CN107916451B - A kind of casting polysilicon exempts to spray crucible - Google Patents
A kind of casting polysilicon exempts to spray crucible Download PDFInfo
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- CN107916451B CN107916451B CN201711354124.XA CN201711354124A CN107916451B CN 107916451 B CN107916451 B CN 107916451B CN 201711354124 A CN201711354124 A CN 201711354124A CN 107916451 B CN107916451 B CN 107916451B
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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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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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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Abstract
The present invention discloses a kind of casting polysilicon and exempts to spray crucible, which includes crucible body, is successively coated with first layer coating, second layer coating and third layer coating from inside to outside on the inner surface of the crucible body；Based on mass percentage, the ingredient of first layer coating includes the silicon oxynitride of 4.5 ~ 95%, the silica solution of the silica of 4.5 ~ 95% and 0.5 ~ 5%；The ingredient of second layer coating includes the silicon oxynitride of 5 ~ 50%, the silica of 0.5 ~ 50%, the silicon nitride of 0.5 ~ 50%, the PVA of the silica solution of 0.5 ~ 5% and 0.5 ~ 5%；The ingredient of third layer coating includes the silicon oxynitride of 0.5 ~ 95%, the silicon nitride of 0.5 ~ 95%, the PAA of the PVA of 0.5 ~ 5% and 0.5 ~ 5%；Silicon nitride coating in the second layer coating and third layer coating includes the silicon nitride of two kinds of partial sizes；The silicon oxynitride is prepared using ad hoc approach.Polycrystalline silicon ingot casting of the invention, which exempts from spray crucible, can reduce the risk that silicon nitride falls into silicon liquid, also increase its effect for stopping impurity and smoothly demoulding.
Description
Technical field
The present invention relates to the preparation fields of polysilicon casting crucible coating layer, and in particular to a kind of efficient polysilicon casting
With exempt from spray crucible.
Background technique
Photovoltaic is a kind of important green sustainable energy, and casting polysilicon is the most important former material for preparing photovoltaic module
One of material.The fewer higher photoelectric conversion efficiency in order to obtain, impurity and the defect for casting polysilicon the better.Polysilicon is being cast
In the process, generally use high-purity silica crucible as container, but silicon material is in the case where high temperature melting, will and quartz, also
It is that silica reacts, silicon liquid is caused to penetrate into inside crucible, in the case where the coefficient of expansion of quartz and silicon is inconsistent,
The infiltration of silicon liquid may result in crucible rupture, so that the silicon liquid of high temperature flows out, it is possible to cause serious safety accident.Cause
This, to solve this problem, quartz crucible surface is often sprayed one layer of silicon nitride coating.Since silicon nitride is a kind of high temperature resistant
Ceramics, it not only property stablize, the silicon liquid for high temperature of getting along well reacts, and silicon liquid is bad to its wetability so that its
It is not easy infiltration to enter to adhere to crucible, so that ingot casting goes on smoothly and smoothly demoulds.But although by silicon nitride spray finishing
In crucible as release agent, however it remains many problems: first, the impurity inside silica crucible still can be spread at high temperature to be worn
It crosses silicon nitride coating and enters silicon liquid, cause the increase of polycrystalline silicon impurities and defect, reduce the efficiency of photovoltaic module.Second, nitrogen
SiClx itself and silica crucible binding force be not strong, so that silicon nitride is easy to fall in silicon liquid during ingot casting, forms nitridation
Sila particle, silicon nitride inclusions point hardness is very high, not only increases silicon ingot internal flaw, and the photoelectricity for reducing photovoltaic module turns
Efficiency is changed, and be easy to cause diamond wire to break when subsequent Buddha's warrior attendant wire cutting, leads to production accident.Third, nitrogen
The angle of wetting of SiClx itself and silicon liquid is 45 °~50 °, and in the case where angle of wetting is lower than 90 °, solid liquid interface still has wetting
The case where, not only make the nitrogen in silicon nitride diffuse more readily into inside silicon liquid the pollution caused to silicon ingot in this way, but also
It is not smooth or even a possibility that split ingot to increase demoulding, ultimately causes the unstable of Ingot quality.
To solve the above-mentioned problems, the researcher in the industry proposes many schemes.Application number
201110281457.0 Chinese patent discloses one kind before spraying silicon nitride, increases in crucible surface containing silica solution~solidifying
The glass structure layer of glue increases the blocking to impurity in this way, but still without solving silicon nitride and silica binding force not
Strong problem, the silicon nitride on surface still have the risk polluted in the silicon liquid fallen into.Application No. is 201620841199.5
Chinese profession disclose the isolation method of a kind of barium silicate crystal layer and silicon nitride coating bilayer, barium silicate crystal layer air-tightness
By force, hardness is high, can prevent impurity inside crucible from spreading by bubble to silicon ingot, reduce pollution of the crucible to silicon ingot.But
Silicic acid crystal of barium itself contains barium metal, at high temperature, be inevitably largely diffused into inside silicon ingot cause it is serious
The pollution of metal ion.The researchers such as XiaoxiaoGong use mixes 3.8wt% nano-silica in silicon nitride coating
SiClx (GongX, DuH, Zhang X, et al.Influence of the coating preparation method and
of nanosilica addition on the bonding character of Si3N4, layer on a silica
Crucible [J] .Ceram ics International, 2014,40 (5): 7523 ~ 7529.), to increase silicon nitride
The compactness and intensity of film forming reduce erosion of the silicon liquid to silicon nitride layer infiltration and to crucible.But the silica of nanometer
It is not only at high cost, it is not easy to prepare, and be very easy to reunion and micron-sized silicon nitride particle mismatch, it is difficult to uniformly mixing,
It is difficult to reach corresponding effect in large-scale production process.
Summary of the invention
Exempt to spray crucible the present invention provides a kind of polycrystalline silicon ingot casting.
Technical solution of the present invention specifically:
A kind of casting polysilicon exempts to spray crucible, which includes crucible body, by interior on the inner surface of the crucible body
To being successively coated with first layer coating, second layer coating and third layer coating outside；Based on mass percentage, first layer coating
Ingredient includes the silicon oxynitride of 4.5~~ 95%, the silica of 4.5~~ 95% and the silica solution of 0.5~~ 5%, the painting
In layer, the sum of all components mass percentage is 100%；The ingredient of second layer coating includes the silicon oxynitride of 5~~ 50%,
0.5~50% silica, 0.5~50% silicon nitride, 0.5~5% silica solution and 0.5~5% PVA, the coating
In, the sum of all components mass percentage is 100%；The ingredient of third layer coating includes 0.5~95% silicon oxynitride,
0.5~95% silicon nitride, the PAA of 0.5~5% PVA and 0.5~5%, in the coating, all components mass percentage
The sum of be 100%；
As a kind of optimal technical scheme, the ingredient of the first layer coating includes 5~70% silicon oxynitride, 25~
90% silica and 1~5% silica solution；The ingredient of the second layer coating includes 10~50% silicon oxynitride, 5~
40% silica, 5~40% silicon nitride, 1~5% silica solution and 1~5% PVA；The third layer coating at
Divide the silicon oxynitride including 10~35%, 60~85% silicon nitride, the PAA of 1~5% PVA and 1~5%.
It is further preferred that the ingredient of the first layer coating includes 5~28% silicon oxynitride, 70~90% dioxy
SiClx and 2~5% silica solution, still more preferably, the ingredient of the first layer coating includes 10~25% silicon oxynitride,
72~85% silica and 2~5% silica solution；The ingredient of the second layer coating includes 30~50% nitrogen oxidation
Silicon, 20~35% silica, 20~35% silicon nitride, 2~5% silica solution and 2~5% PVA；The third layer
The ingredient of coating includes 10~25% silicon oxynitride, 65~85% silicon nitride, the PAA of 2~5% PVA and 2~5%.
Silicon nitride coating in the second layer coating and third layer coating includes the silicon nitride of two kinds of partial sizes；
Silicon oxynitride in the first layer coating, second layer coating and third layer coating is prepared using following steps: (1)
Silicon powder is subjected to humidification process；(2) under nitrogen oxygen atmosphere, the silicon power raw material that step (1) is obtained carries out high-temperature calcination, wait react
Silicon oxynitride is obtained after completely.
The silicon nitride of above two partial size include the partial size of silicon nitride A and silicon nitride B, the silicon nitride A be 5~50 μm and
It does not include 5 μm, the partial size of the silicon nitride B is 0.1~5 μm；Preferably, the partial size of the silicon nitride A is 10~20 μm, described
The partial size of silicon nitride B is 0.5~2 μm.The silicon nitride A and silicon nitride B mass ratio are 1:0.01~1；Preferably 1:0.2-
0.5。
Biodiversity percentage composition is 0.2- in silicon powder in the preparation process of the silicon oxynitride after humidification process
10%；Preferably 0.5-5%；Further preferably 1-3%.
The water of the humidification process is conductivity >=0.5m Ω cm water, preferably deionized water.
Purity >=99.99% of the silicon powder, the D90 of particle diameter distribution are 0.2~10 μm, it is preferred that the partial size point
The D90 of cloth is 1-5 μm.
The process of high-temperature calcination described in step (2) are as follows: the silicon power raw material that step (1) obtains is heated to 1000-1300
DEG C, 5-15h is kept the temperature, then be warming up to 1300-1500 DEG C, keeps the temperature 10-30h；Preferably, it is heated to 1250-1300 DEG C, heat preservation
10-15h, then it is warming up to 1400-1450 DEG C, keep the temperature 20-30h.It is brilliant that the two steps annealing method first step forms part silicon oxynitride
Kind, so that finally being easier to be completely transformed into pure silicon oxynitride, improve final conversion ratio.
Pressure in step (2) described high-temperature burning process is 1~10 atmospheric pressure, and the volume ratio of nitrogen and oxygen is 1:
0.01~0.1；Preferably, the pressure is 1-5 atmospheric pressure, and the volume ratio of nitrogen and oxygen is 1:0.01-0.05.
The first layer coating with a thickness of 20~40 μm, the second layer coating with a thickness of 30~50 μm, described
Three-layer coating with a thickness of 50~100 μm.
The purity of the silica, silicon nitride and silica solution >=99.99%, alcoholysis degree >=98% of the PVA；Institute
State molecular weight >=1250000 PAA.The crucible effect prepared using above-mentioned standard is best, but not limited to this.
Polycrystalline silicon ingot casting of the invention exempts to spray crucible, by the painting for preparing three layers of heterogeneity in high-purity silica pot inner wall
Layer, is utilized a kind of interphase as silicon nitride and silica of silicon oxynitride, constitutive property not only and silicon nitride, but also and
Silica has stronger similitude, so itself and silicon nitride, silica have stronger binding force, so that whole coating tool
There are bigger intensity and higher consistency, to be substantially reduced the risk that silicon nitride falls off, reduces the number of impure point in silicon liquid
Amount, the final quantity for reducing ingot casting red sector, improves the yield rate of ingot casting, and increase the photoelectric conversion efficiency of photovoltaic module.
In addition the silicon oxynitride in its first layer coating, second layer coating and third layer coating is during the preparation process first to silicon
Powder carries out humidification and introduces a large number of water molecules, and water-molecule dissociation is hydrogen and oxygen at high temperature, and hydrogen can not only restore silicon table
The oxide in face promotes the progress of reaction, shortens the incubation period of reaction, and can inhibit titanium dioxide always in reaction process
Silicon generates, so that reaction is carried out towards silicon oxynitride direction always, and then smoothly obtains high-purity silicon oxynitride.
Silicon nitride therein is mixed by using the silicon nitride particle of two kinds of partial sizes, and thickness collocation, little particle can fill
Into the gap between bulky grain, the consistency and intensity of silicon nitride coating are increased, reduces the risk that silicon nitride falls into silicon liquid,
Also increase its effect for stopping impurity and smoothly demoulding.
Compared with prior art, the present invention has the advantage that
Polycrystalline silicon ingot casting of the invention, which exempts to spray crucible, had been utilized silicon oxynitride not only and silicon nitride, but with silica have compared with
Strong binding force solves crucible surface direct spraying silicon nitride, silicon nitride and the not strong problem of silica surface binding force.
By preparing the coating of three kinds of heterogeneities, the ingenious variation that three kinds of ingredients are utilized: first layer coating contains silica and nitrogen
Silica ingredient and sidewall of crucible have very strong binding force；Second layer coating contains silica, silicon oxynitride and silicon nitride, belongs to
The middle layer of first layer and third layer can get up first layer and third layer firm connection；Third layer silicon nitride comprising and nitrogen oxygen
SiClx, it is both strong with second layer binding force, in turn ensure that silicon ingot smoothly demoulds.The coating of three layers of different formulations must be set in order
It sets, experiment shows if the adhesive force of coating will be significantly reduced by exchanging coating order.
In addition mixed using the high-purity nitrogen silica of ad hoc approach preparation and the silicon nitride particle of two kinds of partial sizes in each coating
The consistency and intensity of coating can be increased by closing, and reduce the risk that silicon nitride falls into silicon liquid, also increased it and stopped impurity and suitable
The effect of benefit demoulding.
In short, enhance the intensity and consistency of coating by the design of above-mentioned coating, reduce impurity in silicon ingot and
Defect improves the yield rate of silicon ingot, finally improves the stability and photoelectric conversion efficiency of photovoltaic module.
Detailed description of the invention
Fig. 1 is that polycrystalline silicon ingot casting exempts to spray the longitdinal cross-section diagram of crucible.
Wherein, 1-crucible body, 2-first layer coatings, 3-second layer coatings, 4-third layer coatings
Specific embodiment
Below by specific embodiment, the invention will be further described, but protection scope of the present invention be not limited to it is following
Embodiment.
The silicon oxynitride of the preparation high-purity of embodiment 1
Preparation example 1: being that the high-purity silicon powder that 99.99%, D90 is 0.2 micron carries out humidification process with deionized water by purity,
So that the mass percentage of moisture reaches 0.5% in silicon powder.Then above-mentioned silicon powder is heated to 1200 DEG C, keeps the temperature 5h, then rise
Temperature keeps the temperature 10h to 1300 DEG C, is passed through excessive nitrogen oxygen atmosphere in heating process always, nitrogen and oxygen volume ratio are 1:
0.01, holding atmosphere pressures are 2 atmospheric pressure.After high-temperature calcination, cooling obtains the silicon oxynitride that purity is up to 99.2%,
Its silica content is less than 0.1%, and for silicon nitride content less than 0.1%, metal impurities total amount is less than 100ppm.
Preparation example 2: it is that the high-purity silicon powder that 99.99%, D90 is 1 micron carries out humidification process with deionized water by purity, makes
The mass percentage for obtaining moisture in silicon powder reaches 1%.Then above-mentioned silicon powder is heated to 1250 DEG C, keeps the temperature 10h, then be warming up to
1450 DEG C, 20h is kept the temperature, is passed through excessive nitrogen oxygen atmosphere in heating process always, nitrogen and oxygen volume ratio are 1:0.05, are protected
Holding atmosphere pressures is 5 atmospheric pressure.After high-temperature calcination, cooling obtains the silicon oxynitride that purity is up to 99.8%, aoxidizes
Silicone content is less than 0.1%, and for silicon nitride content less than 0.1%, metal impurities total amount is less than 100ppm.
Preparation example 3: it is that the high-purity silicon powder that 99.99%, D90 is 3 microns carries out humidification process with deionized water by purity, makes
The mass percentage for obtaining moisture in silicon powder reaches 3%.Then above-mentioned silicon powder is heated to 1300 DEG C, keeps the temperature 15h, then be warming up to
1400 DEG C, 30h is kept the temperature, is passed through excessive nitrogen oxygen atmosphere in heating process always, nitrogen and oxygen volume ratio are 1:0.03, are protected
Holding atmosphere pressures is 3 atmospheric pressure.After high-temperature calcination, cooling obtains the silicon oxynitride that purity is up to 99.9%, aoxidizes
Silicone content is less than 0.1%, and for silicon nitride content less than 0.1%, metal impurities total amount is less than 100ppm.
Preparation example 4: it is high-purity silicon powder that 99.99%, D90 is 5 microns into deionized water row humidification process by purity, makes
The mass percentage for obtaining moisture in silicon powder reaches 5%.Then above-mentioned silicon powder is heated to 1100 DEG C, keeps the temperature 15h, then be warming up to
1500 DEG C, 10h is kept the temperature, is passed through excessive nitrogen oxygen atmosphere in heating process always, nitrogen and oxygen volume ratio are 1:0.1, are protected
Holding atmosphere pressures is 10 atmospheric pressure.After high-temperature calcination, cooling obtains the silicon oxynitride that purity is up to 99.4%, aoxidizes
Silicone content is less than 0.1%, and for silicon nitride content less than 0.1%, metal impurities total amount is less than 100ppm.
It prepares comparative example 1: being that the high-purity silicon powder that 99.99%, D90 is 0.2 micron is humidified with deionized water by purity
Processing, so that the mass percentage of moisture reaches 0.1% in silicon powder.Then above-mentioned silicon powder is heated to 1200 DEG C, keeps the temperature 5h,
It is warming up to 1300 DEG C again, keeps the temperature 10h, is passed through excessive nitrogen oxygen atmosphere always in heating process, nitrogen and oxygen volume ratio are
1:0.01, holding atmosphere pressures are 2 atmospheric pressure.After high-temperature calcination, cooling obtains silicon nitride, silica and nitrogen oxidation
Silicon mass ratio is the mixture of 1:1:1.Comparative example the results show that in silicon powder the mass percentage of moisture significantly affect it is made
The quality of standby silicon oxynitride.
Embodiment 2
The polycrystalline silicon ingot casting exempts to spray crucible to include crucible body 1, on the inner surface of the crucible body from inside to outside successively
It is coated with first layer coating 2, second layer coating 3 and third layer coating 4；
First layer coating is prepared, based on mass percentage, ingredient includes 10% silicon oxynitride, 85% titanium dioxide
Silicon, 5% silica solution.
Second layer coating is prepared, based on mass percentage, ingredient includes 50% silicon oxynitride, 20% titanium dioxide
Silicon, 20% silicon nitride, 5% silica solution, 5% PVA.
Third layer coating is prepared, based on mass percentage, ingredient includes 10% silicon oxynitride, 80% nitridation
Silicon, 5% PVA, 5% PAA.
Wherein, the silicon oxynitride that the silicon oxynitride is prepared for the preparation example 2 in embodiment 1, purity 99.8%,
The purity of the silica, silicon nitride and silica solution is both greater than 99.99%；The alcoholysis degree of the PVA is 98%, PAA molecule
Amount is 1250000.
Silicon nitride in each coating uses the silicon nitride A and silicon nitride B of two kinds of partial sizes, wherein silicon nitride A partial size be 10~
14 μm, silicon nitride B partial size is 1~2 μm.Silicon nitride A and silicon nitride B mass ratio are 1:0.5.
Firstly, in quartz crucible surface even application first layer coating, then, in first layer coating surface even application
Two layers of coating, finally, in second layer coating surface even application third layer coating.The first layer coating layer thickness is 20~30 μ
M, the second layer coating layer thickness are 30~40 μm, and the third layer coating layer thickness is 80~100 μm.
Coating manufactured in the present embodiment is subjected to adhesive force test, as a result 901kPa, is much higher than common coating, i.e. stone
The adhesive force that English crucible surface directly sprays silicon nitride is 310kPa.The crucible for being coated with this coating is applied to casting polysilicon,
Then the polysilicon cast is sliced, obtains A piece (high-quality silicon wafer) yield and reach 93.6%, is obtained much higher than common coating
90.3% yield.This is because consistency (the 4.99g/cm of this coating3) and intensity be improved so that entering ingot casting
In impure point tail off, to ingot casting carry out Buddha's warrior attendant wire cutting when, accordingly due to impure point and chipping even collapse line probability become
It is few, so that whole slice yield is improved.In this way, greatly improving whole yield rate and production efficiency.
Embodiment 3
The polycrystalline silicon ingot casting exempts to spray crucible to include crucible body 1, on the inner surface of the crucible body from inside to outside successively
It is coated with first layer coating 2, second layer coating 3 and third layer coating 4；
First layer coating is prepared, based on mass percentage, ingredient includes 20% silicon oxynitride, 76% titanium dioxide
Silicon, 4% silica solution.
Second layer coating is prepared, based on mass percentage, ingredient includes 40% silicon oxynitride, 26% titanium dioxide
Silicon, 26% silicon nitride, 4% silica solution, 4% PVA.
Third layer coating is prepared, based on mass percentage, ingredient includes 20% silicon oxynitride, 72% nitridation
Silicon, 4% PVA, 4% PAA.
Wherein, the silicon oxynitride that the silicon oxynitride is prepared for the preparation example 3 in embodiment 1, purity 99.9%,
The purity of the silica, silicon nitride and silica solution is both greater than 99.99%；The alcoholysis degree of the PVA is 98%, PAA molecule
Amount is 3000000.
Silicon nitride in each coating uses the silicon nitride A and silicon nitride B of two kinds of partial sizes, wherein silicon nitride A partial size be 13~
17 μm, silicon nitride B partial size is 0.5~2 μm.Silicon nitride A and silicon nitride B mass ratio are 1:0.2.
Firstly, in quartz crucible surface even application first layer coating, then, in first layer coating surface even application
Two layers of coating, finally, in second layer coating surface even application third layer coating.The first layer coating layer thickness is 30~35 μ
M, second layer coating layer thickness are 40~45 μm, and third layer coating layer thickness is 65~80 μm.
Coating manufactured in the present embodiment is subjected to adhesive force test, as a result 948kPa, is much higher than common coating, i.e. stone
The adhesive force that English crucible surface directly sprays silicon nitride is 310kPa.The crucible for being coated with this coating is applied to casting polysilicon,
Then the polysilicon cast is sliced, obtains A piece (high-quality silicon wafer) yield and reach 94.2%, is obtained much higher than common coating
90.3% yield.This is because consistency (the 5.23g/cm of this coating3) and intensity be improved so that entering ingot casting
In impure point tail off, to ingot casting carry out Buddha's warrior attendant wire cutting when, accordingly due to impure point and chipping even collapse line probability become
It is few, so that whole slice yield is improved.In this way, greatly improving whole yield rate and production efficiency.
Embodiment 4
The polycrystalline silicon ingot casting exempts to spray crucible to include crucible body 1, on the inner surface of the crucible body from inside to outside successively
It is coated with first layer coating 2, second layer coating 3 and third layer coating 4；
First layer coating is prepared, based on mass percentage, ingredient includes 25% silicon oxynitride, 72% titanium dioxide
Silicon, 3% silica solution.
Second layer coating is prepared, based on mass percentage, ingredient includes 30% silicon oxynitride, 32% titanium dioxide
Silicon, 32% silicon nitride, 3% silica solution, 3% PVA.
Third layer coating is prepared, based on mass percentage, ingredient includes 25% silicon oxynitride, 69% nitridation
Silicon, 3% PVA, 3% PAA.
Wherein, the silicon oxynitride that the silicon oxynitride is prepared for the preparation example 2 in embodiment 1, purity 99.8%,
The purity of the silica, silicon nitride and silica solution is both greater than 99.99%；The alcoholysis degree of the PVA is 98%, PAA molecule
Amount is 4000000.
Silicon nitride in each coating uses the silicon nitride A and silicon nitride B of two kinds of partial sizes, wherein silicon nitride A partial size be 16~
20 μm, silicon nitride B partial size is 1~2 μm.Silicon nitride A and silicon nitride B mass ratio are 1:0.4.
Firstly, in quartz crucible surface even application first layer coating, then, in first layer coating surface even application
Two layers of coating, finally, in second layer coating surface even application third layer coating.The first layer coating layer thickness is 35~40 μ
M, second layer coating layer thickness are 45~50 μm, and third layer coating layer thickness is 50~65 μm.
Coating manufactured in the present embodiment is subjected to adhesive force test, as a result 957kPa, is much higher than common coating, i.e. stone
The adhesive force that English crucible surface directly sprays silicon nitride is 310kPa.The crucible for being coated with this coating is applied to casting polysilicon,
Then the polysilicon cast is sliced, obtains A piece (high-quality silicon wafer) yield and reach 94.5%, is obtained much higher than common coating
90.3% yield.This is because consistency (the 5.25g/cm of this coating3) and intensity be improved so that entering ingot casting
In impure point tail off, to ingot casting carry out Buddha's warrior attendant wire cutting when, accordingly due to impure point and chipping even collapse line probability become
It is few, so that whole slice yield is improved.In this way, greatly improving whole yield rate and production efficiency.
Comparative example 1
On the contrary, using technological parameter same as Example 4, but silicon oxynitride is not added, specific scheme is as follows:
The polycrystalline silicon ingot casting exempts to spray crucible to include crucible body 1, on the inner surface of the crucible body from inside to outside successively
It is coated with first layer coating 2, second layer coating 3 and third layer coating 4；
First layer coating is prepared, based on mass percentage, 25% silicon nitride, 72% silica, 3% silicon is molten
Glue.
Second layer coating is prepared, based on mass percentage, 32% silica, 62% silicon nitride, 3% silicon is molten
Glue, 3% PVA.
Third layer coating is prepared, based on mass percentage, 94% silicon nitride, 3% PVA, 3% PAA.
Wherein, the purity of the silica, silicon nitride and silica solution is both greater than 99.99%；The alcoholysis degree of the PVA is
98%, PAA molecular weight are 4000000.
Silicon nitride in each coating uses the silicon nitride A and silicon nitride B of two kinds of partial sizes, wherein silicon nitride A partial size be 16~
20 μm, silicon nitride B partial size is 1~2 μm.Silicon nitride A and silicon nitride B mass ratio are 1:0.4.
Firstly, in quartz crucible surface even application first layer coating, then, in first layer coating surface even application
Two layers of coating, finally, in second layer coating surface even application third layer coating.The first layer coating layer thickness is 35~40 μ
M, second layer coating layer thickness are 45~50 μm, and third layer coating layer thickness is 50~65 μm.
Crucible coating layer prepared by this comparative example carries out adhesive force test, as a result 379kPa, close to common coating, i.e.,
The adhesive force that quartz crucible surface directly sprays silicon nitride is 310kPa, and coating consistency is 3.28g/cm3, this coating will be coated with
Crucible be applied to casting polysilicon, then the polysilicon cast is sliced, A piece (high-quality silicon wafer) yield is obtained and reaches
90.9%, 90.3% yield that slightly above common coating obtains.
Comparative example 2
By in embodiment 4 first layer coating and second layer coating exchange, other conditions are identical.To prepared earthenware
Crucible coating carries out adhesive force test, as a result 637kPa, is significantly higher than common coating, i.e. quartz crucible surface directly sprays nitridation
The adhesive force of silicon is 310kPa.But it is far below the coating adhesion of embodiment 2~4.Coating consistency is 4.32g/cm3, will
The crucible for being coated with this coating is applied to casting polysilicon, is then sliced the polysilicon cast, obtains A piece (high quality silicon
Piece) yield reaches 91.8%, higher than 90.3% yield that common coating obtains, but it is far below the coating of embodiment 2.3.4.
Claims (18)
1. a kind of casting polysilicon exempts to spray crucible, which is characterized in that the crucible includes crucible body, the interior table of the crucible body
First layer coating, second layer coating and third layer coating are successively coated on face from inside to outside；Based on mass percentage, first
Layer coating ingredient include 4.5 ~ 95% silicon oxynitride, 4.5 ~ 95% silica and 0.5 ~ 5% silica solution；The second layer applies
The ingredient of layer includes 5 ~ 50% silicon oxynitride, 0.5 ~ 50% silica, 0.5 ~ 50% silicon nitride, 0.5 ~ 5% silica solution
With 0.5 ~ 5% PVA；The ingredient of third layer coating includes 0.5 ~ 95% silicon oxynitride, 0.5 ~ 95% silicon nitride, and 0.5 ~ 5%
The PAA of PVA and 0.5 ~ 5%；
Silicon nitride coating in the second layer coating and third layer coating includes the silicon nitride of two kinds of partial sizes；
Silicon oxynitride in the first layer coating, second layer coating and third layer coating is prepared using following steps: (1) by silicon
Powder carries out humidification process；(2) under nitrogen oxygen atmosphere, the silicon power raw material that step (1) is obtained carries out high-temperature calcination, to fully reacting
After obtain silicon oxynitride.
2. casting polysilicon according to claim 1 exempts to spray crucible, which is characterized in that the silicon nitride packet of described two partial sizes
Include silicon nitride A and silicon nitride B, the silicon nitride A partial size is 5 ~ 50 μm and does not include 5 μm, the partial size of the silicon nitride B is
0.1~5μm。
3. casting polysilicon according to claim 2 exempt from spray crucible, which is characterized in that the partial size of the silicon nitride A be 10 ~
20 μm, the partial size of the silicon nitride B is 0.5 ~ 2 μm.
4. casting polysilicon according to claim 2 exempts to spray crucible, which is characterized in that the silicon nitride A and silicon nitride B matter
Amount is than being 1:0.01 ~ 1.
5. casting polysilicon according to claim 4 exempts to spray crucible, which is characterized in that the silicon nitride A and silicon nitride B matter
Amount is than being 1:0.2-0.5.
6. casting polysilicon according to claim 1 exempts to spray crucible, which is characterized in that the preparation process of the silicon oxynitride
Biodiversity percentage composition is 0.2-10% in silicon powder after middle humidification process.
7. casting polysilicon according to claim 6 exempts to spray crucible, which is characterized in that the preparation process of the silicon oxynitride
Biodiversity percentage composition is 0.5-5% in silicon powder after middle humidification process.
8. casting polysilicon according to claim 7 exempts to spray crucible, which is characterized in that the preparation process of the silicon oxynitride
Biodiversity percentage composition is 1-3% in silicon powder after middle humidification process.
9. casting polysilicon according to claim 1 or 6 exempts to spray crucible, which is characterized in that the water of the humidification process
For conductivity >=0.5m Ω cm water.
10. casting polysilicon according to claim 9 exempts to spray crucible, which is characterized in that the water of the humidification process is
Deionized water.
11. casting polysilicon according to claim 1 exempts to spray crucible, which is characterized in that the purity of the silicon powder >=
99.99%, the D90 of particle diameter distribution is 0.2 ~ 10 μm.
12. casting polysilicon according to claim 11 exempts to spray crucible, which is characterized in that the D90 of the particle diameter distribution is
1-5μm。
13. casting polysilicon according to claim 1 exempts to spray crucible, which is characterized in that high-temperature calcination described in step (2)
Process are as follows: the silicon power raw material that step (1) obtains is heated to 1000-1300 DEG C, keeps the temperature 5-15h, then be warming up to 1300-1500
DEG C, keep the temperature 10-30h.
14. casting polysilicon according to claim 13 exempts to spray crucible, which is characterized in that high temperature described in step (2) is forged
The process of burning are as follows: the silicon power raw material that step (1) obtains is heated to 1250-1300 DEG C, keeps the temperature 10-15h, then be warming up to 1400-
1450 DEG C, keep the temperature 20-30h.
15. casting polysilicon according to claim 1 exempts to spray crucible, which is characterized in that step (2) described high-temperature calcination
Pressure in journey is 1 ~ 10 atmospheric pressure, and the volume ratio of nitrogen and oxygen is 1:0.01 ~ 0.1.
16. casting polysilicon according to claim 15 exempts to spray crucible, which is characterized in that the pressure is 1-5 big
The volume ratio of air pressure, nitrogen and oxygen is 1:0.01-0.05.
17. casting polysilicon according to claim 1 exempts to spray crucible, which is characterized in that the thickness of the first layer coating
Be 20 ~ 40 μm, the second layer coating with a thickness of 30 ~ 50 μm, the third layer coating with a thickness of 50 ~ 100 μm.
18. casting polysilicon according to claim 1 exempt from spray crucible, which is characterized in that the silica, silicon nitride and
The purity of silica solution >=99.99%, alcoholysis degree >=98% of the PVA；Molecular weight >=1250000 PAA.
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| CN110803943B (en) * | 2019-11-30 | 2022-03-08 | 中材江苏太阳能新材料有限公司 | Low-impurity spray-free crucible for casting polycrystal and ingot single crystal and preparation method thereof |
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| CN102417308A (en) * | 2011-09-03 | 2012-04-18 | 江西旭阳雷迪高科技股份有限公司 | Baking-free process for silicon nitride coating of quartz crucible for ingot casting |
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Effective date of registration: 20210811 Address after: 212000 No. 18, Xingye North Road, new energy industrial park, Youfang Town, Yangzhong City, Zhenjiang City, Jiangsu Province Patentee after: Zhenjiang Runchi New Material Technology Co.,Ltd. Address before: 212218 Yangzhong Changwang new material industrial park, Zhenjiang City, Jiangsu Province Patentee before: JIANGSU RUNCHI SOLAR ENERGY MATERIAL SCIENCE & TECHNOLOGY Co.,Ltd. |