CN103922344A - Method for recovering and preparing solar-grade silicon material - Google Patents
Method for recovering and preparing solar-grade silicon material Download PDFInfo
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- CN103922344A CN103922344A CN201410166001.3A CN201410166001A CN103922344A CN 103922344 A CN103922344 A CN 103922344A CN 201410166001 A CN201410166001 A CN 201410166001A CN 103922344 A CN103922344 A CN 103922344A
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- 239000002210 silicon-based material Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 74
- 229910021422 solar-grade silicon Inorganic materials 0.000 title abstract 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 151
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 61
- 239000010703 silicon Substances 0.000 claims abstract description 61
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
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- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000011863 silicon-based powder Substances 0.000 claims description 89
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- 230000003647 oxidation Effects 0.000 claims description 39
- 238000007254 oxidation reaction Methods 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 25
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 238000011084 recovery Methods 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 11
- 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
- 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
- 230000002269 spontaneous effect Effects 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 40
- 239000012535 impurity Substances 0.000 abstract description 35
- 239000000377 silicon dioxide Substances 0.000 abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 14
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000005520 cutting process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000428 dust Substances 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 29
- 229910052796 boron Inorganic materials 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 14
- 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
- 239000010410 layer Substances 0.000 description 12
- 239000011856 silicon-based particle Substances 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 229960001866 silicon dioxide Drugs 0.000 description 11
- 239000002245 particle Substances 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
- 238000007670 refining Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 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
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- 229910052760 oxygen Inorganic materials 0.000 description 4
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- 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
- 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
- 230000007423 decrease Effects 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
- 239000007790 solid phase Substances 0.000 description 3
- 239000004484 Briquette Substances 0.000 description 2
- 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
- 125000004429 atom Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 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
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- 238000000746 purification Methods 0.000 description 2
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- 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
- 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
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- 239000002173 cutting fluid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses a method for recovering and preparing a solar-grade silicon material, relates to a preparation method of a solar-grade silicon material, and provides a method for manufacturing a silicon material by using silica micropowder with a silicon dioxide layer on the surface. The method comprises the following steps: collecting silica micropowder, and putting into an airtight furnace; heating to a temperature range below the melting point in a pure hydrogen atmosphere; insulating heat under the condition of continuously introducing dry hydrogen so that the silicon dioxide layer and other impurities on the surface of silica micropower can be removed, so as to obtain the solar-grade silicon material. According to the method, the solar-grade silicon material can be prepared by using the recovered silica micropowder with the silicon dioxide layer on the surface. and the method comprises preparation of the solar-grade silicon material by using saw-dust generated in the silicon crystal cutting and machining processes.
Description
Technical field
The present invention relates to the preparation method of solar level silicon materials.Be specifically related to utilize the silicon powder reclaiming 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 following following period of time, crystalline silicon still can be held dominant position in the continuation of insurance of photovoltaic industry relaying.The content that the silicon materials that photovoltaic cell is used require major impurity wherein ppma (by 1,000,000 of atom/) in level or lower scope, metallurgical grade (MG) silicon materials can not directly not used because reaching this purity requirement, therefore, must make the purity of metallurgical grade silicon material reach the standard of solar level silicon materials by purification.
In semi-conductor industry, also use HIGH-PURITY SILICON, unicircuit require impurity in crystalline silicon ppba (by atom part per billion) scope within.Utilize chemical process can make this highly purified crystalline silicon, operational path in this method is: metallurgical grade silicon reaction forms gas or liquid, for example i.e. silane or halogenated silanes, then their rectifying is arrived to the purity needing, finally, by for example method concentrated gas or the liquid of thermolysis, form crystalline silicon.This method technique is loaded down with trivial details and consume a large amount of energy, thereby causes the expensive of semiconductor crystal silicon.
In photovoltaic industry, often with the crystalline silicon fragment of semi-conductor industry, reduce material cost, but after the consumption demand of solar level silicon materials (SoG) surpasses 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, and the while is also in the utilization ratio that improves SoG.
The general technology flow process of producing at present solar panel is: first crystalline silicon raw material saws dice, and then thinly slices.The sawdust that sawing crystalline silicon produces is comprised of to the silicon particle in several micrometer ranges in submicron size, sawing process can change the silicon crystal raw material of half into sawdust, this just need to reclaim silicon particle from sawdust, and it is used as to solar level silicon materials again.But, in sawing process, produce in sawdust, not only contain abrasive, the metal particle that sawline comes off, the Si oxide forming on silicon particle surface owing to contacting with oxygen, and crystalline silicon is placed on borosilicate glass and is carried out while operating due to sawing, under the high temperature action producing 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 is that to disclose a kind of particle diameter producing in silicon wafer manufacturing processed that utilizes be the method that the sawdust of 40 μ m is produced silicon materials to the European patent of EP0158563; 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 of fusing to prevent the material in contaminating impurity container as protective layer, hydrogen wherein can adulterate in argon gas atmosphere.In silicon materials prepared by this method, foreign matter content is higher, does not reach solar level standard.
In American National renewable energy source in August calendar year 2001 laboratory, report, " by refined metallurgy silicon (MG) liquid, produce solar energy level silicon material (SoG); in document, point out the metallurgical grade silicon of melting to be purified and be obtained producing solar level silicon materials (SoG); in the liquid phase of refining; vacuum-treat is in conjunction with the use of slag former, be blown into reactant gases (wet argon gas, preferably wet hydrogen) simultaneously; all impurity elements that exist in metallurgical grade silicon can reduce to ppma level level, then directional freeze.The summary of test-results is partly pointed out in the text, adopts separately a kind of technology not reach effect, must adopt the combination of multiple technologies, but also propose, and the impurity that removes dephosphorization and boron is the most difficult, by reaction below, can remove boron.
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.The method must be heated to metallurgical grade silicon material molten state can realize Impurity removal, purifies and to obtain solar level silicon materials, and not only energy consumption is high but also need to use slag former.
The patent No. is a kind of method that the patent of WO2008031229 World Intellectual Property Organization WIPO group has proposed Refining molten state silicon, and the method, by using a rotating drum type stove of oxygen-enriched burner heating, provides a kind of H of comprising on the surface of liquid-state silicon
2, O
2, CO and CO
2oxidizing atmosphere, on melts, be covered with slag, in slag, contain the several metal oxide that can absorb Al, Ba, Ca, K, Mg, Na, Sr, Zn, C and B element, utilize the absorption of oxide compound can remove Al, Ba, Ca, K, Mg, Na, Sr, Zn, C and B, experimental data in this piece of document shows, can remove 23%～26% boron by this method.Clearance for the extremely difficult boron impurity of removing in silicon crystal is lower.
Publication number is a kind of method that the United States Patent (USP) of US20070202029 discloses Refining solid state si, under condition of negative pressure, in argon gas atmosphere, (conventionally select micro-wet argon gas), particle diameter is that the solid-state silicon particle of 90-500 μ m is warming up to the temperature lower than fusing point, preferred temperature range is 1300～1400 ℃, 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 the P in solid state si, Ca, Cu, Mg, Mn, Na, Sn and Zn all decrease through processing, and wherein the clearance of phosphorus is only 23%～76%.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 that will solve in the method for existing metallurgical grade silicon material Refining silicon for boron, phosphoric, and the method for preparing solar level silicon materials that reclaims is provided.
The present invention utilizes surface with the silicon powder of silicon dioxide layer, by Refining silicon, prepares solar level silicon materials, utilizes the zone of oxidation degree of depth of silicon powder to remove the impurity elements such as boron wherein, phosphorus 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 is had to 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 to dry hydrogen gas;
Four, heat up and to make vessels crucible in sintering oven and the temperature of silicon powder rise to t ℃, T-400≤t < T wherein, the fusing point that T is silicon powder, insulation continues to pass into dry hydrogen gas in insulating process;
Five, continuing to pass under the condition of dry hydrogen gas, cooling makes the temperature of silicon phase lower than 300 ℃, obtains solar level silicon materials.
The zone of oxidation that it is considered herein that silicon powder surface is not a kind of trouble, but a kind of favourable condition, utilize dry hydrogen gas, make dry hydrogen, with zone of oxidation and the impurity element of silicon powder, complicated reacting occur, when removing in silicon materials zone of oxidation, impurity element is removed, effective equally for the boron, the phosphoric that are arranged in structure cell.Therefore, the present invention a kind ofly utilizes the silicon powder that surface has zone of oxidation by refining, to prepare the method for solar level silicon materials.
The inventive method can rapidly and efficiently be removed two kinds of difficult elements of removing of P in metallurgical grade silicon material lattice, B, 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 low and short feature of time of energy consumption.
Adopt method of the present invention compared with less energy-consumption, do not change silicon materials phase in the situation that, solar level crystalline silicon raw material sawdust being purified, to reach the target of recycling.
The present invention is obtained to solar level silicon materials and in oxygen-free environment, heat immediately founding and become large-sized ingot casting, just can be for photovoltaic industry, as solar level silicon material.
Accompanying drawing explanation
Fig. 1 is the electron microscopic pattern photo of testing the sawdust that contains silicon powder particle in 3;
Fig. 2 is the photo of the sawdust after test 3 is processed; Small-particle is wherein silicon grain;
Fig. 3 is the electron microscopic pattern photo of the sawdust after test 3 is processed; Spherical particle is wherein silicon grain;
Fig. 4 is the photo of testing the solar level ingot casting obtaining after the solar energy level silicon material granule heating and melting cooling processing by near-spherical in 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 is had to 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 to dry hydrogen gas;
Four, heat up and to make vessels crucible in sintering oven and the temperature of silicon powder rise to t ℃, at t ℃, insulation continues to pass into dry hydrogen gas in insulating process; T-400≤t < T wherein, the fusing point that T is silicon powder, unit is ℃;
Five, continuing to pass under the condition of dry hydrogen gas, cooling makes the temperature of silicon phase lower than 300 ℃, obtains solar level silicon materials.
Embodiment two: present embodiment is different from embodiment one: in step 1, silicon powder is placed in the containers such as crucible rear silicon powder compacting.Other is identical with embodiment one.
Compacting operation can prevent that silicon powder from being dispelled by argon gas or hydrogen etc. in body of heater vacuumizes or pass into the process of gas.Or along with gas flow discharge system, make loss of material serious.
Embodiment three: present embodiment is different from embodiment one or two is that the zone of oxidation that surface in step 1 has a silicon powder of zone of oxidation 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, thereby forms silicon dioxide layer in its surface.The thickness of this silicon dioxide layer is arbitrarily, and it can be by being just exposed in air and obtains.The zone of oxidation on silicon powder surface can be also the silicon dioxide layer initiatively applying.How much thickness of the method oxide skin of present embodiment is for being all effectively, and thickness directly has influence on the amounts of hydrogen of needs and the speed of chemical reaction.
Embodiment four: what present embodiment was different from embodiment one to three is that the container described in step 1 is silicon nitride crucible or alumina crucible with cover.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: what present embodiment was different from one of embodiment one to four is that described rare gas element is argon gas.Other are identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to six is that the dry hydrogen gas described in step 3 is 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 hydrogen, this strict purity requirement means that silicon phase hydrogen above should constantly supplement, replace with fresh hydrogen to present embodiment, thereby the chemical substance of generation is transferred out, if discontinuous, pass into fresh dry hydrogen, reaction can stop.
Embodiment seven: present embodiment is different from embodiment six be dry hydrogen gas refer to foreign matter content lower than 1,000,000/hydrogen (ppma).Other is identical with embodiment six.
In present embodiment, foreign matter content lower than 1,000,000/hydrogen (ppma), namely purity surpasses 99.9999% hydrogen.
Embodiment eight: what present embodiment was different from embodiment six is that dry hydrogen gas refers to that foreign matter content is lower than the hydrogen of 1/100000000th (ppba).Other is identical with embodiment six.
In present embodiment, foreign matter content is lower than the hydrogen of 1/100000000th (ppba), and namely purity surpasses 99.9999999% hydrogen, with such hydrogen, and can be better to the removal effect of the impurity in silicon powder.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is to be also included in the operation vacuumizing before heating.Other are identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different from one of embodiment one to eight is to be also included in sintering oven temperature to rise to 300 ℃ of operations that vacuumize before.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 before sintering oven heats up be evacuated in by the furnace chamber of sintering oven, also can be evacuated in by 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 ℃.
Embodiment 11: present embodiment is different from one of embodiment one to ten is that soaking time in step 4 is 1 minute to 15 hours.Other is identical with embodiment one to ten.
In present embodiment, in certain temperature range below silicon powder fusing point, keep certain hour, to guarantee 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 says, be depend on hydrogen be diffused into melting or solid-state silicon-dioxide phase and silicon phase mass transfer velocity size and determine.
Embodiment 12: present embodiment is different from one of embodiment one to 11 is that the silicon powder that surface has a zone of oxidation is to utilize water or aqueous mixture to produce in the process of machine silicon material.Other is identical with one of embodiment one to 11.
The silicon powder that the utilization of present embodiment has a zone of oxidation is prepared 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, the surperficial silicon powder with zone of oxidation is to utilize water or aqueous mixture to produce in the process of machine silicon material, and this silica soot with zone of oxidation is reclaimed, for the preparation of silicon materials, significant.
Embodiment 13: what present embodiment was different from embodiment 12 is to utilize water or aqueous mixture to be in the process of machine silicon material: by sawing, grinding, milling Xian, cutting, polishing or the bending process of water-cooled diamond saw processing silicon ingot or silicon wafer.Other is identical with embodiment 12.
Embodiment 14: present embodiment is different from embodiment 13 is that silicon ingot or silicon wafer are for photovoltaic device.Other is identical with embodiment 13.
Embodiment 15: what present embodiment was different from embodiment 14 is that photovoltaic device is solar cell.Other is identical with embodiment 14.
Embodiment 16: present embodiment is different from one of embodiment one to 15 is after the operation of step 4 completes, to carry out operation below again: heat up again and make vessels crucible in sintering oven and the temperature of silicon powder rise to t ' ℃, T < t '≤T+300 wherein, T is the fusing point of silicon powder, unit is ℃ that insulation, makes silicon powder melting at t ' ℃, form liquid-phase silicone, in insulating process, continue to pass into dry hydrogen gas.Other is identical with one of embodiment one to 15.
More than being warming up to the fusing point of silicon powder in present embodiment, make silicon powder melting, form liquid-phase silicone, more cooling, directional freeze, can be transformed into bulk by powdery by silicon powder like this, can also further remove impurity.
Embodiment 17: present embodiment is different from embodiment 16: while being incubated at t ' ℃, continuing to pass into dry hydrogen gas is to be injected in the liquid-phase silicone of melting.Other is identical with embodiment one to 11.
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 is different from embodiment 17: single hole or porous plug are set in crucible, and hydrogen is passed in melt by the single hole in crucible or porous plug.Other is identical with embodiment 17.
Embodiment 19: what present embodiment was different from one of embodiment 16 to 18 is that the time being incubated at t ' ℃ is 0.5～10 hour.Other is identical with one of embodiment 16 to 18.
In present embodiment, when the impurity such as oxide compound and boron, phosphorus are after the solid phase stage is removed, furnace temperature rises to t ' silicon particle can melting, and then cooling in hydrogen atmosphere, directional freeze, obtains silicon crystal block.
Embodiment 20: present embodiment is different from one of embodiment one to 19 is that temperature fall time in step 5 is 5～20 hours.Other is identical with one of embodiment one to 19.
In present embodiment preferred cooling time be 10 hours or more than.Speed of cooling is too fast, and the time is too short, can affect the purity of silicon materials, if speed of cooling is crossed slow meeting, wastes hydrogen and power consumption because cooling time is long.
Embodiment 21: present embodiment is different from one of embodiment one to 20 be the surface in step 1 there is zone of oxidation silicon powder through cleanup acid treatment.Other is identical with one of embodiment one to 20.
In present embodiment, through cleanup acid treatment, can remove the part metals impurity in silicon powder.
Embodiment 22: present embodiment is different from embodiment 19 is that silicon powder that surface in step 1 has a zone of oxidation is to be 10%～20% by mass percentage concentration hydrochloric acid carries out cleanup acid treatment.Other is identical with embodiment 19.
Embodiment 22: present embodiment is different from embodiment one to 21: the recovery of present embodiment is prepared the method for solar level silicon materials and carried out according to the following steps:
One, being 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 in sawdust, contain the silicon powder that surface has 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 to dry hydrogen gas;
Four, heat up and to make vessels crucible in sintering oven and the temperature of sawdust rise to t ℃, at t ℃, insulation continues to pass into dry hydrogen gas in insulating process; T-500≤t < T wherein, T is the fusing point of silicon powder in sawdust, unit is ℃; Heat up again and make vessels crucible in sintering oven and the temperature of sawdust rise to t ' ℃, T < t '≤T+300 wherein, insulation at t ' ℃, make silicon powder melting in sawdust, form liquid-phase silicone, in insulating process, continue dry hydrogen gas to pass into vessels crucible by single hole or porous plug bottom vessels crucible;
Five, continuing to pass under the condition of dry hydrogen gas, cooling makes the temperature of silicon phase lower than 300 ℃, obtains solar level silicon materials.
In present embodiment, in the sawdust producing in sawing crystalline silicon process, contain the silicon powder that surface has zone of oxidation, the size of the silicon particle in sawdust is in submicron arrives several micrometer ranges, in sawdust except silicon particle, also contain metal particle that abrasive, cutting steel wire come off, cutting cooling fluid and owing to contact with oxygen at the Si oxide of silicon particle surface formation.
After overpickling, can remove the most of metal particle in sawdust.
When temperature is t ℃, remove the oxide compound on silicon particle surface and the impurity element of silicon particle intracell, as B, P etc., be warming up to again t ' ℃, silicon particle is melt into micron-sized small droplets with this understanding, the hydrogen passing into from single hole or the porous plug of vessels crucible bottom, when guaranteeing that small droplets is not oxidized, also form disturbance, small droplets is blown out to suspended state, increased the chance being in contact with one another between small droplets, under the effect of silicon Surface Tension of Liquid Drops, the small droplets of contact can be fused to larger drop, thereby 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.
With following embodiment, prove beneficial effect of the present invention:
Test 1: the recovery of this test is prepared the method for solar level silicon materials and carried out according to the following steps:
One, the silicon powder that surface is had to 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 to dry hydrogen gas; Wherein the purity of dry hydrogen gas is 99.9999%;
Four, heat up and to make the temperature of vessels crucible in sintering oven and silicon powder rise to 1400 ℃ and be incubated 4 hours, under this temperature condition, silicon powder is still solid-state;
Five, continuing to pass under the condition of dry hydrogen gas, muffle furnace is down to 250 ℃, obtains solar level silicon materials.
To thering are the solar level silicon materials that obtain in the silicon powder of zone of oxidation and step 5 in the step 1 of this test, test, check is carried out with French National Laboratory's application glow discharge mass spectrometry instrument (GDMS), this instrument is applicable to the impurity analysis of ppb level in metal and above content thereof, can detect trace and ultratrace impurity element in 5N, 6N high pure metal aluminium, copper, zinc, polysilicon, application GDMS has carried out full elemental range analysis, and the result obtaining is as shown in table 1.
In table 1 test 1, there is the silicon powder of zone of oxidation and the composition of solar level silicon materials
The solar level that surface in step 1 is had to the silicon powder of zone of oxidation and obtain after step 5 is processed for silicon materials glow discharge spectrometry (GDMS) carry out whole element scanning, 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 recovery of this test is prepared the method for solar level silicon materials and carried out according to the following steps:
One, the silicon powder that surface is had to 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 to dry hydrogen gas; Wherein the purity of dry hydrogen gas is 99.9999%;
Four, heat up and to make the temperature of vessels crucible in sintering oven and silicon powder rise to 1700 ℃ and be incubated 6 hours, under this temperature condition, silicon powder is still solid-state;
Five, continuing to pass under the condition of dry hydrogen gas, muffle furnace is down to 250 ℃, obtains solar level silicon materials.
To having the full elemental range analysis of solar level silicon materials GDMS obtaining in the silicon powder of zone of oxidation and step 5 in the step 1 of this test, the result obtaining is as shown in table 2.
In table 2 test 2, there is the silicon powder of zone of oxidation and the composition of solar level silicon materials
By the surface in step 1 have the silicon powder of zone of oxidation and the solar level after step 5 is processed for silicon materials glow discharge spectrometry (GDMS) carry out whole element scanning, 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.
From above two tests, can prove the impurity silicon, the impurity that comprises boron and phosphorus is to be that solid phase is removed during the stage at silicon.
Test 3: contain silicon powder particle in the sawdust of sawing silicon ingot and silicon wafer, the sawdust that contains 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 μ m, particle shape is irregular, and silicon powder is contaminated, in silicon powder, mainly contain silicon, silicon carbide, silicon-dioxide, carbon and iron, the metallic impurity such as copper, by French National Laboratory's application glow discharge mass spectrometry instrument (GDMS), measure forming of sawdust, its result is as shown in table 3.
The composition of the sawdust producing in table 3 line cutting 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 |
With the sawdust of such containing silicon micro powder, do the test that solar energy level silicon is prepared in recovery below, concrete steps are as follows:
One, the sawdust of containing silicon micro powder first being put into mass percentage concentration is that 15% salt acid soak is after 8 hours, sawdust is filtered out, water cleans 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 to dry hydrogen gas; Wherein the purity of dry hydrogen gas is 99.9999%;
Four, heat up and to make vessels crucible in sintering oven and the temperature of silicon powder rise to 1300 ℃, at 1300 ℃, be incubated 10.5 hours, in insulating process, continue to pass into dry hydrogen gas; Heat up again and make vessels crucible in sintering oven and the temperature of silicon powder rise to 1700 ℃, make silicon powder melting, form liquid-phase silicone, and 1700 ℃ of insulations 3 hours, in insulating process, continue single hole or the porous plug by crucible bottom by dry hydrogen gas and pass into crucible;
Five, pass under the condition of dry hydrogen gas continuing, last 9 hours the temperature of retort furnace is down to 250 ℃, obtain block solar level silicon materials.
The photo of the sawdust after the method for this test is processed 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, in Fig. 2 as a comparison standard be the coin of a piece 5 jiaos, 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, solidifies, and obtains spherical block silicon materials, and the weight of sawdust is 54.3g, has reduced 5.3g, and these weight loss are because removal and the impurity volatilization loss of zone of oxidation cause.
From sawdust by the solar energy level silicon granule sieving of class spherical shape out, the carbon that silicon grain top layer is adhered to, silicon carbide etc. remove, the composition of silicon grain inside has carried out full elemental range analysis through French National Laboratory's application glow discharge mass spectrometry instrument (GDMS), measures its composition and content as shown in table 4.
Composition and the composition of the solar energy level silicon material granule of the table 4 test 3 class spherical shape that 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, wherein contain the silicon powder with silicon dioxide layer, its one-tenth is grouped in table 3 have been listed, the composition of the silicon grain of the near-spherical obtaining after this test is processed and mass content are listed in table 4 and have suffered, more known, with the impurity in the silicon powder of silicon dioxide layer, be removed, the impurity in the silicon grain obtaining is extremely low, can be used as solar level silicon materials.
The solar energy level silicon material granule of the class spherical shape of this test preparation is sieved out, the carbon that silicon grain top layer is adhered to, silicon carbide etc. remove, then pack in the alumina crucible that diameter is 20cm, put into retort furnace and be heated to melting, then cooling, obtain solar energy level silicon ingot casting, the photo of solar energy level silicon ingot casting is as shown in Figure 4, thereby the method that this test is described can be for the preparation of for solar energy level silicon ingot casting, for actual production.
Test four: the method concrete steps that the silicon powder that the utilization surface of this test has a zone of oxidation is prepared solar level silicon materials are as follows:
One, the metallurgical grade silicon micro mist that 50 grams of surfaces is had to 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 to dry hydrogen gas; Wherein the purity of dry hydrogen gas is 99.9999%;
Four, heat up and to make the temperature of container in stoving oven and the silicon powder in container rise to 1400 ℃ and be incubated 12 hours, in insulating process, continue to pass into dry hydrogen gas; And then be warming up to 1600 ℃ and be incubated 4 hours, and make silicon powder melting, form liquid-phase silicone, the continuous dry hydrogen gas that passes in insulating process;
Five, pass under the condition of dry hydrogen gas continuing, last 10 hours the temperature of silicon phase in retort furnace is down to 250 ℃, obtain block solar level silicon materials.
The silicon powder that in this test, surface has a zone of oxidation 1400 ℃ of insulations to remove zone of oxidation and to comprise the impurity of B, P, then by after silicon powder melting, solidify, obtain solar level bulk silicon material, the weight of silico briquette is 43.8g, reduced 6.2g, these weight loss are because removal and the Impurity removal of zone of oxidation cause.
The block solar level silicon materials that this test is obtained, have carried out full elemental range analysis through French National Laboratory's application glow discharge mass spectrometry instrument (GDMS), and its composition and content are as shown in table 5.
Table 5, composition and the composition of test 4 silico briquettes that obtain
This test Raw is the silicon powder with silicon dioxide layer, and before processing, with becoming to be grouped into and be listed in table 5 after processing, as can be seen from Table 5, the impurity in silicon powder is removed, and the impurity in the silico briquette obtaining is extremely low, can be used as solar level silicon materials.
Claims (10)
1. reclaim the method for preparing solar level silicon materials, it is characterized in that the method comprises the following steps:
One, the silicon powder that surface is had to 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 to dry hydrogen gas;
Four, heat up and to make vessels crucible in sintering oven and the temperature of silicon powder rise to t ℃, at t ℃, insulation continues to pass into dry hydrogen gas in insulating process; T-400≤t < T wherein, the fusing point that T is silicon powder, unit is ℃;
Five, continuing to pass under the condition of dry hydrogen gas, cooling makes the temperature of silicon phase lower than 300 ℃, obtains solar level silicon materials.
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 applies.
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 or alumina crucible with cover.
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 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.
6. 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.
7. the method for solar level silicon materials is prepared in recovery according to claim 1 and 2, characterized by further comprising the operation vacuumizing before heating.
8. the method for solar level silicon materials is prepared in recovery according to claim 1 and 2, after the operation that it is characterized in that step 4 completes, also to carry out operation below: heat up again and make container in sintering oven and the temperature of silicon powder rise to t ' ℃, T < t '≤T+300 wherein, the fusing point that T is silicon powder, unit is ℃, insulation at t ' ℃, make silicon powder melting, form liquid-phase silicone, in insulating process, continue to pass into dry hydrogen gas.
9. the method for solar level silicon materials is prepared in recovery according to claim 1 and 2, it is characterized in that silicon powder that the surface in step 1 has zone of oxidation is through cleanup acid treatment.
10. 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 prepare solar level silicon materials and carries out according to the following steps:
One, being 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 in sawdust, contain the silicon powder that surface has 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 to dry hydrogen gas;
Four, heat up and to make vessels crucible in sintering oven and the temperature of sawdust rise to t ℃, at t ℃, insulation continues to pass into dry hydrogen gas in insulating process; T-500≤t < T wherein, T is the fusing point of silicon powder in sawdust, unit is ℃; Heat up again and make vessels crucible in sintering oven and the temperature of sawdust rise to t ' ℃, T < t '≤T+300 wherein, insulation at t ' ℃, make silicon powder melting in sawdust, form liquid-phase silicone, in insulating process, continue dry hydrogen gas to pass into vessels crucible by single hole or porous plug bottom vessels crucible;
Five, continuing to pass under the condition of dry hydrogen gas, cooling makes the temperature of silicon phase lower than 300 ℃, obtains solar level silicon materials.
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| CN110357115A (en) * | 2019-08-12 | 2019-10-22 | 东北大学 | A method of nano silica is prepared with crystalline silicon diamond wire cutting waste material |
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Cited By (6)
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| CN111032569A (en) * | 2017-07-25 | 2020-04-17 | 道达尔太阳能国际公司 | Method for recovering submicron silicon particles from silicon wafer production process |
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| CN111032569B (en) * | 2017-07-25 | 2024-02-20 | 道达尔太阳能国际公司 | Method for recovering submicron silicon particles from silicon 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 |
| CN110357115A (en) * | 2019-08-12 | 2019-10-22 | 东北大学 | A method of nano silica is prepared with crystalline silicon diamond wire cutting waste material |
| 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 |
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