slowly descends and is immersed in the molten silicon liquid, the monocrystalline silicon which is just crystallized is in a semi-crystalline and semi-dissolved state, and when the seed rod is lifted away from the molten silicon liquid again, secondary crystallization is performed, the secondary crystallization is performed in the cladding of the primary crystallization of the outer layer, partial vacancy is eliminated, and further the cavity type defects are reduced.
In one embodiment, the crucible rotates in a self-rotation mode deviating from the central line of the crucible shaft, and simultaneously, the lower part of the seed crystal or the silicon wafer in the molten silicon is crystallized, and the impurities are located on the crucible wall farthest from the central line of the crucible shaft due to the fact that the central line of the crucible shaft deviates from the central line of the crucible shaft, and the impurities at the corresponding position of the lower part of the seed crystal or the silicon wafer in the molten silicon are reduced. The crucible of the eccentric czochralski silicon single crystal furnace rotates in a self-rotation way deviating from the central line of the crucible shaft, and the molten silicon liquid in the crucible rotates along with the crucible; those skilled in the art know that the larger the diameter of the crucible, the better the impurity separation effect, but the higher the cost, including heating input and heat dissipation loss, etc.; the self-rotation of the crucible deviated from the central line of the crucible shaft is equivalent to the increase of the caliber of the crucible, so that the separation effect on impurities is greater than that of a non-eccentric crucible. In addition, due to the surface tension action of the crucible wall, the surface tension can pull impurities to be transferred to the crucible wall deviated from the rotation center, and therefore, the impurities on the crystalline silicon rod can be effectively reduced through the autorotation of the crucible deviated from the central line of the crucible shaft.
The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.

Claims (8)

1. An eccentric czochralski silicon single crystal furnace is characterized in that: the crucible is arranged in the furnace body, molten silicon liquid is filled in the crucible, and the crucible rotates by self-rotation deviating from the central line of a crucible shaft; the seed rod is arranged in the furnace body, the seed rod rotates along the central line of the self axis, and the seed rod can be lifted relative to the crucible along the self axis.
2. The eccentric czochralski silicon single crystal furnace according to claim 1, wherein: the rotating central line of the crucible is superposed with the rotating central line of the seed rod.
3. The eccentric czochralski silicon single crystal furnace according to claim 1, wherein: the czochralski silicon single crystal furnace also comprises an air inlet pipe and a shunting baffle, wherein the shunting baffle is a fence-shaped annular plate fixed on the cover body, and the air inlet pipe is positioned above the shunting baffle.
4. The eccentric czochralski silicon single crystal furnace according to claim 1, wherein: the crucible is arranged on an output shaft of the first motor, the bottom of the crucible is stably fixed on the output shaft of the first motor through the support frame, and the central line of the output shaft of the first motor is not overlapped with the central line of the crucible shaft.
5. The eccentric czochralski silicon single crystal furnace according to claim 1, wherein: the czochralski silicon single crystal furnace also comprises a cover body and a lifting device, wherein the seed rod is positioned in the cover body and is connected with the lifting device through a connecting rope.
6. An eccentric czochralski silicon single crystal furnace according to claim 5, wherein: the lifting device comprises a plurality of studs, a gear and a second motor, the studs are meshed with the periphery of the gear, the projections of the studs on the same horizontal plane are positioned on a circle, the upper end of one stud in the studs is installed on an output shaft of a third motor, the upper ends of other studs are directly fixed to the top of the inner side of the furnace body, a base of the third motor is fixed to the top of the inner side of the furnace body, the third motor drives the gear to rotate when rotating, the gear rises or falls in the rotating process, the gear drives the third motor to rise or fall in the rising or falling process, and the output shaft of the third motor is connected with a seed rod, so that the seed rod rotates along the axis of the seed rod, and the seed rod can rise or fall relative to the crucible along the axial direction of the seed rod.
7. A process for pulling crystal by using the eccentric Czochralski silicon single crystal furnace of claim 1, wherein: the seed rod is slowly lifted up with the silicon rod, the seed crystal or the lower part of the silicon wafer in the molten silicon liquid is crystallized, after the seed rod is lifted up by 1-2 cm slowly, the seed rod is descended by 2-3 cm within 1-2 seconds, then ascended by 2-3 cm within 1-2 seconds, and then ascended by 1-2 cm slowly within 1-2 seconds, so that the bottom of the silicon rod which is just crystallized is recrystallized, and the primary defects are reduced.
8. A process for pulling crystal in an eccentric Czochralski silicon single crystal furnace in accordance with claim 7, wherein: when the crucible rotates in a self-rotation mode deviating from the central line of the crucible shaft, the lower part of the seed crystal or the silicon wafer in the molten silicon liquid is crystallized, and the rotating central line of the crucible deviates from the central line of the crucible shaft, so that impurities are located on the crucible wall farthest from the rotating central line of the crucible, and the impurities at the corresponding position of the lower part of the seed crystal or the silicon wafer in the molten silicon liquid are reduced.
CN202210922506.2A 2022-08-02 2022-08-02 Eccentric Czochralski silicon single crystal furnace and crystal pulling process thereof Pending CN115323481A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001019592A (en) * 1999-06-29 2001-01-23 Mitsubishi Materials Silicon Corp Device for pulling single crystal
CN1632919A (en) * 2003-12-25 2005-06-29 北京有色金属研究总院 Method for eliminating primary pit defects of silicon monocrystal device making area
CN111041551A (en) * 2020-01-06 2020-04-21 北京北方华创真空技术有限公司 Czochralski silicon single crystal furnace
CN112160023A (en) * 2020-10-09 2021-01-01 西安奕斯伟硅片技术有限公司 Method and system for centering seed crystal rotating rod and crucible rotating base

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001019592A (en) * 1999-06-29 2001-01-23 Mitsubishi Materials Silicon Corp Device for pulling single crystal
CN1632919A (en) * 2003-12-25 2005-06-29 北京有色金属研究总院 Method for eliminating primary pit defects of silicon monocrystal device making area
CN111041551A (en) * 2020-01-06 2020-04-21 北京北方华创真空技术有限公司 Czochralski silicon single crystal furnace
CN112160023A (en) * 2020-10-09 2021-01-01 西安奕斯伟硅片技术有限公司 Method and system for centering seed crystal rotating rod and crucible rotating base

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Application publication date: 20221111