CN110541190A - method for preparing silicon single crystal rod - Google Patents
method for preparing silicon single crystal rod Download PDFInfo
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- CN110541190A CN110541190A CN201910983360.0A CN201910983360A CN110541190A CN 110541190 A CN110541190 A CN 110541190A CN 201910983360 A CN201910983360 A CN 201910983360A CN 110541190 A CN110541190 A CN 110541190A
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- silicon
- chlorosilane
- silicon liquid
- single crystal
- silane
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
Abstract
the invention relates to a method for preparing a single crystal silicon rod, which comprises the following steps: s1, putting a certain amount of polycrystalline silicon into a quartz crucible in a Czochralski single crystal furnace; s2, arranging an air inlet ceramic tube in the Czochralski crystal growing furnace; s3, vacuumizing the furnace, heating and melting the polycrystalline silicon to form silicon liquid, and immersing the lower end of the air inlet ceramic tube into the silicon liquid in the quartz crucible; s4, introducing chlorosilane from the air inlet ceramic tube, decomposing the chlorosilane into granular silicon on the tube wall, and further bubbling the unreacted chlorosilane in the silicon liquid for decomposition and melting into silicon liquid; s5, stopping introducing chlorosilane after the silicon liquid reaches a certain height, and vacuumizing to 3Pa for maintaining; and S6, pulling out the single crystal silicon rod by using the seed crystal. In the method, chlorosilane or silane is directly introduced into the silicon liquid, and the chlorosilane or silane can be decomposed in two stages of bubbling in the silicon liquid and the tube wall, so that the decomposition efficiency is greatly improved, no silicon dust is generated, and the method is used for solving the problem of low conversion rate of the silicon rod of the czochralski silicon crystal manufactured by silane in the prior art.
Description
Technical Field
the invention belongs to the technical field of polycrystalline silicon preparation, and particularly relates to a method for preparing a single crystal silicon rod.
background
The improved Siemens method is the current mainstream polysilicon preparation method, and the market application ratio is over 90 percent. The improved Siemens method is a chemical purification method, introduces a tail gas recovery and a silicon tetrachloride hydrogenation process on the basis of the Siemens method, realizes closed-loop circulation of a production process, and can be used for producing solar-grade and electronic-grade polysilicon. The main advantages of the improved Siemens method are the most mature process, strong safety and high product quality, the main defects are that the conversion rate is only 10-20%, the energy consumption is high, and the reduction power consumption of polycrystalline silicon reaches 45 KW/KG.
In order to solve the problem of over-main energy consumption of the improved Siemens method, a process for reducing silicon particles in a silane fluidized bed is developed domestically, the reduction power consumption of the process reaches 20-25KW/KG, but the problems of high silane price, excessive product micro silicon powder, low yield and the like exist.
further, according to the application No. 201610839529.1, the invention relates to an apparatus and a method for manufacturing a silicon rod of a czochralski single crystal from silane, the apparatus is composed of a silane decomposition reactor and a czochralski single crystal furnace, the silane decomposition reactor comprises a hollow tube reactor and a heating component on the outer wall of the hollow tube reactor, and the czochralski single crystal furnace comprises a furnace body, a heating pipe, a heat preservation layer, a heating unit, a crucible rotating motor, a crucible tray, a graphite crucible, a quartz crucible, a guide cylinder and a crystal lifting motor. The invention also provides a method for pulling the single crystal silicon rod by using the equipment, silane is thermally decomposed in the hollow tube reactor to generate solid silicon powder, the solid silicon powder enters the quartz crucible through the heating tube to form liquid silicon, and the liquid silicon is pulled into the high-quality single crystal silicon rod through the growth processes of seeding, shouldering, shoulder rotating, constant diameter, ending and the like by the crystal lifting motor. The method also has the problems of high price of silane, low yield and the like.
Disclosure of Invention
The invention aims to provide a method for preparing a silicon single crystal rod, which is used for solving the problem of low conversion rate of the silicon single crystal rod prepared by using silane in the prior art.
in order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a single crystal silicon rod, comprising the steps of:
S1, putting a certain amount of polycrystalline silicon into a quartz crucible in a Czochralski single crystal furnace;
s2, arranging an air inlet ceramic tube in the Czochralski crystal growing furnace;
S3, vacuumizing the furnace, heating and melting the polycrystalline silicon to form silicon liquid, and immersing the lower end of the air inlet ceramic tube into the silicon liquid in the quartz crucible;
s4, introducing chlorosilane or silane from the gas inlet ceramic tube, wherein the chlorosilane or silane starts to decompose into granular silicon on the tube wall and falls into the quartz crucible to be melted into silicon liquid, and the unreacted chlorosilane or silane is further bubbled in the silicon liquid to decompose and melt into the silicon liquid;
S5, stopping introducing chlorosilane or silane after the silicon liquid reaches a certain height, and vacuumizing to 3Pa for a certain time;
And S6, pulling out the single crystal silicon rod by using the seed crystal.
Further, the air inlet ceramic tube is made of quartz ceramic materials.
Further, the charging amount of the chlorosilane is 10Nm 3/h.
Further, the chlorosilane is trichlorosilane or dichlorosilane.
Further, the step S5 includes:
S501, stopping introducing chlorosilane after the silicon liquid reaches a certain height, and vacuumizing to 3 Pa;
s502, continuously vacuumizing, and blowing argon into the silicon liquid to remove hydrogen chloride and hydrogen in the silicon liquid;
s503, stopping introducing the argon, vacuumizing to 3Pa, and keeping degassing for a certain time.
The invention has the beneficial effects that:
(1) in the method, chlorosilane or silane is directly introduced into the silicon liquid, and the chlorosilane or silane can be decomposed in two stages of bubbling in the silicon liquid and the tube wall, so that the decomposition efficiency is greatly improved, no silicon dust is generated, and the method is used for solving the problem of low conversion rate of the silicon rod of the czochralski silicon crystal manufactured by silane in the prior art.
(2) The bubbling in the silicon liquid is used for producing the silicon liquid to replace the precipitation to generate the solid silicon, the reaction efficiency reaches over 90 percent, and the method greatly exceeds the traditional method.
(3) cheap dichlorosilane is used as a gas source to replace expensive silane, and the safety is higher.
(4) The silicon liquid is directly combined to draw the silicon single crystal rod, so that the material melting process of pulling the single crystal is omitted, and the power consumption is further saved.
(5) the tail gas of the reaction only contains hydrogen chloride and dichlorosilane, and the tail gas recovery device only needs three-stage condensation, so that the adsorption, desorption and carbon tower adsorption processes in the tail gas recovery process of the Siemens method are omitted, and the tail gas recovery cost is saved.
Detailed Description
In order to better understand the present invention, the following embodiments are further described.
example one
A method of preparing a single crystal silicon rod comprising the steps of:
S1, preparing a vapor deposition single crystal furnace, and putting 10KG polycrystalline silicon into a quartz crucible in the single crystal furnace;
S2, arranging an air inlet ceramic tube (made of quartz ceramic) in the single crystal furnace;
S3, vacuumizing the furnace, heating and melting the polycrystalline silicon to form silicon liquid, and immersing the lower end of the air inlet ceramic tube into the silicon liquid in the quartz crucible;
s4, introducing 10Nm3/h (Nm3/h index standard cubic meter per hour, N represents a Nominal working Condition, namely the Condition of air is that dichlorosilane (SiH2Cl2) with standard atmospheric pressure, temperature of 0 ℃ and relative humidity of 0% starts to decompose into granular silicon at the tube wall and falls into a quartz crucible to be melted into silicon liquid, and unreacted dichlorosilane is further bubbled in the silicon liquid to decompose and melt into the silicon liquid;
s5, stopping introducing the dichlorosilane after the silicon liquid reaches a certain height, and vacuumizing to 3 Pa; continuously vacuumizing, blowing argon into the silicon liquid for 1 hour, and removing hydrogen chloride and hydrogen in the silicon liquid; stopping introducing argon, vacuumizing to 3Pa, and keeping degassing for 2 hours;
S6, pulling out a single crystal silicon rod by using seed crystals;
S7, after the single crystal is pulled, the liquid level in the crucible is not lower than 100 mm.
example two
The difference between this embodiment and the first embodiment is only: the lower end of the gas inlet ceramic tube is positioned above the silicon liquid in the quartz crucible and is not immersed in the silicon liquid.
EXAMPLE III
a method of preparing a single crystal silicon rod comprising the steps of:
S1, preparing a vapor deposition single crystal furnace, and putting 10KG polycrystalline silicon into a quartz crucible in the single crystal furnace;
S2, arranging an air inlet ceramic tube in the single crystal furnace;
S3, vacuumizing the furnace, heating and melting the polycrystalline silicon to form silicon liquid, and immersing the lower end of the air inlet ceramic tube into the silicon liquid in the quartz crucible;
s4, introducing 10Nm3/h of trichlorosilane (SiHCl3) into the air inlet ceramic tube, decomposing the trichlorosilane into granular silicon on the tube wall, dropping the granular silicon into the quartz crucible to be melted into silicon liquid, and further bubbling unreacted trichlorosilane in the silicon liquid to decompose and melt the silicon liquid;
s5, stopping introducing trichlorosilane after the silicon liquid reaches a certain height, and vacuumizing to 3 Pa; continuously vacuumizing, blowing argon into the silicon liquid for 1 hour, and removing hydrogen chloride and hydrogen in the silicon liquid; stopping introducing argon, vacuumizing to 3Pa, and keeping degassing for 2 hours;
s6, pulling out a single crystal silicon rod by using seed crystals;
S7, after the single crystal is pulled, the liquid level in the crucible is not lower than 100 mm.
example four
The difference between this embodiment and the third embodiment is only: the lower end of the gas inlet ceramic tube is positioned above the silicon liquid in the quartz crucible and is not immersed in the silicon liquid.
EXAMPLE five
A method of preparing a single crystal silicon rod comprising the steps of:
S1, preparing a vapor deposition single crystal furnace, and putting 10KG polycrystalline silicon into a quartz crucible in the single crystal furnace;
S2, arranging an air inlet ceramic tube in the single crystal furnace;
s3, vacuumizing the furnace, heating and melting the polycrystalline silicon to form silicon liquid, and immersing the lower end of the air inlet ceramic tube into the silicon liquid in the quartz crucible;
S4, introducing 10Nm3/h of silane from the gas inlet ceramic tube, decomposing the silane into granular silicon on the tube wall, dropping the granular silicon into the quartz crucible to be melted into silicon liquid, and further bubbling the unreacted silane in the silicon liquid to decompose and melt the unreacted silane into the silicon liquid;
S5, stopping introducing silane after the silicon liquid reaches a certain height, and vacuumizing to 3 Pa; continuously vacuumizing, and blowing argon into the silicon liquid for 1 hour to remove hydrogen in the silicon liquid; stopping introducing argon, vacuumizing to 3Pa, and keeping degassing for 2 hours;
S6, pulling out a single crystal silicon rod by using seed crystals;
s7, after the single crystal is pulled, the liquid level in the crucible is not lower than 100 mm.
EXAMPLE six
The difference between this embodiment and the fifth embodiment is only: the lower end of the gas inlet ceramic tube is positioned above the silicon liquid in the quartz crucible and is not immersed in the silicon liquid.
comparative example
The present embodiment is a currently used siemens method, which adopts a CVD vapor deposition furnace, and silicon raw materials are: trichlorosilane.
The following table shows a comparison table of examples one to six and a comparison example in terms of a primary conversion rate, a reduction power consumption of polycrystalline silicon, and a price of silicon raw material.
| First conversion rate | reduction power consumption of polycrystalline silicon | Price of silicon raw material | |
| Example one | 95％ | 10KW/KG | Dichlorosilane 12000 yuan/ton |
| Example two | 70％ | 10KW/KG | Dichlorosilane 12000 yuan/ton |
| EXAMPLE III | 30％ | 10KW/KG | 4000 yuan/ton trichlorosilane |
| Example four | 15％ | 10KW/KG | 4000 yuan/ton trichlorosilane |
| EXAMPLE five | 99％ | 25KW/KG | silane 20000 yuan/ton |
| EXAMPLE six | 95％ | 25KW/KG | Silane 20000 yuan/ton |
| comparative example | 10％ | 45KW/KG | 4000 yuan/ton trichlorosilane |
the above description is only an application example of the present invention, and certainly, the present invention should not be limited by this application, and therefore, the present invention is still within the protection scope of the present invention by equivalent changes made in the claims of the present invention.
Claims (5)
1. A method for preparing a single crystal silicon rod, comprising the steps of:
S1, putting a certain amount of polycrystalline silicon into a quartz crucible in a Czochralski single crystal furnace;
S2, arranging an air inlet ceramic tube in the Czochralski crystal growing furnace;
S3, vacuumizing the furnace, heating and melting the polycrystalline silicon to form silicon liquid, and immersing the lower end of the air inlet ceramic tube into the silicon liquid in the quartz crucible;
S4, introducing chlorosilane or silane from the gas inlet ceramic tube, wherein the chlorosilane or silane starts to decompose into granular silicon on the tube wall and falls into the quartz crucible to be melted into silicon liquid, and the unreacted chlorosilane or silane is further bubbled in the silicon liquid to decompose and melt into the silicon liquid;
S5, stopping introducing chlorosilane or silane after the silicon liquid reaches a certain height, and vacuumizing to 3Pa for a certain time;
And S6, pulling out the single crystal silicon rod by using the seed crystal.
2. the method according to claim 1, wherein the gas inlet ceramic tube is made of quartz ceramic.
3. the method as set forth in claim 1, wherein the chlorosilane feed rate is 10Nm 3/h.
4. The method of claim 1, wherein the chlorosilane is trichlorosilane or dichlorosilane.
5. the method as set forth in claim 1, wherein the step S5 comprises:
s501, stopping introducing chlorosilane after the silicon liquid reaches a certain height, and vacuumizing to 3 Pa;
S502, continuously vacuumizing, and blowing argon into the silicon liquid to remove hydrogen chloride and hydrogen in the silicon liquid;
S503, stopping introducing the argon, vacuumizing to 3Pa, and keeping degassing for a certain time.
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| CN201910983360.0A CN110541190A (en) | 2019-10-16 | 2019-10-16 | method for preparing silicon single crystal rod |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014853A (en) * | 2013-01-11 | 2013-04-03 | 天津英利新能源有限公司 | Polysilicon ingot casting device and ingot casting method |
| CN106319618A (en) * | 2016-09-22 | 2017-01-11 | 上海交通大学 | Equipment and method for manufacturing czochralski silicon rod from silane |
| CN108301038A (en) * | 2017-01-12 | 2018-07-20 | 新疆知信科技有限公司 | A kind of drawing method of pulling silicon single crystal stove and growing single-crystal silicon |
| CN108301039A (en) * | 2017-01-12 | 2018-07-20 | 新疆知信科技有限公司 | A kind of drawing device and drawing method of growing single-crystal silicon |
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2019
- 2019-10-16 CN CN201910983360.0A patent/CN110541190A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014853A (en) * | 2013-01-11 | 2013-04-03 | 天津英利新能源有限公司 | Polysilicon ingot casting device and ingot casting method |
| CN106319618A (en) * | 2016-09-22 | 2017-01-11 | 上海交通大学 | Equipment and method for manufacturing czochralski silicon rod from silane |
| CN108301038A (en) * | 2017-01-12 | 2018-07-20 | 新疆知信科技有限公司 | A kind of drawing method of pulling silicon single crystal stove and growing single-crystal silicon |
| CN108301039A (en) * | 2017-01-12 | 2018-07-20 | 新疆知信科技有限公司 | A kind of drawing device and drawing method of growing single-crystal silicon |
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Application publication date: 20191206 |
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