CN102453956B - A kind of quartz glass crucibles and preparation method thereof - Google Patents
A kind of quartz glass crucibles and preparation method thereof Download PDFInfo
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- CN102453956B CN102453956B CN201110040454.8A CN201110040454A CN102453956B CN 102453956 B CN102453956 B CN 102453956B CN 201110040454 A CN201110040454 A CN 201110040454A CN 102453956 B CN102453956 B CN 102453956B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
- C03B19/095—Other methods of shaping glass by fusing powdered glass in a shaping mould by centrifuging, e.g. arc discharge in rotating mould
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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
- 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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Abstract
The invention discloses a kind of quartz glass crucibles, the internal surface of the crucible base of described quartz glass crucibles is coated with the Clear coating that theoretic throat is 50 ~ 500 μm, described Clear coating is prepared by the quartz sand of melting doped with alkali earth metal, described alkali earth metal refers to magnesium elements, barium element, strontium element or calcium constituent, described alkali earth metal comes from barium oxide, the alkali of alkaline-earth metal, the mixture of the salt arbitrary proportion of the salt of alkaline-earth metal or the alkali of alkaline-earth metal and alkaline-earth metal, described is 400 ~ 2000ppm doped with the mass percentage of alkali earth metal in the quartz sand of alkali earth metal.The invention also discloses the preparation method of described quartz glass crucibles.Quartz glass crucibles provided by the invention has higher durable usability, and in crucible use procedure, ablation etc. causes disadvantageous effect phenomenon to crystal pulling process not easily occurs internal surface Clear coating, and the dislocation-free ratio of drawn monocrystalline silicon is high, and crystal pulling is effective.
Description
(1) technical field
The present invention relates to a kind of quartz glass crucibles, the quartz glass crucibles particularly used in crystal pulling method manufacture order crystal silicon, and the preparation method of described quartz glass crucibles.
(2) background technology
Quartz crucible is widely adopted as the container holding polycrystalline silicon material in pulling of silicon single crystal process, and therefore quartz crucible is as the object directly contacted with silicon single crystal material, determines the key factor that can silicon single crystal be produced smoothly.Wherein in vertical pulling method manufacture order crystal silicon process, cause a major cause of crystal pulling failure, cause in the middle of the silicon melt entering melting after the cristobalite that quartz glass crucibles internal surface is formed comes off.
At present, in the method for head it off, the crystallization promoter that many employings contain alkaline-earth metal is coated on inner surface of crucible, with the commitment at crystal-pulling, inner surface of crucible forms fine and close cristobalite crystallizing layer to be suppressed to come off, and such as Chinese patent 03108420 is coated metal oxide coating on the side all or in part of crucible; Adopt in Chinese patent 02154513.8 be coated with crystallization promoter on crucible surface after, carry out the method that high temperature burns till, coating is burnt till on crucible.
But in these coating processes, there is following problem:
(1) bonding force due to the coating on inner surface of crucible and inner surface of crucible is more weak, and coating easily comes off in transport and use procedure, makes coating can not play this due effect, even causes retroaction;
(2) adhesive power due to these coatings is more weak, is therefore very easy to be rinsed in washing process, especially can not meet crucible and carry out the clean requirement of pickling;
(3) this technique is after crucible completes, the coating of carrying out processing, and technical process is long, complicated operation, and there is crucible and to be easily secondary polluted etc. and to have a strong impact on the risk of crucible quality.
And US Patent No. 6,641,663B2 discloses the method using and make crucible internal layer doped with the quartz sand containing Ba element, though solve the problems referred to above, but the crucible inner layer B a constituent content lower (5 ~ 150ppm) that the method makes, the crucible internal layer of making is thicker (0.2 ~ 1.0mm).Contriver finds in an experiment, according to patent US6, and 641, disclosed in 663B2, method prepares quartz glass crucibles, because its inner layer B a constituent content is low, obtained crucible, in the process of pulling monocrystal, easily causes cristobalite crystallizing layer at inner surface of crucible skewness.And in order to ensure crystal pulling effect, just need the thickness increasing crucible internal layer, and the thickness increase of the internal layer adverse influence such as cristobalite layer can be caused blocked up, and obviously internal layer thickness increases the consumption that will increase internal layer quartz sand, strengthens cost.
(3) summary of the invention
The object of the invention is to provide a kind of quartz glass crucibles and preparation method thereof, with solve crucible in use above internal surface quartz crystals pull-up fall and cristobalite crystallizing layer skewness or cristobalite crystallizing layer is thicker etc. produces dysgenic problem to crystal pulling.
The technical solution used in the present invention is:
A kind of quartz glass crucibles, described quartz glass crucibles comprises crucible base, the internal surface that it is characterized in that the crucible base of described quartz glass crucibles is coated with the Clear coating that theoretic throat is 50 ~ 500 μm, described Clear coating is prepared by the quartz sand of melting doped with alkali earth metal, described quartz sand is natural siliceous sand, synthetic quartz sand or both are with the mixing of arbitrary proportion, preferred synthetic quartz sand, described alkali earth metal refers to magnesium elements, barium element, strontium element or calcium constituent, preferred barium element, described alkali earth metal comes from barium oxide, the alkali of alkaline-earth metal, the mixture of the salt arbitrary proportion of the salt of alkaline-earth metal or the alkali of alkaline-earth metal and alkaline-earth metal, described is 400 ~ 2000ppm doped with the mass content of alkali earth metal in the quartz sand of alkali earth metal, described internal surface refers to the bottom interior surface of crucible base, the wall portion internal surface of crucible base or whole internal surfaces of crucible base.
The alkali of described alkaline-earth metal is following one or more mixing: magnesium hydroxide, hydrated barta, strontium hydroxide or calcium hydroxide, preferred hydrated barta.
The salt of described alkaline-earth metal is earth alkali inorganic salt and/or alkaline-earth metal organic salt.Described earth alkali inorganic salt be following in one or more mixing: MeX
n, n is 1 or 2, and wherein Me is Mg
2+, Ba
2+, Sr
2+or Ca
2+, X is F
-, Cl
-, COO
-, CH
3cOO
-, C
2h
5cOO
-, CO
3 2-, SiO
3 2-or C
2o
4 2-; X is F
-, Cl
-, COO
-, CH
3cOO
-, C
2h
5cOO
-time, n=2; X is CO
3 2-, SiO
3 2-or C
2o
4 2-time, n=1.Described alkaline-earth metal organic salt be following in one or more mixing: (R)
2m, wherein M is Mg, Ba, Sr or Ca, and R is C
mh
2m+1the integer of COO, m=3 ~ 8.
The theoretic throat of described Clear coating is 50 ~ 500 μm, preferably 50 μm ~ 100 μm, the area S of the thickness b of Clear coating and the internal surface of expectation coating on the estimation, the required quality consumption m doped with the quartz sand of alkali earth metal can be calculated by formula m=K × S × b × ρ, wherein K is different size diameter crucible experience factor, K=1.5 ~ 2.0, ρ is the density of the quartz sand doped with alkali earth metal, and then melting obtains described Clear coating.The described formula m=K × S × b × ρ of pressing is when calculating, and each Parameter units must be unified.
ρ of the present invention is the normal density of quartz sand before high-temperature fusion doped with alkali earth metal; doped with the quartz sand of alkali earth metal after melting; density can increase usually; thickness and the consistency of thickness estimating Clear coating of the Clear coating obtained to make actual melting; when calculating the required quartz sand quality consumption m doped with alkali earth metal; doped with the multiple that the quartz sand of alkali earth metal increases compared to the density of the quartz sand before melting after melting, be also embodied among COEFFICIENT K.Described Clear coating is by when preparing quartz glass crucible base body with crucible die, after crucible base melt molding, on described crucible die, receiving electrode passes into strong current again, and then in described mould, form the electric arc of the condition of high temperature (being greater than 2000 DEG C) instantaneously, then the quartz sand doped with alkali earth metal is dropped into equably, after high-temperature fusion, be coated in the internal surface of quartz glass crucible base body, obtain described Clear coating.
More specifically, the crucible base of described quartz glass crucibles is obtained by natural siliceous sand melting.
Describedly be preferably 800ppm ~ 1200ppm doped with the mass content of alkali earth metal in the quartz sand of alkali earth metal.
More specifically, the described quartz sand doped with alkali earth metal can obtain by the following method: by barium oxide, the alkali of alkaline-earth metal, the mixture of the salt arbitrary proportion of the salt of alkaline-earth metal or the alkali of alkaline-earth metal and alkaline-earth metal is mixed with the solution that mass percentage is 0.01 ~ 50%, join in quartz sand, described quartz sand is natural siliceous sand, synthetic quartz sand or both are with the mixing of arbitrary proportion, fully be uniformly mixed, then dry 1 ~ 10 hour (preferably 200 ~ 300 DEG C at dry 2 ~ 5 hours) at 50 ~ 1000 DEG C, obtain the quartz sand doped with alkali earth metal, the mass content of alkali earth metal in quartz sand is made to be 400 ~ 2000ppm.
Described solution is the aqueous solution or organic solution, and more specifically, the alkali of described barium oxide, alkaline-earth metal, earth alkali inorganic salt or the alkali of alkaline-earth metal and the mixture of earth alkali inorganic salt water-solublely can only be made into the aqueous solution usually; Described alkaline-earth metal organic salt usually can only be dissolved in organic solvent and be made into organic solution, described organic solvent is following one or more mixing: the alkyl substituted benzene of the alcohol of C1 ~ C5, the ester of C2 ~ C8, C7 ~ C11, organic solvent is preferably following one or more mixing: methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, isopropylcarbinol, 1-amylalcohol, 2-amylalcohol, 2-methyl-2 amylalcohol, primary isoamyl alcohol, toluene, dimethylbenzene, ethyl acetate, most preferably toluene or ethyl acetate.
The described solution prepared joins in quartz sand, fully be uniformly mixed, then the drying operation of 1 ~ 10 hour under 50 ~ 1000 DEG C (preferably 200 ~ 300 DEG C), repeatedly can carry out, make the mass content of alkali earth metal in quartz sand be 400 ~ 2000ppm.During multi-pass operations, described solution can be that the identical solution gradation prepared adds, and gradation is dry, also can be that different solution gradation adds, and gradation is dry, finally makes the mass content of alkali earth metal in quartz sand be 400 ~ 2000ppm.Especially for alkali earth metal come from the alkali of alkaline-earth metal organic salt and alkaline-earth metal, alkaline-earth metal organic salt and earth alkali inorganic salt or alkaline-earth metal organic salt, the alkali of alkaline-earth metal, earth alkali inorganic salt three kinds mixing time, alkaline-earth metal organic salt is dissolved in organic solvent and is made into organic solution, the alkali of the alkali of alkaline-earth metal, earth alkali inorganic salt or alkaline-earth metal, the mixing of both earth alkali inorganic salt is water-soluble is respectively made into the aqueous solution, then organic solution must be separated with the aqueous solution and operated.This should be the known treatment processs of those skilled in the art.
Comparatively concrete, quartz glass crucibles of the present invention obtains in accordance with the following methods:
(1) mixture of the alkali of the alkali of barium oxide, alkaline-earth metal, the salt of alkaline-earth metal or alkaline-earth metal and the salt arbitrary proportion of alkaline-earth metal is mixed with the solution that mass percentage is 0.01 ~ 50%, join in quartz sand, described quartz sand is natural siliceous sand, synthetic quartz sand or both are with the mixing of arbitrary proportion, fully be uniformly mixed, then under 50 ~ 1000 DEG C (preferably 200 ~ 300 DEG C) dry 1 ~ 10 hour, obtain the quartz sand doped with alkali earth metal, make the mass content of alkali earth metal in quartz sand be 400 ~ 2000ppm; The alkali of described alkaline-earth metal is following one or more mixing: magnesium hydroxide, hydrated barta, strontium hydroxide or calcium hydroxide, preferred hydrated barta.
The salt of described alkaline-earth metal is earth alkali inorganic salt and/or alkaline-earth metal organic salt.Described earth alkali inorganic salt be following in one or more mixing: MeX
n, n is 1 or 2, and wherein Me is Mg
2+, Ba
2+, Sr
2+or Ca
2+, X is F
-, Cl
-, COO
-, CH
3cOO
-, C
2h
5cOO
-, CO
3 2-, SiO
3 2-or C
2o
4 2-; X is F
-, Cl
-, COO
-, CH
3cOO
-, C
2h
5cOO
-time, n=2; X is CO
3 2-, SiO
3 2-or C
2o
4 2-time, n=1.Described alkaline-earth metal organic salt be following in one or more mixing: (R)
2m, wherein M is Mg, Ba, Sr or Ca, and R is C
mh
2m+1the integer of COO, m=3 ~ 8;
(2) natural siliceous sand is put into the crucible die of rotation, under centrifugal action, described natural siliceous sand forms crucible shape, then the electric arc that strong current forms more than the 2000 DEG C conditions of high temperature is passed into the electrode above crucible die, lentamente natural siliceous sand melted and form crucible base, after crucible base melt molding, by the quartz sand doped with alkali earth metal that step (1) obtains, the internal surface of crucible base is evenly put into the speed of 50 ~ 100g/ minute, described internal surface is the bottom interior surface of crucible base, the wall portion internal surface of crucible base or whole internal surfaces of crucible base, feed intake and to terminate and after melting completes, take out after cooling, i.e. obtained described quartz glass crucibles.The quality consumption m of the described quartz sand doped with alkali earth metal is to estimate the thickness b of Clear coating and to estimate the area S of the internal surface applied, calculate according to formula m=K × S × b × ρ, wherein K is different size diameter crucible experience factor, K=1.5 ~ 2.0, ρ is the density of the quartz sand doped with alkali earth metal, and the thickness b of described expectation Clear coating is 50 ~ 500 μm.In described step (1), the alkali of described alkaline-earth metal is preferably hydrated barta; Described earth alkali inorganic salt is preferably barium carbonate or barium silicate, the preferred barium stearate of described alkaline-earth metal organic salt or isocaprylic acid barium.
Quartz glass crucibles provided by the invention is in the pyroprocess of pulling single crystal silicon, due in the Clear coating of inner surface of crucible doped with alkali earth metal, just define the cristobalite layer of even compact at the commitment inner surface of crucible of crystal-pulling, consequently can obtain the silicon single crystal of high dislocation-free ratio.
Therefore beneficial effect of the present invention is mainly reflected in:
(1) Clear coating due to the internal surface of this quartz glass crucibles adhering to, produce in arc process the internal surface in the melting process of crucible, quartz sand evenly being put into crucible to be formed, therefore, it has good even distribution at the internal surface of crucible.
(2) quartz crucible of the present invention is owing to improve the content of alkali earth metal in internal surface transparent layer, thinner internal surface Clear coating can be obtained, the thinnest can to 50 μm, thinner internal surface Clear coating can prevent the cristobalite crystallizing layer formed in crystal pulling process from coming off or molten silicon liquid enters the generation of the bad accidents such as cristobalite crystallizing layer, and cristobalite crystallizing layer is evenly distributed at inner surface of crucible, be beneficial to carrying out smoothly of crystal pulling.
(3) quartz glass crucibles provided by the invention has higher durable usability, in crucible use procedure not easily there is ablation etc. causes disadvantageous effect phenomenon to crystal pulling process in internal surface Clear coating, the dislocation-free ratio of drawn monocrystalline silicon is high, and crystal pulling is effective.
(4) quartz glass crucibles of the inventive method making is after standing pickling and high-pressure washing, and internal surface Clear coating still exists.
(5) because the inventive method is the coating on inner surface realized in quartz glass crucibles melting process, therefore the preparation method of this crucible is simple to operate, the crucible technological process of production is shorter.
(6) whole quartz glass crucibles production process adopts and automatically carries out, and achieves the uniformity consistency of crucible batch production.
(4) accompanying drawing explanation
The quartz glass crucibles cross section picture that Fig. 1 embodiment 1 is obtained, in figure, 1 indication is Clear coating.
The quartz glass crucibles that before Fig. 2 uses in crystal pulling environment, embodiment 1 is obtained.
The quartz glass crucibles that after Fig. 3 uses in crystal pulling environment, embodiment 1 is obtained.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is conducted further description, but protection scope of the present invention is not limited in this:
Compound method doped with the quartz sand of alkali earth metal barium: the compound containing alkali earth metal barium taking certain mass, be dissolved in solvent and be mixed with solution, then this solution is added in quartz sand, fully be uniformly mixed rear drying, the quartz sand containing alkali earth metal barium can be obtained.
Preparation is containing the quartz sand of alkali earth metal barium according to the method described above, concrete compound, solvent etc. containing alkali earth metal corresponding and to application quantity etc. as following table 1:
Table 1
Embodiment 1
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the condition of high temperature electric arc of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by synthetic quartz sand 417g (the anticipated thickness b=500 μm doped with alkaline-earth metal barium 400ppm of model a, estimate that the bottom interior surface of coating amasss s=3500cm
2, density p=1.4g/cm
3get COEFFICIENT K=1.7), the bottom interior surface of quartz glass crucible base body is evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 500 μm) of barium, and contrast with comparative example, assay the results are shown in Table 2.
Embodiment 2
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by synthetic quartz sand 375g (the anticipated thickness b=450 μm doped with alkaline-earth metal barium 400ppm of model b, estimate the wall portion internal surface area s=3500cm of coating
2, density p=1.4g/cm
3get COEFFICIENT K=1.7), the wall portion internal surface of quartz glass crucible base body is evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 450 μm) of barium, and contrast with comparative example, assay the results are shown in Table 2.
Embodiment 3
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by the synthetic quartz sand 666g doped with alkaline-earth metal barium 600ppm of model c, whole internal surfaces of quartz glass crucible base body are evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 400 μm) of barium, contrast with comparative example, assay the results are shown in Table 2.
Embodiment 4
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by the synthetic quartz sand 583g doped with alkaline-earth metal barium 800ppm of model d, whole internal surfaces of quartz glass crucible base body are evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 350 μm) of barium, contrast with comparative example, assay the results are shown in Table 2.
Embodiment 5
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by the synthetic quartz sand 500g doped with alkaline-earth metal barium 1000ppm of model e, whole internal surfaces of quartz glass crucible base body are evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 300 μm) of barium, contrast with comparative example, assay the results are shown in Table 2.
Embodiment 6
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by the synthetic quartz sand 208g doped with alkaline-earth metal barium 1200ppm of model f, the wall portion internal surface of quartz glass crucible base body is evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 250 μm) of barium, contrast with comparative example, assay the results are shown in Table 2.
Embodiment 7
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by the synthetic quartz sand 167g doped with alkaline-earth metal barium 1400ppm of model g, the bottom interior surface of quartz glass crucible base body is evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 200 μm) of barium, contrast with comparative example, assay the results are shown in Table 2.
Embodiment 8
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by the synthetic quartz sand 125g doped with alkaline-earth metal barium 1600ppm of model h, the wall portion internal surface of quartz glass crucible base body is evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 150 μm) of barium, contrast with comparative example, assay the results are shown in Table 2.
Embodiment 9
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by model i doped with the natural siliceous sand of alkaline-earth metal barium 1800ppm and the mixed sand 167g of synthetic quartz sand, whole internal surfaces of quartz glass crucible base body are evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 100 μm) of barium, contrast with comparative example, assay the results are shown in Table 2.
Embodiment 10
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by the mixed sand 83g of the synthetic quartz sand doped with alkaline-earth metal barium 2000ppm of model j, whole internal surfaces of quartz glass crucible base body are evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 50 μm) of barium, contrast with comparative example, assay the results are shown in Table 2.
Embodiment 11
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by the synthetic quartz sand 334g doped with alkaline-earth metal barium 400ppm of model k, whole internal surfaces of quartz glass crucible base body are evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 200 μm) of barium, contrast with comparative example 4, assay the results are shown in Table 2.
Embodiment 12
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by the natural siliceous sand 167g doped with alkaline-earth metal barium 1200ppm of model 1, whole internal surfaces of quartz glass crucible base body are evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 100 μm) of barium, contrast with comparative example, assay the results are shown in Table 2.
Comparative example 1:
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible, take out after cooling, obtain without the common quartz crucible of surface-treated.
Comparative example 2:
The natural siliceous sand of 25Kg is put into 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape.Then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, treat quartz crucible matrix melt molding, take out after cooling, obtain without the common quartz crucible matrix of surface-treated, then on whole internal surfaces of quartz crucible matrix, even application 100g concentration is the barium hydroxide solution of 1.5%, and at 200 DEG C dry 2 hours, obtained internal surface is coated with the quartz glass crucibles of barium.
Comparative example 3:
The natural siliceous sand of 25Kg is put into 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape.Then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, treat quartz crucible matrix melt molding, take out after cooling, obtain without the common quartz crucible matrix of surface-treated, then on the bottom interior surface of quartz crucible matrix, even application contains the toluene solution that 100g concentration is the isovaleric acid barium of 1.5%, and at 800 DEG C dry 3 hours, obtained internal surface is coated with the quartz glass crucibles of barium.
Comparative example 4
The natural siliceous sand of 25Kg is put in 20 inch crucible moulds of rotation, by centrifugal action, this natural siliceous sand is formed quartz crucible shape, then strong current is passed into the electrode above mould, and then in mould, form the electric arc of the condition of high temperature of > 2000 DEG C instantaneously, slowly quartz sand is melted into quartz crucible matrix, after quartz crucible matrix melt molding, adjustment commissioning pipe position, by the synthetic quartz sand 334g doped with alkaline-earth metal barium 150ppm, whole internal surfaces of quartz glass crucible base body are evenly put into the speed of 100g/ minute, after wait the end that feeds intake, also melting completes, after cooling, crucible is taken out, obtained internal surface is doped with the quartz glass crucibles of the Clear coating (theoretic throat is 200 μm) of barium.
The contrast properties of baric solution coatings crucible is applied in order to characterize quartz crucible of the present invention and internal surface, the characterizing method adopted respectively is: (1) is the high pressure water washing inner surface of crucible 25 minutes of 0.2MPa with pressure, contrast rinse before and after the amount of metal oxide that remains of inner surface of crucible per surface area; (2) in concentration be 10% HF acid in soak after 5 minutes, then clean inner surface of crucible with pure water, the amount of the metal oxide that inner surface of crucible per surface area remains before and after contrast pickling is clean; (3) crucible is carried out monocrystal pulling test, contrast the dislocation-free ratio (method of calculation of dislocation-free ratio are that the quality of dislocation-free single crystal accounts for the mass ratio loading polysilicon in crucible) of the silicon single crystal that several crucible draws out.Test result is as shown in table 2 below.
Table 2
Claims (3)
1. a preparation method for quartz glass crucibles, is characterized in that described method is:
(1) mixture of the alkali of the alkali of barium oxide, alkaline-earth metal, the salt of alkaline-earth metal or alkaline-earth metal and the salt arbitrary proportion of alkaline-earth metal is mixed with the solution that mass percentage is 0.01 ~ 50%, join in quartz sand, described quartz sand is natural siliceous sand, synthetic quartz sand or both are with the mixing of arbitrary proportion, fully be uniformly mixed, then at 50 ~ 1000 DEG C dry 1 ~ 10 hour, obtain the quartz sand doped with alkali earth metal, make the mass percentage 400 ~ 2000ppm of alkali earth metal in quartz sand; The alkali of described alkaline-earth metal is following one or more mixing: magnesium hydroxide, hydrated barta, strontium hydroxide or calcium hydroxide;
The salt of described alkaline-earth metal is earth alkali inorganic salt and/or alkaline-earth metal organic salt, described earth alkali inorganic salt be following in one or more mixing: MeX
n, n is 1 or 2, and wherein Me is Mg
2+, Ba
2+, Sr
2+or Ca
2+, X is F
-, Cl
-, COO
-, CH
3cOO
-, C
2h
5cOO
-, CO
3 2-, SiO
3 2-or C
2o
4 2-; X is F
-, Cl
-, COO
-, CH
3cOO
-, C
2h
5cOO
-time, n=2; X is CO
3 2-, SiO
3 2-or C
2o
4 2-time, n=1; Described alkaline-earth metal organic salt be following in one or more mixing: (R)
2m, wherein M is Mg, Ba, Sr or Ca, and R is C
mh
2m+1the integer of COO, m=3 ~ 8;
(2) natural siliceous sand is put into the crucible die of rotation, under centrifugal action, described natural siliceous sand forms crucible shape, then the electric arc that strong current forms more than the 2000 DEG C conditions of high temperature is passed into the electrode above crucible die, lentamente natural siliceous sand melted and form crucible base, after crucible base melt molding, by the quartz sand doped with alkali earth metal that step (1) obtains, the internal surface of crucible base is evenly put into the speed of 50 ~ 100g/ minute, described internal surface is the bottom interior surface of crucible base, the wall portion internal surface of crucible base or whole internal surfaces of crucible base, feed intake and to terminate and after melting completes, take out after cooling, i.e. obtained described quartz glass crucibles, the quality consumption m of the described quartz sand doped with alkali earth metal is to estimate the thickness b of Clear coating and to estimate the area S of the internal surface applied, calculate according to formula m=Κ × S × b × ρ, wherein Κ is different size diameter crucible experience factor, Κ=1.2 ~ 1.8, ρ is the density of the quartz sand doped with alkali earth metal, and the thickness b of described expectation Clear coating is 50 ~ 500 μm.
2. the method for claim 1, is characterized in that the alkali of described alkaline-earth metal is hydrated barta; Described earth alkali inorganic salt is barium carbonate or barium silicate, and described alkaline-earth metal organic salt is barium stearate or isocaprylic acid barium.
3. the method for claim 1, is characterized in that the mass percentage of described alkali earth metal in quartz sand is 800 ~ 1200ppm, and the thickness b of described expectation Clear coating is 50 ~ 100 μm.
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| CN2010105220283 | 2010-10-27 | ||
| CN201010591172.2 | 2010-12-16 | ||
| CN201010591172 | 2010-12-16 | ||
| CN2010105911722 | 2010-12-16 | ||
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| JP6828811B2 (en) * | 2017-05-02 | 2021-02-10 | 株式会社Sumco | Quartz glass crucible and its manufacturing method |
| CN114436506B (en) * | 2021-12-27 | 2023-11-24 | 深圳众诚达应用材料股份有限公司 | Glass powder smelting method |
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| CN1417387A (en) * | 2001-10-16 | 2003-05-14 | 日本超精石英株式会社 | Surface modifying method for quartz glass crucible and surface modified crucible |
| CN1448685A (en) * | 2002-03-29 | 2003-10-15 | 日本超精石英株式会社 | Surface modified quartz glass crucible and its modification process |
| CN1522230A (en) * | 2001-03-08 | 2004-08-18 | 赫罗伊斯石英玻璃股份有限两合公司 | Method of producing a quartz glass crucible |
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| US6641663B2 (en) * | 2001-12-12 | 2003-11-04 | Heracus Shin-Estu America | Silica crucible with inner layer crystallizer and method |
| US6875515B2 (en) * | 2002-05-10 | 2005-04-05 | General Electric Company | Fused quartz article having controlled devitrification |
| CN1890407A (en) * | 2003-12-03 | 2007-01-03 | 通用电气公司 | Quartz crucibles having reduced bubble content and method of making thereof |
| JP2005306708A (en) * | 2004-03-26 | 2005-11-04 | Kuramoto Seisakusho Co Ltd | Quartz crucible |
| US7427327B2 (en) * | 2005-09-08 | 2008-09-23 | Heraeus Shin-Etsu America, Inc. | Silica glass crucible with barium-doped inner wall |
| TW200730672A (en) * | 2005-11-29 | 2007-08-16 | Japan Super Quartz Corp | Quartz glass crucible, method of producing the same, and application thereof |
| US20120006254A1 (en) * | 2009-02-10 | 2012-01-12 | Masaru Fujishiro | Quartz glass crucible for pulling single-crystal silicon and process for producing single-crystal silicon |
| CN101956230A (en) * | 2010-10-27 | 2011-01-26 | 杭州先进石英材料有限公司 | Quartz glass crucible and preparation method thereof |
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| CN1522230A (en) * | 2001-03-08 | 2004-08-18 | 赫罗伊斯石英玻璃股份有限两合公司 | Method of producing a quartz glass crucible |
| CN1417387A (en) * | 2001-10-16 | 2003-05-14 | 日本超精石英株式会社 | Surface modifying method for quartz glass crucible and surface modified crucible |
| CN1448685A (en) * | 2002-03-29 | 2003-10-15 | 日本超精石英株式会社 | Surface modified quartz glass crucible and its modification process |
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Address after: No. 23, Guangming West Road, Yinchuan economic and Technological Development Zone, Ningxia Patentee after: Ningxia dunyuan poly core semiconductor technology Co.,Ltd. Address before: No. 23, Guangming West Road, Yinchuan economic and Technological Development Zone, Ningxia Patentee before: FERROTEC (NINGXIA) ADVANCED QUARTZ MATERIAL Co.,Ltd. |