CN104276572A - Slagging agent for melting of polysilicon medium and application method thereof - Google Patents
Slagging agent for melting of polysilicon medium and application method thereof Download PDFInfo
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- CN104276572A CN104276572A CN201310273232.XA CN201310273232A CN104276572A CN 104276572 A CN104276572 A CN 104276572A CN 201310273232 A CN201310273232 A CN 201310273232A CN 104276572 A CN104276572 A CN 104276572A
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- slag former
- medium melting
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Abstract
The invention belongs to the field of polysilicon medium melting, and relates to a slagging agent for melting of a polysilicon medium and an application method thereof. The slagging agent is formed by mixing the following raw materials: 40%-80% of SiO2, 10%-40% of CaO, 1%-15% of Al2O3 and 1%-5% of NaF. The usage steps are shown as following: (1) adding a silicon material into a graphite crucible, and heating to obtain completely-melt silicon; (2) adding the slagging agent into a mixer for uniform mixing; (3) adding the mixed slagging agent into the melt silicon, and keeping warm for medium melting; (4) after medium melting is finished, pouring out generated old slag; and (5) repeating the steps (3) and (4) for 2-4 times, cooling and solidifying the melt silicon, and using ICP-MS to measure the boron content of the silicon. The advantages comprise that (1) the slagging agent is capable of effectively improving the partition coefficient L[B] by 1-2 and improving the boron removal effect; and (2) slag adding for multiple times helps to effectively improve the utilization rate of the slag by 30% or more.
Description
Technical field
The invention belongs to polycrystalline silicon medium melting field, be specifically related to a kind of slag former and using method thereof of polycrystalline silicon medium melting.
Background technology
World today's energy dilemma and environmental pollution pressure are also deposited, and people are badly in need of cleaning, safety, continuable new forms of energy.Sun power, as meeting the energy required like this, always is the target that people pursue.People are the utilizations of its heat effect to the use of sun power the earliest, but are difficult to the needs meeting modern society completely.Until the discovery of photoresistance, the manufacture of solar cell, the Land use systems that people find sun power new.Silicon is as the most desirable feedstock of solar cell, impurity wherein mainly contains the nonmetallic impuritys such as metallic impurity and B, P such as Fe, Al, Ca, and these impurity elements can reduce the Compound Degree of silicon crystal grain interface photo-generated carrier, and the Compound Degree of photo-generated carrier determines the photoelectric transformation efficiency of solar cell, removing these impurity so effective has vital effect in the application aspect of solar cell.
The development of solar photovoltaic industry depends on the purification to silicon raw material, comprises medium melting, directional freeze, electron beam purification and casting ingot process in the process of polycrystalline silicon purifying.Metallurgy method has development potentiality because possessing simple, the lower-cost advantage of technique.Require that equipment is the simplest with slag practice in all multi-methods, the easiest industrialization promotion.Thus the researching value of medium melting most reality and application prospect.
Partition ratio reflects the transfer ability of solute in two-phase and separation efficiency.The ratio of the massfraction of boron in slag agent and the massfraction in silicon liquid, boron partition ratio, uses L
brepresent.After it illustrates that slag agent takes off boron, the allocation proportion that boron reaches between slag agent and silicon liquid.At present, the actual allocated coefficient L of domestic and international existing slag system
blower, numerical value 2-4, thus mean except effect of boron is not very desirable.
Summary of the invention
The object of this invention is to provide a kind of slag former and using method thereof of polycrystalline silicon medium melting, effectively can improve boron partition ratio L
b, improve except effect of boron.
The slag former of a kind of polycrystalline silicon medium melting of the present invention, is mixed by following raw material: SiO
240% ~ 80%, CaO10% ~ 40%, Al
2o
31%-15% and NaF1%-5%.
The slag former using method of polycrystalline silicon medium melting of the present invention, carry out according to following steps:
(1) silicon material is joined in plumbago crucible, adopt medium-frequency induction furnace to be heated to silicon material and be all fused into silicon liquid;
(2) slag former is joined in mixer mix according to raw material composition;
(3) slag former after mixing joins in silicon liquid, and medium melting is carried out in insulation;
(4), after medium melting terminates, the old slag produced all is poured out;
(5) repeating step (3) ~ (4) 2 ~ 4 times, silicon liquid, through cooled and solidified, measures its Boron contents through ICP-MS.
Wherein, preferably adopt following scheme in step (1): add in plumbago crucible by silicon material, adopt medium-frequency induction furnace hoisting power to 50 ~ 250kW, make silicon material all be fused into silicon liquid through 30 ~ 80min.
In step (2), mixing time is preferably 5 ~ 20min.
In step (3), the mass ratio of slag former and silicon liquid is preferably 0.3 ~ 1.2:1.
In step (3) can by the slag former after mixing disposable add after, keep power 30 ~ 150kW, keep melt upper surface temperature to be 1650 ~ 1750 DEG C, insulation 20 ~ 60min carries out medium melting.Also the slag former after mixing can be divided into 4 ~ 10 parts, interval 10 ~ 20min adds successively, keeps power 50 ~ 200kW, after adding completely, keep power 30 ~ 150kW, keep melt upper surface temperature to be 1650 ~ 1750 DEG C, insulation 20 ~ 60min carries out medium melting.
Preferably adopt following scheme in step (4): after medium melting terminates, the old slag produced all pours out by control temperature 1500 ± 20 DEG C.
Adopt slag former of the present invention and using method, the Boron contents of silicon material can be reduced to below 0.28ppmw.
The invention has the advantages that: (1) slag former combination of the present invention can effectively improve partition ratio L
bnumerical value 1-2, improves except effect of boron; (2) gradation adds the utilization ratio more than 30% that slag effectively can improve slag.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1:
Select slag former, mixed by following raw material: SiO
280% and CaO10%, Al
2o
35%, NaF5%.
When polycrystalline silicon medium melting except the slag former using method of boron, carry out according to following steps:
(1) 100kg silicon material is joined in plumbago crucible, adopt medium-frequency induction furnace hoisting power to 150W, make silicon material all be fused into silicon liquid through 60min;
(2) slag former is joined in mixer and mixes according to raw material composition, mixing time 10min;
(3), after the slag former after mixing is got that 50kg is disposable and added, keep power 100kW, keep melt upper surface temperature to be 1650 DEG C, insulation 35min carries out medium melting;
(4), after medium melting terminates, the old slag produced all pours out by control temperature 1500 ± 20 DEG C;
(5) repeating step (3) ~ (4) 2 times, silicon liquid, through cooled and solidified, obtains the polysilicon 78kg of refining, and to take multiple measurements polysilicon through ICP-MS and average, wherein B content is 0.27ppmw.
Embodiment 2:
Select slag former, mixed by following raw material: SiO
240% and CaO40%, Al
2o
315%, NaF5%.
When polycrystalline silicon medium melting except the slag former using method of boron, carry out according to following steps:
(1) 100kg silicon material is joined in plumbago crucible, adopt medium-frequency induction furnace hoisting power to 100kW, make silicon material all be fused into silicon liquid through 80min;
(2) slag former is joined in mixer and mixes according to raw material composition, mixing time 15min;
(3) 100kg got by the slag former after mixing, and is divided into 10 parts, and interval 15min adds successively, keeps power 50kW, after adding completely, keeps power 50kW, keeps melt upper surface temperature to be 1700 DEG C, and insulation 60min carries out medium melting;
(4), after medium melting terminates, the old slag produced all pours out by control temperature 1500 ± 20 DEG C;
(5) repeating step (3) ~ (4) 3 times, silicon liquid, through cooled and solidified, obtains the polysilicon 82kg of refining, and to take multiple measurements polysilicon through ICP-MS and average, wherein B content is 0.19ppmw.
Embodiment 3:
Select slag former, mixed by following raw material: SiO
260% and CaO30%, Al
2o
37%, NaF3%.
When polycrystalline silicon medium melting except the slag former using method of boron, carry out according to following steps:
(1) 100kg silicon material is joined in plumbago crucible, adopt medium-frequency induction furnace hoisting power to 200kW, make silicon material all be fused into silicon liquid through 40min;
(2) slag former is joined in mixer and mixes according to raw material composition, mixing time 20min;
(3) 30kg got by the slag former after mixing, and is divided into 6 parts, and interval 10min adds successively, keeps power 200kW, after adding completely, keeps power 150kW, keeps melt upper surface temperature to be 1750 DEG C, and insulation 20min carries out medium melting;
(4), after medium melting terminates, the old slag produced all pours out by control temperature 1500 ± 20 DEG C;
(5) repeating step (3) ~ (4) 4 times, silicon liquid, through cooled and solidified, obtains the polysilicon 80kg of refining, and to take multiple measurements polysilicon through ICP-MS and average, wherein B content is 0.21ppmw.
Embodiment 4:
Select slag former, mixed by following raw material: SiO
265% and CaO20%, Al
2o
310%, NaF5%.
When polycrystalline silicon medium melting except the slag former using method of boron, carry out according to following steps:
(1) 100kg silicon material is joined in plumbago crucible, adopt medium-frequency induction furnace hoisting power to 250kW, make silicon material all be fused into silicon liquid through 30min;
(2) slag former is joined in mixer and mixes according to raw material composition, mixing time 10min;
(3) 70kg got by the slag former after mixing, and is divided into 7 parts, and interval 15min adds successively, keeps power 250kW, after adding completely, keeps power 100kW, keeps melt upper surface temperature to be 1700 DEG C, and insulation 30min carries out medium melting;
(4), after medium melting terminates, the old slag produced all pours out by control temperature 1500 ± 20 DEG C;
(5) repeating step (3) ~ (4) 2 times, silicon liquid, through cooled and solidified, obtains the polysilicon 86kg of refining, and to take multiple measurements polysilicon through ICP-MS and average, wherein B content is 0.23ppmw.
Claims (8)
1. a slag former for polycrystalline silicon medium melting, is characterized in that being mixed by following raw material: SiO
240% ~ 80%, CaO10% ~ 40%, Al
2o
31%-15% and NaF1%-5%.
2. the slag former using method of polycrystalline silicon medium melting according to claim 1, is characterized in that carrying out according to following steps:
(1) silicon material is joined in plumbago crucible, adopt medium-frequency induction furnace to be heated to silicon material and be all fused into silicon liquid;
(2) slag former is joined in mixer mix according to raw material composition;
(3) slag former after mixing joins in silicon liquid, and medium melting is carried out in insulation;
(4), after medium melting terminates, the old slag produced all is poured out;
(5) repeating step (3) ~ (4) 2 ~ 4 times, silicon liquid, through cooled and solidified, measures its Boron contents through ICP-MS.
3. the slag former using method of polycrystalline silicon medium melting according to claim 2, it is characterized in that in step (1), silicon material being added in plumbago crucible, adopt medium-frequency induction furnace hoisting power to 50 ~ 250kW, make silicon material all be fused into silicon liquid through 30 ~ 80min.
4. the slag former using method of polycrystalline silicon medium melting according to claim 2, is characterized in that in step (2), mixing time is 5 ~ 20min.
5. the slag former using method of polycrystalline silicon medium melting according to claim 2, is characterized in that the mass ratio of slag former and silicon liquid in step (3) is 0.3 ~ 1.2:1.
6. the slag former using method of polycrystalline silicon medium melting according to claim 2, it is characterized in that after disposable for the slag former after mixing adding in step (3), keep power 30 ~ 150kW, keep melt upper surface temperature to be 1650 ~ 1750 DEG C, insulation 20 ~ 60min carries out medium melting.
7. the slag former using method of polycrystalline silicon medium melting according to claim 2, it is characterized in that, in step (3), the slag former after mixing is divided into 4 ~ 10 parts, interval 10 ~ 20min adds successively, keep power 50 ~ 200kW, after adding completely, keep power 30 ~ 150kW, keep melt upper surface temperature to be 1650 ~ 1750 DEG C, insulation 20 ~ 60min carries out medium melting.
8. the slag former using method of polycrystalline silicon medium melting according to claim 2, after it is characterized in that step (4) medium melting terminates, the old slag produced all pours out by control temperature 1500 ± 20 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555015A (en) * | 2009-05-19 | 2009-10-14 | 厦门大学 | Purifying method and device for removing boron from polysilicon |
| CN102001661A (en) * | 2010-11-22 | 2011-04-06 | 东海晶澳太阳能科技有限公司 | Method for slagging, boron removal and purification of metalluragical silicon |
| CN102530954A (en) * | 2012-03-07 | 2012-07-04 | 昆明理工大学 | Composite refining agent for secondary refining to purify industrial silicon and remove boron |
| CN102616787A (en) * | 2012-03-22 | 2012-08-01 | 厦门大学 | Method for removing boron-phosphorus impurities from silicon metal |
-
2013
- 2013-07-02 CN CN201310273232.XA patent/CN104276572B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555015A (en) * | 2009-05-19 | 2009-10-14 | 厦门大学 | Purifying method and device for removing boron from polysilicon |
| CN102001661A (en) * | 2010-11-22 | 2011-04-06 | 东海晶澳太阳能科技有限公司 | Method for slagging, boron removal and purification of metalluragical silicon |
| CN102530954A (en) * | 2012-03-07 | 2012-07-04 | 昆明理工大学 | Composite refining agent for secondary refining to purify industrial silicon and remove boron |
| CN102616787A (en) * | 2012-03-22 | 2012-08-01 | 厦门大学 | Method for removing boron-phosphorus impurities from silicon metal |
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