CN101928002A - Method for producing polysilicon with silicon tetrafluoride reduced by plasmas - Google Patents
Method for producing polysilicon with silicon tetrafluoride reduced by plasmas Download PDFInfo
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- CN101928002A CN101928002A CN 201010246191 CN201010246191A CN101928002A CN 101928002 A CN101928002 A CN 101928002A CN 201010246191 CN201010246191 CN 201010246191 CN 201010246191 A CN201010246191 A CN 201010246191A CN 101928002 A CN101928002 A CN 101928002A
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Abstract
The invention discloses a method for producing polysilicon with silicon tetrafluoride reduced by plasmas, specifically comprising the following steps: pumping the mixture of the silicon tetrafluoride gas and hydrogen as the raw materials into a plasma reactor filled with hydrogen, heating the silicon tetrafluoride gas and hydrogen to 1200-3500 DEG C instantaneously under the action of the plasmas and the silicon tetrafluoride gas and hydrogen carrying out chemical reaction to produce the polysilicon solid and the hydrogen fluoride gas; the produced polysilicon solid and hydrogen fluoride gas and the unreacted silicon tetrafluoride gas and hydrogen jointly entering into a gas-solid separation device, separating the polysilicon solid from the gases, the purity being more than 99.9999% and producing the finished product; and the hydrogen fluoride gas and the unreacted silicon tetrafluoride gas and hydrogen jointly entering into a condenser, condensing the hydrogen fluoride gas to liquid and the silicon tetrafluoride gas and hydrogen returning to the plasma reactor. The method has the advantages of novel and reasonable process routes, low equipment requirements, easy industrialization realization and low energy consumption.
Description
Technical field
The present invention relates to a kind of method of producing polysilicon, more specifically saying so a kind of is the method for raw material production polysilicon or polysilicon chip with silicon tetrafluoride and hydrogen.
Background technology
As everyone knows, the production method of the polysilicon that uses as the raw material of semi-conductor or solar power generation cell has a variety of, wherein has several in industrial enforcement.
For example, application number is the patent application of 200710121059 " producing the method for polysilicon ", and disclose a kind of method: with industrial silicon and hydrogenchloride is raw material, and reaction generates trichlorosilane; With described trichlorosilane after purifying and hydrogen reaction, thereby reduction generates polysilicon; Collect and generate the tail gas that trichlorosilane, purify trichlorosilane and generation polysilicon process produce, handle the back and recycle.
Application number is the patent application of 02137592 " with the method for trichlorosilane and silicon tetrachloride producing polysilicon with mixed source ", discloses a kind of method: the SiCl that the Siemens process polycrystalline silicon production process is produced and reclaims the concise purification in back
4With SiHCl
3Enter reduction furnace together, control certain flow, and reduction temperature is brought up to 1145 ℃～1155 ℃, shaft, bottom temperature keep 150 ℃, can obtain silicon deposition rates fast, promptly make polysilicon product in stove on the silicon rod.
Application number is the patent application of 200780028580 " the preparation equipment of preparation method of polycrystalline silicon and polysilicon ", a kind of method is disclosed: make trichlorosilane and hydrogen reaction generate the step of silicon and effluent, produce the tail gas of polysilicon and processing production process.Wherein, described effluent comprises silicomethane class (the formula SiH that contains silicon tetrachloride
nCl
(4-n), n=0～4) and contain the polymkeric substance of Trisilicopropane class or tetrasilane class at least; By above-mentioned effluent and hydrogen being supplied in the conversion reactor and, making described silicon tetrachloride reaction be converted into trichlorosilane and make described polymer reaction be converted into the silicomethane class 600～1400 ℃ scope heating.
Application number is the patent application of 200610010654 " a kind of methods that prepare solar-grade polysilicon ", a kind of method is disclosed: adopt metallurgical grade silicon as raw material, behind broken mill granularity is a silica flour material more than 50 orders, the silica flour material is respectively the hydrochloric acid of 1～6mol/L with concentration, concentration is that the nitric acid of 0.5～6mol/L and hydrofluoric acid that concentration is 1～5mol/L carry out acidleach and handles, add after the acidleach and carry out the vacuum refinement processing in the vacuum oven, vacuum refinement in two stages, fs is vor refining, temperature is 1430～1500 ℃ in the control stove, vacuum tightness is 90000～1000Pa, subordinate phase, be vacuum distilling refining and vacuum outgas stage, control stove vacuum tightness 10
-2～10
-5Pa, 1430～1500 ℃ of temperature after directional freeze and crop are handled, obtain the solar-grade polysilicon product.The purity of its silicon is more than 99.9999%, surpasses 0.4 Ω cm than resistance, to satisfy the requirement of the required silicon raw material of solar cell industry.
Application number is the patent application of 200710063653 " plasma producing method of polysilicon and devices thereof ", disclose a kind of method: feed temperature after preheating as the silane of raw material or halogenated silanes gas and hydrogen is 1450～1550 ℃ plasma switch room, mixture is heated to isoionic state in moment, in process of cooling, generate liquid or the fine powder and the gaseous by-product of silicon monomer, the liquid silicon monomer flows out through the liquid-state silicon spout, the silicon monomer fine powder enters the tail gas separate chamber with gaseous by-product to be separated, and isolated gas by-product enters the tail gas hold-up vessel.
Application number is the patent application of 200710045392 " making the devices and methods therefor of solar-grade polysilicon ", a kind of method is disclosed: select the low industrial silicon material of phosphorus and boron content for use, put into smelting pot, and crucible put into vacuum chamber, be evacuated earlier, again under the effect of plasma generator and Medium frequency induction coil, the silicon material is molten into silicon liquid, keeping the silicon liquid temp is 1410～1800 ℃, by increasing the power of ruhmkorff coil, silicon liquid is suspended then, then in plasma gun, feed reactant gases, produce plasma body, make the impurity reaction in reactant gases and the silicon liquid, remove the impurity in the silicon after, the moulding of silicon liquid, directional solidification, cut the part end to end of impurity enriched, rest part just becomes the polysilicon product that can be used for solar level.
Above method, in always having the following disadvantages one or multinomial:
1, investment is huge; The investment cost of polysilicon production capacity per ton is up to more than 1,000,000 yuan.
2, raw material availability is low.
3, high energy consumption.
4, production cost height.
5, tail gas or byproduct for treatment difficulty are big.
6, environmental pollution is serious.
7, poor product quality.
8, some gases of production process are inflammable and explosive, the accident of very easily blasting, poor stability.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of operational path novelty, reasonable is provided, and Equipment Requirement is low, realizes the method for industrialized less energy-consumption production polysilicon easily, this method is a raw material with silicon tetrafluoride and hydrogen, produces polysilicon or polysilicon chip.
The technical solution used in the present invention is as follows: a kind of method of producing polysilicon with silicon tetrafluoride reduced by plasmas, concrete steps are as follows: silicon tetrafluoride gas and hydrogen mixing back feeding as raw material have been full of in the plasma reactor of hydrogen, under the effect of plasma body, silicon tetrafluoride gas and hydrogen moment are heated to 1200 ℃～3500 ℃ concurrent biochemical reactions, generate polysilicon solid and hydrogen fluoride gas; The polysilicon solid, hydrogen fluoride gas, unreacted silicon tetrafluoride gas and the hydrogen that generate enter gas-solid separating device jointly, and polysilicon solid is separated, and purity can reach more than 99.9999%, becomes product; Hydrogen fluoride gas, unreacted silicon tetrafluoride gas and hydrogen enter condenser together, and hydrogen fluoride is condensed into liquid, and silicon tetrafluoride gas and hydrogen turn back to plasma reactor again.
Preferably, before the article on plasma reactor vacuumizes, be that substrate or substrate are put into plasma reactor with the polysilicon substrate material, the polysilicon that chemical reaction generates can directly deposit polysilicon membrane on substrate material; When sedimentary polysilicon membrane reaches certain thickness, can from plasma reactor, take out, as the raw material of making multi-crystal silicon film solar battery.
Preferably, the purity of silicon tetrafluoride gas is 99.99%～99.999%; The purity of hydrogen is 99.9999%～99.99999%.
Molar ratio when preferably, silicon tetrafluoride gas and hydrogen mix is 1: 2～1: 10.
Preferably, it be-15 ℃～10 ℃ that hydrogen fluoride gas is condensed into liquid temperature, and under this temperature, unreacted silicon tetrafluoride gas and hydrogen remain gaseous phase, can turn back in the interior or plasma reactor of mixing tank.
Preferably, before silicon tetrafluoride gas and hydrogen feeding plasma reactor, plasma reactor and intrasystem all devices vacuumize earlier, feed hydrogen then and carry out the system airflow cleaning, make total system be full of hydrogen after the cleaning; Open the plasma reactor power supply, produce plasma body in the plasma reactor.
Preparation method provided by the present invention, the main chemical reactions principle that relates to is as follows:
A. silicon tetrafluoride and hydrogen reaction generate silicon and hydrogen fluoride:
SiF
4+H
2→Si↓+2HF↑
Compared with prior art, the present invention has following beneficial effect:
1, operational path novelty, reasonable, Equipment Requirement is low, realizes suitability for industrialized production easily.
2, equipment is simple, reduced investment; The investment cost of polysilicon per ton has only 1/tens of existing production of polysilicon line.
3, production process simple, convenient, can form full-automatic Controlling System.
4, the production process energy consumption is very low, and raw materials consumption is very low, and starting material are very cheap, can reduce the production cost of polysilicon greatly.
5, quality product can meet the requirement of solar level.
6, produce the used hydrogen fluoride raw material of silicon tetrafluoride at the production system internal recycle, do not have byproduct, also can not produce environmental pollution.
Description of drawings
Fig. 1 is the process flow sheet of polysilicon powder;
Fig. 2 is the process flow sheet of polysilicon chip.
Embodiment
Following the present invention is described in conjunction with specific embodiments, but does not limit its protection domain.
Embodiment one:
1, is 99% silicon-dioxide powdery and hydrogen fluoride reaction to content, generates silicon tetrafluoride and water.It is 99.99% that silicon tetrafluoride gas is purified to purity; It to purity 99.9999% high-purity hydrogen the technical grade hydrogen purification.
2, silicon tetrafluoride gas behind the purifying and hydrogen are mixed in mixing tank.
3, plasma reactor and total system are vacuumized earlier, feed hydrogen behind the purifying then and carry out system airflow and clean, make total system be full of hydrogen after the cleaning; Open the plasma reactor power supply then, produce plasma body in the plasma reactor.
4, mixed hydrogen and silicon tetrafluoride gas are fed in the reactor.Chemical reaction produces immediately, the polysilicon powder occurs.
5, under the effect of air pump, mixed gas and polysilicon powder in the reactor come out from reactor together, enter gas-solid separator, and polysilicon solid is separated at this, becomes product, detect by analysis, and purity is 99.9999%.
6, mixed gas enters condenser, and under-5 ℃～-10 ℃ states, hydrogen fluoride gas is condensed into liquid state and stays in the condensate trap.Remaining gas comes back to mixing tank, recycles.
When 7, the hydrogen fluoride liquid state in the condensate trap accumulates to some amount, with pump delivery to the silicon tetrafluoride production equipment, with silicon dioxde reaction production silicon tetrafluoride gas again.
Embodiment two:
1, the purity of outsourcing is that the purity of 99.99% silicon tetrafluoride gas and outsourcing is that 99.9999% hydrogen is as raw material.
2, silicon tetrafluoride gas and hydrogen are mixed in mixing tank.
3, the substrate material that is used to produce solar battery sheet is inserted in the plasma reactor.
4, plasma reactor and follow up device are vacuumized earlier, feed hydrogen behind the purifying then and carry out system airflow and clean, make total system be full of hydrogen after the cleaning; Open the plasma reactor power supply then, produce plasma body in the plasma reactor.
5, mixed hydrogen and silicon tetrafluoride gas are fed in the reactor.Chemical reaction produces immediately, the polysilicon powder occurs, and deposits on underlay substrate; When depositing to certain thickness, polysilicon chip is taken out, directly become the material of making solar battery sheet.
6, under the effect of air pump, mixed gas and not sedimentary polysilicon powder in the reactor come out from reactor together, enter gas-solid separator, and polysilicon solid is separated at this, becomes product, detect by analysis, and purity is 99.9999%.
7, mixed gas enters condenser, and under-5 ℃～-10 ℃ states, hydrogen fluoride gas is condensed into liquid state and stays in the condensate trap.Remaining gas comes back to mixing tank, recycles.
When 8, the hydrogen fluoride liquid state in the condensate trap accumulates to some amount, with pump delivery to the silicon tetrafluoride production equipment, with silicon dioxde reaction production silicon tetrafluoride gas again.
Embodiment three:
1, selecting content for use is that 85%～99% silicon-dioxide powdery and content are 75%～99% Calcium Fluoride (Fluorspan) powder, is that 92%～100% sulfuric acid mixes the back chemical reaction takes place with content, produces silicon tetrafluoride gas.It is 99.99% that silicon tetrafluoride gas is purified to purity;
2, outsourcing purity is that 99.9999% high-purity hydrogen does raw material.
3, silicon tetrafluoride gas behind the purifying and high-purity hydrogen are mixed in mixing tank.
4, plasma reactor and follow up device are vacuumized earlier, feed hydrogen behind the purifying then and carry out system airflow and clean, make total system be full of hydrogen after the cleaning; Open the plasma reactor power supply then, produce plasma body in the plasma reactor.
5, mixed hydrogen and silicon tetrafluoride gas are fed in the reactor.Chemical reaction produces immediately, the polysilicon powder occurs.
6, under the effect of air pump, mixed gas and polysilicon powder in the reactor come out from reactor together, enter gas-solid separator, and polysilicon solid is separated at this, becomes product, detect by analysis, and purity is 99.9999%.
7, mixed gas enters condenser, and under-5 ℃～-10 ℃ states, hydrogen fluoride gas is condensed into liquid state and stays in the condensate trap.Remaining gas comes back to mixing tank, recycles.
When 8, the hydrogen fluoride liquid state in the condensate trap accumulates to some amount, with pump delivery to the silicon tetrafluoride production equipment, with silicon dioxde reaction production silicon tetrafluoride gas again.
Claims (6)
1. the method for a producing polysilicon with silicon tetrafluoride reduced by plasmas, it is characterized in that silicon tetrafluoride gas and hydrogen mixing back feeding as raw material have been full of in the plasma reactor of hydrogen, under the effect of plasma body, silicon tetrafluoride gas and hydrogen moment are heated to 1200 ℃～3500 ℃ concurrent biochemical reactions, generate polysilicon solid and hydrogen fluoride gas; The polysilicon solid, hydrogen fluoride gas, unreacted silicon tetrafluoride gas and the hydrogen that generate enter gas-solid separating device jointly, and polysilicon solid is separated, and purity can reach more than 99.9999%, becomes product; Hydrogen fluoride gas, unreacted silicon tetrafluoride gas and hydrogen enter condenser together, and hydrogen fluoride is condensed into liquid, and silicon tetrafluoride gas and hydrogen turn back to plasma reactor again.
2. the method for production polysilicon according to claim 1, it is characterized in that: be that substrate or substrate are put into plasma reactor with the polysilicon substrate material before the article on plasma reactor vacuumizes, the polysilicon that chemical reaction generates can directly deposit polysilicon membrane on substrate material; When sedimentary polysilicon membrane reaches certain thickness, can from plasma reactor, take out, as the raw material of making multi-crystal silicon film solar battery.
3. the method for production polysilicon according to claim 1 is characterized in that: the purity of silicon tetrafluoride gas is 99.99%～99.999%; The purity of hydrogen is 99.9999%～99.99999%.
4. the method for production polysilicon according to claim 1 is characterized in that: the molar ratio when silicon tetrafluoride gas and hydrogen mix is 1: 2～1: 10.
5. the method for production polysilicon according to claim 1, it is characterized in that: it is-15 ℃～10 ℃ that hydrogen fluoride gas is condensed into liquid temperature, under this temperature, unreacted silicon tetrafluoride gas and hydrogen remain gaseous phase, can turn back in the mixing tank or plasma reactor in.
6. the method for production polysilicon according to claim 1, it is characterized in that: before silicon tetrafluoride gas and hydrogen feeding plasma reactor, plasma reactor and intrasystem all devices vacuumize earlier, feed hydrogen then and carry out the system airflow cleaning, make total system be full of hydrogen after the cleaning; Open the plasma reactor power supply, produce plasma body in the plasma reactor.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101669A (en) * | 2011-04-07 | 2011-06-22 | 应盛荣 | Method for producing high-purity silicon carbide and hydrogen fluoride by taking silicon tetrafluoride as raw material |
| CN105271239A (en) * | 2015-10-28 | 2016-01-27 | 内江师范学院 | Method for preparing nanometer metallic silicon by plasma method |
| CN107515274A (en) * | 2016-06-15 | 2017-12-26 | 上海韵申新能源科技有限公司 | A kind of polycrystalline silicon production system quality evaluating method and device |
| CN113233422A (en) * | 2021-06-02 | 2021-08-10 | 四川大学 | Method and system for separating SiF4 and HF mixed gas |
| CN114394597A (en) * | 2022-01-24 | 2022-04-26 | 贵州理工学院 | Method for preparing silicon film by using silicon tetrafluoride as raw material |
| CN114560443A (en) * | 2022-03-02 | 2022-05-31 | 瓮福（集团）有限责任公司 | Microwave plasma device for simultaneously preparing hydrogen fluoride and crystalline silicon product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239723A (en) * | 2007-02-07 | 2008-08-13 | 北京明远通科技有限公司 | Plasma producing method and device for polycrystalline silicon |
| CN101688297A (en) * | 2007-06-07 | 2010-03-31 | 应用材料股份有限公司 | Be used to deposit the equipment and the manufacture method thereof of uniform silicon film |
-
2010
- 2010-08-05 CN CN 201010246191 patent/CN101928002A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239723A (en) * | 2007-02-07 | 2008-08-13 | 北京明远通科技有限公司 | Plasma producing method and device for polycrystalline silicon |
| CN101688297A (en) * | 2007-06-07 | 2010-03-31 | 应用材料股份有限公司 | Be used to deposit the equipment and the manufacture method thereof of uniform silicon film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101669A (en) * | 2011-04-07 | 2011-06-22 | 应盛荣 | Method for producing high-purity silicon carbide and hydrogen fluoride by taking silicon tetrafluoride as raw material |
| CN105271239A (en) * | 2015-10-28 | 2016-01-27 | 内江师范学院 | Method for preparing nanometer metallic silicon by plasma method |
| CN107515274A (en) * | 2016-06-15 | 2017-12-26 | 上海韵申新能源科技有限公司 | A kind of polycrystalline silicon production system quality evaluating method and device |
| CN113233422A (en) * | 2021-06-02 | 2021-08-10 | 四川大学 | Method and system for separating SiF4 and HF mixed gas |
| CN114394597A (en) * | 2022-01-24 | 2022-04-26 | 贵州理工学院 | Method for preparing silicon film by using silicon tetrafluoride as raw material |
| CN114560443A (en) * | 2022-03-02 | 2022-05-31 | 瓮福（集团）有限责任公司 | Microwave plasma device for simultaneously preparing hydrogen fluoride and crystalline silicon product |
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Application publication date: 20101229 |