CN105819451B - A kind of DC electric field induces alloy directionally solidified growth, the technique of reinforced alloys refining process - Google Patents
A kind of DC electric field induces alloy directionally solidified growth, the technique of reinforced alloys refining process Download PDFInfo
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- CN105819451B CN105819451B CN201610131620.8A CN201610131620A CN105819451B CN 105819451 B CN105819451 B CN 105819451B CN 201610131620 A CN201610131620 A CN 201610131620A CN 105819451 B CN105819451 B CN 105819451B
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Abstract
The invention discloses a kind of alloy directionally solidified growth of DC electric field induction, the technique of reinforced alloys refining process：Si M foundry alloys are heated to corresponding liquidus temperature, Si M alloy melts are obtained, DC electric field is introduced into Si M alloy melts makes the silicon atom in Si M alloy melts that displacement occur, and is enriched with the bottom of graphite crucible, supersaturated region is formed, so as to forming core, growth in crystalline silicon substrate；In growth course, by continuous addition raw silicon at the top of graphite crucible, the continuous growth of crystalline silicon is realized.After growth terminates, thermal source is closed, dc source is closed after cooled and solidified.The present invention realizes the oriented growth pattern of high accurancy and precision, effectively reduce refining temperature, and the segregation coefficient of various impurity, reduce energy consumption, refining effect is enhanced, different impurities is redistributed under electric field action, by constantly adding raw silicon, silicon atom can continuously be provided while solidification separates out silicon, realizes the continuous growth of silicon.
Description
Technical field
The invention belongs to metallurgy method technology growth purifying polycrystalline silicon technical field, specifically a kind of DC electric field induction
Alloy directionally solidified growth, the technique of reinforced alloys refining process.
Background technology
Metallurgy method is a kind of exclusive purifying technique for manufacturing solar-grade polysilicon and proposing.This method uses metallurgical
Level silicon (MG-Si) is raw material, according to impurity and the otherness of silicon physicochemical properties, optimization set pickling, slag refining, vacuum
Smelt, carry the methods of beam melting, solidification refining, gradually reduce impurity content in silicon, realize impurity high selectivity, gradient type point
From the material of solar energy level silicon is finally prepared；
Alloy graining method of refining is proposed by northeastern Japan university Obinata and Komatsu in nineteen fifty-seven earliest, nowadays eastern
Capital university, University of Toronto, Dalian University of Technology, Kunming University, process study Suo Dengduosuo colleges and universities of the Chinese Academy of Sciences and scientific research institution
Researcher this is conducted extensive research.Alloy graining refining mainly utilizes impurity under low temperature to have thermodynamics in Si
Unstable property, i.e. with the reduction of temperature, the solid solubility of impurity gradually reduces.The addition metal into MG-Si is attempted to be formed
Silicon binary or multicomponent alloy melt so that Si separates out as primary phase under less than Si fusing points, is utilized in Si recrystallization processes
The reallocation behavior purification MG-Si of impurity；
The Moria and Yoshikawa of Tokyo University have carried out deep thermodynamic study and refining to Al-Si alloy systems
The research of effect.Under 1273K refining temperatures, 99% or so Fe, Ti can be removed by solidifying method of refining using a Si-Al
Impurity, reach the permission content of Fe and Ti in solar-grade polysilicon, at the same can also effectively remove 95%~98.6% B, P it is miscellaneous
Matter, but be difficult to once up to standard.Wu etc. has carried out Si-Sn alloys refining-directional solidification separation, purification MG-Si research, this method
Sn rubbish pollution is avoided, by total metals content impurity in MG-Si by 58.3x10-6Ppm is reduced to 7.6x10-6ppm。
Oshima etc. discusses the macroscopic property of Cu in Si using the method for balancing each other, and Cu solid solubility is about in Si at a temperature of 1273K
10ppma, while grown using directional freeze method in Si-Cu alloys and obtain block Si, Cu flux is effectively prevent to primary crystal
The pollution of silicon.Ban etc. have studied the dedoping step that Si-Al alloys refine under different electromagnetic field intensity, and research is found：With smaller
The metal impurities of segregation coefficient can be not only enriched in alloy phase, and partial impurities can also form similar such as Al with Si7Fe2Si and
Al5The interphase of the compounds such as FeSi；Zou etc. is carried out at MG-Si solidification refinings using the mode of heating (RMF) of rotating excitation field
Reason, enrichment SI layers can be formed in the edge of Si-Al alloys using the technology, are advantageous to Si and the separation of alloy phase.
Although MG-Si can be purified to certain effect by the purification technique studied at present, refining temperature declines, energy consumption
Substantially reduce, but due to introducing solvent metal, the final product for solidifying refining is alloy phase and primary phase, necessarily has Si and Al
Eutectic phase is formed, causes the primary phase of precipitation limited, while unavoidably causes rubbish pollutions of the solvent metal Al to primary silicon,
Efficiently separating for primary silicon and alloy is limited, makes later separation program cumbersome, increases production cost.Traditional directional solidification simultaneously
Technique is by Temperature Field Control, due to the limitation of actual experiment device, it is difficult to ensure that temperature is accurate, so as to not reach preferably
The effect of directional solidification growth.Therefore, a kind of to improve purification precision, the DC electric field for reaching desired orientation solidification growth result lures
Lead alloy directionally solidified growth, the technique of reinforced alloys refining process is urgently researched and developed.
The content of the invention
According to technical problem set forth above, and a kind of alloy directionally solidified growth of DC electric field induction is provided, strengthens and closes
The technique of gold refining process.The technological means that the present invention uses is as follows：
A kind of DC electric field induces alloy directionally solidified growth, the technique of reinforced alloys refining process, it is characterised in that tool
Have the following steps：
S1, the one or several kinds of metallic elements of selection, alloy is formed with elements Si；
S2, according to alloy phase diagram, alloy proportion needed for selection, and according to the proportioning, prepare melting and obtain Si-M foundry alloys；
S3, selection graphite crucible the insulation of graphite crucible madial wall, are placed high-purity as melting kettle in graphite crucible bottom
The broken grain of silicon is placed in graphite crucible as substrate, then by Si-M foundry alloys；
S4, Si-M foundry alloys are heated to corresponding liquidus temperature, obtain Si-M alloy melts, graphite electrode I is inserted
Enter in the Si-M alloy melts, start dc source, the graphite electrode I and graphite crucible connect the two of dc source respectively
Pole, can be according to the direction of metal M and Si electronegativity discrepancy adjustment both positive and negative polarity, to ensure that crystalline silicon can be in crucible bottom forming core simultaneously
Grow, corresponding liquidus temperature refers in alloy phase diagram, the liquidus temperature corresponding to required alloy proportion composition；
S5, from adding raw silicon into Si-M alloy melts at the top of graphite crucible, keep Si-M under the liquidus temperature
The proportioning of alloy melt, while keep the continuous growth of crystalline silicon；
After S6, end to be grown, thermal source is closed, dc source is closed after cooled and solidified.
The metallic element includes element al, Sn, Fe, Cu and Zn.
Insulating sleeve is set graphite crucible madial wall is insulated by the madial wall in the graphite crucible.
The bottom outer wall of the graphite crucible is provided with graphite electrode II, the graphite crucible by the graphite electrode II with
Dc source connects.
The source that preparation melting obtains the elements Si in Si-M foundry alloys is metallurgical grade silicon, and the raw silicon is metallurgical grade
Silicon.
Traditional handicraft uses the directional solidification growth of Temperature Field Control alloy, and control precision is not high, and the present invention is using straight
Electric field controls atomic migration is flowed, realizes the oriented growth pattern of high accurancy and precision；The present invention is replaced simple using Si-M alloy systems
The solidification purification of Si systems, effectively reduces refining temperature, and the segregation coefficient of various impurity, reduces energy consumption, enhance and carry
Pure effect；The application introduces DC electric field in alloy refining process, different impurities is redistributed under electric field action；This hair
It is bright to additionally provide a kind of continuous purifying technique, by constantly adding raw silicon, keep Si-M under the corresponding liquidus temperature to close
The proportioning of golden melt, silicon atom can continuously be provided while solidification separates out silicon, realizes the continuous growth of silicon.
The present invention can be widely popularized in fields such as metallurgy method technology growth purifying polycrystalline silicon technologies for the foregoing reasons.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is that a kind of DC electric field induces alloy directionally solidified growth, reinforced alloys in embodiment of the invention
The structural representation of refining process device.
Embodiment
As shown in figure 1, a kind of DC electric field induces alloy directionally solidified growth, the technique of reinforced alloys refining process, tool
Have the following steps：
S1, one or several kinds are selected in element al, Sn, Fe, Cu and Zn, alloy is formed with elements Si；
S2, according to alloy phase diagram, alloy proportion needed for selection, and according to the proportioning, prepare melting and obtain Si-M foundry alloys；
S3, selection graphite crucible 1 are used as melting kettle, the insulation of the madial wall of graphite crucible 1, are placed in the bottom of graphite crucible 1
The broken grain 2 of HIGH-PURITY SILICON is used as substrate, then Si-M foundry alloys are placed in graphite crucible 1；
S4, Si-M foundry alloys are heated to liquidus temperature, obtain Si-M alloy melts 3, graphite electrode I 4 is inserted into institute
State in Si-M alloy melts 3, start dc source 5, the graphite electrode I 4 and graphite crucible 1 connect the two of dc source 5 respectively
Pole, in the presence of DC electric field, displacement occurs for the silicon atom in Si-M alloy melts 3, and in the graphite crucible 1
Inwall bottom forming core, growth；
S5, raw silicon 6 is added into Si-M alloy melts 3, keep Si-M alloy melts 3 under the liquidus temperature into
Distribution ratio；
After S6, end to be grown, thermal source is closed, dc source 5 is closed after cooled and solidified.
The madial wall of the graphite crucible 1 has insulating sleeve 7.
The bottom outer wall of the graphite crucible 1 is provided with graphite electrode II 8, and the graphite crucible 1 passes through the graphite electrode
II 8 are connected with dc source 5.
The source that preparation melting obtains the elements Si in Si-M foundry alloys is metallurgical grade silicon, and the raw silicon 6 is metallurgical grade
Silicon.
The outer wall of the graphite crucible 1, which is provided with, is used to heating the heating coils 9 of Si-M alloys, and the two of the graphite crucible 1
End is respectively equipped with upper cover 10 and lower cover 11, and the graphite electrode I 4 is through the upper cover 10 and is inserted into the Si-M conjunctions
In golden liquation 3, the graphite electrode II 8 is connected through lower cover 11 with the graphite crucible 1, and the upper cover 10 is provided with charging
Mouth 12, the raw silicon 6 is dropped into the Si-M alloy melts 3 by feed device 13 from the charging aperture 12
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (3)
1. a kind of DC electric field induces alloy directionally solidified growth, the technique of reinforced alloys refining process, it is characterised in that has
Following steps：
S1, the one or several kinds of metallic elements of selection, alloy is formed with elements Si；
S2, according to alloy phase diagram, alloy proportion needed for selection, and according to the proportioning, prepare melting and obtain Si-M foundry alloys；
S3, selection graphite crucible the insulation of graphite crucible madial wall, HIGH-PURITY SILICON are placed in graphite crucible bottom as melting kettle
Broken grain is placed in graphite crucible as substrate, then by Si-M foundry alloys；
S4, Si-M foundry alloys are heated to corresponding liquidus temperature, obtain Si-M alloy melts, graphite electrode I is inserted into institute
State in Si-M alloy melts, start dc source, the graphite electrode I and graphite crucible connect the two poles of the earth of dc source, root respectively
According to the direction of metal M and Si electronegativity discrepancy adjustment both positive and negative polarity, to ensure that crystalline silicon in crucible bottom forming core and can grow；
S5, from adding raw silicon into Si-M alloy melts at the top of graphite crucible, keep Si-M alloys under the liquidus temperature
The proportioning of melt, while ensure the continuous growth of crystalline silicon；
Thermal source is closed after S6, end to be grown, dc source is closed after cooled and solidified；
The metallic element includes element al, Sn, Fe, Cu and Zn；
Insulating sleeve is set graphite crucible madial wall is insulated by the madial wall in the graphite crucible.
2. a kind of DC electric field induction according to claim 1 alloy directionally solidified growth, reinforced alloys refining process
Technique, it is characterised in that：The bottom outer wall of the graphite crucible is provided with graphite electrode II, and the graphite crucible passes through the graphite
Electrode II is connected with the electrode of dc source.
3. a kind of DC electric field induction according to claim 1 alloy directionally solidified growth, reinforced alloys refining process
Technique, it is characterised in that：The source that preparation melting obtains the elements Si in Si-M foundry alloys is metallurgical grade silicon, and the raw silicon is
Metallurgical grade silicon.
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| 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 |
| 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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