CN103922344B - Reclaim the method preparing solar level silicon materials - Google Patents
Reclaim the method preparing solar level silicon materials Download PDFInfo
- Publication number
- CN103922344B CN103922344B CN201410166001.3A CN201410166001A CN103922344B CN 103922344 B CN103922344 B CN 103922344B CN 201410166001 A CN201410166001 A CN 201410166001A CN 103922344 B CN103922344 B CN 103922344B
- Authority
- CN
- China
- Prior art keywords
- silicon
- solar level
- silicon powder
- silicon materials
- sawdust
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 84
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 79
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 155
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 93
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 62
- 239000010703 silicon Substances 0.000 claims abstract description 62
- 230000008569 process Effects 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 238000011084 recovery Methods 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims description 41
- 230000003647 oxidation Effects 0.000 claims description 38
- 238000007254 oxidation reaction Methods 0.000 claims description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000002269 spontaneous effect Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 32
- 239000000377 silicon dioxide Substances 0.000 abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000005520 cutting process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 229910052796 boron Inorganic materials 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 229910052698 phosphorus Inorganic materials 0.000 description 13
- 235000013339 cereals Nutrition 0.000 description 12
- 229910021419 crystalline silicon Inorganic materials 0.000 description 12
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 12
- 239000011856 silicon-based particle Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 229960001866 silicon dioxide Drugs 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000004484 Briquette Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
Reclaim the method preparing solar level silicon materials, it relates to the preparation method of solar level silicon materials, it provides the method for a kind of surface with the silicon powder manufacture silicon materials of silicon dioxide layer.It is as follows that present method comprises step: collect silicon powder, be placed in sealed furnace, in pure hydrogen atmosphere, be heated to the temperature range of below fusing point, continuing to be incubated under the condition passing into dry hydrogen gas, the silicon dioxide layer on Si powder surface and other impurity are removed, obtain solar level silicon materials.Utilize this law that the surface of recovery can be utilized to prepare solar level silicon materials with the silicon powder of silicon dioxide layer, comprise and utilize the sawdust in silicon crystal cutting processing process to prepare solar level silicon materials.
Description
Technical field
The present invention relates to the preparation method of solar level silicon materials.Be specifically related to utilize the silicon powder reclaimed from photovoltaic Special cutting fluid to prepare the method for solar-grade polysilicon.
Background technology
At present, the main raw material(s) of photovoltaic industry is crystalline silicon, and in the following period of time in future, crystalline silicon still can hold dominant position in the continuation of insurance of photovoltaic industry relaying.The silicon materials that photovoltaic cell uses require that the content of wherein major impurity is in ppma (on an atomic basis 1,000,000/) level or lower scope, metallurgical grade (MG) silicon materials can not directly use because not reaching this purity requirement, therefore, the purity of metallurgical grade silicon material must be made to reach the standard of solar level silicon materials by purifying.
Also use HIGH-PURITY SILICON in semi-conductor industry, the impurity in unicircuit requirement crystalline silicon is within the scope of ppba (on an atomic basis part per billion).Utilize chemical process can obtain this highly purified crystalline silicon, at the operational path of this method be: metallurgical grade silicon reaction forms gas or liquid, such as i.e. silane or halogenated silanes, then the purity of their rectifying to needs, finally by method concentrated gas or the liquid of such as thermolysis, form crystalline silicon.This method technique is loaded down with trivial details and consume a large amount of energy, thus causes the expensive of semiconductor crystal silicon.
In photovoltaic industry, the normal crystalline silicon fragment of semi-conductor industry that uses reduces material cost, but after the consumption demand of solar level silicon materials (SoG) exceedes the remaining crystal silicon chip of semi-conductor industry, this method is just no longer applicable.This situation makes people more pay close attention to the exploitation of SoG novel process, simultaneously also in the utilization ratio improving SoG.
The general technology flow process of current production solar panel is: first crystalline silicon raw material saws dice, and then thinly slices.The sawdust that sawing crystalline silicon produces is made up of to the silicon particle in a few micrometer range in submicron size, the silicon crystal converting feedstock of half can be sawdust by sawing process, this just needs to reclaim silicon particle from sawdust, and it is used as solar level silicon materials again.But, produce in sawing process in sawdust, not only containing abrasive, the metal particle that sawline comes off, owing to contacting with oxygen at the Si oxide that silicon particle surface is formed, and carry out owing to crystalline silicon being placed on borosilicate glass during sawing operation, under the high temperature action produced when sawing, boron, the impurity such as phosphorus can enter into the intracell of crystal silica flour, impurity in sawdust from kind and quantitatively, suitable with the impurity level of metallurgical grade silicon, how by the Impurity removal in these sawdust, make solar level crystalline silicon, it is the difficult problem that technician faces.
Publication number be EP0158563 to European patent discloses a kind of particle diameter produced in silicon wafer manufacturing processed that utilizes be that the method for silicon materials produced by the sawdust of 40 μm; the method is: in argon gas atmosphere; with arc discharge method, the sawdust under container mesexine is heated until fusing; do not have the top layer sawdust melted prevents in contaminating impurity container material as protective layer, wherein can adulterate in argon gas atmosphere hydrogen.In silicon materials prepared by this method, foreign matter content is higher, does not reach solar level standard.
Report in National Renewable Energy in August calendar year 2001 laboratory, " produce solar energy level silicon material (SoG) by refined metallurgy silicon (MG) liquid; pointing out in document the metallurgical grade silicon of melting to be purified obtain producing solar level silicon materials (SoG); in the liquid phase of refining; vacuum-treat in conjunction with slag former use, be blown into reactant gases (wet argon gas, preferably wet hydrogen) simultaneously; all impurity elements existed in metallurgical grade silicon can reduce to ppma level level, then directional freeze.The summary part of test-results is pointed out in the text, adopts separately a kind of technology not reach effect, must adopt the combination of multiple technologies, but also propose, except the impurity of dephosphorization and boron is the most difficult, can remove boron by reaction below.
SiO(g)+1/2H
2(g)+B(l)→Si(l)+HBO(g)(I)
By above-mentioned reaction, the HBO gas of generation just can be separated together with Purge gas from melts.Metallurgical grade silicon heating materials must can be realized Impurity removal to molten state by the method, purify obtain solar level silicon materials, not only energy consumption high and also need use slag former.
The patent No. is a kind of method that the patent of WO2008031229 World Intellectual Property Organization WIPO group proposes Refining molten state silicon, and the method heats a rotating drum type stove by using oxygen-enriched burner, provides one to comprise H on the surface of liquid-state silicon
2, O
2, CO and CO
2oxidizing atmosphere, melts is covered with slag, the several metal oxide of Absorbable rod Al, Ba, Ca, K, Mg, Na, Sr, Zn, C and B element is contained in slag, the absorption of oxide compound is utilized to remove Al, Ba, Ca, K, Mg, Na, Sr, Zn, C and B, experimental data in this section of document shows, can be removed the boron of 23% ~ 26% by this method.Clearance for the boron impurity removed extremely difficult in silicon crystal is lower.
Publication number is a kind of method U.S. patents disclosing Refining solid state si of US20070202029, under condition of negative pressure, (micro-wet argon gas is usually selected) in argon gas atmosphere, particle diameter is the temperature that the solid-state silicon particle of 90-500 μm is warming up to lower than fusing point, preferred temperature range is 1300 ~ 1400 DEG C, vacuum tightness is 1 ~ 100Pa, be incubated 36 hours, and solid-state silicon particle is the metallurgical grade silicon of mechanical grinding.Experimental data in literary composition shows that P, Ca, Cu, Mg, Mn, Na, Sn and Zn in solid state si all decrease, and wherein the clearance of phosphorus is only 23% ~ 76% through process.The method belongs to physical refining method of purification, has that soaking time is long, energy consumption is huge, and the defect that removal of impurity is low, cannot reach the standard of solar level silicon materials.
Summary of the invention
The present invention is the technical problem that clearance is low, energy consumption is high for boron, phosphoric in the method that will solve existing metallurgical grade silicon material Refining silicon, and provides the method reclaiming and prepare solar level silicon materials.
The present invention utilizes surface with the silicon powder of silicon dioxide layer, prepares solar level silicon materials by Refining silicon, utilizes the zone of oxidation degree of depth removal impurity element such as boron, phosphorus wherein of silicon powder simultaneously.
The method that solar level silicon materials are prepared in recovery of the present invention comprises the following steps:
One, the silicon powder that surface has a zone of oxidation is placed in the containers such as crucible, then the containers such as crucible are placed in airtight high temperature sintering furnace;
Two, in airtight stoving oven, pass into rare gas element, make silicon powder be placed in inert atmosphere;
Three, the rare gas element in airtight stoving oven is replaced with dry hydrogen gas;
Four, intensification makes the temperature of the vessels crucible in sintering oven and silicon powder rise to t DEG C, and wherein T-400≤t < T, T are the fusing point of silicon powder, and insulation, continues to pass into dry hydrogen gas in insulating process;
Five, continuing under the condition passing into dry hydrogen gas, cooling makes the temperature of silicon phase lower than 300 DEG C, obtains solar level silicon materials.
It is considered herein that the zone of oxidation on silicon powder surface is not a kind of trouble, but a kind of favourable condition, utilize dry hydrogen gas, make the zone of oxidation of dry hydrogen and silicon powder and impurity element that complicated reaction occur, in removal silicon materials while zone of oxidation, impurity element is removed, effective equally for boron, the phosphoric being arranged in structure cell.Therefore, the present invention is a kind of silicon powder utilizing surface to have zone of oxidation prepares solar level silicon materials method by refining.
The inventive method rapidly and efficiently can remove the element that in metallurgical grade silicon material lattice, P, B two kinds difficulty is removed, and reaches above-mentioned effect in the solid phase stage, and making metallurgical grade silicon be transformed into solar level silicon materials becomes possibility, has the advantages that energy consumption is low and the time is short.
Adopt method of the present invention can when compared with less energy-consumption, do not change silicon materials phase solar level crystalline silicon raw material sawdust is purified, reach the target of recycling.
The present invention is obtained solar level silicon materials in oxygen-free environment, to heat founding immediately become large-sized ingot casting, just may be used for photovoltaic industry, as solar level silicon material.
Accompanying drawing explanation
Fig. 1 is the electron microscopic pattern photo of the sawdust containing silicon powder particle in test 3;
Fig. 2 is the photo of the sawdust after test 3 processes; Small-particle is wherein silicon grain;
Fig. 3 is the electron microscopic pattern photo of the sawdust after test 3 processes; Spherical particle is wherein silicon grain;
Fig. 4 is the photo with the solar level ingot casting obtained after the solar energy level silicon material granule heating and melting cooling process of near-spherical in test 3.
Embodiment
Embodiment one: the method that solar level silicon materials are prepared in the recovery of present embodiment comprises the following steps:
One, the silicon powder that surface has a zone of oxidation is placed in the containers such as crucible, then the containers such as crucible are placed in airtight high temperature sintering furnace;
Two, in airtight stoving oven, pass into rare gas element, make silicon powder be placed in inert atmosphere;
Three, the rare gas element in airtight stoving oven is replaced with dry hydrogen gas;
Four, intensification makes the temperature of the vessels crucible in sintering oven and silicon powder rise to t DEG C, is incubated, continues to pass into dry hydrogen gas in insulating process at t DEG C; Wherein T-400≤t < T, T are the fusing point of silicon powder, and unit is DEG C;
Five, continuing under the condition passing into dry hydrogen gas, cooling makes the temperature of silicon phase lower than 300 DEG C, obtains solar level silicon materials.
Embodiment two: present embodiment and embodiment one unlike: in step one, silicon powder is placed on after in the containers such as crucible silicon powder compacting.Other is identical with embodiment one.
Compacting operation can prevent from silicon powder from vacuumizing or passing at body of heater in the process of gas being dispelled by argon gas or hydrogen etc.Or discharge system along with gas flow, make loss of material serious.
Embodiment three: present embodiment and embodiment one or two have the silicon powder of zone of oxidation zone of oxidation unlike the surface in step one is spontaneous or initiatively applies.Other are identical with embodiment one or two.
The self-assembling formation of the zone of oxidation on the silicon powder surface in present embodiment refers to: silicon grain is exposed in oxygen-containing gas, thus forms silicon dioxide layer in its surface.The thickness of this silicon dioxide layer is arbitrary, and it can obtain by just exposing in atmosphere.The zone of oxidation on silicon powder surface also can be the silicon dioxide layer of initiatively coating.The thickness of the method oxide skin of present embodiment is how much be all effective, and thickness directly has influence on the amounts of hydrogen of needs and the speed of chemical reaction.
Embodiment four: present embodiment and embodiment one to three are silicon nitride crucible with cover or alumina crucible unlike the container described in step one.Other are identical with one of embodiment one to three.
The container of the silicon powder of splendid attire band zone of oxidation, can be crucible, silicon powder is put into crucible, then crucible is put into sintering oven.Crucible can be silicon nitride (Si
3n
4) crucible or aluminum oxide (Al
2o
3) crucible, crucible can be with lid, and the material of lid is silicon nitride (Si
3n
4) or aluminum oxide (Al
2o
3).
Embodiment five: one of present embodiment and embodiment one to four are argon gas unlike described rare gas element.Other are identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to six unlike the dry hydrogen gas described in step 3 for referring to that moisture content is lower than H
2, H
2o, Si and SiO
2h in the phasor of system
2the hydrogen of the equilibrium pressure line of force of O.Other are identical with one of embodiment one to three.
For this strict purity requirement of hydrogen, present embodiment means that the hydrogen above silicon phase should constantly carry out supplementing, replacing with fresh hydrogen, thus the chemical substance of generation is transferred out, if pass into fresh dry hydrogen discontinuous, reaction can stop.
Embodiment seven: present embodiment and embodiment six refer to the hydrogen of foreign matter content lower than 1,000,000/(ppma) unlike dry hydrogen gas.Other is identical with embodiment six.
In present embodiment, foreign matter content lower than the hydrogen of 1,000,000/(ppma), the namely hydrogen of purity more than 99.9999%.
Embodiment eight: present embodiment and embodiment six refer to the hydrogen of foreign matter content lower than 1/100000000th (ppba) unlike dry hydrogen gas.Other is identical with embodiment six.
In present embodiment, foreign matter content is lower than the hydrogen of 1/100000000th (ppba), and the namely hydrogen of purity more than 99.9999999%, with such hydrogen, understands better to the removal effect of the impurity in silicon powder.
Embodiment nine: one of present embodiment and embodiment one to eight are unlike also comprising the operation vacuumized before heating.Other are identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to eight are unlike being also included in the operation vacuumized before sintering oven temperature rises to 300 DEG C.Other are identical with one of embodiment one to eight.
In embodiment nine and ten, in order to remove volatile matter from silicon powder end, can be evacuated in the furnace chamber of sintering oven before sintering oven heats up, also can be evacuated in the furnace chamber of sintering oven at the sintering oven initial stage of heating up, preferably in step 4, sintering oven vacuumizes before being warming up to 300 DEG C.
Embodiment 11: one of present embodiment and embodiment one to ten are 1 minute to 15 hours unlike the soaking time in step 4.Other is identical with embodiment one to ten.
In present embodiment, in certain temperature range below silicon powder fusing point, keep certain hour, to ensure that the oxide compound on silicon grain surface contacts with hydrogen completely.This period of hold-time is from several minutes by several hours.The length of hold-time is determined according to reaction kinetics, more accurately puts, and is to depend on hydrogen be diffused into the size of the mass transfer velocity of melting or solid silica phase and silicon phase and determine.
Embodiment 12: the silicon powder that one of present embodiment and embodiment one to ten one have zone of oxidation unlike surface utilizes water or aqueous mixture to produce in the process of machine silicon material.Other is identical with one of embodiment one to ten one.
The silicon powder that the utilization of present embodiment has a zone of oxidation prepares the method for silicon materials, of many uses.Wherein, utilizing the surface of reclaiming to prepare silicon materials with the silicon powder of silicon dioxide layer is exactly one of them.In present embodiment, surface has the silicon powder of zone of oxidation is utilize water or aqueous mixture to produce in the process of machine silicon material, the silica soot of this band zone of oxidation is reclaimed, for the preparation of silicon materials, significant.
Embodiment 13: present embodiment and embodiment 12 unlike utilizing water or aqueous mixture in the process of machine silicon material are: process the sawing of silicon ingot or silicon wafer, grinding, milling Xian, cutting, polishing or the process of bending with water-cooled diamond saw.Other is identical with embodiment 12.
Embodiment 14: present embodiment and embodiment 13 unlike silicon ingot or silicon wafer for photovoltaic device.Other is identical with embodiment 13.
Embodiment 15: present embodiment and embodiment 14 are solar cell unlike photovoltaic device.Other is identical with embodiment 14.
Embodiment 16: after one of present embodiment and embodiment one to ten five complete unlike the operation of step 4, operation below to be carried out again: heating up makes the temperature of the vessels crucible in sintering oven and silicon powder rise to t ' DEG C again, wherein T < t '≤T+300, T is the fusing point of silicon powder, unit is DEG C, is incubated, makes silicon powder melting at t ' DEG C, form liquid-phase silicone, continue to pass into dry hydrogen gas in insulating process.Other is identical with one of embodiment one to ten five.
Be warming up to more than the fusing point of silicon powder in present embodiment, make silicon powder melting, form liquid-phase silicone, then cool, directional freeze, silicon powder can be transformed into bulk by powdery like this, impurity can also be removed further.
Embodiment 17: present embodiment and embodiment 16 unlike: when being incubated at t ' DEG C, continuing to pass into dry hydrogen gas is be injected in the liquid-phase silicone of melting.Other is identical with embodiment one to ten one.
In present embodiment, pass into dry hydrogen gas as rinsing gas, dry hydrogen gas be injected into silicon mutually in, when especially silicon is liquid phase mutually, avoid silicon oxidized.
Embodiment 18: present embodiment and embodiment 17 unlike: arrange single hole or porous plug in crucible, hydrogen is passed in melt by the single hole in crucible or porous plug.Other is identical with embodiment 17.
Embodiment 19: one of present embodiment and embodiment ten six to ten eight are 0.5 ~ 10 hour unlike the time be incubated at t ' DEG C.Other is identical with one of embodiment ten six to ten eight.
When oxide compound and the impurity such as boron, phosphorus are after the solid phase stage is removed in present embodiment, furnace temperature rises to t ' silicon particle meeting melting, then cools in hydrogen atmosphere, directional freeze, obtains silicon crystal block.
Embodiment 20: one of present embodiment and embodiment one to ten nine are 5 ~ 20 hours unlike the temperature fall time in step 5.Other is identical with one of embodiment one to ten nine.
In present embodiment, preferred cooling time is 10 hours or more.Speed of cooling is too fast, and the time is too short, can affect the purity of silicon materials, grows if speed of cooling is crossed slowly and wastes hydrogen and power consumption due to cooling time.
Embodiment 21: one of present embodiment and embodiment one to two ten are through cleanup acid treatment unlike silicon powder that the surface in step one has a zone of oxidation.Other is identical with one of embodiment one to two ten.
In present embodiment, through cleanup acid treatment, the part metals impurity in silicon powder can be removed.
Embodiment 22: the silicon powder that present embodiment and embodiment 19 have zone of oxidation unlike the surface in step one carries out cleanup acid treatment with the hydrochloric acid that mass percentage concentration is 10% ~ 20%.Other is identical with embodiment 19.
Embodiment 22: the method that present embodiment and embodiment one to two 11 prepare solar level silicon materials unlike the recovery of: present embodiment is carried out according to the following steps:
One, be placed in the containers such as crucible with the sawdust after cleanup acid treatment, then the containers such as crucible are placed in airtight high temperature sintering furnace; Wherein there is containing surface in sawdust the silicon powder of zone of oxidation;
Two, in airtight stoving oven, pass into rare gas element, make sawdust be placed in inert atmosphere;
Three, the rare gas element in airtight stoving oven is replaced with dry hydrogen gas;
Four, intensification makes the temperature of the vessels crucible in sintering oven and sawdust rise to t DEG C, is incubated, continues to pass into dry hydrogen gas in insulating process at t DEG C; Wherein T-500≤t < T, T are the fusing point of silicon powder in sawdust, and unit is DEG C; Heating up makes the temperature of the vessels crucible in sintering oven and sawdust rise to t ' DEG C again, wherein T < t '≤T+300, be incubated at t ' DEG C, make silicon powder melting in sawdust, form liquid-phase silicone, in insulating process, continue dry hydrogen gas to pass into vessels crucible by the single hole bottom vessels crucible or porous plug;
Five, continuing under the condition passing into dry hydrogen gas, cooling makes the temperature of silicon phase lower than 300 DEG C, obtains solar level silicon materials.
In present embodiment, there is containing surface in the sawdust produced in sawing crystalline silicon process the silicon powder of zone of oxidation, the size of the silicon particle in sawdust in submicron in a few micrometer range, in sawdust except silicon particle, the metal particle also come off containing abrasive, cutting steel wire, cutting cooling fluid and owing to contact with oxygen at the surperficial Si oxide formed of silicon particle.
After overpickling, the most of metal particle in sawdust can be removed.
When temperature is t DEG C, remove the oxide compound on silicon particle surface and the impurity element of silicon particle intracell, as B, P etc., be warming up to t ' DEG C again, silicon particle is melt into micron-sized small droplets with this understanding, from the hydrogen that the single hole bottom vessels crucible or porous plug pass into, while guarantee small droplets is not oxidized, also form disturbance, small droplets is blown out suspended state, add the chance contacted with each other between small droplets, under the effect of silicon Surface Tension of Liquid Drops, the small droplets of contact can be fused to larger drop, thus micron-sized small droplets pools the large drop of grade and even centimetre-sized, in follow-up process of cooling, large droplet solidification becomes silicon grain, be dispersed in the impurity such as abrasive (silicon carbide), silicon grain is sieved out from impurity, obtain solar level silicon materials.
Beneficial effect of the present invention is proved by following embodiment:
Test 1: the method that solar level silicon materials are prepared in the recovery of this test is carried out according to the following steps:
One, the silicon powder that surface has a zone of oxidation is placed in the containers such as crucible, covers the lid of aluminum oxide, then crucible is placed in retort furnace, airtight furnace chamber; Wherein in alumina crucible and lid, the quality purity of aluminum oxide is 99.7%;
Two, in airtight stoving oven, pass into argon gas, make silicon powder be placed in argon gas atmosphere;
Three, the argon gas in airtight stoving oven is replaced with dry hydrogen gas; Wherein the purity of dry hydrogen gas is 99.9999%;
Four, intensification makes the temperature of the vessels crucible in sintering oven and silicon powder rise to 1400 DEG C and is incubated 4 hours, and under this temperature condition, silicon powder is still solid-state;
Five, continuing, under the condition passing into dry hydrogen gas, muffle furnace to be down to 250 DEG C, solar level silicon materials are obtained.
Test to having the solar level silicon materials obtained in the silicon powder of zone of oxidation and step 5 in the step one of this test, inspection is carried out with French National Laboratory's application glow discharge mass spectroscopy (GDMS), this instrument is applicable to the impurity analysis of ppb level and above content thereof in metal, the trace in 5N, 6N high pure metal aluminium, copper, zinc, polysilicon and ultratrace impurity element can be detected, application GDMS has carried out full elemental range analysis, and the result obtained is as shown in table 1.
The composition of silicon powder and the solar level silicon materials with zone of oxidation tested in 1 by table 1
The silicon powder surface in step one with zone of oxidation and the solar level silicon materials glow discharge spectrometry (GDMS) obtained after step 5 process carry out whole elemental scan, result shows, after treatment, boron and phosphorus mass content all obviously decline, wherein the content of boron is down to 1.1ppm from 25ppm, and the content of phosphorus is down to 2.1ppm from 62ppm.
Test 2: the method that solar level silicon materials are prepared in the recovery of this test is carried out according to the following steps:
One, the silicon powder that surface has a zone of oxidation is placed in the containers such as crucible, covers the lid of aluminum oxide, then crucible is placed in retort furnace, airtight furnace chamber; Wherein in alumina crucible and lid, the quality purity of aluminum oxide is 99.7%;
Two, in airtight stoving oven, pass into argon gas, make silicon powder be placed in argon gas atmosphere;
Three, the argon gas in airtight stoving oven is replaced with dry hydrogen gas; Wherein the purity of dry hydrogen gas is 99.9999%;
Four, intensification makes the temperature of the vessels crucible in sintering oven and silicon powder rise to 1700 DEG C and is incubated 6 hours, and under this temperature condition, silicon powder is still solid-state;
Five, continuing, under the condition passing into dry hydrogen gas, muffle furnace to be down to 250 DEG C, solar level silicon materials are obtained.
To having the full elemental range analysis of solar level silicon materials GDMS obtained in the silicon powder of zone of oxidation and step 5 in the step one of this test, the result obtained is as shown in table 2.
The composition of silicon powder and the solar level silicon materials with zone of oxidation tested in 2 by table 2
Surface in step one had the silicon powder of zone of oxidation and the solar level silicon materials glow discharge spectrometry (GDMS) after step 5 process carries out whole elemental scan, result shows, after treatment, boron and phosphorus mass content all obviously decline, wherein the content of boron is down to 2.1ppm from 14ppm, and the content of phosphorus is down to 1.7ppm from 31ppm.
Can prove the impurity silicon from above two tests, the impurity comprising boron and phosphorus is removed when silicon is the solid phase stage.
Test 3: containing silicon powder particle in the sawdust of sawing silicon ingot and silicon wafer, the sawdust containing silicon powder particle from water silicon mud with membrane filtration out, silicon powder particle surface wherein has silicon dioxide layer, the electron microscopic pattern photo of this sawdust as shown in Figure 1, as can be seen from Figure 1 in sawdust, the footpath grain of silicon powder particle is 2 ~ 5 μm, particle shape is irregular, and silicon powder is contaminated, main containing silicon in silicon powder, silicon carbide, silicon-dioxide, carbon and iron, the metallic impurity such as copper, apply glow discharge mass spectroscopy (GDMS) by French National Laboratory and measure forming of sawdust, its result is as shown in table 3.
The composition of the sawdust produced in table 3 Linear cut process
| Element | Composition (wt.%) |
| Si | 70.24785 |
| SiC | 0.1002 |
| SiO 2 | 28.011 |
| C | 0.205 |
| B | 0.0065 |
| P | 0.0057 |
| Al | 1.33 |
| Ca | 0.024 |
| Ti | 0.0019 |
| Cr | 0.0004 |
| Fe | 0.04 |
| Cu | 0.02 |
| Ni | 0.0038 |
| Mg | 0.0016 |
| Mn | 0.00052 |
| S | 0.001 |
| Cl | 0.00041 |
| K | 0.00012 |
Prepare the test of solar energy level silicon with the recovery done below of the sawdust of such containing silicon micro powder, concrete steps are as follows:
One, the sawdust of containing silicon micro powder first being put into mass percentage concentration is that the salt acid soak of 15% is after 8 hours, sawdust is filtered out, with water cleaning to neutral, after oven dry, take 59.6 grams of sawdust with being placed in alumina crucible, cover the lid of aluminum oxide, then crucible is placed in retort furnace, airtight furnace chamber; Wherein in alumina crucible and lid, the quality purity of aluminum oxide is 99.7%;
Two, in airtight retort furnace, pass into argon gas, make sawdust be placed in argon gas atmosphere;
Three, the rare gas element in airtight stoving oven is replaced with dry hydrogen gas; Wherein the purity of dry hydrogen gas is 99.9999%;
Four, intensification makes the temperature of the vessels crucible in sintering oven and silicon powder rise to 1300 DEG C, is incubated 10.5 hours, continues to pass into dry hydrogen gas in insulating process at 1300 DEG C; Heating up makes the temperature of the vessels crucible in sintering oven and silicon powder rise to 1700 DEG C again, makes silicon powder melting, forms liquid-phase silicone, and 1700 DEG C of insulations 3 hours, in insulating process, continue dry hydrogen gas to pass into crucible by the single hole of crucible bottom or porous plug;
Five, continuing under the condition passing into dry hydrogen gas, lasting 9 hours and the temperature of retort furnace is down to 250 DEG C, obtaining block solar level silicon materials.
The photo of the sawdust after the method process of this test as shown in Figure 2, as can be seen from Figure 2, the solar energy level silicon material granule of class spherical shape is distributed in sawdust, the particle diameter of spherical solar level silicon is 3 ~ 5mm, as standard of comparison in Fig. 2 is the coin of a piece 5 jiaos, and this coin diameter is 2 centimetres.The electron microscopic pattern photo of sawdust as shown in Figure 3.
After silicon powder melting in this test in sawdust, small droplets accumulates large drop, solidification, and obtain spherical block silicon materials, the weight of sawdust is 54.3g, decreases 5.3g, and these weight loss are because the removal of zone of oxidation and impurity volatilization loss cause.
From sawdust by the solar energy level silicon granule sieving of class spherical shape out, carbon, silicon carbide etc. that silicon grain top layer is adhered to are removed, the composition of silicon grain inside has carried out full elemental range analysis through French National Laboratory's application glow discharge mass spectroscopy (GDMS), measure its composition and content as shown in table 4.
Table 4 tests composition and the composition of the solar energy level silicon material granule of the class spherical shape that 3 obtain
| Element | Composition (ppm wt) |
| Si | Matrix |
| C | 31 |
| O | 14 |
| B | 10 |
| P | 28 |
| Al | 8.6 |
| Ca | 15 |
| Ti | 10 |
| Cr | 3 |
| Fe | 18 |
| Cu | 9.8 |
| Ni | 1.9 |
| Mg | 7.5 |
| Mn | 2.3 |
| S | 7.8 |
| Cl | 1.9 |
| K | 0.8 |
This test Raw is sawdust, silicon powder wherein containing band silicon dioxide layer, its one-tenth is grouped into have been listed in table 3, composition and the mass content of the silicon grain of the near-spherical obtained after this test process have arranged in table 4, more known, be removed with the impurity in the silicon powder of silicon dioxide layer, the impurity in the silicon grain obtained is extremely low, can be used as solar level silicon materials.
The solar energy level silicon material granule of the class spherical shape this test prepared sieves out, carbon, silicon carbide etc. that silicon grain top layer is adhered to are removed, then loading diameter is in the alumina crucible of 20cm, put into retort furnace and be heated to melting, then cool, obtain solar energy level silicon ingot casting, the photo of solar energy level silicon ingot casting as shown in Figure 4, thus illustrate that the method for this test may be used for for the preparation of solar energy level silicon ingot casting, for actual production.
Test four: the method concrete steps that the surperficial silicon powder with zone of oxidation of utilization of this test prepares solar level silicon materials are as follows:
One, the metallurgical grade silicon micro mist that 50 grams of surfaces have a zone of oxidation is placed in silicon nitride crucible, covers the lid of silicon nitride, then crucible is placed in retort furnace, airtight furnace chamber; Wherein in alumina crucible and lid, the quality purity of silicon nitride is 99.7%;
Two, in airtight retort furnace, pass into argon gas, make silicon powder be placed in argon gas atmosphere;
Three, the rare gas element in airtight stoving oven is replaced with dry hydrogen gas; Wherein the purity of dry hydrogen gas is 99.9999%;
Four, intensification makes the temperature of the container in stoving oven and the silicon powder in container rise to 1400 DEG C and be incubated 12 hours, continues to pass into dry hydrogen gas in insulating process; And then be warming up to 1600 DEG C and be incubated 4 hours, make silicon powder melting, form liquid-phase silicone, continue in insulating process and pass into dry hydrogen gas;
Five, continuing under the condition passing into dry hydrogen gas, lasting 10 hours by the temperature of silicon phase in retort furnace and be down to 250 DEG C, obtain block solar level silicon materials.
The impurity that the silicon powder that in this test, surface has zone of oxidation is incubated to remove oxide layer at 1400 DEG C and comprises B, P, then by after silicon powder melting, solidification, obtain solar level bulk silicon material, the weight of silico briquette is 43.8g, decrease 6.2g, these weight loss are because the removal of zone of oxidation and Impurity removal cause.
The block solar level silicon materials this test obtained, have carried out full elemental range analysis through French National Laboratory application glow discharge mass spectroscopy (GDMS), its composition and content as shown in table 5.
Table 5, the composition of the silico briquette that test 4 obtains and composition
This test Raw is the silicon powder of band silicon dioxide layer, before process with process after become to be grouped into and be listed in table 5, as can be seen from Table 5, the impurity in silicon powder is removed, and the impurity in the silico briquette obtained is extremely low, can as solar level silicon materials.
Claims (9)
1. reclaim the method preparing solar level silicon materials, it is characterized in that the method comprises the following steps:
One, the silicon powder that surface has a zone of oxidation is placed in vessels crucible, then vessels crucible is placed in airtight stoving oven;
Two, in airtight stoving oven, pass into rare gas element, make silicon powder be placed in inert atmosphere;
Three, the rare gas element in airtight stoving oven is replaced with dry hydrogen gas;
Four, intensification makes the temperature of the vessels crucible in sintering oven and silicon powder rise to t DEG C, is incubated, continues to pass into dry hydrogen gas in insulating process at t DEG C; Wherein T-400≤t < T, T are the fusing point of silicon powder, and unit is DEG C;
Five, continuing under the condition passing into dry hydrogen gas, cooling makes the temperature of silicon phase lower than 300 DEG C, obtains solar level silicon materials;
Described dry hydrogen gas refers to that moisture content is lower than H
2, H
2o, Si and SiO
2h in the phasor of system
2the hydrogen of the equilibrium pressure line of force of O.
2. the method for solar level silicon materials is prepared in recovery according to claim 1, it is characterized in that the zone of oxidation that surface has a silicon powder of zone of oxidation is spontaneous or initiatively coating.
3. the method for solar level silicon materials is prepared in recovery according to claim 1 and 2, it is characterized in that described container is silicon nitride crucible with cover or alumina crucible.
4. the method for solar level silicon materials is prepared in recovery according to claim 1 and 2, it is characterized in that described rare gas element is argon gas.
5. the method for solar level silicon materials is prepared in recovery according to claim 1 and 2, it is characterized in that described dry hydrogen gas is that foreign matter content is lower than millionth hydrogen.
6. the method for solar level silicon materials is prepared in recovery according to claim 1 and 2, characterized by further comprising the operation vacuumized before heating.
7. the method for solar level silicon materials is prepared in recovery according to claim 1 and 2, after it is characterized in that the operation of step 4 completes, also to carry out operation below: heating up makes the temperature of the container in sintering oven and silicon powder rise to t ' DEG C again, wherein T < t '≤T+300, T is the fusing point of silicon powder, and unit is DEG C, be incubated at t ' DEG C, make silicon powder melting, form liquid-phase silicone, continue to pass into dry hydrogen gas in insulating process.
8. the method for solar level silicon materials is prepared in recovery according to claim 1 and 2, and silicon powder that the surface that it is characterized in that in step one has a zone of oxidation is through cleanup acid treatment.
9. the method for solar level silicon materials is prepared in recovery according to claim 1 and 2, it is characterized in that reclaiming the method preparing solar level silicon materials and carries out according to the following steps:
One, be placed in vessels crucible with the sawdust after cleanup acid treatment, then vessels crucible is placed in airtight stoving oven; Wherein there is containing surface in sawdust the silicon powder of zone of oxidation;
Two, in airtight stoving oven, pass into rare gas element, make sawdust be placed in inert atmosphere;
Three, the rare gas element in airtight stoving oven is replaced with dry hydrogen gas;
Four, intensification makes the temperature of the vessels crucible in sintering oven and sawdust rise to t DEG C, is incubated, continues to pass into dry hydrogen gas in insulating process at t DEG C; Wherein T-400≤t < T, T are the fusing point of silicon powder in sawdust, and unit is DEG C; Heating up makes the temperature of the vessels crucible in sintering oven and sawdust rise to t ' DEG C again, wherein T < t '≤T+300, be incubated at t ' DEG C, make silicon powder melting in sawdust, form liquid-phase silicone, in insulating process, continue dry hydrogen gas to pass into vessels crucible by the single hole bottom vessels crucible or porous plug;
Five, continuing under the condition passing into dry hydrogen gas, cooling makes the temperature of silicon phase lower than 300 DEG C, obtains solar level silicon materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410166001.3A CN103922344B (en) | 2014-04-23 | 2014-04-23 | Reclaim the method preparing solar level silicon materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410166001.3A CN103922344B (en) | 2014-04-23 | 2014-04-23 | Reclaim the method preparing solar level silicon materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103922344A CN103922344A (en) | 2014-07-16 |
| CN103922344B true CN103922344B (en) | 2016-03-09 |
Family
ID=51140780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410166001.3A Expired - Fee Related CN103922344B (en) | 2014-04-23 | 2014-04-23 | Reclaim the method preparing solar level silicon materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103922344B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3434646A1 (en) * | 2017-07-25 | 2019-01-30 | Total Solar International | Method for recycling sub-micron si-particles from a si wafer production process |
| CN108373157A (en) * | 2018-03-22 | 2018-08-07 | 宁夏东梦能源股份有限公司 | 2N grades of low borosilicate technologies are produced using Buddha's warrior attendant wire cutting waste silicon powder and technique is integrated |
| CN110357115B (en) * | 2019-08-12 | 2022-12-27 | 东北大学 | Method for preparing nano silicon dioxide by using crystalline silicon diamond wire cutting waste material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481111A (en) * | 2009-01-23 | 2009-07-15 | 晶海洋半导体材料（东海）有限公司 | Method for preparing high-purity silicon by high temperature gas-solid reaction |
| CN103482631A (en) * | 2013-09-12 | 2014-01-01 | 中国恩菲工程技术有限公司 | System and method for activating and drying silicon powder and catalytic agents |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007513048A (en) * | 2003-12-04 | 2007-05-24 | ダウ・コーニング・コーポレイション | Method for removing impurities from metallurgical grade silicon to produce solar grade silicon |
-
2014
- 2014-04-23 CN CN201410166001.3A patent/CN103922344B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481111A (en) * | 2009-01-23 | 2009-07-15 | 晶海洋半导体材料（东海）有限公司 | Method for preparing high-purity silicon by high temperature gas-solid reaction |
| CN103482631A (en) * | 2013-09-12 | 2014-01-01 | 中国恩菲工程技术有限公司 | System and method for activating and drying silicon powder and catalytic agents |
Non-Patent Citations (1)
| Title |
|---|
| "Removal of Boron from Silicon by Moist Hydrogen Gas";ERLEND F. NORDSTRAND et al.;《METALLURGICAL AND MATERIALS TRANSACTIONS B》;20120501;第43B卷;第814-822页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103922344A (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100457615C (en) | Method of removing impurities from metallurgical grade silicon to produce solar grade silicon | |
| US7811356B2 (en) | Method of purifying metal | |
| US8329133B2 (en) | Method and apparatus for refining metallurgical grade silicon to produce solar grade silicon | |
| JP5311930B2 (en) | Method for producing silicon | |
| CN102498064A (en) | Polycrystalline silicon mass and process for producing polycrystalline silicon mass | |
| CN101379227A (en) | Crystalline composition, device, and associated method | |
| CN103922344B (en) | Reclaim the method preparing solar level silicon materials | |
| JPWO2010029894A1 (en) | High purity crystalline silicon, high purity silicon tetrachloride and methods for producing them | |
| Zhang et al. | Preparation of low-boron silicon from diamond wire sawing waste by pressure-less sintering and CaO–SiO2 slag treatment | |
| US20130001816A1 (en) | Method for recovering silicon and method for producing silicon | |
| EP2172424A1 (en) | Method of solidifying metallic silicon | |
| JP5246702B2 (en) | Silicon purification method | |
| CN101628718A (en) | Method for removing impurity of phosphorus from metallurgical grade silicon | |
| WO2003078319A1 (en) | Method of purifying silicon, silicon produced by the method and solar cell | |
| CN101775650A (en) | Preparation method of solar polycrystalline silicon cast ingot and device thereof | |
| KR102631060B1 (en) | Silicon granules for the production of trichlorosilane and related production methods | |
| US20230322562A1 (en) | Preparation method of high purity sic powder | |
| WO2011099870A1 (en) | Method for recovering solar grade silicon | |
| JP2003213345A (en) | Method for refining metal | |
| CN102452651A (en) | Process for removing boron impurity out of silicon by utilizing wet argon plasma | |
| JP2000327488A (en) | Production of silicon substrate for solar battery | |
| CN102190301B (en) | Method for preparing high purity silica by using rice husks | |
| RU2588627C1 (en) | Method of refining metallurgical silicon | |
| JP2010208862A (en) | Method for refining silicon | |
| JP5716167B2 (en) | Silicon recycling system and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160309 |