CN101497440B - Method for removing native polysilicon bar end-face graphite - Google Patents
Method for removing native polysilicon bar end-face graphite Download PDFInfo
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- CN101497440B CN101497440B CN2008100800891A CN200810080089A CN101497440B CN 101497440 B CN101497440 B CN 101497440B CN 2008100800891 A CN2008100800891 A CN 2008100800891A CN 200810080089 A CN200810080089 A CN 200810080089A CN 101497440 B CN101497440 B CN 101497440B
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- raw material
- polysilicon
- acid
- graphite
- carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 29
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 25
- 239000010439 graphite Substances 0.000 title claims abstract description 25
- 229920005591 polysilicon Polymers 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 5
- 238000009423 ventilation Methods 0.000 claims description 5
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052710 silicon Inorganic materials 0.000 abstract description 13
- 239000010703 silicon Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract 2
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000002210 silicon-based material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The invention relates to a method for removing graphite on the end face of a protogenetic polysilicon rod, belongs to the technical field of processing of polysilicon rod materials, and provides a method for conveniently and fully removing the graphite on the end face of the silicon rod by a chemical method. The method adopts a proposal that: firstly, knocking away raw materials, which are provided with graphite chucks, on both ends of the polysilicon rod; secondly, crushing the raw materials into small blocks; thirdly, performing heat treatment on carbon-bearing raw materials on both ends of protogenetic polysilicon; fourthly, performing acid washing on the obtained product; fifthly, performing water washing on the obtained product until the obtained product is neutral; and sixthly, drying the obtained product. The heat treatment method comprises the following steps: packaging the carbon-bearing raw materials on both ends of the protogenetic polysilicon into a quartz boat, raising the temperature of a muffle furnace to between 880 and 920 DEG C at a temperature rise rate of between 8 and 15 DEG C per minute, maintaining at the temperature for 2 hours, and naturally cooling the obtained product. The method is widely applied to processing of the polysilicon rod materials in batches.
Description
Technical field
A kind of method of removing native polysilicon bar end-face graphite of the present invention belongs to polysilicon bar processing technique field.
Background technology
Because environmental pollution, energy shortage, promoted the fast development of photovoltaic industry, crystal silicon solar energy battery is present topmost solar cell, its raw materials used waste material in primary polysilicon, the chip manufacture process, scrap stock in the silicon chip working process etc. of mainly containing, and wherein primary polysilicon is main raw material, this several years photovoltaic industries develop rapidly, the supply of polycrystalline silicon raw material is very well sold and in short supply, and price is also than higher, and the price of polycrystalline silicon raw material per ton is more than 300 ten thousand.
During polycrystalline silicon growth, need with the elongated silicon core of graphite chuck clamping two ends, graphite chuck is as the heating of electrode pair silicon core, and the gaseous state silicon material in the furnace chamber progressively is deposited on the silicon core, thereby grows polycrystalline silicon rod.Along with the deposition of silicon material on the silicon core, the silicon material package that graphite chuck and silicon core progressively are deposited is covered, the polycrystalline silicon rod two ends that grow are embedded with graphite chuck, because of carbon and silicon are with gang's element, their chemical property and atomic structure are all very close, at high temperature interpenetrate, thus the graphite chuck of removing silicon rod two ends difficulty relatively, if but this part raw material to handle well also be good raw material.
Usually people adopt physical method to remove the graphite chuck at silicon rod two ends, at first two ends are pounded, and then the knock fragment, the raw material of carbon-bearing and not carbon-bearing raw material separately, to the raw material of carbon-bearing, grind off the graphite on surface with emery wheel, this working method needs one one grinding, and quite trouble is unfavorable for batch machining, grind simultaneously in the process of graphite and often will grind off part silicon raw material, loss is also bigger.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, and problem to be solved provides a kind of chemical process of utilizing, and removes the method for silicon rod end face graphite conveniently, fully.
In order to address the above problem, the scheme that the present invention adopts is: a kind of method of removing the native polysilicon bar end-face graphite chuck, the raw material that the polycrystalline silicon rod two ends is had graphite chuck strikes earlier, again raw material crushing is become fritter, then the raw material of primary polysilicon two ends carbon-bearing is heat-treated, pickling again, washing is neutral then, and oven dry at last gets final product; It is characterized in that above-mentioned heat-treating methods is: with the raw material dress quartz boat of primary polysilicon two ends carbon-bearing, the temperature rise rate with 8-15 ℃/min in retort furnace is added to 880-920 ℃, constant temperature two hours, naturally cooling then.
The method of above-mentioned oven dry is: toasted two hours down at 110-130 ℃.
Above-mentioned heat treated whole process keeps ventilation state.
The method of above-mentioned pickling is: get nitric acid and hydrofluoric acid earlier, ratio by weight is nitric acid: hydrofluoric acid=6-10: 1 forms mixing acid, then the raw material after the thermal treatment is immersed mixing acid, embathes in mixing acid raw material 3-5 minute, stirs while embathing.
The weight percent concentration of above-mentioned nitric acid is between the 70%-98%, and the weight percent concentration of hydrofluoric acid is between the 35%-55%.
Beneficial effect of the present invention is: at the deficiency of physics method, the present invention adopts chemical process to remove the graphite on polycrystalline silicon raw material surface, but the chemical property of carbon is highly stable, normal temperature is difficult to and other substance reaction down, be adjacent element of the same clan simultaneously because of silicon and carbon, chemical property is close, separates relatively difficulty.There is very big-difference in the oxidation products of considering silicon and carbon, can form two fine and close fosterization silicon layers on the surface behind the silicon oxidation, this silicon dioxide layer is in case form, the silicon of the inside can be coated, stop internal-response to carry out, but generate gasiform carbon monoxide or carbon dioxide behind the oxidation of coal, can continue reaction goes down, after treating that carbon has reacted, adopt nitric acid and hydrofluoric acid can remove silicon dioxide layer and other impurity of raw material surface coverage easily again, thereby can obtain clean silicon material.We have tested two kinds of method for oxidation and have removed graphite, and a kind of is the mixed solution oxidation raw material of using the potassium permanganate and the vitriol oil under the normal temperature, and another kind is heating raw oxidation in retort furnace.Experiment is found to have used superpower oxidant potassium permanganate in the first method, and blast is not too safe easily, speed of response is not very fast simultaneously, and method of the present invention is easy and simple to handle, safety, the oxidation effectiveness ideal is so we adopt back kind method to remove the graphite on raw material surface.
Embodiment
Embodiment 1
Earlier the raw material that the polycrystalline silicon rod two ends is had graphite chuck strikes, and raw material crushing is become fritter, the raw material of carbon-bearing and separating of carbon-bearing not; The raw material of carbon-bearing dress quartz boat, the temperature rise rate with 10 ℃/min of per minute in retort furnace is added to 900 ℃ again, and constant temperature two hours will stay ventilation opening, naturally cooling then in the furnace chamber in the calcination process; To cool off good raw material then, come out of the stove, wipe the ashes on raw material surface with the stainless steel pocket knife off; Get the nitric acid of q.s and the mixing acid of hydrofluoric acid again and embathed raw material 4 minutes, the weight percent concentration of nitric acid is 90%, the weight percent concentration of hydroflouric acid is 47%, nitric acid is 8: 1 with the ratio of the weight part of hydroflouric acid, raw material is all immersed under the liquid level of mixing acid, stir raw material while cleaning; Using the acid pickling on pure water rinsing raw material surface again, is neutral until the raw material surface; And then dried two hours under 120 ℃, after the cooling, package stock gets final product.
Embodiment 2
Earlier the raw material that the polycrystalline silicon rod two ends is had graphite chuck strikes, and raw material crushing is become fritter, the raw material of carbon-bearing and separating of carbon-bearing not; The raw material of carbon-bearing dress quartz boat, the temperature rise rate with 15 ℃/min of per minute in retort furnace is added to 920 ℃ again, and constant temperature two hours will stay ventilation opening, naturally cooling then in the furnace chamber in the calcination process; To cool off good raw material then, come out of the stove, wipe the ashes on raw material surface with the stainless steel pocket knife off; Get the nitric acid of q.s and the mixing acid of hydrofluoric acid again and embathed raw material 5 minutes, the weight percent concentration of nitric acid is 70%, the weight percent concentration of hydroflouric acid is 55%, nitric acid is 10: 1 with the ratio of the weight part of hydroflouric acid, raw material is all immersed under the liquid level of mixing acid, stir raw material while cleaning; Using the acid pickling on pure water rinsing raw material surface again, is neutral until the raw material surface; And then dried two hours under 130 ℃, after the cooling, package stock gets final product.
Embodiment 3
Earlier the raw material that the polycrystalline silicon rod two ends is had graphite chuck strikes, and raw material crushing is become fritter, the raw material of carbon-bearing and separating of carbon-bearing not; The raw material of carbon-bearing dress quartz boat, the temperature rise rate with 8 ℃/min of per minute in retort furnace is added to 880 ℃ again, and constant temperature two hours will stay ventilation opening, naturally cooling then in the furnace chamber in the calcination process; To cool off good raw material then, come out of the stove, wipe the ashes on raw material surface with the stainless steel pocket knife off; Get the nitric acid of q.s and the mixing acid of hydrofluoric acid again and embathed raw material 3 minutes, the weight percent concentration of nitric acid is 98%, the weight percent concentration of hydroflouric acid is 35%, nitric acid is 6: 1 with the ratio of the weight part of hydroflouric acid, raw material is all immersed under the liquid level of mixing acid, stir raw material while cleaning; Using the acid pickling on pure water rinsing raw material surface again, is neutral until the raw material surface; And then dried two hours under 110 ℃, after the cooling, package stock gets final product.
Claims (4)
1. method of removing native polysilicon bar end-face graphite, the raw material that earlier the polycrystalline silicon rod two ends is had graphite chuck strikes, and again raw material crushing is become fritter, then the raw material of primary polysilicon two ends carbon-bearing is heat-treated, pickling again, washing is neutral then, and oven dry at last gets final product; It is characterized in that above-mentioned heat-treating methods is: with the raw material of the primary polysilicon two ends carbon-bearing quartz boat of packing into, the temperature rise rate with 8-15 ℃/min in retort furnace is added to 880-920 ℃, constant temperature two hours, naturally cooling then.
2. method according to claim 1 is characterized in that the method for drying is: toasted two hours down at 110-130 ℃.
3. method according to claim 1 is characterized in that: above-mentioned heat treated whole process keeps ventilation state.
4. method according to claim 1 and 2, the method that it is characterized in that pickling is: get nitric acid and hydrofluoric acid earlier, ratio by weight is nitric acid: hydrofluoric acid=6-10: 1 forms mixing acid, then the raw material after the thermal treatment is immersed mixing acid, in mixing acid, embathed raw material 3-5 minute, and stirred while embathing;
The weight percent concentration of above-mentioned nitric acid is between the 70%-98%, and the weight percent concentration of hydrofluoric acid is between the 35%-55%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100800891A CN101497440B (en) | 2008-12-10 | 2008-12-10 | Method for removing native polysilicon bar end-face graphite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100800891A CN101497440B (en) | 2008-12-10 | 2008-12-10 | Method for removing native polysilicon bar end-face graphite |
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| Publication Number | Publication Date |
|---|---|
| CN101497440A CN101497440A (en) | 2009-08-05 |
| CN101497440B true CN101497440B (en) | 2011-08-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100800891A Expired - Fee Related CN101497440B (en) | 2008-12-10 | 2008-12-10 | Method for removing native polysilicon bar end-face graphite |
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| CN (1) | CN101497440B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101623695B (en) * | 2009-08-13 | 2011-05-04 | 合肥景坤新能源有限公司 | Method for cleaning graphitic silicon materials |
| CN102962224B (en) * | 2012-11-06 | 2014-11-12 | 安徽日能中天半导体发展有限公司 | Method for cleaning parent polycrystalline carbon head material |
| CN108516553B (en) * | 2018-04-23 | 2020-03-27 | 亚洲硅业(青海)股份有限公司 | Method for removing clamping petals of polycrystalline silicon rod |
| EP4021849B1 (en) * | 2019-08-29 | 2024-01-03 | Wacker Chemie AG | Method for producing silicon fragments |
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- 2008-12-10 CN CN2008100800891A patent/CN101497440B/en not_active Expired - Fee Related
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| CN101497440A (en) | 2009-08-05 |
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