CN102107873B - New multicrystal silicon reduction production technology - Google Patents
New multicrystal silicon reduction production technology Download PDFInfo
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- CN102107873B CN102107873B CN2011100844124A CN201110084412A CN102107873B CN 102107873 B CN102107873 B CN 102107873B CN 2011100844124 A CN2011100844124 A CN 2011100844124A CN 201110084412 A CN201110084412 A CN 201110084412A CN 102107873 B CN102107873 B CN 102107873B
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Abstract
The invention relates to a multicrystal silicon reduction production technology. In the initial stage of the reaction, by increasing the temperature, the deposition rate can be increased and the silicon rod can grow fast; as the total flow rate in the furnace is low, even the hydrogen content is low, the occurrence rate of the side reaction is relatively low; in the medium stage of the reaction, when the silicon rod grows continuously, by reducing the temperature and increasing the hydrogen content, the pyrolytic reaction and side reaction can be inhibited; by increasing the total flow rate, the reaction rate can be increased; and in the later stage of the reaction, by further increasing the hydrogen content and the flow rate and maintaining the temperature, the violent side reaction caused by the increase of the active area can be inhibited. By optimizing the reaction conditions of reduction, trichlorosilane can be effectively converted and the silicon rod can grow better; meanwhile, the pyrolytic reaction can be inhibited, the main reduction reaction can be performed better and the effect is obvious; and the by-products can be reduced and the comprehensive cost of multicrystal silicon can be reduced.
Description
Technical field
The present invention relates to a kind of production of polysilicon technology, particularly a kind of polysilicon reduction production.
Background technology
At present, the most improvement Siemens Methods that adopt of domestic polysilicon factory are made rod-like polycrystal silicon, promptly in the bell jar stove; Under certain temperature, pressure; At trichlorosilane hydrogen and hydrogen, through the chemical vapor deposition (CVD) method, the high temperature reduction trichlorosilane prepares rod-like polycrystal silicon.Because this reduction reaction has a lot of side reactions to take place, possible principal reaction is following:
SiHCl
3+H
2＝Si+3HCl↑(1050-1100℃)
4SiHCl
3=Si+2H
2↑+3SiCl
4(thermolysis)
2SiHCl
3=Si+2HCl ↑+SiCl
4(thermolysis)
SiHCl
3＝SiH
2Cl
2+HCl↑(900-1000℃)
SiCl
4+ 2H
2=Si+4HCl ↑ (under the high temperature)
Si+4HCl=2H
2↑+SiCl
4(corrosion)
Si+3HCl=H
2↑+HSiCl
3(corrosion)
Main reaction is reduction reaction (1) and pyrolysis (2) (3); All the other are side reaction, if therefore temperature, pressure, proportioning raw materials are controlled the improper selectivity that will reduce reaction, effective transformation efficiency of trichlorosilane are descended; Silicon tetrachloride produces more, and makes finished product silicon rod visual appearance relatively poor.
Can know that according to main reaction (1) 1 ton of polysilicon of every production does not have silicon tetrachloride and produces, and can find out that from (2) (3) producing 1 ton of polysilicon while by-produced tetrachlorosilane is respectively 18 tons and 6 tons.And, because various reactions are simultaneous in the certain bell jar stove of technology, and the possibility reversible, therefore, in the industrial production, be to guarantee speed of reaction, by-produced tetrachlorosilane is inevitable.
Can find out that from main reaction (1) (2) (3) content of increase hydrogen helps reaction (1) and takes place, but if the interior trichlorosilane content of the too high then unit volume of hydrogen content descends and silicon deposition rates is descended; Increase the thermotonus faster, but surpass certain temperature on the contrary the speed of growth slow down, side reaction increases, and because local temperature is too high, then causes in the reduction furnace temperature inhomogeneous, is unfavorable for that reaction carries out.
At present, domestic each factory 1 ton of polysilicon of every production just has 14～20 tons of silicon tetrachlorides of by-product, and the per pass conversion of trichlorosilane is lower, and about 13～15%.These numerals show, reaction (2) has comparative advantage, and the poor efficiency utilization that this not only causes raw material trichlorosilane has increased energy consumption, and have brought burden for the processing of later stage silicon tetrachloride (even employing hydrogenation).
Summary of the invention
The technical problem that the present invention will solve is the deficiency to prior art; Proposed a kind of through optimizing the reaction conditions in the reduction; Improve the utilization ratio and the per pass conversion of raw material trichlorosilane, reduce by product, reduce the polysilicon reduction production of polysilicon comprehensive cost.
The technical problem that the present invention will solve realizes that through following technical scheme a kind of polysilicon reduction production is characterized in: it is 0.1～0.6MPa that whole process keeps the reduction furnace internal pressure;
1. after starting reduction furnace, through regulating size of current control silicon wicking surface temperature between 1100 ℃～1250 ℃, with amount of substance than the H that is 2～4
2/ HSiCl
3Gas mixture is that 0.005～0.01m/s reacts in stove with flow velocity in total initial stove, improves H through regulating valve
2/ HSiCl
3Ratio be 6～8, the lifting amplitude is 0.1/h, and after evenly increasing flow velocity to 0.06 in the stove～0.08m/s with 0.001～0.002m/s/h acceleration stresses, keeps reaction 10～20h.
2. when silicon rod diameter during at 50～70mm, the electric current increase stops, and keep overall flow rate constant this moment, makes silicon wicking surface temperature reduce to 1050～1100 ℃, and this process is 5～10h, keeps this TR to continue reaction 5～10h then.
3. recover to increase electric current, keeping silicon wicking surface temperature is 1080～1100 ℃, and the speed with 0.1～0.2/h improves H simultaneously
2/ HSiCl
3Ratio to 8～10, flow velocity increases flow velocity to 0.15～0.16m/s with the acceleration stresses of 0.003～0.005m/s/h in total stove, this process time is 10～20h, keeps then 3～5 hours.
4. when the silicon rod diameter is 100～110mm, stop to increase electric current, the speed with 0.1/h improves H simultaneously
2/ HSiCl
3Ratio, and total gas flow rate in the stove increased to 0.2～0.3m/s with the acceleration stresses of 0.004～0.005m/s/h, when temperature is reduced to 1000～1050 ℃, keep flow velocity constant, recovering increases electric current, maintains under this temperature and makes H
2/ HSiCl
3Ratio reach 10～12, keep reaction 10～15 hours afterwards.
5. when the silicon rod diameter reaches 120～130mm, with the speed of 0.2～0.3/h with H
2/ HSiCl
3Ratio bring up to 12～14, simultaneously the acceleration stresses with 0.003～0.004m/s/h increases overall flow rate, this process keep temperature of reaction between 1000～1050 ℃ until blowing out.
In the present invention, the initial stage, because the total surface of silicon core is less, silicon rod is grown up fast through improving temperature increase sedimentation rate, because overall flow rate is little in the stove, even adopt lower hydrogen content, rate of side effects is also relatively low; React mid-term, along with constantly growing up of silicon rod, it is big that total surface area becomes, through generations such as reduction temperature, the content inhibition pyrolytic reaction that improves hydrogen and side reactions, and through increasing overall flow rate raising speed of reaction; The reaction later stage, further improve hydrogen content and flow velocity, keep temperature, suppress to increase the fierce side reaction that brings because of active area.Therefore, keep H
2/ HSiCl
3Ratio along with the growth of silicon rod and the increase of overall flow rate steadily increase, not only help promoting effective conversion of trichlorosilane, also help the better growth of silicon rod; Simultaneously, temperature of reaction is slowly reduced until being stabilized in 1000～1050 ℃, the inhibited reaction pyrolysis is carried out, it is obvious to make main reduction reaction carry out effect better.The present invention compared with prior art through optimizing the reaction conditions in the reduction, improves the utilization ratio and the per pass conversion of raw material trichlorosilane, reduces by product, has reduced the polysilicon comprehensive cost.
Embodiment
A kind of polysilicon reduction production, it is 0.1～0.6MPa that whole process keeps the reduction furnace internal pressure;
1. after starting reduction furnace, through regulating size of current control silicon wicking surface temperature between 1100 ℃～1250 ℃, with amount of substance than the H that is 2～4
2/ HSiCl
3Gas mixture is that 0.005～0.01m/s reacts in stove with flow velocity in total initial stove, improves H through regulating valve
2/ HSiCl
3Ratio be 6～8, the lifting amplitude is 0.1/h, and after evenly increasing flow velocity to 0.06 in the stove～0.08m/s with 0.001～0.002m/s/h acceleration stresses, keeps reaction 10～20h.
2. when silicon rod diameter during at 50～70mm, the electric current increase stops, and keep overall flow rate constant this moment, makes silicon wicking surface temperature reduce to 1050～1100 ℃, and this process is 5～10h, keeps this TR to continue reaction 5～10h then.
3. recover to increase electric current, keeping silicon wicking surface temperature is 1080～1100 ℃, and the speed with 0.1～0.2/h improves H simultaneously
2/ HSiCl
3Ratio to 8～10, flow velocity increases flow velocity to 0.15～0.16m/s with the acceleration stresses of 0.003～0.005m/s/h in total stove, this process time is 10～20h, keeps then 3～5 hours.
4. when the silicon rod diameter is 100～110mm, stop to increase electric current, the speed with 0.1/h improves H simultaneously
2/ HSiCl
3Ratio, and total gas flow rate in the stove increased to 0.2～0.3m/s with the acceleration stresses of 0.004～0.005m/s/h, when temperature is reduced to 1000～1050 ℃, keep flow velocity constant, recovering increases electric current, maintains under this temperature and makes H
2/ HSiCl
3Ratio reach 10～12, keep reaction 10～15 hours afterwards.
5. when the silicon rod diameter reaches 120～130mm, with the speed of 0.2～0.3/h with H
2/ HSiCl
3Ratio bring up to 12～14, simultaneously the acceleration stresses with 0.003～0.004m/s/h increases overall flow rate, this process keep temperature of reaction between 1000～1050 ℃ until blowing out.
In the present invention, reaction pressure is 0.1～0.6MPa, and better, reaction pressure is 0.2～0.6MPa, for enhancing productivity, and 0.4～0.6MPa preferably;
Step 1. in, better, silicon wicking surface temperature remains on 1150～1200 ℃, with amount of substance than the H that is 3
2/ HSiCl
3Gas mixture is that 0.06m/s reacts in stove with flow velocity in total initial stove, makes H
2/ HSiCl
3Ratio be increased to 7, increasing degree is 0.1/h, after total gas flow rate reached 0.07m/s in the stove, the maintenance reaction times was 12～15h;
Step 2. in, better, the silicon rod diameter is when 50～60mm, when being preferably in 60mm, the electric current increase stops, keeping overall flow rate constant this moment, makes silicon wicking surface temperature reduce to 1050～1100 ℃, then holding temperature reaction 5～8h;
Step 3. in, better, recover to increase electric current, and improve H with the speed of 0.15/h
2/ HSiCl
3Ratio to 8～10, flow velocity increases flow velocity to 0.15m/s with the acceleration stresses of 0.004m/s/h in total stove, process keeps silicon wicking surface temperature between 1080～1100 ℃, this process time needs 10～20h approximately, keeps 5h then.
Step 4. in, better, when the silicon rod diameter reaches 100mm, stop to increase electric current, simultaneously the speed with 0.1/h improves H
2/ HSiCl
3Ratio, and total gas flow rate in the stove increased to 0.22～0.24m/s with the acceleration stresses of 0.005m/s/h, when temperature is reduced to 1000～1050 ℃, keep flow velocity constant, recovering increases electric current, maintains under this temperature and makes H
2/ HSiCl
3Ratio reach 10～11, preferably 10, keep reaction 12～15h afterwards.
Step 5. in, better, when the silicon rod diameter reaches 130mm, with the speed of 0.2/h with H
2/ HSiCl
3Ratio bring up to 13～14, simultaneously the acceleration stresses with 0.003m/s/h increases overall flow rate in the stove, this process keep temperature of reaction between 1000～1050 ℃ until blowing out.
Step 2., 3., 4. in the heating-cooling amplitude do not have strict restriction, as long as reach target temperature, preferably along with the even variation that is of reacting gets final product.
Step 2.～5. in, in the ascending, descending temperature and when keeping temperature operation, to flow velocity and H in total stove
2/ HSiCl
3Special restriction is not done in the variation of ratio, gets final product according to the variation of describing in the invention, and mainly be to apply electric current through adjustment, come controlled temperature to change.
H among the present invention
2/ HSiCl
3The amount of substance ratio is 2～4, is to adopt normally used form of presentation in the existent technique, just refers to H
2: HSiCl
3Ratio be 2～4: 1, other quantity relative ratio relationship improves its amount ratio by that analogy, is to realize through the amount that improves hydrogen.
Through the present invention, can realize following target:
1, the trichlorosilane per pass conversion that will improve Siemens Method production rod-like polycrystal silicon brings up to 22%.
2, produce one ton of polysilicon by-produced tetrachlorosilane and will be 7 tons.
3, average silicon deposition rates reaches 1.5mm/h in the reduction furnace.
4, the reduction power consumption of polysilicon is reduced to 60kwh/kg-Si.
Claims (1)
1. polysilicon reduction production is characterized in that: it is 0.1～0.6MPa that whole process keeps the reduction furnace internal pressure,
1. after starting reduction furnace, through regulating size of current control silicon wicking surface temperature between 1100 ℃～1250 ℃, with amount of substance than the H that is 2～4
2/ HSiCl
3Gas mixture is that 0.005～0.01m/s reacts in stove with flow velocity in total initial stove, improves H through regulating valve
2/ HSiCl
3Ratio be 6～8, the lifting amplitude is 0.1/h, and after evenly increasing flow velocity to 0.06 in the stove～0.08m/s with 0.001～0.002m/s/h acceleration stresses, keeps reaction 10～20h;
2. when silicon rod diameter during at 50～70mm, the electric current increase stops, and keep overall flow rate constant this moment, makes silicon wicking surface temperature reduce to 1050～1100 ℃, and this process is 5～10h, keeps this TR to continue reaction 5～10h then;
3. recover to increase electric current, keeping silicon wicking surface temperature is 1080～1100 ℃, and the speed with 0.1～0.2/h improves H simultaneously
2/ HSiCl
3Ratio to 8～10, flow velocity increases flow velocity to 0.15～0.16m/s with the acceleration stresses of 0.003～0.005m/s/h in total stove, this process time is 10～20h, keeps then 3～5 hours;
4. when the silicon rod diameter is 100～110mm, stop to increase electric current, the speed with 0.1/h improves H simultaneously
2/ HSiCl
3Ratio, and total gas flow rate in the stove increased to 0.2～0.3m/s with the acceleration stresses of 0.004～0.005m/s/h, when temperature is reduced to 1000～1050 ℃, keep flow velocity constant, recovering increases electric current, maintains under this temperature and makes H
2/ HSiCl
3Ratio reach 10～12, keep reaction 10～15 hours afterwards;
5. when the silicon rod diameter reaches 120～130mm, with the speed of 0.2～0.3/h with H
2/ HSiCl
3Ratio bring up to 12～14, simultaneously the acceleration stresses with 0.003～0.004m/s/h increases overall flow rate, this process keep temperature of reaction between 1000～1050 ℃ until blowing out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100844124A CN102107873B (en) | 2011-04-06 | 2011-04-06 | New multicrystal silicon reduction production technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100844124A CN102107873B (en) | 2011-04-06 | 2011-04-06 | New multicrystal silicon reduction production technology |
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| Publication Number | Publication Date |
|---|---|
| CN102107873A CN102107873A (en) | 2011-06-29 |
| CN102107873B true CN102107873B (en) | 2012-07-11 |
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|---|---|---|---|
| CN2011100844124A Expired - Fee Related CN102107873B (en) | 2011-04-06 | 2011-04-06 | New multicrystal silicon reduction production technology |
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| CN (1) | CN102107873B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923709B (en) * | 2011-08-11 | 2016-08-31 | 内蒙古盾安光伏科技有限公司 | Feeding system and method for production of polysilicon |
| CN103510156A (en) * | 2012-06-29 | 2014-01-15 | 三菱综合材料株式会社 | Polycrystalline silicon rod |
| CN104003397B (en) * | 2014-06-18 | 2015-09-30 | 四川永祥多晶硅有限公司 | Trichlorosilane reduction process control method |
| CN107555441A (en) * | 2017-09-27 | 2018-01-09 | 江苏康博新材料科技有限公司 | A kind of improved method of polycrystalline silicon raw material production |
| CN109319787B (en) * | 2018-11-02 | 2021-12-21 | 中国南玻集团股份有限公司 | Reduction device and process for efficiently producing polycrystalline silicon |
| CN111591997B (en) * | 2020-06-15 | 2021-05-14 | 亚洲硅业(青海)股份有限公司 | Automatic control method for polycrystalline silicon reduction furnace |
| CN112624121B (en) * | 2020-12-21 | 2021-09-28 | 亚洲硅业(青海)股份有限公司 | Polycrystalline silicon production control system and control method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6365225B1 (en) * | 1999-02-19 | 2002-04-02 | G.T. Equipment Technologies, Inc. | Cold wall reactor and method for chemical vapor deposition of bulk polysilicon |
| CN201050940Y (en) * | 2007-05-31 | 2008-04-23 | 无锡中彩科技有限公司 | Inlet and outlet pipe device of high temperature reducing furnace |
| CN101654249A (en) * | 2009-09-22 | 2010-02-24 | 江苏中能硅业科技发展有限公司 | Production method of polysilicon rod |
-
2011
- 2011-04-06 CN CN2011100844124A patent/CN102107873B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6365225B1 (en) * | 1999-02-19 | 2002-04-02 | G.T. Equipment Technologies, Inc. | Cold wall reactor and method for chemical vapor deposition of bulk polysilicon |
| CN201050940Y (en) * | 2007-05-31 | 2008-04-23 | 无锡中彩科技有限公司 | Inlet and outlet pipe device of high temperature reducing furnace |
| CN101654249A (en) * | 2009-09-22 | 2010-02-24 | 江苏中能硅业科技发展有限公司 | Production method of polysilicon rod |
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| CN102107873A (en) | 2011-06-29 |
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