CN103274583A - Quartz crucible and production method thereof, and P-type silicon casting ingot and production method thereof - Google Patents
Quartz crucible and production method thereof, and P-type silicon casting ingot and production method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
- C03B19/066—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction for the production of quartz or fused silica articles
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- 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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- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/10—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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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/30—Doped silica-based glasses containing metals
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2203/00—Production processes
- C03C2203/10—Melting processes
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Abstract
The invention provides a quartz crucible and a production method thereof, and a P-type silicon casting ingot and a production method thereof. The quartz crucible production method comprises a treatment process, wherein the treatment process comprises sequentially carrying out slurry injection, demolding, drying and sintering on crucible raw materials to obtain the quartz crucible, the crucible raw materials comprise a high purity inorganic gallium salt and high purity quartz sand, a weight ratio of the gallium to the high purity quartz sand in the crucible raw materials is 3.7-370 g:1000 kg, the quartz crucible production method can adopt the existing process in the prior art, and the gallium content in the obtained quartz crucible is 0.296-29.6 g/100 kg only by requiring addition of a suitable amount of the inorganic gallium salt to the crucible raw materials and control of the gallium element content in the crucible raw materials to 3.7-370 g/1000 kg, such that improvement of resistivity of a P-type polycrystalline silicon casting ingot obtained by adopting the quartz crucible as a container can be achieved, a process is simple, and an effect is significant.
Description
Technical field
The present invention relates to solar cell and make the field, in particular to a kind of quartz crucible and preparation method thereof, P type silicon ingot casting and preparation method thereof.
Background technology
Crystalline silicon at first will mix to crystalline silicon before making solar cell, obtains a specific electrical resistivity range and conduction type silicon ingot casting by doping.Choosing aspect the doping agent, overriding concern be exactly foreign atom at the segregation coefficient of crystalline silicon inside, so-called segregation coefficient refers to the ratio of the solubleness of impurity in solid phase and the solubleness of impurity in liquid phase.If the segregation coefficient of doped element in silicon liquid process of setting is more close to 1, doped element distributed density on the crystalline silicon crystallization direction is just more even so, thereby the electrical property of the solar cell that obtains is just more good.
Solar cell is made industry for improving the silicon materials utilization ratio at present, all adopts the method for doped with boron element to make P type silicon crystal as the substrate of solar cell.Just ingot casting production at present, in the conventional P type polysilicon castingprocesses, mix high purity boron powder or high-purity borosilicate mother alloy in the silicon material as doping agent, because boron segregation coefficient in silicon liquid has only 0.8, and about about 30 hours of silicon ingot crystallization time, the fractional condensation time is long, causes last silicon ingot top to bottom resistance rate to become the Gradient distribution state, the silicon ingot bottom is big because of the concentration small resistor rate of boron, and the top causes resistivity little because of the concentration height of boron.Owing to need carry out the N-type part that PN junction is made in phosphorous diffusion at P type silicon chip surface in the battery making processes, resistivity is inconsistent at the bottom of the top of silicon ingot, and the phosphorous diffusion concentration coherence request in the battery making processes is very high, finally cause the battery sheet PN junction junction depth of different positions silicon wafer to manufacture on the silicon ingot inconsistent, influence the solar cell power generation effect.And during solar cell working in boron and the silicon crystal residual oxygen under illumination condition, form the B-O complex body easily, form B-Fe with impurity iron Fe and be combined, make battery the photo attenuation phenomenon occur, cause the efficiency of conversion of solar cell to reduce.
At present, the general employing mixed an amount of gallium in boron doped P type polysilicon, reduce the photo attenuation phenomenon of solar cell, improves the efficiency of conversion of battery.But, because the segregation coefficient of gallium in silicon solution is very little, have only about 0.008, adopt existing polycrystalline casting ingot process or pulling of crystals technology, directly with high purity gallium piece (or powder) or directly the gallium silicon alloy is doped to and carries out ingot casting or pulling monocrystal rod in the silicon material, will make the serious segregation phenomena of appearance in silicon ingot or the silicon rod, make gallium element concentration seriously unequal in silicon crystal, cause silicon ingot or silicon rod inhomogeneous along the resistivity of the direction of growth simultaneously, and then be difficult to obtain the qualified silicon crystal of electrical property.
Summary of the invention
The present invention aims to provide a kind of quartz crucible and preparation method thereof, P type silicon ingot casting and preparation method thereof, adopts the resulting P type of quartz crucible of the prior art polycrystal silicon ingot along the serious inhomogeneous problem of resistivity of the direction of growth to solve.
To achieve these goals, according to an aspect of the present invention, a kind of making method of quartz crucible is provided, making method comprises the treating processes of the crucible raw material being passed through successively slip casting, the demoulding, drying, sintering, obtain quartz crucible, the crucible raw material comprises high-purity inorganic gallium salt and glass sand, and wherein the weight ratio of gallium and glass sand is 3.7～370g:1000kg in the crucible raw material.
Further, above-mentioned high-purity inorganic gallium salt is gallium oxide, gallium arsenide or gallium phosphide.
Further, the granularity of above-mentioned high-purity inorganic gallium salt is less than 0.1mm; The granularity of glass sand is less than 0.1mm.
Further, above-mentioned making method also comprised before slip casting: glass sand is carried out ball milling, homogenizing processing; Glass sand, high-purity inorganic gallium salt and deionized water after the homogenizing processing are mixed, obtain the crucible raw material.
According to a further aspect in the invention, provide a kind of quartz crucible, this quartz crucible is made by above-mentioned making method, and quartz crucible comprises that weight content is the gallium of 0.296g～29.6g/100kg.
Further, above-mentioned quartz crucible comprises that weight content is the gallium of 10g～20g/100kg.
According to another aspect of the invention, provide a kind of preparation method of P type polycrystalline silicon ingot casting, the preparation method comprises silicon material, boron material is carried out the ingot casting process that in quartz crucible this quartz crucible is the above-mentioned quartz crucible of the present invention.
Further, above-mentioned boron material is the borosilicate mother alloy.
Further, above-mentioned ingot casting process comprises: silicon material and boron material are heated 10～20h fusing down at 1500～1580 ℃;
The bottom of quartz crucible is cooled off.
According to another aspect of the invention, provide a kind of P type polycrystalline silicon ingot casting, this P type polycrystalline silicon ingot casting is prepared from by above-mentioned preparation method.
Use technical scheme of the present invention, the making method of above-mentioned quartz crucible all can adopt existing technical process in the prior art, the content that only need add an amount of inorganic gallium salt in the crucible raw material and control gallium element in the crucible raw material is between 3.7～370g/1000kg, the gallium weight content is between 0.296g～29.6g/100kg in the quartz crucible that obtains, gallium exists in the quartz crucible with the form of salt, can realize improving with it is the purpose of the resistivity of the P type polycrystalline silicon ingot casting for preparing of container, and technology is simple, effect is obvious.
Description of drawings
The Figure of description that constitutes a part of the present invention is used to provide further understanding of the present invention, and illustrative examples of the present invention and explanation thereof are used for explaining the present invention, do not constitute improper restriction of the present invention.In the accompanying drawings:
Fig. 1 shows the process flow sheet that slip casting method is produced quartz crucible.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the feature among the embodiment among the present invention can make up mutually.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
When how the present invention solves the serious inhomogeneous problem of the resistivity of P type polycrystal silicon ingot in research, find a new way and start with from making the used quartz crucible of P type polycrystalline silicon ingot casting, contain the quartz crucible that the gallium material obtains containing gallium by in the glass sand of making quartz crucible, adding, and expectation utilizes in the ingot casting process under the high temperature high diffusibility of gallium to replenish gallium element in prepared P type polycrystalline silicon ingot casting, with balance because the serious inhomogeneous resistivity that the boron skewness causes.The making method of quartz crucible can adopt method commonly used in the prior art such as slip casting method.
In a kind of typical embodiment of the present invention, a kind of making method of quartz crucible is provided, this making method comprises the treating processes of the crucible raw material being passed through successively slip casting, the demoulding, drying, sintering, obtain quartz crucible, above-mentioned crucible raw material comprises high-purity inorganic gallium salt and glass sand, and wherein the weight ratio of gallium and glass sand is 3.7～370g:1000kg in the crucible raw material.
The making method of above-mentioned quartz crucible all can adopt existing technical process in the prior art, the content that only need add an amount of inorganic gallium salt in the crucible raw material and control gallium element in the crucible raw material is between 3.7～370g/1000kg, the gallium weight content is between 0.296g～29.6g/100kg in the quartz crucible that obtains, gallium exists in the quartz crucible with the form of gallium salt, and improved the homogeneity of the resistivity of P type polycrystalline silicon ingot casting effectively, can realize improving with it is the purpose of the resistivity of the P type polycrystalline silicon ingot casting for preparing of container, and above-mentioned making method technology is simple, effect is obvious.And the different crucibles of inorganic gallium salt react, and can not cause quality influence to crucible.
The contriver has analyzed the mechanism of improving resistivity, is summarized as follows: in the process of preparation P type polycrystalline silicon ingot casting, because gallium is triels, as acceptor atom, identical with the boron effect in the process that forms P type polycrystal silicon ingot.When the quartz crucible that utilizes the present invention to contain gallium element carried out ingot casting, the silicon ingot bottom position was extended influence by the interior gallium element of quartz crucible, and concentration is more and more lower from the bottom to top in silicon ingot to cause gallium element; And the boron that silicon ingot mixes is because dephlegmation, concentration is more and more higher from the bottom to top in silicon ingot, and aspect conduction type, two kinds of elements act on simultaneously, finally cause silicon ingot that a triels distribution gradient is stably arranged from the bottom to top, silicon ingot resistivity difference from the bottom to top diminishes.
Above-mentioned high-purity inorganic gallium salt and glass sand are purity known in those skilled in the art at inorganic gallium salt and quartz sand more than 99.9%.
Selection those skilled in the art for above-mentioned high-purity inorganic gallium salt have the ability to get rid of quartz crucible or the influential gallium salt of P type polycrystalline silicon ingot casting quality, the preferred above-mentioned high-purity inorganic gallium salt of the present invention is gallium oxide, gallium arsenide or gallium phosphide, further preferred gallium oxide.
In order further to improve physical property and the thermal property of resulting quartz crucible, the granularity of preferred above-mentioned high-purity inorganic gallium salt is less than 0.1mm; The granularity of preferred glass sand is less than 0.1mm.
In a kind of preferred embodiment of the present invention, above-mentioned making method also comprised before slip casting: glass sand is carried out ball milling, homogenizing processing; Glass sand, high-purity inorganic gallium salt and deionized water after the homogenizing processing are mixed, obtain the crucible raw material.If the granularity of quartz sand does not satisfy service requirements, preferably quartz sand is carried out ball milling, homogenizing processing, make quartz sand size reduce, dispersed better, thereby its contact area of mixing back quartz sand and inorganic gallium salt with inorganic gallium salt and deionized water is increased, and then make in the resulting quartz crucible each element distribution comparatively even.
In the another kind of typical embodiment of the present invention, a kind of quartz crucible is provided, this quartz crucible comprises that weight content is the gallium element of 0.296g～29.6g/100kg.Utilizing above-mentioned quartz crucible to prepare in the process of P type polycrystalline silicon ingot casting, because it is gallium is triels, as acceptor atom, identical with the boron effect in the process that forms P type polycrystal silicon ingot.When the quartz crucible that utilizes the present invention to contain gallium element carried out ingot casting, the silicon ingot bottom position was extended influence by the interior gallium element of quartz crucible, and concentration is more and more lower from the bottom to top in silicon ingot to cause gallium element; And the boron that silicon ingot mixes is because dephlegmation, concentration is more and more higher from the bottom to top in silicon ingot, and aspect conduction type, two kinds of elements act on simultaneously, finally cause silicon ingot that a triels distribution gradient is stably arranged from the bottom to top, silicon ingot resistivity difference from the bottom to top diminishes.
The content of gallium changes along with the variation of the amount of inorganic gallium salt used in the raw material in the above-mentioned quartz crucible, and in order to improve the resistivity of P type polycrystal silicon ingot better, preferred quartz crucible comprises that weight content is the gallium of 10g～20g/100kg.
In another typical embodiment of the present invention, a kind of preparation method of P type polycrystalline silicon ingot casting is provided, the preparation method comprises silicon material, boron material is carried out the ingot casting process that in quartz crucible the used quartz crucible of above-mentioned ingot casting process is above-mentioned quartz crucible.
In the above-mentioned ingot casting process, silicon material and boron material fusing post crystallization form the main body of P type polycrystalline silicon ingot casting, when utilizing the quartz crucible making P type polycrystalline silicon ingot casting of doped gallium element, gallium element in the quartz crucible spreads in the silicon liquid that forms P type polycrystalline silicon ingot casting and silicon solid, be diffused into the gallium element in the silicon liquid because its segregation coefficient in silicon liquid recrystallization process is less, only keep a seldom part in the silicon solid, most of final fractional condensation is to the silicon ingot upper surface; And the crystallisation stage crucible bottom has been finished crystallization, the gallium element that is diffused into silicon ingot bottom margin position by crucible bottom then spreads in silicon ingot under hot conditions, finally obtain along the less P type polycrystalline silicon ingot casting of crystallization direction resistivity difference, and then effectively reduce the photo attenuation effect of P type polycrystal silicon cell.
Can be used for boron material of the present invention and include but not limited to boron oxide, borosilicate mother alloy and resistivity less than 1 Ω cm, conduction type is the silicon material of P type, and preferred above-mentioned boron material is the borosilicate mother alloy of resistivity between 0.001 Ω cm to 0.01 Ω cm scope.
In another kind of preferred embodiment of the present invention, above-mentioned ingot casting process comprises heating 10～20h fusing under 1500～1580 ℃ with silicon material and boron material; The bottom of quartz crucible is cooled off.Silicon material and the mixing of boron material are placed in the above-mentioned quartz crucible, and heat in ingot furnace, silicon material and boron material can melt behind heating 10～20h down fully at 1500～1580 ℃.And then the thermal window of opening quartz crucible bottom is to the bottom cooling of lowering the temperature, make silicon liquid begin crystallization in crucible bottom, in crystallisation process, silicon liquid at first begins crystallization from crucible bottom and forms nucleus, the solid-liquid face moves on progressively then, finishes until whole silicon ingot crystallization.In said process, because crucible is in the condition of high temperature always, gallium oxide is in active state always in the quartz crucible, constantly to silicon liquid and silicon solid internal diffusion, be diffused into the gallium element in the silicon liquid because its segregation coefficient in silicon liquid recrystallization process is less, only keep a seldom part in the silicon solid, most of final fractional condensation is to the silicon ingot upper surface; And the crystallisation stage crucible bottom has been finished crystallization, the gallium element that is diffused into silicon ingot bottom margin position by crucible bottom then spreads in silicon ingot under hot conditions, finally obtain the P type polycrystalline silicon ingot casting along crystallization direction resistivity unanimity, and then effectively reduce the photo attenuation effect of P type polycrystal silicon cell.
The P type polycrystalline silicon ingot casting that adopts preparation method of the present invention to obtain, the resistivity difference of each several part reduces greatly, thereby after being made into P type polycrystal silicon cell, reduced the photo attenuation effect of this P type polycrystal silicon cell effectively, improved the generating efficiency of solar cell.
Below with reference to embodiment and Comparative Examples, further specify beneficial effect of the present invention.
Embodiment 1
The purity of quartz sand is 99.99%, and granularity is between 0.01～0.1mm; Gallium oxide is powdery, purity is 99.99%, granularity between 0.001～0.1mm, the above-mentioned gallium oxide of doping 5g in the above-mentioned quartz sand of 1000kg, adopting the slip casting method manufactured size shown in the accompanying drawing 1 is the quartz crucible of 840mm*840mm*420mm, as the quartz crucible of embodiment 1.
Utilize the quartz crucible casting 400kg conduction type of embodiment 1 to be the polycrystal silicon ingot of P type, raw material is that primary silicon material and the 313.8 gram g resistivity of 400kg are the borosilicate mother alloy of 0.007 Ω cm, and concrete castingprocesses is for to mix above-mentioned raw materials in the quartz crucible of above-described embodiment 1; Quartz crucible is placed ingot furnace, make raw material melt formation silicon liquid fully behind the heating 10h down at 1580 ℃; The thermal window of opening the quartz crucible bottom dispels the heat and makes the silicon liquid of quartz crucible bottom begin crystallization; Finish the P type polycrystalline silicon ingot casting that crystallization obtains embodiment 1 behind the 27h.
Embodiment 2
The purity of quartz sand is 99.95%, and granularity is between 0.005～0.01mm; Gallium oxide is powdery, purity is 99.99%, granularity between 0.01～0.1mm, the above-mentioned gallium oxide of doping 500g in the above-mentioned quartz sand of 1000kg, adopting the slip casting method manufactured size shown in the accompanying drawing 1 is the quartz crucible of 840mm*840mm*420mm, as the quartz crucible of embodiment 2.
Utilize the quartz crucible casting 400kg conduction type of embodiment 2 to be the polycrystal silicon ingot of P type, raw material is that primary silicon material and the 313.4g resistivity of 400kg is the borosilicate mother alloy of 0.007 Ω cm, and concrete castingprocesses is for to mix above-mentioned raw materials in the quartz crucible of above-described embodiment 2; Quartz crucible is placed ingot furnace, make raw material melt formation silicon liquid fully behind the heating 20h down at 1500 ℃; The thermal window of opening the quartz crucible bottom dispels the heat and makes the silicon liquid of quartz crucible bottom begin crystallization; 26.5h after finish the P type polycrystalline silicon ingot casting that crystallization obtains embodiment 2.
Embodiment 3
The purity of quartz sand is 99.99%, and granularity is between 0.01～0.1mm; Gallium arsenide is powdery, purity is 99.99%, granularity between 0.005～0.01mm, the above-mentioned gallium arsenide of doping 420g in the above-mentioned quartz sand of 1000kg, adopting the slip casting method manufactured size shown in the accompanying drawing 1 is the quartz crucible of 840mm*840mm*420mm, as the quartz crucible of embodiment 3.
Utilize the quartz crucible casting 400kg conduction type of embodiment 3 to be the polycrystal silicon ingot of P type, raw material is that primary silicon material and the 313.4g resistivity of 400kg is the borosilicate mother alloy of 0.007 Ω cm, and concrete castingprocesses is for to mix above-mentioned raw materials in the quartz crucible of above-described embodiment 3; Quartz crucible is placed ingot furnace, make raw material melt formation silicon liquid fully behind the heating 17h down at 1550 ℃; The thermal window of opening the quartz crucible bottom dispels the heat and makes the silicon liquid of quartz crucible bottom begin crystallization; 26.7h after finish the P type polycrystalline silicon ingot casting that crystallization obtains embodiment 3.
Embodiment 4
The purity of quartz sand is 99.99%, and granularity is between 0.01～0.1mm; Gallium phosphide is powdery, purity is 99.99%, granularity between 0.005～0.01mm, the above-mentioned gallium phosphide of doping 300g in the above-mentioned quartz sand of 1000kg, adopting the slip casting method manufactured size shown in the accompanying drawing 1 is the quartz crucible of 840mm*840mm*420mm, as the quartz crucible of embodiment 4.
Utilize the quartz crucible casting 400kg conduction type of embodiment 4 to be the polycrystal silicon ingot of P type, raw material is that primary silicon material and the 313.4g resistivity of 400kg is the borosilicate mother alloy of 0.007 Ω cm, and concrete castingprocesses is for to mix above-mentioned raw materials in the quartz crucible of above-described embodiment 4; Quartz crucible is placed ingot furnace, make raw material melt formation silicon liquid fully behind the heating 8h down at 1600 ℃; The thermal window of opening the quartz crucible bottom dispels the heat and makes the silicon liquid of quartz crucible bottom begin crystallization; Finish the P type polycrystalline silicon ingot casting that crystallization obtains embodiment 4 behind the 28h.
Embodiment 5
The purity of quartz sand is 99.99%, and granularity is between 0.01～0.1mm; Gallium oxide is powdery, purity is 99.99%, granularity between 0.005～0.01mm, the above-mentioned gallium oxide of doping 170g in the above-mentioned quartz sand of 1000kg, adopting the slip casting method manufactured size shown in the accompanying drawing 1 is the quartz crucible of 840mm*840mm*420mm, as the quartz crucible of embodiment 5.
Utilize the quartz crucible casting 400kg conduction type of embodiment 5 to be the polycrystal silicon ingot of P type, the primary silicon material of 400kg and 313.4g resistivity are the borosilicate mother alloy of 0.007 Ω cm, and concrete castingprocesses is for to mix above-mentioned raw materials in the quartz crucible of above-described embodiment 5; Quartz crucible is placed ingot furnace, make raw material melt formation silicon liquid fully behind the heating 15h down at 1550 ℃; The thermal window of opening the quartz crucible bottom dispels the heat and makes the silicon liquid of quartz crucible bottom begin crystallization; 26.4h after finish the P type polycrystalline silicon ingot casting that crystallization obtains embodiment 5.
Embodiment 6
The purity of quartz sand is 99.99%, and granularity is between 0.01～0.1mm; Gallium oxide is powdery, purity is 99.99%, granularity between 0.005～0.01mm, the above-mentioned gallium oxide of doping 340g in the above-mentioned quartz sand of 1000kg, adopting the slip casting method manufactured size shown in the accompanying drawing 1 is the quartz crucible of 840mm*840mm*420mm, as the quartz crucible of embodiment 6.
Utilize the quartz crucible casting 400kg conduction type of embodiment 6 to be the polycrystal silicon ingot of P type, the primary silicon material of 400kg and 313.4g resistivity are the borosilicate mother alloy of 0.007 Ω cm, and concrete castingprocesses is for to mix above-mentioned raw materials in the quartz crucible of above-described embodiment 6; Quartz crucible is placed ingot furnace, make raw material melt formation silicon liquid fully behind the heating 15h down at 1550 ℃; The thermal window of opening the quartz crucible bottom dispels the heat and makes the silicon liquid of quartz crucible bottom begin crystallization; Finish the P type polycrystalline silicon ingot casting that crystallization obtains embodiment 6 behind the 28h.
Comparative Examples 1
The purity of quartz sand is 99.99%, and granularity is raw material with this quartz sand between 0.01～0.1mm, and adopting the slip casting method manufactured size shown in the accompanying drawing 1 is the quartz crucible of 840mm*840mm*420mm, as a comparison case 1 quartz crucible.Utilize the quartz crucible casting 400kg conduction type of above-mentioned Comparative Examples 1 to be the polycrystal silicon ingot of P type, the primary silicon material of 400kg and 313.4g resistivity are the borosilicate mother alloy of 0.007 Ω cm, and concrete castingprocesses is for to mix above-mentioned raw materials in above-mentioned conventional quartz crucible; Quartz crucible is placed ingot furnace, make raw material melt formation silicon liquid fully behind the heating 17h down at 1550 ℃; The thermal window of opening the quartz crucible bottom dispels the heat and makes the silicon liquid of quartz crucible bottom begin crystallization; 26.8h after finish the P type polycrystalline silicon ingot casting that crystallization obtains Comparative Examples 1.
Comparative Examples 2
The purity of quartz sand is 99.99%, and granularity is between 0.01～0.1mm; Gallium oxide is powdery, purity is 99.99%, granularity between 0.005～0.01mm, the above-mentioned gallium oxide of doping 600g in the above-mentioned quartz sand of 1000kg, adopting the slip casting method manufactured size shown in the accompanying drawing 1 is the quartz crucible of 840mm*840mm*420mm, as a comparison case 2 quartz crucible.
Calculate the silicon ingot volume recovery of embodiment 1 to 6 and Comparative Examples 1 and 2, calculation result sees Table 1; Gallium element content and dioxide-containing silica in the quartz crucible of employing ICP-OES inductive coupling plasma emission spectrograph detection embodiment 1 to 6 and Comparative Examples 1 and 2, detected result sees Table 1; Adopt the folding strength tester to detect the physical property of the quartz crucible of embodiment 1 to 6 and Comparative Examples 1 and 2, adopt the Laser emission method in the transient state method to detect the crucible thermal property, detected result sees Table 1.
Boron content and gallium element content in the P type polycrystalline silicon ingot casting of employing ICP-OES inductive coupling plasma emission spectrograph detection embodiment 1 to 6 and Comparative Examples 1, detected result sees Table 2; The top of the P type polycrystalline silicon ingot casting of employing four point probe resistivity measurement method detection embodiment 1 to 6 and Comparative Examples 1 and the resistivity of bottom, detected result sees Table 2; Attenuation degree after 15 days of the solar cell that the P type polycrystalline silicon ingot casting that adopts current-voltage characteristic curve to detect embodiment 1 to 6 and Comparative Examples 1 prepares, detected result sees Table 1.
Table 1
Table 2
By the content in the table 1 as can be seen, the quartz crucible that adopts making method of the present invention to obtain not only has gallium element, and its physical property and thermal property all satisfy standard-required; But because the addition of gallium too much causes the degradation of crucible, be unsuitable for the ingot casting of P type polycrystalline silicon ingot casting in the Comparative Examples 2; By the data in the table 2 as can be seen, adopt the resistivity difference of the top of the P type polycrystalline silicon ingot casting that quartz crucible of the present invention makes and bottom less, and reduced the photo attenuation rate significantly, and then can improve the generating efficiency of solar cell effectively.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the making method of a quartz crucible, described making method comprises the treating processes of the crucible raw material being passed through successively slip casting, the demoulding, drying, sintering, obtain described quartz crucible, it is characterized in that, described crucible raw material comprises high-purity inorganic gallium salt and glass sand, and the weight ratio of gallium and described glass sand is 3.7～370g:1000kg in the wherein said crucible raw material.
2. making method according to claim 1 is characterized in that, described high-purity inorganic gallium salt is gallium oxide, gallium arsenide or gallium phosphide.
3. making method according to claim 2 is characterized in that, the granularity of described high-purity inorganic gallium salt is less than 0.1mm; The granularity of described glass sand is less than 0.1mm.
4. according to each described making method in the claim 1 to 3, it is characterized in that described making method also comprised before slip casting:
Described glass sand is carried out ball milling, homogenizing processing;
Glass sand, described high-purity inorganic gallium salt and deionized water after the described homogenizing processing are mixed, obtain described crucible raw material.
5. a quartz crucible is characterized in that, described quartz crucible is made by each described making method in the described claim 1 to 4, and described quartz crucible comprises that weight content is the gallium of 0.296g～29.6g/100kg.
6. quartz crucible according to claim 5 is characterized in that, described quartz crucible comprises that weight content is the gallium of 10g～20g/100kg.
7. the preparation method of a P type polycrystalline silicon ingot casting, described preparation method comprise silicon material, boron material are carried out the ingot casting process in quartz crucibles, it is characterized in that described quartz crucible is claim 5 or 6 described quartz crucibles.
8. preparation method according to claim 7 is characterized in that, described boron material is the borosilicate mother alloy.
9. preparation method according to claim 7 is characterized in that, described ingot casting process comprises:
Described silicon material and described boron material are heated 10～20h fusing down at 1500～1580 ℃;
The bottom of described quartz crucible is cooled off.
10. a P type polycrystalline silicon ingot casting is characterized in that, described P type polycrystalline silicon ingot casting is prepared from by each described preparation method in the claim 7 to 9.
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| PCT/CN2014/079184 WO2014194830A1 (en) | 2013-06-07 | 2014-06-04 | Quartz crucible and fabrication method thereof, and p-type silicon ingot and fabrication method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628128A (en) * | 2013-12-12 | 2014-03-12 | 英利集团有限公司 | Crucible, production method of crucible and casting method of polycrystalline silicon ingot |
| WO2014194830A1 (en) * | 2013-06-07 | 2014-12-11 | 英利能源（中国）有限公司 | Quartz crucible and fabrication method thereof, and p-type silicon ingot and fabrication method thereof |
| CN104846437A (en) * | 2015-06-02 | 2015-08-19 | 江苏协鑫硅材料科技发展有限公司 | Gallium-doped crystalline silicon with uniformly distributed resistivity and preparation method thereof |
| CN108531983A (en) * | 2018-05-22 | 2018-09-14 | 英利能源（中国）有限公司 | It mixes the preparation method of gallium polycrystal silicon ingot and mixes gallium polycrystal silicon ingot |
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| JP2002160998A (en) * | 2000-11-27 | 2002-06-04 | Shin Etsu Handotai Co Ltd | Quartz crucible and method for producing silicon crystal |
| CN102312290A (en) * | 2010-07-05 | 2012-01-11 | 赵钧永 | Doped casting polycrystalline silicon and preparation method |
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| CN101348324A (en) * | 2008-08-27 | 2009-01-21 | 常熟华融太阳能新型材料有限公司 | Non-transparent quartz crucible for polysilicon crystallization and manufacturing method thereof |
| CN102181926A (en) * | 2011-04-08 | 2011-09-14 | 光为绿色新能源有限公司 | Polycrystalline silicon ingot doping method and ingot casting equipment for implementing method |
| CN102978699B (en) * | 2012-11-16 | 2015-11-11 | 浙江中晶科技股份有限公司 | The growth of the heavily doped p type single crystal silicon that boron gallium is mixed altogether and adulterating method |
| CN103274583B (en) * | 2013-06-07 | 2016-03-30 | 英利能源（中国）有限公司 | Quartz crucible and preparation method thereof, P-type silicon ingot casting and preparation method thereof |
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| JPS6461399A (en) * | 1987-09-02 | 1989-03-08 | Mitsubishi Electric Corp | Charting of gallium melt into crucible |
| JP2002160998A (en) * | 2000-11-27 | 2002-06-04 | Shin Etsu Handotai Co Ltd | Quartz crucible and method for producing silicon crystal |
| CN102312290A (en) * | 2010-07-05 | 2012-01-11 | 赵钧永 | Doped casting polycrystalline silicon and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014194830A1 (en) * | 2013-06-07 | 2014-12-11 | 英利能源（中国）有限公司 | Quartz crucible and fabrication method thereof, and p-type silicon ingot and fabrication method thereof |
| CN103628128A (en) * | 2013-12-12 | 2014-03-12 | 英利集团有限公司 | Crucible, production method of crucible and casting method of polycrystalline silicon ingot |
| CN103628128B (en) * | 2013-12-12 | 2016-06-15 | 英利集团有限公司 | Crucible and preparation method thereof, polycrystal silicon ingot casting method |
| CN104846437A (en) * | 2015-06-02 | 2015-08-19 | 江苏协鑫硅材料科技发展有限公司 | Gallium-doped crystalline silicon with uniformly distributed resistivity and preparation method thereof |
| CN108531983A (en) * | 2018-05-22 | 2018-09-14 | 英利能源（中国）有限公司 | It mixes the preparation method of gallium polycrystal silicon ingot and mixes gallium polycrystal silicon ingot |
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| WO2014194830A1 (en) | 2014-12-11 |
| CN103274583B (en) | 2016-03-30 |
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