CN103124693A - Silicon ingot manufacturing vessel - Google Patents
Silicon ingot manufacturing vessel Download PDFInfo
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- CN103124693A CN103124693A CN2011800487252A CN201180048725A CN103124693A CN 103124693 A CN103124693 A CN 103124693A CN 2011800487252 A CN2011800487252 A CN 2011800487252A CN 201180048725 A CN201180048725 A CN 201180048725A CN 103124693 A CN103124693 A CN 103124693A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/002—Crucibles or containers for supporting the melt
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00939—Uses not provided for elsewhere in C04B2111/00 for the fabrication of moulds or cores
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
Abstract
Disclosed is a silicon ingot manufacturing vessel capable of repeated use in the manufacture of silicon ingots and capable of manufacturing high-quality silicon ingots. A silicon ingot manufacturing vessel used for solidifying a silicon melt and growing a silicon polycrystal is configured such that a mold release material of silicon nitride is formed on the inner surface of a vessel main body which comprises a porous body of silicon nitride or silicon carbide. Further, the open porosity of the porous body configuring the vessel main body is 10-40%. Because a mold release material is formed robustly on the inner surface of the vessel main body, damage to the mold release material caused by stress accompanying volume expansion during silicon solidification is effectively prevented. Further, keeping the metal impurity concentration of the vessel to 10ppm or less makes it possible to prevent generation of solid SiC suspended on the melt surface, which is a hindrance to the growth of single crystal Si.
Description
Technical field
The present invention relates to the silicon ingot manufacturing container for the manufacture of the silicon ingot of solar cell grade.
Background technology
All the time, manufacture method as the silicon ingot that is used for solar cell etc., knownly hold silicon melt and this silicon melt is solidified from the below and make the casting (cast, casting) of polycrystalline silicon growth in the container (crucible or mold etc.) of graphite-made or quartzy system.
According to this casting, because the direction of crystal when silicon melt solidifies growth is aligned to necessarily, thereby can make the high-quality wafer that suppresses the ratio resistance increase that crystal boundary causes.In addition, according to casting, can carry out a large amount of productions of silicon ingot.
Generally speaking, the internal surface at the container that is used for casting forms release materials.In the situation that make silicon ingot by casting, if silicon and container material reaction when silicon melt is solidified in container, silicon crystal is fixed in container, becomes to be difficult to take out ingot.Therefore, in the internal surface formation release materials of container, silicon crystal does not directly contact with container thus.As such release materials, generally use silicon nitride (Si
3N
4), silicon-dioxide (SiO
2) or mix these material.
, form by Si at inner surface of container
3N
4In situation Deng the release materials that consists of, use following methods: will be at Si
3N
4Tackiness agents such as powder mixing pva and the aqueous slurry made is coated inner surface of container, and burn till under oxygen atmosphere.
Known, this Si
3N
4Coking property (solidify when the aggregate with pressed powder heats at lower than the temperature of melting point and become the character of the fine and close object that is called as sintered compact) is low, in the situation that do not add the sintering adjuvant such as metallic impurity, intensity is low and fragile.Therefore, be formed at inner surface of container by Si
3N
4The possibility of the release materials that sintered compact consists of damage the manufacturing process of silicon ingot when container takes out (during the maintenance of silicon melt, during the crystal growth, from) is high.
For example, the density of silicon melt is 2.5g/cm
3, but solid density is 2.33g/cm
3, thereby, when silicon melt is solidified in container, approximately 7% volumetric expansion.If the volumetric expansion when following this silicon to solidify and produce excessive stress in container, release materials is damaged.
And, if release materials is damaged in the manufacturing process of a series of silicon ingots, the decline of the stress-retained silicon ingot in cultivating of volumetric expansion, thereby the crystal quality such as increase that shift.Suppose that silicon ingot is not damaged, the decline of crystal quality is also inevitable.
In addition, if release materials is damaged in crystal growth, because silicon crystal contacts with container and fixes, thereby the taking-up of silicon ingot further worsens, result, and the release materials of peeling off is sneaked into silicon ingot, causes crystalline decline.And, owing to can not again utilize container to former state, thereby become the major cause that manufacturing cost increases.
So expect such silicon ingot manufacturing container: it has good release property, and can prevent that release materials is damaged in the manufacturing process of silicon ingot.
For example, in patent documentation 1 to 3, disclose Si
3N
4, SiO
2Or the mixture of these materials is stacked and to make release materials be the technology of multi-ply construction.In addition, in patent documentation 4,5, disclose resin has been sneaked into Si
3N
4Technology etc. release materials.In addition, in patent documentation 6,7, disclose with aluminium nitride (AlN) or cerium dioxide (CeO
2), yttrium oxide (Y
2O
3) be the technology of the formation release materials of sintering adjuvant.Like this, generally form in release materials and add metal oxide or carbon in operation, as the method that strengthens release materials.
Patent documentation
Patent documentation 1: TOHKEMY 2003-313023 communique
Patent documentation 2: Japanese Unexamined Patent Application Publication 2007-534590 communique
Patent documentation 3: TOHKEMY 2006-327912 communique
Patent documentation 4: TOHKEMY 2006-218537 communique
Patent documentation 5: TOHKEMY 2007-191345 communique
Patent documentation 6: TOHKEMY 2008-230932 communique
Patent documentation 7: Japanese kokai publication hei 7-206419 communique.
Non-patent literature
Non-patent literature 1: crystal growth magazine (Journal of Crystal Growth), 79 (1986), 583-589.
Summary of the invention
The problem that invention will solve.
Yet, in the situation that formation contains the release materials of metal oxide or carbon, in release materials slurry firing process, Formed SiClx (SiC).Then, the SiC that generates sneaks into silicon ingot, separates out at the crystal crystal boundary, and the quality as ingot is descended, but also becomes the obstacle when silicon ingot processing is become wafer.
In addition, contained metal oxide or the carbon of release materials slurry becomes the reason that makes container deteriorated.For example, be formed at the release materials of the inner surface of container of graphite-made, easily peel off into membranaceously because carbonization (SiCization) becomes, thereby release property is also insufficient, and result consumes crystal vessel.
In addition, for the intensity that makes release materials improves, generally silicon-dioxide is added (for example non-patent literature 1) in slurry as sintering adjuvant, but in the situation that the graphite-made container, due to graphite and the silicon dioxde reaction as container material, thereby accelerated above-mentioned undesirable condition.
On the other hand, in the situation that the inner surface of container of quartz system forms release materials, although do not have release materials and the deteriorated undesirable condition of container material in the slurry firing process, but, distortion deteriorated due to container under the high temperature when crystal is grown, as a result, can not effectively prevent the damage of release materials and container.
In addition, in the technology that patent documentation 1 to 3 is put down in writing, be multi-ply construction owing to making release materials, thereby the formation of release materials cost is artificial and cost.In the technology that patent documentation 4 to 7 is put down in writing, the intensity of release materials is high and become and be difficult to damage, but might sneak into silicon ingot as impurity by contained resin or the metal of release materials, makes crystal quality decline.For example, the contained metal oxide of release materials and container forms in operation in release materials and works as the catalyzer that generates SiC.The SiC that generates becomes melting liquid level suspended substance, hinders the crystal such as caochralski (Czochralski) method or Kai Luobo Lars (Kyropoulos) method to lift the monocrystalline that causes.
The present invention makes for addressing the above problem, and its purpose is, such silicon ingot manufacturing container is provided: it can be reused in the manufacturing of silicon ingot, and can yield rate make well the silicon ingot with better quality.
For the technical scheme of dealing with problems.
The invention that technical scheme 1 is put down in writing is the silicon ingot manufacturing container that makes polycrystalline silicon growth be used to silicon melt is solidified, it is characterized in that, the internal surface of the container body that consists of at the porous insert by silicon nitride or silicon carbide is formed with the release materials that is made of silicon nitride.
The invention that technical scheme 2 is put down in writing is characterized in that, with in container, the open porosity of aforementioned porous insert is more than 10% below 40% in silicon ingot manufacturing that technical scheme 1 is put down in writing.At this, open porosity is exactly that the summation of volume of the emptying aperture that is communicated with the outside is with respect to the ratio of the apparent volume of porous insert.
The invention that technical scheme 3 is put down in writing is characterized in that, makes in container at silicon ingot that technical scheme 1 is put down in writing, and the open porosity of aforementioned porous insert is more than 20% below 30%.
The invention that technical scheme 4 is put down in writing, it is characterized in that, silicon ingot that any one in technical scheme 1 to 3 is put down in writing is made in container, and the metallic impurity (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body that is made of the porous insert of aforementioned silicon nitride are respectively below 1000ppm.
The invention that technical scheme 5 is put down in writing, it is characterized in that, make in container at silicon ingot that technical scheme 4 is put down in writing, the metallic impurity (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body that is made of the porous insert of aforementioned silicon carbide are respectively below 10ppm.
The invention that technical scheme 6 is put down in writing, it is characterized in that, the silicon ingot that any one in technical scheme 1 to 3 is put down in writing is made in container, the metallic impurity (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body that is made of the porous insert of aforementioned silicon carbide are respectively below 100ppm, expect for below 10ppm.
The invention that technical scheme 7 is put down in writing, it is characterized in that, make in container at silicon ingot that technical scheme 6 is put down in writing, the metallic impurity (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body that is made of the porous insert of aforementioned silicon carbide are respectively below 10ppm.
The invention that technical scheme 8 is put down in writing is characterized in that, the silicon ingot that any one in technical scheme 1 to 7 is put down in writing is made in container, and the thickness of aforementioned release materials is 300 to 1000 μ m.
The invention that technical scheme 9 is put down in writing is characterized in that, in the silicon ingot that technical scheme 8 is put down in writing was made container, the thickness of aforementioned releasing agent was 350 to 600 μ m.
The effect of invention.
According to the present invention, be formed at securely the internal surface of container body due to the release materials with excellent releasability from mode, thereby can prevent effectively that the stress of the volumetric expansion owing to following silicon to solidify from causing release materials to be damaged.So, can reuse in the manufacturing of silicon ingot, and can yield rate make well the silicon ingot with better quality.
Description of drawings
Fig. 1 is the sectional view that container is used in silicon ingot manufacturing applicable of the present invention.
Fig. 2 is the figure of an example of crystal growing apparatus that show to use the container of embodiment.
Embodiment
Below, based on accompanying drawing, describe embodiments of the present invention in detail.
Fig. 1 is the sectional view that container is used in silicon ingot manufacturing applicable of the present invention.As shown in Figure 1, the related silicon ingot manufacturing of embodiment possesses with container (below, container) 10 the release property raising that to have stable on heating container body 11 and to cultivate silicon ingot in order making and is formed at the release materials 12 of the internal surface of container body 11.
Compare with the container of quartz system, by Si
3N
4Or container body 11 excellent heat resistances of the porous formed body formation of SiC, not deteriorated in the high temperature when silicon ingot is made, distortion.So, when the manufacturing of silicon ingot, can effectively prevent release materials 12 due to container body 11 deteriorated, the distortion damage.In addition, at container body 11 by Si
3N
4Porous formed body situation about consisting of under, the metallic impurity that contain (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) are respectively below 1000ppm, expect for below 10ppm.In the situation that container body 11 is made of the porous formed body of SiC, metallic impurity (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) are respectively below 100ppm, expect for below 10ppm.
By reducing release materials and the contained metal oxide of container, can reduce the generation of SiO gas in the growth of Si crystal, suppress the generation of the SiC foreign matter that the reaction due to release materials and the contained carbon of container and above-mentioned SiO gas causes.Thus, the SiC foreign matter is not suspended in the melting liquid level, thereby the crystal of Czoncharlski method or Kai Luobo Lars method etc. lifts the monocrystalline that operation causes and becomes easy.In addition, by manufacturing Si polycrystalline such as castings the time, also can prevent SiC melting liquid level suspended substance to sneak into crystal, result, the Si crystal quality improves.
Because container body 11 is made of porous insert, thereby the slurry of coating container body 11 soaks into to the pore of container body 11.In addition, utilize the container body 11 that consisted of by porous insert with the bubble deaeration in slurry.Owing to burning till under this state, thereby release materials 12 is formed at the internal surface of container body 11 securely.So, can prevent effectively that release materials 12 is damaged when the manufacturing of silicon ingot.
If bubble residues in release materials 12, exist according to the quantity of residual bubble or size the tendency that when the manufacturing of silicon ingot release materials 12 becomes easily damaged, therefore, all the time, when when container body forms release materials, implement decompression and wait the deaeration that causes to process.On the other hand, in the situation that the container 10 of present embodiment there is no need to implement deaeration and processes when the formation of release materials 12, can form simply release materials 12.
In addition, be formed at securely the internal surface of container body 11 due to release materials 12, thereby there is no need to be multi-ply construction as prior art.So the artificial and cost that the making of container 10 spends does not increase, the thickness of release materials 12 is increased.And, owing to there is no need to use the sintering adjuvants such as silicon-dioxide or metal oxide when forming release materials 12, thereby can prevent that impurity concentration in silicon ingot from increasing and crystallinity descends.That is, in the growth of Si crystal, contain the SiO of metal oxide
2The generation of the SiO gas that causes of thermolysis descend, can prevent to make the generation of the SiC foreign matter that crystal quality descends.According to same principle, by not using existing quartzy container made, can suppress as SiO
2The generation of SiO gas of thermolysis resultant.
Fig. 2 is the figure of an example of crystal growing apparatus that show to use the container of embodiment.Crystal growing apparatus 1 shown in Figure 2 uses when making silicon ingot.In crystal growing apparatus 1, container 10 is supported by the pedestal 13 of graphite-made, disposes well heater 14 in the periphery of pedestal 13.
In the situation that use crystal growing apparatus 1 to make silicon ingot by casting, and at first, with silicon raw material (for example silicon melt) the 15 input containers 10 of specified amount.Then cooling gradually makes silicon melt solidify and make polysilicon 15a growth from the melting liquid level of container 10 thus, makes silicon ingot.
In the situation that the open porosity of container material is little, release materials becomes and easily peels off, and becomes melting liquid level suspended substance in the crystal growth, hinders the monocrystalline from Si melting liquid level.On the other hand, in the situation that the open porosity of container material is excessive, the thickness of release materials becomes below 300 μ m, and the volumetric expansion stress that release materials causes relaxes and becomes insufficient, sees the crack on ingot.Below, be displayed in Table 1 and use Si
3N
4The result of the test of crucible.
[table 1]
[embodiment 1]
In the situation that open porosity is 10%, the bubble when smearing slurry with bristle is residual and produce large depression on the surface, after burning till, produces a lot of cracks take depression as starting point.Although can take out ingot from container, the large tendency in crack in the R part (bend on the border of diapire and sidewall) that exists at container bottom is seen the crack in the bottom of the Si ingot that solidifies from the melting liquid level.
[embodiment 2,3]
In the situation that open porosity is 20% and 30%, bubble is not residual smear slurry with bristle after, even the thick 600 μ m that reach of thickness do not see the crack yet.Solidify and the ingot made is the level and smooth form that there is no concave-convex surface or crack from Si melting face in the container that forms such release materials, can easily take out from container.
[embodiment 4]
In the situation that open porosity 40%, soaking into of release materials slurry is large, and becoming is difficult to thicken release materials.In the situation that the thickness of release materials less than 300 μ m, exists the lower surface at ingot to produce concavo-convex tendency.Although can take out ingot from container, in the R of container bottom part, see the crack on ingot.
[comparative example 1]
In the situation that open porosity surpasses 40%, do not see the crack on release materials, be difficult to make thickness to increase but become.Just solidify from Si melting liquid level in container, fused solution just occurs from the bottom leak.Think that the fused solution of crystal bottom is compressed, fused solution soaks into to pore part.
[comparative example 2]
In the situation that open porosity less than 10%, the release materials slurry is difficult on container material wetting, and is easily residual with the groove that bristle is smeared after slurry, due to concavo-convex changes fierceness from the foaming of slurry and on the whole, produces the crack after burning till.Because bubble fierceness and release materials become fragile, thereby to be difficult to make thickness be more than 400 μ m.When Si was solidified from the melting liquid level, container and a Si part adhered to, and ingot breaks.
As mentioned above, the open porosity of container material was associated with thickness and the having or not of crack of release materials.But the demoulding scope of Si ingot is: open porosity 10% to 40% is preferably 20% to 30%.
[embodiment 5]
In the crystal growing apparatus 1 of Fig. 1, use container 10 that Si is solidified from the melting liquid level after melting, this container 10 the size of top internal diameter 68.2mm, bottom internal diameter 36mm, degree of depth 48mm, thickness 2mm and all metallic impurity (Na, Ca, Al, Cr, Cu, Fe, Ni, Ti, W, V, Zn, Zr) be respectively SiC container body below 10ppm (open porosity: 20%) 11 internal surface be formed with the release materials 12 of thickness 350 to 600 μ m.
Particularly, hold 100g silicon raw material in container 10, be warming up to 1550 ° of C and silicon is melted under the 1atm argon atmospher.Subsequently, well heater is lowered the temperature with 10 ° of C/min.
[embodiment 6,7]
In embodiment 6, after forming release materials with the SiC inner surface of container of embodiment 5 same sizes, carry out the baking of 1550 ° of C * 12 hour under the 1atm argon, then, carry out the melting and solidification of silicon by the method identical with embodiment 5.
In embodiment 7, be respectively 10 to 1000ppm Si at the size of top internal diameter 84.4mm, bottom internal diameter 48mm, degree of depth 48mm, thickness 10mm and metallic impurity (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr)
3N
4Inner surface of container forms release materials, then, carries out the melting and solidification of silicon by the method identical with embodiment 5.Be displayed in Table 2 these results.
[table 2]
In the embodiment 5,6,7 of the container material that uses open porosity 20%, do not see peeling off of release materials.Resulting silicon ingot is unfixing with container 10, just can easily take out as long as container 10 is turned over.
Observe the surface of silicon ingot and the internal surface of the container 10 after manufacturing, the surperficial dead smooth of silicon ingot, the sign that does not also exist release materials 12 to damage on the internal surface of container 10.Think, owing to the time not producing bubble fully the release materials slurry being coated the porous container surface, thereby form firmly release materials of the even and highdensity utmost point.Think thus, due to the mode generation volumetric expansion of silicon ingot to slide along release materials 12, produce hardly friction at the interface of release materials 12 and silicon ingot, thereby effectively relax the stress of the volumetric expansion when following silicon to solidify.
In addition, because release materials 12 and container body 11 do not damage, thereby container 10 can utilize again, can reuse more than 10 times in the manufacturing of silicon ingot.
[comparative example 3]
In comparative example 3, use forms the container of the release materials identical with embodiment, manufacturing silicon ingot under create conditions identical with embodiment at the internal surface of the container body of quartz system.
Resulting silicon ingot is compared with the silicon ingot that obtains in an embodiment, concavo-convex fierceness, and especially distortion is fierce in ingot upper side and bottom, cracks on ingot.Think, be absorbed in the irregular surface of tool of the silicon ingot that takes out due to the release materials of peeling off, thereby the stress of the thermal distortion of the container that causes of the volumetric expansion owing to following silicon to solidify and high temperature causes release materials to be damaged, and a part and the container of silicon ingot are fixed, so crack on ingot.Think in addition, produce the SiC as melting liquid level suspended substance in the crystal growth, with sneak into silicon ingot together with the release materials of peeling off in growth in, the crystal quality of silicon ingot worsens.
[comparative example 4]
In comparative example 4, at the Si of top internal diameter 84.4mm, bottom internal diameter 48mm, degree of depth 48mm, thickness 10mm
3N
4After inner surface of container forms release materials, carry out the baking of 1550 ° of C * 12 hour under the 1atm argon, then, carry out melting and solidification by the method identical with embodiment 5.
Learn, just tried to open stove and taken out container, the Si fused solution just spills from container bottom.Si distributes in the wetting diffusion of release materials, but does not leak from the side.Think, due to Si is solidified from the melting liquid level, thereby see through porous material at the compressed fused solution of container bottom.
In the situation that embodiment 5,6 SiC container do not produce melting liquid level suspended substance in the crystal growth, but at the Si of embodiment 7
3N
4Situation under produce the SiC suspended substance of volume.When a large amount of SiC suspended substances produced, a large amount of SiO also was attached to the furnace wall.Think that SiO generates SiC with the carbon reaction that residues in release materials.
Show the result that compares the concentration of metallic impurities in the Si crystal in following table 3.
[table 3]
If be not to use sintering process but use making Si ingot in low metallic impurity SiC (POCO system) container that conversion method makes as embodiment 5,6, with at the Si that makes by sintering process as embodiment 7
3N
4Compare when container is made the Si ingot, can reduce the metallic impurity that residue in Si.Form the container of release materials by baking before crystal growth operation, can reduce the metallic impurity such as Fe, Al, Ca, Cu, Cr.In addition, in the situation that the less SiC container of concentration of metallic impurities confirms not produce the SiC as melting liquid level suspended substance.
In comparative example 4, difference and the storing time of the container weight that comprises release materials before and after baking learn, decreasing weight speed is 0.2wt%/h.After baking, SiO is attached in stove in a large number.In the situation of the SiC container of the low metallic impurity after toasting under the same conditions (embodiment 6), do not find out a large amount of generations of SiO during weight reduces and crystal is grown.Therefore, exist and contain a lot of SiO
2Si with metal oxide
3N
4The Si of container body and adjacency
3N
4Release materials is thermal decomposited the possibility into SiO.That is, think due to by SiO
2The Si of the release materials that covers
3N
4The coking property of particle descends in baking, thereby the fused solution leakage occurs in comparative example 4.
As mentioned above, the container 10 of embodiment is by Si
3N
4Or the internal surface of the container body 11 of the porous insert of SiC formation is formed with by Si
3N
4The release materials 12 that consists of.In addition, the open porosity that consists of the porous insert of container body 11 is more than 10% below 40%, and expectation is 20% above less than 40%.
In this container 10, be formed at securely the internal surface of container body 11 due to the release materials 12 with excellent releasability from mode, thereby can prevent effectively that the stress of the volumetric expansion owing to following silicon to solidify from causing release materials 12 to be damaged.
In addition, the porous SiC of the low metallic impurity that will make by conversion method thus, can be made and contain the Si that makes by existing sintering process than using as container material
3N
4The situation of container is still less the Si ingot of metallic impurity far away.And, state before use in the situation of SiC container, than aforementioned Si
3N
4Container more toasts under the condition of high temperature, can reduce the metallic impurity in the Si ingot.By hanging down the metallic impurity container as Si ingot manufacturing container, can suppress SiC foreign matter sneaking in the fused solution.
So, can reuse in the manufacturing of silicon ingot, and can make the silicon ingot with better quality.
Above, understand specifically based on embodiment the invention of being made by the present inventor, but the invention is not restricted to above-mentioned embodiment, but can change in the scope that does not break away from its main idea.
The container 10 of embodiment not only can use in casting, and can use in all silicon ingot manufacturing processs that remain on the Si fused solution in container and it is solidified.For example, can and lift this seed crystal and silicon melt is used make the Kai Luobo Lars method of silicon monocrystal growth from surface solidification at the Surface Contact that makes seed crystal and silicon melt.This be because, suppress to hinder from the generation of the melting liquid level suspended substance of seed crystal monocrystalline, can cause by the stress that solves the volumetric expansion owing to following silicon to solidify on the porous container material that release materials is formed at securely low metallic impurity the problem of release materials damage.
In addition, at container body 11, not only can be suitable for Si
3N
4Or SiC is configured as the parts of crucible shape, and can be suitable for and make Si
3N
4Or SiC is configured as tabular a plurality of plate-shaped members combination and as the packaging parts of mold.
Should think, this time disclosed embodiment illustrates in all respects for example, rather than restriction.Scope of the present invention is not to be represented by above-mentioned explanation, but is represented by claims, and intention comprises the implication that is equal to claims and all changes in scope.
The explanation of symbol
1 crystal growing apparatus
10 silicon ingot manufacturing containers
11 container bodys
12 release materials
13 pedestals
14 well heaters
15 silicon raw materials (silicon melt)
The 15a polysilicon.
Claims (9)
1. silicon ingot manufacturing container makes the silicon ingot manufacturing container of polycrystalline silicon growth for being used for that silicon melt is solidified, it is characterized in that,
The internal surface of the container body that consists of at the porous insert by silicon nitride or silicon carbide is formed with the release materials that is made of silicon nitride.
2. silicon ingot manufacturing container according to claim 1, is characterized in that, the open porosity of described porous insert is more than 10% below 40%.
3. silicon ingot manufacturing container according to claim 1, is characterized in that, the open porosity of described porous insert is more than 20% below 30%.
4. the described silicon ingot manufacturing of any one according to claim 1 to 3 container, it is characterized in that, the metallic impurity (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body that is made of the porous insert of described silicon nitride are respectively below 1000ppm.
5. silicon ingot manufacturing container according to claim 4, it is characterized in that, the metallic impurity (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body that is made of the porous insert of described silicon nitride are respectively below 10ppm.
6. the described silicon ingot manufacturing of any one according to claim 1 to 3 container, it is characterized in that, the metallic impurity (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body that is made of the porous insert of described silicon carbide are respectively below 100ppm.
7. silicon ingot manufacturing container according to claim 6, it is characterized in that, the metallic impurity (Fe, Al, Mn, Mg, Ca, Cu, Ti, Cr, Ni, W, V, Zn, Zr) of the container body that is made of the porous insert of described silicon carbide are respectively below 10ppm.
8. the described silicon ingot manufacturing of any one according to claim 1 to 7 container, is characterized in that, the thickness of described releasing agent is 300 to 1000 μ m.
9. silicon ingot manufacturing container according to claim 8, is characterized in that, the thickness of described releasing agent is 350 to 600 μ m.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010228607 | 2010-10-08 | ||
| JP2010-228607 | 2010-10-08 | ||
| PCT/JP2011/072724 WO2012046673A1 (en) | 2010-10-08 | 2011-10-03 | Silicon ingot manufacturing vessel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103124693A true CN103124693A (en) | 2013-05-29 |
| CN103124693B CN103124693B (en) | 2015-07-22 |
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| CN201180048725.2A Expired - Fee Related CN103124693B (en) | 2010-10-08 | 2011-10-03 | Silicon ingot manufacturing vessel |
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|---|---|
| JP (1) | JP5788891B2 (en) |
| CN (1) | CN103124693B (en) |
| TW (1) | TWI565657B (en) |
| WO (1) | WO2012046673A1 (en) |
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| CN103060908A (en) * | 2013-01-06 | 2013-04-24 | 奥特斯维能源（太仓）有限公司 | Dual-layer ceramic crucible |
| FR3003272A1 (en) * | 2013-03-14 | 2014-09-19 | Saint Gobain Ct Recherches | CRUCIBLE |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357393A (en) * | 2007-08-02 | 2009-02-04 | 通用电气公司 | Silicon release coating, method of making same, and method of using same |
| JP2009274905A (en) * | 2008-05-14 | 2009-11-26 | Covalent Materials Corp | Crucible for melting silicon |
| JP2010052996A (en) * | 2008-08-29 | 2010-03-11 | Covalent Materials Corp | Vessel for producing polycrystalline silicon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000351688A (en) * | 1999-06-10 | 2000-12-19 | Mitsubishi Materials Corp | Crucible for producing crystalline silicon and its production |
| JP4471692B2 (en) * | 2004-03-25 | 2010-06-02 | 東ソー・クォーツ株式会社 | Method for manufacturing container for melting silicon having release layer |
| TWI400369B (en) * | 2005-10-06 | 2013-07-01 | Vesuvius Crucible Co | Crucible for the crystallization of silicon and process for making the same |
| JP4850501B2 (en) * | 2005-12-06 | 2012-01-11 | 新日鉄マテリアルズ株式会社 | High purity silicon manufacturing apparatus and manufacturing method |
| JP5040521B2 (en) * | 2007-08-17 | 2012-10-03 | 株式会社Ｓｕｍｃｏ | Silicon casting equipment |
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2011
- 2011-10-03 CN CN201180048725.2A patent/CN103124693B/en not_active Expired - Fee Related
- 2011-10-03 WO PCT/JP2011/072724 patent/WO2012046673A1/en active Application Filing
- 2011-10-03 JP JP2012537690A patent/JP5788891B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357393A (en) * | 2007-08-02 | 2009-02-04 | 通用电气公司 | Silicon release coating, method of making same, and method of using same |
| JP2009274905A (en) * | 2008-05-14 | 2009-11-26 | Covalent Materials Corp | Crucible for melting silicon |
| JP2010052996A (en) * | 2008-08-29 | 2010-03-11 | Covalent Materials Corp | Vessel for producing polycrystalline silicon |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI565657B (en) | 2017-01-11 |
| CN103124693B (en) | 2015-07-22 |
| WO2012046673A1 (en) | 2012-04-12 |
| TW201228934A (en) | 2012-07-16 |
| JP5788891B2 (en) | 2015-10-07 |
| JPWO2012046673A1 (en) | 2014-02-24 |
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