CN108560048A - Polysilicon fine melt crucible for casting ingots and its preparation method and application - Google Patents
Polysilicon fine melt crucible for casting ingots and its preparation method and application Download PDFInfo
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- CN108560048A CN108560048A CN201810601798.3A CN201810601798A CN108560048A CN 108560048 A CN108560048 A CN 108560048A CN 201810601798 A CN201810601798 A CN 201810601798A CN 108560048 A CN108560048 A CN 108560048A
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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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/225—Nitrides
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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
Abstract
This application discloses a kind of polysilicon fine melt crucible for casting ingots and its preparation method and application, belong to photovoltaic technology field.The preparation method of the polysilicon fine melt crucible for casting ingots, includes the following steps：1) quartz sand particle is fixed into the interior bottom of crucible；2) bottom sprays the first release layer in the crucible for preparing step 1), and crucible madial wall sprays the second release layer；The thickness of first release layer is more than the thickness of the second release layer.First remover and the second remover include silicon nitride.Crucible prepared by the present processes can prevent the oxidation of polysilicon, the viscous pot of polycrystal silicon ingot can be prevented again, the loose rough surface of crucible bottom provides a variety of seeding modes, with quartz sand forming core, gap forming core and silicon nitride forming core, a variety of seedings are simultaneously deposited the period for shortening polycrystalline cast ingot, and the yield of polycrystalline cast ingot is high.
Description
Technical field
This application involves a kind of polysilicon fine melt crucible for casting ingots and its preparation method and application, belong to photovoltaic technology neck
Domain.
Background technology
Using the photovoltaic effect principle of sunlight, luminous energy is changed into electric energy in interface, is solar energy profit
Best mode.Photovoltaic generation also has low stain, noiseless in addition to without geographical restrictions, is easy short-term construction, performance
Securely and reliably, the advantages that practical application is easy.The key foundation of photovoltaic industry is using by series connection and packaging protection solar energy
Battery forms large-scale component, then is subject to other control units and forms solar photovoltaic generation system.
There are many kinds of the materials for making solar cell, can be divided into according to semi-conducting material category division following several:(1)
Polynary semiconducting compound is the solar cell of material；(2) silicon materials solar cell, such as non-crystalline silicon, monocrystalline silicon and polycrystalline
Silion cell material；(3) solar cell based on germanium single crystal material；(4) solar cell of other materials, such as copper, indium and selenium film electricity
Pond, organic polymer solar cell etc..
The method that polycrystalline silicon material prepares solar-grade polysilicon at present mainly has silane decomposition, improvement Siemens
Method, Physical Metallurgy method and fluidized bed process etc. are several.Metallurgy method prepares solar-grade polysilicon, refers to using metallurgical grade silicon as raw material
(98.5%-99.5%).Purity is made in 99.9999% or more the polysilicon for producing solar cell by metallurgy purification
The method of raw material.Metallurgy method is servicing for solar energy power generating industry, and there are at low cost, low energy consumption, output capacity is high, investment
The advantages such as threshold is low carry beam high vacuum metallurgical technology by developing a new generation, purity can be made to reach 6N or more, and in the several years
Inside gradually develop into the mainstream technology of preparing of solar-grade polysilicon.
Current efficient polycrystalline silicon component is the photovoltaic products of mainstream.The preparation method of efficient polycrystalline silicon, which is divided into, has seed crystal efficient
For polycrystalline silicon technology with no seed crystal high-efficiency polycrystalline silicon technology, that is, the fritting being commonly called as is efficiently efficient with fine melt.There is seed crystal efficient polycrystalline silicon
Technology (fritting) carries out epitaxial growth using grade silicon material as nucleating center.Solar battery group is made using silicon materials
Part needs the machining process by a series of complex, is finished to polycrystal silicon ingot growth out of polycrystalline silicon material input ingot furnace
It comes out of the stove.The efficient output capacity of existing polysilicon fritting casting ingot process is relatively low, and the tail portion defect part of ingot casting is longer.Polysilicon is cast
Ingot technique includes silicon material being put into crucible to carry out ingot casting, and the temperature of ingot casting is higher, and the impurity in crucible easily enters polysilicon
Defect of polysilicon is caused in ingot, reduces the average life span of few son.And crucible surface spraying silicon nitride can prevent partial impurities from entering
Polycrystal silicon ingot, but the quality of silicon nitride layer can also influence crystal growth quality or during ingot casting silicon nitride fall off cause it is more
The viscous pot of crystal silicon ingot casting.The quality of crucible influences the quality of polycrystal silicon ingot.
Invention content
According to the one side of the application, a kind of preparation method of polycrystalline silicon ingot casting is provided, the polysilicon of this method
Efficient output capacity is high, and the tail portion defect part of polycrystalline silicon ingot casting is short；The polycrystalline silicon ingot casting of preparation will not occur viscous pot with crucible and show
As.
The preparation method of the polysilicon fine melt crucible for casting ingots, which is characterized in that include the following steps：
1) quartz sand particle is fixed into the interior bottom of crucible；
2) bottom sprays the first release layer in the crucible for preparing step 1), and crucible madial wall sprays the second release layer；Institute
State the surface that the first release layer is loose bumps.
Optionally, the thickness of first release layer is more than the thickness of the second release layer.
Optionally, first remover includes silicon nitride, and second remover includes silicon nitride.
Optionally, the first remover raw material includes silicon nitride, water and Ludox；The second release layer agent includes nitrogen
SiClx, water and Ludox, first releasing agent are different from the ingredient of the second remover.
Optionally, the mass ratio of the silicon nitride, Ludox and water is 10-30%：5%-30%：50%-70%.It is optional
The mass ratio of ground, the silicon nitride and Ludox is 10-30%：5%-30%.
Optionally, the temperature of bottom spraying silicon nitride is 60-100 DEG C in the crucible.
Preferably, the temperature of bottom spraying silicon nitride is 80-100 DEG C in the crucible.
Optionally, the pressure of bottom spraying silicon nitride is 2-4Mpa in the crucible.
Preferably, the pressure of bottom spraying silicon nitride is 3-4Mpa in the crucible.
Optionally, the Spray painting tool outlet of the crucible spraying remover is circle.
According to further aspect of the application, a kind of crucible for polysilicon fine melt ingot casting is provided, which is characterized in that
It is prepared including method described in any one of the above embodiments.
According to another aspect of the application, a kind of polysilicon fine melt casting ingot method is provided, which is characterized in that including institute
The crucible stated.
Optionally, the polysilicon fine melt casting ingot method, which is characterized in that include the following steps：
1) loading stage：Silicon material is packed into crucible, transfer crucible to ingot furnace；
2) heating, melting stage：Heat-insulation cage is closed, ingot furnace is evacuated to vacuum, heating, fusing silicon material, in the melting stage
Crucible inside reach the aperture opened heat-insulation cage after preset temperature and adjust heat-insulation cage；
3) crystal growing stage：The aperture for adjusting heat-insulation cage is the 30%-70% of whole apertures, and long crystalline substance temperature is 1410-1460
℃；
4) annealing, cooling stage：After liquid-state silicon length is brilliant, annealing, cooling obtain polycrystal silicon ingot.
The polysilicon fine melt crucible for casting ingots, which is characterized in that including crucible body and be sequentially fixed at bottom in crucible
Quartz sand and the first release layer, the crucible body medial surface coat the second release layer.
Optionally, first remover includes silicon nitride, and second remover includes silicon nitride.
Optionally, first release layer have first thickness, second release layer have second thickness, described first
Thickness is more than second thickness.
Optionally, first release layer is the surface of substantially loose bumps.
Optionally, second release layer is substantially smooth close surface.
Optionally, the thickness of first release layer is 100-500 μm.
Optionally, the quartz sand, which is uniformly distributed, is fixed on the crucible bottom, and the mesh number of the quartz sand is 40-60
Mesh.
Optionally, the grain size of the silicon nitride is 2-3 μm；The silicon nitride includes α crystalline phases and β crystalline phases.
Optionally, first release layer is to spray to the surface of crucible, first remover include silicon nitride, water and
Ludox；Second release layer is to spray to the surface of crucible, and second releasing agent includes silicon nitride, water and Ludox.
Optionally, the mass ratio of the silicon nitride in first remover and Ludox is 10-30%：5%-30%, it is remaining
Amount is water.
According to the another aspect of the application, a kind of polysilicon fine melt casting ingot process is provided, is used during ingot casting
Crucible includes crucible described in any one of the above embodiments.
Optionally, the polycrystalline silicon casting ingot process includes the following steps：
1) loading stage：Silicon material is packed into crucible, transfer crucible to ingot furnace；
2) heating, melting stage：Heat-insulation cage is closed, ingot furnace is evacuated to vacuum, heating, fusing silicon material, in the melting stage
Crucible inside reach the aperture opened heat-insulation cage after preset temperature and adjust heat-insulation cage；
3) crystal growing stage：The aperture for adjusting heat-insulation cage is the 30%-70% of whole apertures, and long crystalline substance temperature is 1410-1460
℃；
4) annealing, cooling stage：After liquid-state silicon length is brilliant, annealing, cooling obtain polycrystal silicon ingot.
Further, the aperture of crystal growing stage adjustment heat-insulation cage be the range of whole apertures lower limit be selected from 35%,
40%, 45%, 50%, 55% or 60%, the upper limit 65%, 60%, 55%, 50% or 45%.
Optionally, the aperture of the heat-insulation cage of melting stage described in step 2) includes adjusting successively：First aperture 13-
18cm, the second aperture 4-7cm, third aperture 7-11cm.
Preferably, the aperture of the heat-insulation cage of the fusing includes adjusting successively：First aperture 14-18cm, the second aperture
4.5-6cm, third aperture 8-10cm.It inwardly conducts heat from crucible outer wall during polycrystalline silicon ingot casting and melts silicon material, crucible has
The fusing liquid level of temperature gradient, the silicon material in crucible is arc, and the fusing for controlling the silicon material in crucible is uniform, then adjusts in crucible
Melting silicon materials liquid level be the temperature distribution state inside crucible close to horizontal plane.The application adjusts the heat-insulation cage of smelt stage
Aperture so that adjust the silicon material liquid level melted in crucible close to horizontal plane, the long brilliant rate of polysilicon can be improved, improved more
The crystal growth quality of crystal silicon ingot.
Optionally, the aperture of the heat-insulation cage of crystal growing stage described in step 3) includes adjusting successively：First aperture 14-
17cm, the second aperture 18-20cm, third aperture 8-13cm.
Preferably, the aperture of the heat-insulation cage of the fusing includes adjusting successively：First aperture 15-16cm, the second aperture
19-20cm, third aperture 9-12cm.Controlling the climbing speed of the heat-insulation cage of the crystal growing stage of heat-insulation cage reduces long brilliant initial stage
The bottom defect of polycrystal silicon ingot, improves the yield of polycrystalline silicon ingot casting.The growth heat-insulation cage length brilliant time at initial stage is conducive to reduce more
Crystal silicon ingot casting tail portion defect.
Optionally, in step 2) in the normal smelting stage of melting stage：Heat-insulation cage aperture is 4.5-6cm, crucible top
Temperature be 1540-1555 DEG C, retention time 5-7h.The normal smelting stage refers to the Main Stage of melting, i.e. time proportion
Maximum smelt stage.
Optionally, in the normal crystal growing stage of the crystal growing stage in step 3)：Heat-insulation cage aperture is 19-20cm, on crucible
The temperature in portion is 1415-1425 DEG C, retention time 25-29h.Normal crystal growing stage refers to steady crystal growing stage, i.e. time ratio
The maximum crystal growing stage of weight.
Optionally, the silicon material includes reducing polysilicon and polycrystal silicon ingot cycle stock, and reducing polysilicon and polycrystal silicon ingot follow
The weight ratio of ring material is 50-90wt%：10-50wt%.Under the weight ratio of the reducing polysilicon and polycrystal silicon ingot cycle stock
Limit is selected from 50:40、52:48、54:46、55:45、56:44、58:42 or 60:40, the upper limit is selected from 88：22、86:24、85:25、
84:26、82:28 or 80:30.Preferably, the weight ratio of the reducing polysilicon and polycrystal silicon ingot cycle stock is 60-70wt%：
30-40wt%.
Optionally, the polycrystal silicon ingot cycle stock includes polycrystalline silicon ingot casting flaw-piece, polycrystalline silicon ingot casting head, polycrystalline silicon ingot casting
Tail portion, purification at least one of silico briquette and polycrystalline silicon fragments.
As an implementation, the method for the silicon material filling crucible is to be filled out around the polycrystal silicon ingot cycle stock
Fill the virgin polycrystalline silicon.
Optionally, the polycrystalline silicon casting ingot process includes：1) loading stage：Silicon material is packed into crucible, shifts crucible
To ingot furnace；2) heating period：Heat-insulation cage, ingot furnace heating are closed, crucible is kept the temperature completely；3) melting stage：Control fusing temperature
At 1175 DEG C -1560 DEG C, initial stage crucible is kept the temperature degree completely, is radiated in middle and later periods melting stage crucible bottom；4) crystal growing stage：Control
The long brilliant temperature of system is 1410 DEG C -1460 DEG C, and the aperture for adjusting heat-insulation cage has the stage of raising and lowering；5) annealing stage：Control
Annealing temperature processed is 1400 DEG C -1000 DEG C, annealing time 3.5-4.5h；6) cooling stage：Cooling temperature is 1000 DEG C -400 DEG C,
Cooling time is 10-12h.
Optionally, the crucible is silica crucible, and quartz sand, the inner wall of the crucible are fixed in the bottom of the silica crucible
Spraying silicon nitride, the thickness of the bottom nitride silicon of the crucible are more than the thickness of the silicon nitride of crucible wall.
Optionally, the size of the crucible is 1060mm × 1060mm × 540mm.
Optionally, protection gas is filled during the melting stage, crystal growing stage, annealing stage and cooling stage, it is described
Protection gas be argon gas, the pressure in the ingot furnace of control is 600mbar.
The degree of supercooling that the control of the crystal growing stage temperature of the application is formed promotes a large amount of small brilliant flower of long brilliant formation to improve
The efficiency and quality of crystallization.
Optionally, the aperture of the annealing stage heat-insulation cage is 4-6cm.Further, the annealing stage heat-insulation cage
Aperture is 5cm.The annealing stage that the control of the aperture of the heat-insulation cage can both make eliminates the stress inside polycrystalline silicon ingot casting, improves
The quality of polycrystalline silicon ingot casting, and can shorten the time of polycrystalline silicon ingot casting process.
Aperture described herein refers to the length of the opening of heat-insulation cage in the open state.
The advantageous effect that the application can generate includes：
1) silicon nitride layer of polysilicon fritting casting ingot process provided by the present application, the crucible used in the technique was both effective
The impurity in crucible is prevented to enter polycrystal silicon ingot, and silicon nitride layer is not easy to fall off.
2) the preparation process madial wall of the crucible and interior bottom can concurrently set different program sprayings, spraying process letter
Single, the silicon nitride layer of crucible side surface is smooth；The silicon nitride of the spraying of the crucible bottom inner surface is loose rough surface, is had
Quartz sand forming core, gap forming core and silicon nitride forming core, a variety of seedings are simultaneously deposited, and the period, short yield was high, and the silicon nitride layer of preparation can carry
The efficient output capacity of high polysilicon.
3) polysilicon fritting casting ingot process provided by the present application, the efficient output capacity of polysilicon which prepares is high, polycrystalline
The bottom defect that the long brilliant initial stage of silicon ingot is formed is few, and minority carrier life time is long.
Description of the drawings
Attached drawing described herein is used for providing further understanding of the present application, constitutes part of this application, this Shen
Illustrative embodiments and their description please do not constitute the improper restriction to the application for explaining the application.In the accompanying drawings：
Fig. 1 is the partial enlarged view of the interior bottom spraying silicon nitride of the crucible 1# of the embodiment of the present application.
Fig. 2 is the polycrystal silicon ingot bottom crystalline substance floral diagram of the ingot casting 1# of the embodiment of the present application.
Specific implementation mode
Unless otherwise instructed, the raw material in embodiments herein is bought by commercial sources, wherein virgin polycrystalline silicon
Purchased from Asia Kunshan Wu Zheng companies, purity is >=99.9999%；Silicon nitride is purchased from Beijing company of Qing Hua Ziguang, and purity is
99.99%；The purity of argon gas is 99.99%.
The silica crucible used in embodiments herein is purchased from Jiangsu Runchi Solar Energy Material S＆T Co., Ltd.
G61060 models.
The G6 type polycrystalline silicon ingot or purifying furnaces of Jing Gong Group Co., Ltd are used in embodiments herein.
Analysis process is as follows in embodiments herein：
The minority carrier life time of polysilicon is carried out using the minority carrier lifetime tester of the WT-2000 models of semilar companies of Switzerland
Measurement.
The application is described in detail with reference to embodiment and attached drawing, but the application is not limited to these embodiment and attached drawing.
Embodiment 1 prepares the raw material of polycrystal silicon ingot
The raw material for preparing polycrystal silicon ingot is the mixture of virgin polycrystalline silicon and polycrystal silicon ingot cycle stock, polycrystal silicon ingot cycle stock
It is included in the fragment material generated during polycrystalline silicon ingot casting, polycrystalline silicon ingot casting head, polycrystalline silicon ingot casting tail portion, purification silico briquette and side
Cladding.Silicon material 1#~the 3# and compare silicon material D1#, comparison silicon material D2# compositions such as 1 institute of table that polycrystalline silicon ingot casting uses in the present embodiment
Show.
Table 1
2 crucible for casting ingots of embodiment and silicon material placement regulation
By the silicon material 1#-3# in embodiment 1, comparison silicon material D1#, D2# is respectively put into silica crucible 1#-3#, compares crucible
D1#, D2# carry out polycrystalline silicon ingot casting.Silicon material is in the filling rule of silica crucible：High-purity grain of crystallization is laid in silica crucible bottom
Portion is put into one layer of reducing polysilicon later, and bulk cycle stock is placed at center, and reducing polysilicon is placed on surrounding gap and top, follows
The centre that ring silicon material is placed on silica crucible is not contacted with silica crucible.Crucible design parameter is as shown in table 2.By taking crucible 1# as an example
Illustrate that the roughness pattern of crucible is as shown in Figure 1.
Table 2
3 polycrystalline silicon casting ingot process of embodiment
The silica crucible of filling silicon material in embodiment 2 is put into polycrystalline silicon ingot or purifying furnace and carries out polycrystalline silicon ingot casting.It will be real
It applies the silicon material 1#-3# in example 1, comparison silicon material D1# and comparison silicon material D2# is respectively put into crucible 1#-3#, comparison crucible D1#, comparison
Ingot casting 1-3#, ingot casting D1# and ingot casting D2# is made in crucible D2# respectively.
The crucible of the placement silicon material of embodiment 2 is put into polycrystalline silicon ingot or purifying furnace and carries out polycrystalline silicon ingot casting.Polycrystalline silicon ingot casting
Stove includes evacuation system, heating system, temp measuring system, insulating layer jacking system, control pressurer system.Illustrate by taking ingot casting 1# as an example
Polycrystalline silicon ingot casting process, polycrystalline silicon ingot casting include the following steps：
1) loading stage：Silicon material is packed into crucible, transfer crucible to ingot furnace；
2) heating period：Heat-insulation cage, ingot furnace heating are closed, crucible is kept the temperature completely；
3) melting stage：Fusion temperature is controlled at 1400 DEG C -1560 DEG C, initial stage crucible is kept the temperature completely, in the melting stage
Later stage crucible bottom radiates, melting stage continuous applying argon gas；
4) crystal growing stage：The long brilliant temperature of control is 1410 DEG C -1460 DEG C, and the aperture for adjusting heat-insulation cage has raising and lowering
Stage, the continuous applying argon gas of crystal growing stage；
5) annealing stage：It is 1400 DEG C -1000 DEG C to control annealing temperature, annealing time 3.5-4.5h；
6) cooling stage:Cooling temperature be 1000 DEG C -400 DEG C, cooling time 10-12h.
The concrete technology flow process of melting stage includes the following steps：
After M1 enters the thawing stage：Crucible upper temp TC1 rises to 1550~1560 DEG C, when crucible bottom temperature TC2 liters
When to 1415~1425 DEG C, leapfrog to M2；
M2：Heat-insulation cage aperture was opened to 14~18cm with 5~15 minutes, and TC1 set temperatures are lowered 5 compared with previous step
~10 DEG C；
M3：Setting keeps M2 heat-insulation cages aperture 10~30 minutes, and desired temperature is identical as M2；
M4：Heat-insulation cage aperture is down to 4.5~6cm with 10~20 minutes, temperature setting is identical as M1；
M5：It sets heat-insulation cage and keeps aperture identical as M4 5~7 hours, temperature keeps identical as M3；
M6：Heat-insulation cage aperture is risen into 8~10cm with 10~15 minutes, temperature is set as 1520~1530 DEG C；
M7：It is set as melting end step, heat-insulation cage aperture and temperature setting are identical as M6, and it is small that the time is set as 3~5
When, subsequently enter crystal growing stage.
Further, further include：
M8：Heat-insulation cage is risen into 12~15cm with 10~15 minutes, temperature is set as 1460~1500 DEG C；
M9：Setting maintains M8 heat-insulation cages aperture and temperature 30 minutes, subsequently enters crystal growing stage.
The concrete technology flow process of crystal growing stage includes the following steps：
A1:Crystal growing stage is to set 30 minutes~60 minutes first, and temperature is set as 1450~1460 DEG C, heat-insulation cage aperture
It is set as 15~16cm；
A2:Subsequent setting time 26~28 hours, and heat-insulation cage aperture is at the uniform velocity risen into 19~20cm, temperature is down to 1415
~1425 DEG C；
A3:Then it is set as the brilliant end step of edge length, the time sets 3~4 hours, and temperature is set as 1410~1415
DEG C, heat-insulation cage aperture is set as 9~12cm.
Ingot casting 2#-3#, ingot casting D1#, the casting ingot process of ingot casting D2# and ingot casting 1# differences are as shown in table 3.Polysilicon is cast
Heat-insulated aperture during ingot melting stage and crystal growing stage is increased process, and the meaning of the open range in table 3 is with first
It is illustrated for stage, the meaning that first stage open range is 3.2-7cm refers to that the aperture of first stage rises from 3.2cm
To 7.0cm, the time needed for the growth of aperture is taken.The value of temperature in table 3 refers to that temperature changes in this temperature range.
Table 3
4 ingot casting performance detection of embodiment
To preparing the ingot casting 1# of the preparation of embodiment 3, ingot casting 2#, ingot casting 3#, comparing lacking for ingot casting D1# and comparison ingot casting D2#
The sub- service life is detected, and judges that its quality, measurement result are as shown in table 4.Illustrate polycrystalline silicon ingot casting bottom crystalline substance by taking ingot casting 1# as an example
Flower effect is as shown in Figure 2.
Table 4
By the data in table 4 it is found that ingot casting 1#-3# judgements grade is efficient polycrystalline silicon ingot casting, ingot casting D1# is general polycrystalline
Preferable class in silicon ingot casting, D2# are poor class in general polycrystalline silicon ingot casting.The polysilicon fine melt casting ingot process of the application is prepared more
The average life span of crystal silicon ingot casting is long, and the minority carrier life time of polycrystalline silicon ingot casting tail portion is long, and the defect of the bottom at long crystalline substance initial stage is few, polysilicon
Efficient output capacity is high.Ingot casting D1#, the polycrystalline silicon ingot casting tail portion defect length of ingot casting D# are long, and yield is low.
With raw material identical with ingot casting D2# and polycrystalline silicon casting ingot process, difference is that the surface of the crucible used is light
Sliding surface prepares ingot casting D3#.The growth cycle of ingot casting D3# is longer than ingot casting D2#, and few sub- average life span and the yield of ingot casting D2#
It is higher.The crucible bottom of the application is the coarse silicon nitride of bumps, and a variety of seeding modes improve seeding efficiency.
Ingot casting 1#, ingot casting 2#, ingot casting 3# there is a large amount of small crystalline substance to spend brilliant flower grade is level-one for bottom, with high quality
Crystalline structure.The resistivity of polysilicon prepared by the application is relatively low, and the defect of polysilicon is fewer, and crystalline structure is more single, resistance
Rate is smaller.
The silicon nitride portions of crucible internal walls of ingot casting D2# after polycrystalline silicon ingot casting fall off, cause polycrystalline silicon ingot casting with
Crucible occurs to glue pot, and the minority carrier life time of ingot casting D2# is short, and impurity content is more, and yield is low.
5 crucible spraying technique of embodiment
Silica crucible is subjected to different spraying process and prepares crucible 1#, crucible a#, crucible b#, crucible Da# and crucible
Db#, the preparation process with crucible 1# is the difference is that shown in table 5.
Table 5
Polycrystalline silicon ingot casting is carried out using raw material identical with ingot casting 1# and casting ingot process, the difference is that using 5 institute of table
The crucible shown.Respectively crucible a#, crucible b#, comparison crucible Da# and comparison earthenware are used according to the raw material of ingot casting 1# and casting ingot process
Ingot casting a#, ingot casting b#, comparison ingot casting Da# and comparison ingot casting Db# is made in crucible Db# respectively, measures the minority carrier life time of the ingot casting of preparation,
Judge its quality, as shown in table 6.
Table 6
| Silicon ingot is numbered | Average minority carrier lifetime/μ s | Stay high minority carrier life time/μ s | Sentence a grade score | Grade | Yield |
| Ingot casting 1# | 5.76 | 6.85 | 90.22 | H5 | 81.07% |
| Ingot casting a# | 5.71 | 6.80 | 90.15 | H5 | 81.00% |
| Ingot casting b# | 5.68 | 6.81 | 90.19 | H5 | 81.10% |
| Ingot casting Da# | 5.33 | 6.28 | 83.83 | H4 | 71.31% |
| Ingot casting Db# | 5.32 | 6.32 | 82.00 | H4 | 71.97% |
By the data in table 6 it is found that ingot casting 1#, ingot casting a#, ingot casting b# stay high minority carrier life time and average minority carrier lifetime
Higher than ingot casting Da#, ingot casting Db#, and the yield of ingot casting 1#, ingot casting a#, ingot casting b# are high.Compare ingot casting Da#, comparison ingot casting Db#
The silicon nitride portions of crucible internal walls after polycrystalline silicon ingot casting fall off, and polycrystalline silicon ingot casting is caused to occur to glue pot with crucible, right
Minority carrier life time than ingot casting Da#, comparison ingot casting Db# is short, and impurity content is more, and yield is low.And ingot casting 1#, ingot casting a#, ingot casting
The ingot casting period of b# is less than comparison ingot casting Da# and the ingot casting period to not ingot casting Db#.And the spray in the spraying process of crucible
The mist shape of painting is same as fogging degree to influence spraying effect, the best results for the circular nozzle that the spraying of the application uses.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, makes a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of preparation method of polysilicon fine melt crucible for casting ingots, which is characterized in that include the following steps：
1) quartz sand particle is fixed into the interior bottom of crucible；
2) bottom sprays the first release layer in the crucible for preparing step 1), and crucible madial wall sprays the second release layer；
First release layer is the surface of loose bumps.
2. preparation method according to claim 1, which is characterized in that first remover includes silicon nitride, and described the
Two removers include silicon nitride.
3. preparation method according to claim 1, which is characterized in that the first remover raw material includes silicon nitride, water
And Ludox；The second release layer agent includes silicon nitride, water and Ludox, first releasing agent and the second remover at
Divide difference.
4. preparation method according to claim 3, which is characterized in that the mass ratio of the silicon nitride, Ludox and water is
10-30%：5%-30%：50%-70%.
5. preparation method according to claim 1, which is characterized in that the temperature of bottom spraying silicon nitride is in the crucible
60-100℃；Preferably, the temperature of bottom spraying silicon nitride is 80-100 DEG C in the crucible.
6. preparation method according to claim 1, which is characterized in that the pressure of bottom spraying silicon nitride is in the crucible
2-4Mpa；Preferably, the pressure of bottom spraying silicon nitride is 3-4Mpa in the crucible.
7. preparation method according to claim 1, which is characterized in that the Spray painting tool of the crucible spraying remover exports
For circle.
8. a kind of crucible for polysilicon fine melt ingot casting, which is characterized in that want the side described in any one of 1 to 8 including right
Method is prepared.
9. a kind of polysilicon fine melt casting ingot process, which is characterized in that including using the crucible described in claim 9.
10. polysilicon fine melt casting ingot process according to claim 9, which is characterized in that include the following steps：
1) loading stage：Silicon material is packed into crucible, transfer crucible to ingot furnace；
2) heating, melting stage：Heat-insulation cage is closed, ingot furnace is evacuated to vacuum, heating, fusing silicon material, in the earthenware of melting stage
Heat-insulation cage is opened after reaching preset temperature inside crucible and adjusts the aperture of heat-insulation cage；
3) crystal growing stage：The aperture for adjusting heat-insulation cage is the 30%-70% of whole apertures, and long crystalline substance temperature is 1410-1460 DEG C；
4) annealing, cooling stage：After liquid-state silicon length is brilliant, annealing, cooling obtain polycrystal silicon ingot.
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