CN105819451A - Technology for inducing alloy directional solidification growth and reinforcing alloy refining process by direct current electric field - Google Patents
Technology for inducing alloy directional solidification growth and reinforcing alloy refining process by direct current electric field Download PDFInfo
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- CN105819451A CN105819451A CN201610131620.8A CN201610131620A CN105819451A CN 105819451 A CN105819451 A CN 105819451A CN 201610131620 A CN201610131620 A CN 201610131620A CN 105819451 A CN105819451 A CN 105819451A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
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Abstract
The invention discloses a technology for inducing alloy directional solidification growth and reinforcing an alloy refining process by an direct current electric field. The technology comprises the following steps: heating a Si-M mother alloy to a corresponding liquidus temperature in order to obtain a Si-M alloy melt, introducing the direct current electric field to the Si-M alloy melt to realize directional movement of silicon atoms in the Si-M alloy melt, enrichment at the bottom of a graphite crucible and formation of a supersaturated area in order to achieve nucleation and growth on a crystal silicon substrate; continuously adding raw material silicon from the top of the graphite crucible in the growth process in order to realize continuous growth of the crystalline silicon; and powering off a heat source after the growth ends to cool and solidify, and powering off a direct current power supply. The technology realizes a highly-accurate directional growth mode, effectively reduces the refining temperature and the fractional condensation coefficients of various impurities, reduces energy consumption, enhances the purifying effect, makes different impurities be afresh distributed under the action of an electric field, and allows silicon to be solidified and precipitated and the silicon atoms to be continuously provided through continuously adding the raw material silicon in order to realize continuous growth of silicon.
Description
Technical field
The invention belongs to metallurgy method technology growth purifying polycrystalline silicon technical field, specifically a kind of unidirectional current
Field induction alloy directionally solidified growth, the technique of reinforced alloys refining process.
Background technology
Metallurgy method is the exclusive purifying technique of one proposed for manufacturing solar-grade polysilicon.The method makes
It is raw material with metallurgical grade silicon (MG-Si), according to the diversity of impurity with silicon physicochemical properties, optimization set acid
Wash, slag refining, vacuum metling, carry beam melting, the solidification method such as refine, gradually reduce impurity in silicon
Content, it is achieved impurity height selectivity, gradient type separate, and finally prepare the material of solar energy level silicon；
Alloy graining method of refining is carried in nineteen fifty-seven by northeastern Japan university Obinata and Komatsu the earliest
Go out, nowadays Tokyo University, University of Toronto, Dalian University of Technology, Kunming University, Chinese Academy of Sciences's process study
This is conducted extensive research by the researcher of Suo Dengduosuo colleges and universities and scientific research institution.Alloy graining refine is main
It is to utilize impurity under low temperature to have the character of thermodynamic instability in Si, i.e. along with the reduction of temperature, miscellaneous
The solid solubility of matter is gradually lowered.Attempt in MG-Si, add metal and form silicon binary or multicomponent alloy melt,
Si is separated out as primary phase under less than Si fusing point, Si recrystallization process utilizes dividing again of impurity
Join behavior and purify MG-Si；
Moria and Yoshikawa of Tokyo University has carried out deep thermodynamic study to Al-Si alloy system
Research with refining effect.Under 1273K refining temperature, use a Si-Al solidification method of refining just can go
Except Fe, Ti impurity of about 99%, reach the permission content of Fe and Ti in solar-grade polysilicon, simultaneously
Also can effectively remove B, P impurity of 95%～98.6%, but be difficult to the most up to standard.Wu etc. have carried out Si-Sn
Alloy refine-directional solidification separates, purifies the research of MG-Si, this method avoid the rubbish pollution of Sn,
By metals content impurity total in MG-Si by 58.3x10-6Ppm is reduced to 7.6x10-6ppm.Oshima etc. adopt
Discussing the macroscopic property of Cu in Si by the method for balancing each other, at a temperature of 1273K, in Si, Cu solid solubility is about
For 10ppma, use directional freeze method to grow in Si-Cu alloy simultaneously and obtain block Si, be prevented effectively from
The Cu flux pollution to primary silicon.Ban etc. have studied Si-Al alloy refine under different electromagnetic field intensity
Dedoping step, research finds: have the metal impurities of less segregation coefficient not only can be enriched in alloy mutually in,
Partial impurities also can be formed similar such as Al with Si7Fe2Si and Al5The mesophase of the compounds such as FeSi；Zou etc. adopt
Carry out MG-Si with the mode of heating (RMF) of rotating excitation field and solidify refining treatment, apply this technology can be
The edge of Si-Al alloy forms enrichment SI layer, beneficially Si and separates with alloy phase.
Although MG-Si can be purified to certain effect by the purification technique of research at present, refining temperature declines,
Energy consumption is greatly reduced, but owing to introducing solvent metal, the end product of solidification refine is alloy phase and primary crystal
Phase, necessarily has Si Yu Al and forms eutectic phase, causes the primary phase separated out limited, unavoidably causes simultaneously
The solvent metal Al rubbish pollution to primary silicon, limits efficiently separating of primary silicon and alloy, makes follow-up point
Loaded down with trivial details from program, increase production cost.Simultaneously tradition directional solidification processes is by Temperature Field Control, due to
The restriction of actual experiment device, it is difficult to ensure that temperature is accurate, thus does not reaches preferable directional solidification growth
Effect.Therefore, a kind of raising purifies precision, reaches the DC electric field induction of desired orientation solidification growth result
Alloy directionally solidified growth, the technique of reinforced alloys refining process are urgently researched and developed.
Summary of the invention
According to technical problem set forth above, and provide a kind of DC electric field induce alloy directionally solidified growth,
The technique of reinforced alloys refining process.The technological means that the present invention uses is as follows:
A kind of DC electric field induction alloy directionally solidified growth, the technique of reinforced alloys refining process, its feature
It is that there are following steps:
S1, select one or several metallic elements, form alloy with elements Si；
S2, according to alloy phase diagram, select required alloy proportion, and according to this proportioning, preparation melting obtain Si-M
Foundry alloy；
S3, selection graphite crucible are as melting kettle, and insulate in graphite crucible medial wall, bottom graphite crucible
The broken grain of placement HIGH-PURITY SILICON is as substrate, then is placed in graphite crucible by Si-M foundry alloy；
S4, Si-M foundry alloy is heated to corresponding liquidus temperature, obtains Si-M alloy melt, by stone
Electrode ink I inserts in described Si-M alloy melt, starts DC source, described graphite electrode I and graphite earthenware
Crucible connects the two poles of the earth of DC source respectively, can according to the direction of the electronegativity discrepancy adjustment both positive and negative polarity of metal M Yu Si,
To ensure that crystalline silicon can be at crucible bottom forming core and grow, corresponding liquidus temperature refers in alloy phase
Liquidus temperature in figure, corresponding to required alloy proportion composition；
S5, in Si-M alloy melt, added raw silicon by graphite crucible top, keep described liquidus temperature
The proportioning of lower Si-M alloy melt, keeps the continuous growth of crystalline silicon simultaneously；
After S6, end to be grown, close thermal source, after cooled and solidified, close DC source.
Described metallic element includes element al, Sn, Fe, Cu and Zn.
Graphite crucible medial wall is made to insulate by arranging insulated sleeve in the medial wall of described graphite crucible.
The bottom outer wall of described graphite crucible is provided with graphite electrode II, and described graphite crucible is by described graphite electricity
Pole II is connected with DC source.
It is metallurgical grade silicon that preparation melting obtains the source of the elements Si in Si-M foundry alloy, and described raw silicon is smelting
Gold level silicon.
Traditional handicraft uses the directional solidification growth of Temperature Field Control alloy, controls precision the highest, the present invention
DC electric field is used to control atomic migration, it is achieved the oriented growth pattern of high accurancy and precision；The present invention uses Si-M
Alloy system replaces the solidification of simple Si system to purify, and effectively reduces refining temperature, and various impurity
Segregation coefficient, reduces energy consumption, enhances refining effect；The application introduces unidirectional current in alloy refining process
, make different impurities redistribute under electric field action；Present invention also offers a kind of purifying technique continuously,
By constantly adding raw silicon, keep the proportioning of Si-M alloy melt under described corresponding liquidus temperature, solidifying
Admittedly silicon atom can continuously be provided while separating out silicon, it is achieved the continuous growth of silicon.
The present invention extensively can push away in fields such as metallurgy method technology growth purifying polycrystalline silicon technology for the foregoing reasons
Extensively.
Accompanying drawing explanation
The present invention is further detailed explanation with detailed description of the invention below in conjunction with the accompanying drawings.
Fig. 1 be the present invention detailed description of the invention in a kind of DC electric field induce alloy directionally solidified growth, strong
The structural representation of alloy refining process device.
Detailed description of the invention
As it is shown in figure 1, a kind of DC electric field induces alloy directionally solidified growth, reinforced alloys refining process
Technique, has following steps:
S1, in element al, Sn, Fe, Cu and Zn, select one or several, formed with elements Si and close
Gold；
S2, according to alloy phase diagram, select required alloy proportion, and according to this proportioning, preparation melting obtain Si-M
Foundry alloy；
S3, selection graphite crucible 1 are as melting kettle, and insulate in graphite crucible 1 medial wall, at graphite crucible 1
The broken grain 2 of bottom placement HIGH-PURITY SILICON is as substrate, then is placed in graphite crucible 1 by Si-M foundry alloy；
S4, Si-M foundry alloy is heated to liquidus temperature, obtains Si-M alloy melt 3, by graphite electricity
Pole I 4 is inserted in described Si-M alloy melt 3, starts DC source 5, described graphite electrode I 4 and graphite
Crucible 1 connects the two poles of the earth of DC source 5 respectively, under the effect of DC electric field, in Si-M alloy melt 3
Silicon atom generation displacement, and forming core, growth bottom the inwall of described graphite crucible 1；
S5, in Si-M alloy melt 3, add raw silicon 6, keep under described liquidus temperature Si-M to close
The composition proportion of gold melt 3；
After S6, end to be grown, close thermal source, after cooled and solidified, close DC source 5.
The medial wall of described graphite crucible 1 has insulated sleeve 7.
The bottom outer wall of described graphite crucible 1 is provided with graphite electrode II 8, and described graphite crucible 1 is by described stone
Electrode ink II 8 is connected with DC source 5.
It is metallurgical grade silicon that preparation melting obtains the source of the elements Si in Si-M foundry alloy, described raw silicon 6
For metallurgical grade silicon.
The outer wall of described graphite crucible 1 is provided with the heating coil 9 for heating Si-M alloy, described graphite earthenware
Crucible 1 be respectively arranged at two ends with cover 10 and lower cover 11, described graphite electrode I 4 is through described upper cover
10 and be inserted in described Si-M alloy molten solution 3, described graphite electrode II 8 through lower cover 11 with described
Graphite crucible 1 connects, and described upper cover 10 is provided with charging aperture 12, and described raw silicon 6 passes through pay-off
13 drop into described Si-M alloy melt 3 from described charging aperture 12
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office
Being limited to this, any those familiar with the art is in the technical scope that the invention discloses, according to this
The technical scheme of invention and inventive concept thereof in addition equivalent or change, all should contain the protection in the present invention
Within the scope of.
Claims (5)
1. DC electric field induction alloy directionally solidified growth, a technique for reinforced alloys refining process, it is special
Levy and be that there are following steps:
S1, select one or several metallic elements, form alloy with elements Si；
S2, according to alloy phase diagram, select required alloy proportion, and according to this proportioning, preparation melting obtain Si-M
Foundry alloy；
S3, selection graphite crucible are as melting kettle, and insulate in graphite crucible medial wall, bottom graphite crucible
The broken grain of placement HIGH-PURITY SILICON is as substrate, then is placed in graphite crucible by Si-M foundry alloy；
S4, Si-M foundry alloy is heated to corresponding liquidus temperature, obtains Si-M alloy melt, by stone
Electrode ink I inserts in described Si-M alloy melt, starts DC source, described graphite electrode I and graphite earthenware
Crucible connects the two poles of the earth of DC source respectively, can according to the direction of the electronegativity discrepancy adjustment both positive and negative polarity of metal M Yu Si,
To ensure that crystalline silicon can be at crucible bottom forming core and grow；
S5, in Si-M alloy melt, added raw silicon by graphite crucible top, keep described liquidus temperature
The proportioning of lower Si-M alloy melt, ensures the continuous growth of crystalline silicon simultaneously；
Close thermal source after S6, end to be grown, after cooled and solidified, close DC source.
A kind of DC electric field induction alloy directionally solidified growth, reinforced alloys the most according to claim 1
The technique of refining process, it is characterised in that: described metallic element includes element al, Sn, Fe, Cu and Zn.
A kind of DC electric field induction alloy directionally solidified growth, reinforced alloys the most according to claim 1
The technique of refining process, it is characterised in that: make by arranging insulated sleeve in the medial wall of described graphite crucible
Insulate in graphite crucible medial wall.
A kind of DC electric field induction alloy directionally solidified growth, reinforced alloys the most according to claim 1
The technique of refining process, it is characterised in that: the bottom outer wall of described graphite crucible is provided with graphite electrode II, institute
State graphite crucible to be connected with the electrode of DC source by described graphite electrode II.
A kind of DC electric field induction alloy directionally solidified growth, reinforced alloys the most according to claim 1
The technique of refining process, it is characterised in that: preparation melting obtains the source of the elements Si in Si-M foundry alloy and is
Metallurgical grade silicon, described raw silicon is metallurgical grade silicon.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587071A (en) * | 2016-12-30 | 2017-04-26 | 大连理工大学 | Equipment and method for improving purification yield of polycrystalline silicon through transversely solidifying and overlapping electric field |
| CN114875484A (en) * | 2022-04-15 | 2022-08-09 | 大连理工大学 | Method for preparing high-purity silicon by recovering diamond wire cutting silicon powder through electric field coupling directional solidification technology |
| CN115650239A (en) * | 2022-09-13 | 2023-01-31 | 昆明理工大学 | Method for efficiently removing impurities in metallurgical-grade silicon |
| CN115650239B (en) * | 2022-09-13 | 2024-04-26 | 昆明理工大学 | Method for efficiently removing impurities in metallurgical-grade silicon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898763A (en) * | 2009-05-25 | 2010-12-01 | 高向瞳 | Method for preparing electric-field directional solidification purified polysilicon |
| RU2010146687A (en) * | 2010-11-17 | 2012-05-27 | Общество с ограниченной ответственностью "Энергия" (RU) | METHOD FOR CLEANING METALLURGIC SILICON MOISTURIZED BY AC PLASMA IN VACUUM |
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2016
- 2016-03-08 CN CN201610131620.8A patent/CN105819451B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898763A (en) * | 2009-05-25 | 2010-12-01 | 高向瞳 | Method for preparing electric-field directional solidification purified polysilicon |
| RU2010146687A (en) * | 2010-11-17 | 2012-05-27 | Общество с ограниченной ответственностью "Энергия" (RU) | METHOD FOR CLEANING METALLURGIC SILICON MOISTURIZED BY AC PLASMA IN VACUUM |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587071A (en) * | 2016-12-30 | 2017-04-26 | 大连理工大学 | Equipment and method for improving purification yield of polycrystalline silicon through transversely solidifying and overlapping electric field |
| CN106587071B (en) * | 2016-12-30 | 2018-09-04 | 大连理工大学 | A kind of lateral solidification superposition of electric field improves the device and method of polycrystalline silicon purifying yield |
| CN114875484A (en) * | 2022-04-15 | 2022-08-09 | 大连理工大学 | Method for preparing high-purity silicon by recovering diamond wire cutting silicon powder through electric field coupling directional solidification technology |
| CN115650239A (en) * | 2022-09-13 | 2023-01-31 | 昆明理工大学 | Method for efficiently removing impurities in metallurgical-grade silicon |
| CN115650239B (en) * | 2022-09-13 | 2024-04-26 | 昆明理工大学 | Method for efficiently removing impurities in metallurgical-grade silicon |
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