CN102409394B - Crucible used for polycrystalline silicon ingot casting and preparation method thereof - Google Patents
Crucible used for polycrystalline silicon ingot casting and preparation method thereof Download PDFInfo
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- CN102409394B CN102409394B CN201110397705.8A CN201110397705A CN102409394B CN 102409394 B CN102409394 B CN 102409394B CN 201110397705 A CN201110397705 A CN 201110397705A CN 102409394 B CN102409394 B CN 102409394B
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Abstract
The invention discloses a crucible used for polycrystalline silicon ingot casting and a preparation method thereof. The crucible comprises a crucible body, and is characterized in that: the crucible body comprises the following components in percentage by weight: 60-98% of Si3N4 and 2-40% of SiO2 and/or SiNxOy, wherein x and y meet the relational expression of 3x+2y=4. The crucible used for polycrystalline silicon ingot casting can be used for ingot casting of polycrystalline silicon multiple times, and can be repeatedly used for more than 20 times.
Description
Technical field
The invention belongs to polycrystalline silicon ingot casting technical field, be specifically related to a kind of crucible used for polycrystalline silicon ingot casting.
Background technology
Polysilicon is the starting material of photovoltaic industry.The making of polysilicon solar battery slice generally will by procedures such as the ingot casting of polysilicon, evolution, sections.At present, most polycrystalline silicon ingot casting is realized by quartz crucible.In polycrystalline silicon casting ingot process, generally that highly purified polysilicon block material is put into quartz crucible, in rare gas element, (be generally argon gas) be warming up to high temperature (more than 1500 DEG C) fusing, slowly cool to room temperature again, complete silicon ingot is carried out being separated with the quartz crucible of fragmentation and carries out ingot casting.In order to can the demoulding smoothly, one deck release agent material to be sprayed in advance at the internal surface of quartz crucible, the beta-silicon nitride powder of this material normally high purity (more than 99.99%).This high purity silicon nitride silicon coating mainly contains several effect: one is prevent the metal in quartz crucible or nonmetallic impurity from coming in contact with polysilicon molten mass when high temperature, diffuses into polysilicon, highly purified polysilicon is polluted; Two is avoid quartz crucible and silicon ingot to stick together in process of cooling, causes demoulding failure; Three is prevent silicon material from high temperature reacting with quartz or silica glass, produces silicon monoxide gas, pollutes whole electric furnace system.The thermal expansivity of polysilicon is much larger than the thermal expansivity of quartz, if the material of these two kinds of different heat expansion coefficients occurs bonding, can make to produce great stress between polycrystal silicon ingot and crucible, silicon ingot is chapped, breakage, produces a large amount of substandard products.
The quartz crucible that the ingot casting pattern of this polysilicon uses can only use once, and cannot Reusability.This is because the amorphous silica in quartz crucible can be partially converted into crystal aerosil in process of cooling, cause the breaking of crucible, broken.High-purity silicon nitride powder purity requirement on quartz crucible is high, only has minority manufacturer to provide, expensive, generally also can only use once and be difficult to reclaim.The rise of photovoltaic industry makes the usage quantity of quartz crucible greatly increase, and also makes the usage quantity of high purity silicon nitride silicon powder greatly increase.A large amount of productions, the use of these consumptive materials consume a large amount of energy and quartz material, are one of important costs of photovoltaic industry.Exploitation the crucible used for polycrystalline silicon ingot casting of Reusability not only can reduce the usage quantity of quartz crucible greatly, and also can save the use of beta-silicon nitride powder, to energy-saving and emission-reduction, the production cost reducing solar battery sheet is significant.
Silicon nitride is as the release materials of a known inertia, and it and many metallic substance at high temperature all can not react, and may be used for the demoulding of silicon and other various metals materials.The silicon nitride ceramic parts of silicon nitride ceramics crucible and other different shapes has commercially produced product, but be with ceramic process preparations such as isostatic sinterings mostly, that is: the starting material of use are the beta-silicon nitride powder of various purity, this powder, after overmolding, sinters and forms under high temperature (more than 1600 DEG C) high pressure.The physical strength that the silicon nitride ceramics crucible of this mode of manufacture has had, also the resistance to elevated temperatures had, but its stock size is all very little, crucible once can only melting polysilicon number kilogram to tens of kilograms, ingot casting suitability for industrialized production at the polycrystalline silicon ingot casting of hundreds of kilograms cannot be used for.In addition, in order to accelerate to sinter efficiency, often need to add iron, calcium in beta-silicon nitride powder, the metallic impurity such as aluminium are as sintering aid, and the importing of these impurity finally can affect the purity of polysilicon.Do not have large-sized silicon nitride crucible can be used in the ingot casting of polysilicon in the market.
Japanese Patent JP-59-162199 discloses one reaction bonding silicon nitride (RBSN) technology and prepares crucible used for polycrystalline silicon ingot casting method, but because silicon can produce a large amount of heat tempestuously in high-temperature ammonolysis process, if the temperature of crucible local does not add strict control in sintering process, final silicon nitride crucible is easily made to produce tiny crack.In addition, the crucible produced by this technology, the silicon material of melting easily with produce bonding between crucible, when causing the demoulding, crucible breaks, and cannot repeatedly use.
Chinese invention application ZL200780023521.7 discloses a kind of method that the NBSN of application technology prepares silicon nitride crucible, the method uses the mixture of silicon nitride and silica flour after overmolding, nitrogenize in the atmosphere of high temperature purity nitrogen, generates silicon nitride crucible solid plate material.The core of this technology controls pure silicon powder nitride with mixing of beta-silicon nitride powder, and the temperature of spare-crucible is uncontrollable, is difficult to make silica flour fully and completely nitrogenize.
Summary of the invention
The object of the invention is to provide a kind of crucible used for polycrystalline silicon ingot casting, to solve in prior art crucible used for polycrystalline silicon ingot casting adopt quartz crucible and can not reuse, the problem such as other crucibles preparation method is unstable, cannot reuse.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
A kind of crucible used for polycrystalline silicon ingot casting, comprises crucible body, it is characterized in that in described crucible body, component comprises in weight percent content:
Si
3N
460％～98％；
SiO
2and/or SiN
xo
y2% ~ 40%;
Wherein x, y meet relational expression: 3 × x+2 × y=4.
Preferably, in described crucible body, component comprises in weight percent content:
Si
3N
470％～98％；
SiO
2and/or SiN
xo
y2% ~ 30%;
Wherein x, y meet relational expression: 3 × x+2 × y=4.
The preparation method of the crucible used for polycrystalline silicon ingot casting provided described in a kind of claim 1 or 2 is provided, it is characterized in that said method comprising the steps of:
(1) with Si
3n
4powder, SiO
2nano dispersion fluid is that raw material is mixed to form slurry, and by slurry cast in a mold, the demoulding forms demoulding idiosome;
(2) sinter in the atmosphere furnace being selected from nitrogen, ammonia, nitrogen and ammonia gas mixture body or nitrogen and hydrogen gas mixture after the idiosome drying after the demoulding and form described crucible used for polycrystalline silicon ingot casting, final sintering temperature controls in the scope of 1000 DEG C ~ 1600 DEG C.
Preferably, Si in described method Raw
3n
4powder accounts for 40% ~ 98%, SiO of total weight of solids in raw material
2in nano dispersion fluid, silica solid accounts for 2% ~ 60% of total weight of solids in raw material.
Preferably, the Nano-meter SiO_2 used in described method
2the purity of dispersion liquid is more than 99.9%, and Nano-meter SiO_2
2siO in dispersion liquid
2the mean size of primary particle is 1nm ~ 200nm.
Preferably, the Nano-meter SiO_2 used in described method
2the silica solids level of dispersion liquid in 0.5% ~ 60%, described Nano-meter SiO_2
2dispersion liquid is obtained by methyl silicate or ethyl silicate hydrolysis.
Preferably, the volatile solvent dissolved each other with water is contained in the slurry formed in described method, described volatile solvent is selected from one or more any mixing of water, methyl alcohol, ethanol, Virahol or ethylene glycol, and in described slurry, the weight percent of volatile solvent is 3% ~ 40%.
Preferably, the Si used in described method
3n
4the mean particle size of powder is within the scope of 0.1 micron ~ 1 millimeter, and purity is more than 99.9%.
Preferably, the demoulding mould used in described method is gypsum mold, and the drying temperature of the demoulding idiosome after the demoulding is 100 ~ 200 DEG C.
Preferably, SiO in described method
2nano dispersion fluid is silicon sol or gas-phase silica dispersion liquid, is mixed into the Si powder of total weight of solids 0 ~ 55% in described raw material; The mean particle size of Si powder is within the scope of 0.1 micron ~ 0.5 millimeter, and purity is above more than 99.9%.
May containing the Si of 0 ~ 1% in the crucible used for polycrystalline silicon ingot casting body that the present invention obtains.
Preferably, final sintering reaction temperature is within the scope of 1000 ~ 1600 DEG C, and the reaction times is in 20 ~ 48 hours.
Technology of the present invention is for the preparation of the large size needed for photovoltaic industry, repeatedly used crucible, the present invention passes through with highly purified beta-silicon nitride powder, nano silicon as starting material, through the pouring technology similar with producing quartz crucible, again through high-temperature ammonolysis process for producing large size crucible used for polycrystalline silicon ingot casting (also can classify as silicon nitride crucible, nitriding treatment refers to that Pure Silicon Metal or Si oxide generate the process of silazine link after nitrogenous gas process).Technology of the present invention does not need to sinter through the High Temperature High Pressure of common silicon nitride ceramics, and cost is low, practical.Silicon nitride crucible of the present invention can Reusability in the ingot casting of polysilicon, number of times more than 20 times, and can eliminate completely and uses the silicon nitride release layer preparation process of quartz crucible.When making slurry, silicon powder can be used to replace a part of beta-silicon nitride powder raw material, for cost-saving.
Before the crucible sintering that the reusable crucible used for polycrystalline silicon ingot casting of the present invention adopts, the raw-material composition of idiosome is: Si
3n
4powder, Si powder, SiO
2the gas-phase silica dispersion liquid of nano dispersion fluid or comparable purity, requires in raw material to control: silicon nitride solids content is 40% ~ 98%, and silica flour solids content is 0 ~ 55%, and silica solids level is 0.5 ~ 60%.These content all by weight percentage.
Si in the crucible used for polycrystalline silicon ingot casting pot body (or crucible body) of final formation
3n
4content is 60% ~ 98%, SiO
2and SiN
xo
ythe content of (solid) (wherein: 3 × x+2 × y=4) is that 2% ~ 40%, Si content is less than 1%.These content all by weight percentage.
When being prepared, need starting material and water or become slurry with the volatile solvent that water dissolves each other, the content of water and volatile solvent is 3% ~ 40%.In a mold, the demoulding after leaving standstill, forms demoulding idiosome in slurry cast.Demoulding idiosome is dry at 100 ~ 200 DEG C of temperature.Demoulding idiosome sinters in the mixed-gas atmosphere stove of nitrogen or ammonia, nitrogen and ammonia or nitrogen and hydrogen, and final sintering temperature is in the scope of 1000 ~ 1600 DEG C.
Nano-meter SiO_2
2dispersion liquid be purity higher than 99.9% silicon sol, or the gas-phase silica dispersion liquid of comparable purity, the mean size of primary particle is within the scope of 1nm ~ 200nm.Nano-meter SiO_2
2dispersion liquid can be the hydrolyzate of methyl silicate or ethyl silicate.Nano-meter SiO_2
2silicon-dioxide in dispersion liquid is the nano particle of mean particle size at below 200nm, particle surface and the inner hydroxyl containing enriching, there is very high reactive behavior, in the atmosphere of nitrogen or ammonia and under high temperature, these hydroxyls can be excluded, and the substitute is siloxane bond or silazine link.Si
3n
4the mean particle size of powder within the scope of 0.1 micron ~ 1 millimeter, purity more than 99.9%; The mean particle size of Si powder within the scope of 0.1 micron ~ 0.5 millimeter, purity more than 99.9%.The volatile solvent used is water, a kind of or two or more arbitrarily combination of methyl alcohol, ethanol, Virahol, ethylene glycol, and this solvent is Nano-meter SiO_2
2the composition that dispersion liquid is brought into or add corresponding volatile solvent and be formulated in slurry.The mould used can be gypsum mold.
The invention provides a kind of Novel crucible, its main component is silicon nitride.Its preparation technology is: the beta-silicon nitride powder of high purity (> 99.9%) and/or the silica flour of high purity (> 99.9%), the silicon sol (or aqueous liquid dispersion of the gas-phase silica of high purity (> 99.9%)) of high purity (> 99.9%) are mixed, do form slurry.These powders being prepared into the process of slurry, can be stirred by high speed machine, also can be undertaken by the mode of ball milling or sand milling.The slurry prepared is cast in film die shaping, and mould can be gypsum material also can be that other have the material of absorbent function.By dry for the idiosome after shaping, the demoulding, then puts into atmosphere furnace by the crucible idiosome after the demoulding, dry.Again at high temperature, crucible idiosome is carried out nitrogenizing reaction in nitrogen, ammonia or nitrogen ammonia gas mixture body or nitrogen hydrogen gas mixture.
In the nitrogen atmosphere of high temperature (1300 DEG C ~ 1600 DEG C Celsius), high-purity silica flour little by little will be converted into silicon nitride, thus by as a whole for bonding for silicon nitride powder one-tenth.At lower temperatures (within the scope of 500 DEG C in theory ~ 1000 DEG C), it is silicon oxynitride that the nano silicon in silicon sol carries out nitrogenize in nitrogen, ammonia or nitrogen ammonia gas mixture body or nitrogen hydrogen gas mixture.Finally be cooled to room temperature.Core of the present invention does not use traditional silicon nitride ceramics sintering process (sintering temperature reaches 1800 DEG C, carries out under having high-pressure situations), and in the raw material in the present invention, beta-silicon nitride powder is the Si that purity is greater than α or the β phase of 99.9%
3n
4powder, and be preferential with α phase; Silica flour is the Si powder that purity is greater than 99.9%; And the composition of silicon sol or gas-phase silica dispersion liquid is the non-crystal SiO that purity is greater than 99.9%
2.Silica flour or Si
3n
4the mean particle size of powder is between 0.1 micron to 1 millimeter, and the primary particle mean size of nano silicon is at 1nm ~ 200nm.Raw material is mixed to form slurry according to a certain percentage, is then poured into die for molding.Put into atmosphere furnace after drying, pass into high-purity nitrogen, or ammonia carries out normal pressure-sintered.Final sintering temperature is 1000 DEG C ~ 1600 DEG C Celsius.In sintering process, will following reaction (in theory) be there is:
Si (Gu)+N
2(gas) → Si
3n
4(Gu)
Si (Gu)+NH
3(gas) → Si
3n
4(Gu)+H
2
Si (Gu)+SiO
2(Gu) → SiO (gas)
SiO (gas)+NH
3(gas) → SiN
xo
y(Gu)+H
2(wherein: 3 × x+2 × y=4)
SiO
2(Gu)+NH
3(gas) → SiN
xo
y(Gu)+H
2(wherein: 3 × x+2 × y=4);
SiO
2(Gu)+N
2(gas) → SiN
xo
y(Gu)+O
2(wherein: 3 × x+2 × y=4);
SiO
2(Gu)+Si
3n
4(Gu) → SiN
xo
y(Gu) (wherein: 3 × x+2 × y=4).
Although the raw material of crucible of the present invention is not exclusively silicon nitride, containing Pure Silicon Metal and nano silicon oxide, but Pure Silicon Metal can react with nitrogen and becomes silicon nitride, and nano silicon can be nitrided into as silicon oxynitride, the composition of final crucible is silicon nitride, silicon oxynitride, and Pure Silicon Metal content is less than 1%.Final temperature of reaction is more than 1000 DEG C, and the reaction times is more than 20 hours.
Nano silicon must be contained as binding agent in silicon nitride idiosome of the present invention, to provide the physical strength of crucible, but can containing also not containing high purity silica flour.The use of high purity silica flour can make the usage quantity of high-purity silicon nitride powder greatly reduce, cost-saving.But then, the use of silica flour makes the sintering time of idiosome greatly increase, and in addition, can produce a large amount of heat in nitrogenizing reaction process, and temperature is not easy to control.If not containing silica flour in the starting material in the present invention, that is: with high-purity silicon nitride powder and nano silicon for starting material, by the high temperature sintering in nitrogen containing atmosphere, nano silicon nitrogenizing reaction changes into silicon oxynitride, final molding be oxygen containing silicon nitride crucible, then reaction times temperature of reaction can be made greatly to reduce.Nano silicon can be highly purified silicon sol, the dispersion liquid of highly purified gas-phase silica in water, or highly purified tetramethoxy-silicane hydrolyzate, or the hydrolyzate of highly purified tetraethoxysilane.Although can aerobic be contained in the crucible produced with silicon nitride and nano silicon oxide, but the surface of these nano silicons is by being rich in silicon-nitrogen key after nitridation process, follow-up ingot casting is used and can not produce great negative impact, the oxygen level in final silicon ingot also can not be made greatly to increase.The crucible sintered into using silicon nitride powder and nano silicon oxide as raw material can Reusability in polycrystalline silicon ingot casting more than 20 times.In slurry preparation of the present invention, the solvent having mutual solubility with glassware for drinking water can be added in the slurry, as: methyl alcohol, ethanol, Virahol, ethylene glycol etc.Solvent in slurry can be the mixed solvent of water or water and volatile solvent.
Need the term of explanation as follows:
Primary particle refers to the one independently particle containing low porosity, and granule interior can have interface, such as phase boundary, crystal boundary etc.Coacervate: be the larger particle formed by surface force or the effect of solid bridged bond by primary particle. containing interconnective pore network in coacervate. coacervate can be divided into hard agglomeration and soft aggregate two kinds. and the forming process of coacervate makes maximum system energy decline.Second particle: refer to the artificial powder agglomerated particles manufactured; " granulation " of such as preparing indication in the technological process of pottery is exactly manufacture second particle.General, under high multiple electron microscope, can be observed the size of primary particle, but what survey under laser particle analyzer is second particle size.Nano-meter SiO_2 in the present invention
2be generally primary particle in dispersion liquid, wherein need to control Nano-meter SiO_2
2in dispersion liquid, the mean size of primary particle is within the scope of 1nm ~ 200nm.
Relative to scheme of the prior art, advantage of the present invention is:
Technology of the present invention can prepare large-sized crucible used for polycrystalline silicon ingot casting by lower cost, prepared crucible has certain physical strength, its main component is highly purified silicon nitride and silicon oxynitride, and may be used for the repeatedly ingot casting of polysilicon, Reusability number of times is more than 20 times.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described:
Fig. 1 is silicon nitride crucible internal structure schematic diagram.Wherein 1 is silicon oxide or silicon oxynitride particle, and 2 is silicon nitride particle, and 3 is space.
Embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiments are not limited to for illustration of the present invention limit the scope of the invention.The implementation condition adopted in embodiment can do further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
The preparation of embodiment 1 crucible used for polycrystalline silicon ingot casting
Preparation method is as follows:
1) by commercially available silicon nitride powder (α phase, purity > 99.99%), silica flour (purity 99.999%), silicon sol (solid content 30wt%, purity 99.9999%, Suzhou Nano Dispersions Co., Ltd. produces) solid weight ratio according to 5: 2: 3 mixed by ball mill, and the part by weight that water and alcohol account for whole slurry is 21%.
2) slurry prepared is poured in the cavity of gypsum mold, leaves standstill the demoulding after 8 hours.
3) idiosome after the demoulding is put into stoving oven, drying 10 hours at 150 DEG C.
4) dried demoulding idiosome is put into nitrogen atmosphere stove, is slowly warming up to 1250 DEG C of presintering, then be warming up to 1450 DEG C nitridation sintered 48 hours.Then sintering oven is slowly cooled to room temperature, obtain silicon nitride crucible.
The silicon nitride crucible obtained is through chemical analysis, and its oxygen level (weight) is at 3.1wt%, and Pure Silicon Metal content < 0.1wt%, various metallic impurity total content is at below 1000ppm, and porosity is 18%.Use this crucible melting solar-grade polysilicon in the electric furnace of 1550 DEG C in argon gas, and be cooled to room temperature, crucible does not ftracture, and silicon ingot occurs bonding with crucible, and silicon ingot can not damage the prerequisite bottom knockout of crucible.This crucible carried out in argon gas atmosphere intensification cooling melting polycrystalline silicon ingot casting with same process and test 20 times, silicon ingot can the demoulding, and crucible is without obvious strain cracking.
The preparation of embodiment 2 crucible used for polycrystalline silicon ingot casting
Preparation method is as follows:
By commercially available silicon nitride powder (α phase, purity > 99.99%), silicon sol (solid content 40wt%, purity 99.9999%, Suzhou Nano Dispersions Co., Ltd. produces) solid weight ratio according to 8: 2 mixed by ball mill, and the content that the liquid of water and alcohol accounts for whole slurry is 12%.
The slurry prepared is poured in the cavity of gypsum mold, leaves standstill the demoulding after 8 hours.
Idiosome after the demoulding is put into stoving oven, drying 10 hours at 150 DEG C.
Dried demoulding idiosome is put into ammonia atmosphere stove and is warming up to 1100 DEG C of presintering, then by sintering temperature prompting to 1300 DEG C, total sintering time is 48 hours.Then sintering oven is slowly cooled to room temperature, obtain silicon nitride crucible.
The silicon nitride crucible obtained is through chemical analysis, and the weight content of its oxygen is 4.1%, and various metal oxide impurities total content is at below 1000ppm, and porosity is 12%.Use this crucible melting polysilicon in the electric furnace of 1550 DEG C in argon gas, and be cooled to room temperature, crucible does not ftracture, and silicon ingot occurs bonding with crucible.Silicon ingot can not damage the prerequisite bottom knockout of crucible.This crucible carried out in argon gas atmosphere intensification cooling melting polycrystalline silicon ingot casting with same process and test 20 times, silicon ingot can the demoulding, and crucible is without obvious strain cracking.
The preparation of embodiment 3 crucible used for polycrystalline silicon ingot casting
Preparation method is as follows:
By commercially available silicon nitride powder (α phase, purity > 99.99%), silicon sol (solid content 40wt%, purity 99.9999%, Suzhou Nano Dispersions Co., Ltd. produces) solid weight ratio according to 6: 4 mixed by ball mill, and the content that the liquid of water and alcohol accounts for whole slurry is 24%.
The slurry prepared is poured in the cavity of gypsum mold, leaves standstill the demoulding after 8 hours.
Idiosome after the demoulding is put into stoving oven, drying 10 hours at 150 DEG C.
Dried demoulding idiosome is put into ammonia atmosphere stove, is warming up to 1000 presintering, then sintering temperature is risen to 1300 DEG C, total sintering time is 48 hours.Then sintering oven is slowly cooled to room temperature, obtain silicon nitride crucible.
The silicon nitride crucible obtained is through chemical analysis, and the part by weight that its oxygen level accounts for whole crucible is 7.2%, and various metal oxide impurities total content is at below 1000ppm, and porosity is 22%.Use this crucible melting polysilicon in the electric furnace of 1550 DEG C in argon gas, and be cooled to room temperature, crucible does not ftracture, and silicon ingot occurs bonding with crucible.Silicon ingot can not damage the prerequisite bottom knockout of crucible.Carried out being warming up to 1550 DEG C in argon gas atmosphere by this crucible with same process, and be incubated more than 10 hours, ingot casting of then lowering the temperature, revision test 20 times, each silicon ingot can the demoulding, and crucible is without obvious strain cracking.
The preparation of embodiment 4 crucible used for polycrystalline silicon ingot casting
Preparation method is as follows:
By commercially available silicon nitride powder (α phase, purity > 99.99%), silicon sol (solid content 10wt%, purity 99.9999%, Suzhou Nano Dispersions Co., Ltd. produces) solid weight ratio according to 7: 3 mixed by ball mill, and the content that the liquid of water and alcohol accounts for whole slurry is 27%.
The slurry prepared is poured in the cavity of gypsum mold, leaves standstill the demoulding after 8 hours.
Idiosome after the demoulding is put into stoving oven, drying 10 hours at 150 DEG C.
Dried demoulding idiosome is put into nitrogen and hydrogen mixed gas atmosphere stove, is warming up to 1000 presintering, then sintering temperature is improved 1200 DEG C, total sintering time is 48 hours.Then sintering oven is slowly cooled to room temperature, obtain silicon nitride crucible.
The silicon nitride crucible obtained is through chemical analysis, and the part by weight that its oxygen level accounts for whole crucible is 1.9%, and various metal oxide impurities total content is at below 1000ppm, and porosity is 16%.Use this crucible melting polysilicon in the electric furnace of 1550 DEG C in argon gas, and be cooled to room temperature, crucible does not ftracture, and silicon ingot occurs bonding with crucible.Silicon ingot can not damage the prerequisite bottom knockout of crucible.With same process, this crucible is carried out intensification 1550 DEG C in argon gas atmosphere, and be incubated more than 10 hours, ingot casting of then lowering the temperature, revision test 20 times, each silicon ingot can the demoulding, and crucible is without obvious strain cracking.
The preparation of embodiment 5 crucible used for polycrystalline silicon ingot casting
Preparation method is as follows:
By commercially available silicon nitride powder (α phase, purity > 99.99%), gas-phase silica dispersion liquid (solid content 40wt%, purity 99.9999%, Cabot CABOT company of the U.S.) solid weight ratio according to 8: 2 mixed by ball mill, and the content that the liquid of water and alcohol accounts for whole slurry is 15%.
The slurry prepared is poured in the cavity of gypsum mold, leaves standstill the demoulding after 8 hours.
Idiosome after the demoulding is put into stoving oven, drying 10 hours at 150 DEG C.
Dried demoulding idiosome is put into ammonia atmosphere stove, is warming up to 1000 presintering, then sintering temperature is increased to 1500 DEG C, total sintering time is 48 hours.Then sintering oven is slowly cooled to room temperature, obtain silicon nitride crucible.
The silicon nitride crucible obtained is through chemical analysis, and the part by weight that its oxygen level accounts for whole crucible is 1.8%, and various metal oxide impurities total content is at below 1000ppm, and porosity is 28%.Use this crucible melting polysilicon in the electric furnace of 1550 DEG C in argon gas, and be cooled to room temperature, crucible does not ftracture, and silicon ingot occurs bonding with crucible.Silicon ingot can not damage the prerequisite bottom knockout of crucible.Carried out being warming up to 1550 DEG C in argon gas atmosphere by this crucible with same process, and be incubated more than 10 hours, ingot casting of then lowering the temperature, revision test 20 times, each silicon ingot can the demoulding, and crucible is without obvious strain cracking.
Above-mentioned example, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to spirit of the present invention or modification, all should be encompassed within protection scope of the present invention.
Claims (9)
1. a crucible used for polycrystalline silicon ingot casting, comprises crucible body, it is characterized in that in described crucible body, component comprises in weight percent content:
Si
3n
460% ~ 98%; SiO
2and/or SiN
xo
y2% ~ 40%;
Wherein x, y meet relational expression: 3 × x+2 × y=4;
Described crucible used for polycrystalline silicon ingot casting is prepared in accordance with the following steps:
(1) with Si
3n
4powder, SiO
2nano dispersion fluid is that raw material is mixed to form slurry, and by slurry cast in a mold, the demoulding forms demoulding idiosome;
(2) sinter in the atmosphere furnace being selected from nitrogen, ammonia, nitrogen and ammonia gas mixture body or nitrogen and hydrogen gas mixture after the idiosome drying after the demoulding and form described crucible used for polycrystalline silicon ingot casting, final sintering temperature controls in the scope of 1000 DEG C ~ 1600 DEG C.
2. crucible used for polycrystalline silicon ingot casting according to claim 1, is characterized in that in described crucible body, component comprises in weight percent content:
Si
3n
470% ~ 98%; SiO
2and/or SiN
xo
y2% ~ 30%;
Wherein x, y meet relational expression: 3 × x+2 × y=4.
3. a preparation method for the crucible used for polycrystalline silicon ingot casting described in claim 1 or 2, is characterized in that said method comprising the steps of:
(1) with Si
3n
4powder, SiO
2nano dispersion fluid is that raw material is mixed to form slurry, and by slurry cast in a mold, the demoulding forms demoulding idiosome;
(2) sinter in the atmosphere furnace being selected from nitrogen, ammonia, nitrogen and ammonia gas mixture body or nitrogen and hydrogen gas mixture after the idiosome drying after the demoulding and form described crucible used for polycrystalline silicon ingot casting, final sintering temperature controls in the scope of 1000 DEG C ~ 1600 DEG C.
4. method according to claim 3, is characterized in that the Nano-meter SiO_2 used in described method
2the purity of dispersion liquid is at more than 99.9wt%, and Nano-meter SiO_2
2siO in dispersion liquid
2the mean size of primary particle is 1nm ~ 200nm.
5. method according to claim 3, is characterized in that the Nano-meter SiO_2 used in described method
2the silica solids level of dispersion liquid in 0.5% ~ 60%, described Nano-meter SiO_2
2dispersion liquid is obtained by methyl silicate or ethyl silicate hydrolysis.
6. method according to claim 3, it is characterized in that in the slurry formed in described method, containing the volatile solvent dissolved each other with water, described volatile solvent is selected from one or more any mixing of methyl alcohol, ethanol, Virahol or ethylene glycol, and in described slurry, the weight percent of volatile solvent is 3% ~ 40%.
7. method according to claim 3, is characterized in that the Si used in described method
3n
4the mean particle size of powder is within the scope of 0.1 micron ~ 1 millimeter, and purity is at more than 99.9wt%.
8. method according to claim 3, is characterized in that the demoulding mould used in described method is gypsum mold, and the drying temperature of the demoulding idiosome after the demoulding is 100 ~ 200 DEG C.
9. method according to claim 3, is characterized in that SiO in described method
2nano dispersion fluid is silicon sol or gas-phase silica dispersion liquid, is mixed into the Si powder of total weight of solids 0 ~ 55% in described raw material; The mean particle size of Si powder is within the scope of 0.1 micron ~ 0.5 millimeter, and purity is above more than 99.9%.
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| CN103803955B (en) * | 2014-03-03 | 2015-07-15 | 哈尔滨工业大学 | Method for preparing silicon nitride/silicon oxide composite crucible |
| CN105541311B (en) * | 2015-12-09 | 2018-11-13 | 中钢集团洛阳耐火材料研究院有限公司 | The preparation method of polycrystalline silicon ingot casting silicon nitride bonded silicon fused silica crucible |
| US10450669B2 (en) * | 2016-07-29 | 2019-10-22 | Auo Crystal Corporation | Container for silicon ingot fabrication and manufacturing method thereof, and method for manufacturing crystalline silicon ingot |
| CN106747664A (en) * | 2016-11-17 | 2017-05-31 | 苏州阿特斯阳光电力科技有限公司 | The production method of the preparation method, crucible and polysilicon silicon chip of the coating of crucible |
| CN109750351A (en) * | 2018-05-31 | 2019-05-14 | 河北高富氮化硅材料有限公司 | A kind of efficient Si of polycrystalline silicon ingot casting3N4Powder |
| CN111960828A (en) * | 2020-08-03 | 2020-11-20 | 武汉科技大学 | Silicon oxynitride/quartz composite ceramic crucible for smelting photovoltaic silicon and preparation method thereof |
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| CN1302158C (en) * | 2002-08-15 | 2007-02-28 | 克鲁辛股份公司 | Mould parts of silicon nitride and method for producing such mould parts |
| CN101495680A (en) * | 2006-06-23 | 2009-07-29 | Rec斯坎沃佛股份有限公司 | Reusable crucibles and method of manufacturing them |
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| CN101495680A (en) * | 2006-06-23 | 2009-07-29 | Rec斯坎沃佛股份有限公司 | Reusable crucibles and method of manufacturing them |
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