CN102453956A - Quartz glass crucible and manufacturing method thereof - Google Patents
Quartz glass crucible and manufacturing method thereof Download PDFInfo
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- CN102453956A CN102453956A CN2011100404548A CN201110040454A CN102453956A CN 102453956 A CN102453956 A CN 102453956A CN 2011100404548 A CN2011100404548 A CN 2011100404548A CN 201110040454 A CN201110040454 A CN 201110040454A CN 102453956 A CN102453956 A CN 102453956A
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- crucible
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- alkali metal
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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 quartz glass crucible. The inner surface of a crucible substrate of the quartz glass crucible is coated with a transparent coating of which the theoretical thickness is 50-500 mum; the transparent coating is prepared by melting quartz sand doped with alkaline-earth metal elements; the alkaline-earth metal elements refer to magnesium elements, barium elements, strontium elements or calcium elements, and come from barium oxide, alkalis of alkaline-earth metals, salts of the alkaline-earth metals or mixtures of the alkalis of the alkaline-earth metals and the salts of the alkaline-earth metals in any ratio; and the quartz sand doped with the alkaline-earth metal elements contains 400-2,000 parts per million by mass of alkaline-earth metal elements. The invention further discloses a manufacturing method of the quartz glass crucible. The quartz glass crucible provided by the invention has relatively high durability; in the using process of the crucible, the phenomena such as falling, stripping and the like which cause adverse effects on the crystal pulling process do not occur easily on the transparent coating on the inner surface; and the dislocation-free ratio of pulled mono-crystalline silicon is high, and a good crystal pulling effect is achieved.
Description
(1) technical field
The present invention relates to a kind of quartz glass crucibles, the quartz glass crucibles that particularly in crystal pulling method manufacture order crystal silicon, uses, and the preparation method of said quartz glass crucibles.
(2) background technology
Quartz crucible is extensively adopted as the container that holds polycrystalline silicon material in the pulling of silicon single crystal process, so quartz crucible conduct and the object that the silicon single crystal material directly contacts, and has determined 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, in the middle of the cristobalite that forms on the quartz glass crucibles internal surface comes off back entering molten silicon melt, cause.
At present; In the method for head it off; The crystallization promoters that contain earth alkali metal that adopt are coated on the inner surface of crucible more; With the commitment at crystal-pulling, inner surface of crucible forms fine and close cristobalite crystallizing layer to be suppressed to come off, for example Chinese patent 03108420 coated metal oxide coating on the whole of crucible or part side; After being employed on the crucible surface coating crystallization promoter in the Chinese patent 02154513.8, carry out the method that high temperature burns till, coating is burnt till on crucible.
But in these coating processes, exist following problem:
(1) since the bonding force of coating and inner surface of crucible on the inner surface of crucible a little less than, coating easily transport and use in come off, make the effect that coating can not play should be had, even cause retroaction;
(2) since the adhesive power of these coatings a little less than, therefore in washing process, be very easy to be rinsed, especially can not satisfy crucible and carry out the clean requirement of pickling;
(3) this technology is after crucible completes, the coating of carrying out processing, and technical process is long, complicated operation, and exist crucible and be prone to be secondary polluted etc. and have a strong impact on the risk of crucible quality.
And U.S. Pat 6; 641,663B2 discloses and has used the method that is doped with the silica sand making crucible internal layer that contains the Ba element, though solved the problems referred to above; But the crucible inner layer B a constituent content that this method is made lower (5～150ppm), the crucible internal layer thicker (0.2～1.0mm) of making.The contriver finds in experiment, according to patent US6,641; The 663B2 disclosed method prepares quartz glass crucibles; Because its inner layer B a constituent content is low, the crucible that makes is prone to cause the cristobalite crystallizing layer at the inner surface of crucible skewness in the process of pulling monocrystal.And in order to guarantee the crystal pulling effect, just need to increase the thickness of crucible internal layer, and the thickness increase of internal layer can cause adverse influences such as the cristobalite layer is blocked up, and also layer thickness increases the consumption that will increase internal layer silica sand obviously, strengthens cost.
(3) summary of the invention
The objective of the invention is for a kind of quartz glass crucibles and preparation method thereof is provided, with solve crucible in use internal surface top quartz crystals pull-up fall and cristobalite crystallizing layer skewness or cristobalite crystallizing layer are thicker etc. that crystal pulling is produced dysgenic problem.
The technical scheme that the present invention adopts is:
A kind of quartz glass crucibles; Said quartz glass crucibles comprises crucible base; It is characterized in that being coated with the Clear coating that theoretic throat is 50～500 μ m on the internal surface of crucible base of said quartz glass crucibles; Said Clear coating is to prepare through the silica sand that fusion is doped with alkali earth metal; Said silica sand is natural siliceous sand, synthetic quartz sand or both mixing with arbitrary proportion, preferred synthetic quartz sand, and said alkali earth metal is meant magnesium elements, barium element, strontium element or calcium constituent; Preferred barium element; Said alkali earth metal comes from the mixture of salt arbitrary proportion of alkali and earth alkali metal of salt or earth alkali metal of alkali, the earth alkali metal of barium oxide, earth alkali metal, and the mass content of alkali earth metal is 400～2000ppm in the said silica sand that is doped with alkali earth metal, and said internal surface is meant 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 said earth alkali metal is following one or more mixing: Marinco H, hydrated barta, strontium hydroxide or calcium hydroxide, preferred hydrated barta.
The salt of said earth alkali metal is earth alkali metal inorganic salt and/or earth alkali metal organic salt.Said earth alkali metal inorganic salt are one or more the mixing in following: MeX
n, n is 1 or 2, 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
-The time, n=2; X is CO
3 2-, SiO
3 2-Or C
2O
4 2-The time, n=1.Said earth alkali metal organic salt is one or more the mixing in following: (R)
2M, wherein M is Mg, Ba, Sr or Ca, R is C
mH
2m+1COO, the integer of m=3～8.
The theoretic throat of said Clear coating is 50～500 μ m; Preferred 50 μ m～100 μ m, the area S of the thickness b of Clear coating and the internal surface that estimate to apply on the estimation, by formula m=K * S * b * ρ calculates the required quality consumption m that is doped with the silica sand of alkali earth metal; Wherein K is a different size diameter crucible experience factor; K=1.5～2.0, ρ is the density that is doped with the silica sand of alkali earth metal, fusion makes said Clear coating then.When said m=K * S by formula * b * ρ calculated, each parameter unit must unify.
ρ according to the invention is the normal density of silica sand before high-temperature fusion that is doped with alkali earth metal; The silica sand that is doped with alkali earth metal is after fusion; Density can increase usually; For thickness that makes the Clear coating that actual fusion obtains and the consistency of thickness of estimating Clear coating; When calculating the required silica sand quality consumption m that is doped with alkali earth metal, the multiple that the density of the silica sand of the silica sand that is doped with alkali earth metal after the fusion before the fusion increases is also embodied among the COEFFICIENT K.Described Clear coating is through when preparing quartz glass crucible base body with crucible die; After treating the crucible base melt molding; Receiving electrode feeds strong current on described crucible die again, and then the electric arc that moment forms the condition of high temperature (greater than 2000 ℃) in described mould, drops into the silica sand that is doped with alkali earth metal then 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 to be made by the natural siliceous sand fusion.
The mass content of alkali earth metal is preferably 800ppm～1200ppm in the said silica sand that is doped with alkali earth metal.
More specifically; The said silica sand that is doped with alkali earth metal can obtain by following method: it is 0.01～50% solution that the mixture of the salt arbitrary proportion of the alkali of the salt of the alkali of barium oxide, earth alkali metal, earth alkali metal or earth alkali metal and earth alkali metal is mixed with the quality percentage composition; Join in the silica sand; Said silica sand is natural siliceous sand, synthetic quartz sand or both mixing with arbitrary proportion; Fully mix; 50～1000 ℃ dry 1～10 hour down (drying is 2～5 hours under preferred 200～300 ℃), obtain being doped with the silica sand of alkali earth metal then, making the mass content of alkali earth metal in silica sand is 400～2000ppm.
Said solution is the aqueous solution or organic solution, and more specifically, the alkali of the alkali of said barium oxide, earth alkali metal, earth alkali metal inorganic salt or earth alkali metal and the mixture of earth alkali metal inorganic salt can only water-solublely be made into the aqueous solution usually; Said earth alkali metal organic salt can only be dissolved in organic solvent usually and be made into organic solution; Said organic solvent is the alcohol of following one or more mixing: C1～C5, the ester of C2～C8, the alkyl substituted benzene of C7～C11; Organic solvent is preferably following one or more mixing: methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, isopropylcarbinol, 1-amylalcohol, 2-amylalcohol, 2-methyl-2 amylalcohol, primary isoamyl alcohol, toluene, YLENE, ETHYLE ACETATE, most preferably toluene or ETHYLE ACETATE.
The said solution for preparing joins in the silica sand; Fully mix; In 50～1000 ℃ (preferred 200～300 ℃) dry 1～10 hour operation down, can repeatedly carry out then, making the mass content of alkali earth metal in silica sand is that 400～2000ppm gets final product.During multi-pass operations, said solution can be that the identical solution gradation for preparing adds, and gradation is dry, also can be that different solution gradation adds, and gradation is dry, and finally making the mass content of alkali earth metal in silica sand is that 400～2000ppm gets final product.When especially coming from the mixing of three kinds in alkali, earth alkali metal organic salt and earth alkali metal inorganic salt or earth alkali metal organic salt, the alkali of earth alkali metal, earth alkali metal inorganic salt of earth alkali metal organic salt and earth alkali metal for alkali earth metal; Earth alkali metal organic salt is dissolved in organic solvent and is made into organic solution; The alkali of the alkali of earth alkali metal, earth alkali metal inorganic salt or earth alkali metal, the water-soluble respectively aqueous solution that is made into of both mixing of earth alkali metal inorganic salt, 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 according to the invention makes according to following method:
(1) mixture of the salt arbitrary proportion of the alkali of the salt of the alkali of barium oxide, earth alkali metal, earth alkali metal or earth alkali metal and earth alkali metal being mixed with the quality percentage composition is 0.01～50% solution; Join in the silica sand; Said silica sand is natural siliceous sand, synthetic quartz sand or both mixing with arbitrary proportion; Fully mix; Descended dry 1～10 hour at 50～1000 ℃ (preferred 200～300 ℃) then, obtain being doped with the silica sand of alkali earth metal, making the mass content of alkali earth metal in silica sand is 400～2000ppm; The alkali of said earth alkali metal is following one or more mixing: Marinco H, hydrated barta, strontium hydroxide or calcium hydroxide, preferred hydrated barta.
The salt of said earth alkali metal is earth alkali metal inorganic salt and/or earth alkali metal organic salt.Said earth alkali metal inorganic salt are one or more the mixing in following: MeX
n, n is 1 or 2, 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
-The time, n=2; X is CO
3 2-, SiO
3 2-Or C
2O
4 2-The time, n=1.Said earth alkali metal organic salt is one or more the mixing in following: (R)
2M, wherein M is Mg, Ba, Sr or Ca, R is C
mH
2m+1COO, the integer of m=3～8;
(2) natural siliceous sand is put into the crucible die of rotation; Said natural siliceous sand forms the crucible shape under centrifugal action; Electrode to crucible die top feeds the electric arc that strong current forms the condition of high temperature more than 2000 ℃ then, lentamente natural siliceous sand is melted and forms crucible base, treat the crucible base melt molding after; The silica sand that is doped with alkali earth metal that step (1) is obtained; Evenly put into the internal surface of crucible base with 50～100g/ minute speed, said 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, feeds intake to finish and after fusion accomplishes; Take out the cooling back, promptly makes said quartz glass crucibles.The quality consumption m of the said silica sand that is doped with alkali earth metal is with the area S of thickness b that estimates Clear coating and the internal surface of estimating to apply; Calculate according to formula m=K * S * b * ρ; Wherein K is a different size diameter crucible experience factor; K=1.5～2.0, ρ is the density that is doped with the silica sand of alkali earth metal, the thickness b of said expectation Clear coating is 50～500 μ m.In the said step (1), the alkali of said earth alkali metal is preferably hydrated barta; Said earth alkali metal inorganic salt are preferably barium carbonate or barium silicate, preferred barium stearate of said earth alkali metal organic salt or isocaprylic acid barium.
Quartz glass crucibles provided by the invention is in the pyroprocess of pulling single crystal silicon; Owing to be doped with alkali earth metal in the Clear coating of inner surface of crucible; Just form 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) because the Clear coating that adheres on the internal surface of this quartz glass crucibles, be to produce in the melting process of crucible the internal surface that silica sand is evenly put into crucible in arc process to form, therefore, it has uniform distribution property preferably at the internal surface of crucible.
(2) quartz crucible of the present invention is owing to improved the content of alkali earth metal in the internal surface transparent layer; Can make thin internal surface Clear coating; The thinlyyest can arrive 50 μ m; Thin internal surface Clear coating can prevent that the cristobalite crystallizing layer that in the crystal pulling process, forms from coming off or molten silicon liquid gets into the generation of bad accidents such as cristobalite crystallizing layer, and the cristobalite crystallizing layer is evenly distributed at inner surface of crucible, is beneficial to carrying out smoothly of crystal pulling.
(3) quartz glass crucibles provided by the invention has higher durable usability; Ablation etc. causes disadvantageous effect to the crystal pulling process phenomenon be difficult for to take place in the internal surface Clear coating in the crucible use; The dislocation-free ratio of pulling monocrystal 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 the internal surface Clear coating still exists.
(5) because the inventive method is the coating on inner surface of in the quartz glass crucibles melting process, realizing, so 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 has realized the uniformity consistency that crucible is produced in batches.
(4) description of drawings
The quartz glass crucibles xsect picture that Fig. 1 embodiment 1 makes, 1 indication is a Clear coating among the figure.
The quartz glass crucibles that embodiment 1 made before Fig. 2 used in the crystal pulling environment.
The quartz glass crucibles that Fig. 3 uses back embodiment 1 to make in the crystal pulling environment.
(5) embodiment
Below in conjunction with specific embodiment the present invention is further described, but protection scope of the present invention is not limited in this:
Be doped with the compound method of the silica sand of alkali earth metal barium: the compound that contains alkali earth metal barium that takes by weighing certain mass; Be dissolved in and be mixed with solution in the solvent; Then this solution is added in the silica sand; Fully mix after drying, can make the silica sand that contains alkali earth metal barium.
Preparation contains the silica sand of alkali earth metal barium according to the method described above, specifically contain the compound, solvent etc. of alkali earth metal corresponding and to application quantity like following table 1:
Table 1
Embodiment 1
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation; Through centrifugal action this natural siliceous sand is formed the quartz crucible shape; Electrode to mould top feeds strong current then, so in mould moment form＞2000 ℃ condition of high temperature electric arc, slowly silica sand is melted into the quartz crucible matrix; After treating quartz crucible matrix melt molding; Adjustment commissioning pipe position is with the synthetic quartz sand 417g that is doped with earth alkali metal barium 400ppm (expectation thickness b=500 μ m, the long-pending s=3500cm of the bottom interior surface that expectation applies of model a
2, density p=1.4g/cm
3Get COEFFICIENT K=1.7), evenly put into the bottom interior surface of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 500 μ m) that internal surface is doped with barium, compare with comparative example, the assay result sees table 2.
Embodiment 2
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation; Through centrifugal action this natural siliceous sand is formed the quartz crucible shape; Electrode to mould top feeds strong current then, so in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix; After treating quartz crucible matrix melt molding; Adjustment commissioning pipe position is with the synthetic quartz sand 375g that is doped with earth alkali metal barium 400ppm (expectation thickness b=450 μ m, the internal surface area s=3500cm of wall portion that expectation applies of model b
2, density p=1.4g/cm
3Get COEFFICIENT K=1.7), evenly put into the wall portion internal surface of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 450 μ m) that internal surface is doped with barium, compare with comparative example, the assay result sees table 2.
Embodiment 3
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation, through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding after; Adjustment commissioning pipe position; With the synthetic quartz sand 666g that is doped with earth alkali metal barium 600ppm of model c, evenly put into whole internal surfaces of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 400 μ m) that internal surface is doped with barium, compare with comparative example, the assay result sees table 2.
Embodiment 4
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation, through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding after; Adjustment commissioning pipe position; With the synthetic quartz sand 583g that is doped with earth alkali metal barium 800ppm of model d, evenly put into whole internal surfaces of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 350 μ m) that internal surface is doped with barium, compare with comparative example, the assay result sees table 2.
Embodiment 5
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation, through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding after; Adjustment commissioning pipe position; With the synthetic quartz sand 500g that is doped with earth alkali metal barium 1000ppm of model e, evenly put into whole internal surfaces of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 300 μ m) that internal surface is doped with barium, compare with comparative example, the assay result sees table 2.
Embodiment 6
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation, through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding after; Adjustment commissioning pipe position; With the synthetic quartz sand 208g that is doped with earth alkali metal barium 1200ppm of model f, evenly put into the wall portion internal surface of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 250 μ m) that internal surface is doped with barium, compare with comparative example, the assay result sees table 2.
Embodiment 7
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation, through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding after; Adjustment commissioning pipe position; With the synthetic quartz sand 167g that is doped with earth alkali metal barium 1400ppm of model g, evenly put into the bottom interior surface of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 200 μ m) that internal surface is doped with barium, compare with comparative example, the assay result sees table 2.
Embodiment 8
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation, through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding after; Adjustment commissioning pipe position; With the synthetic quartz sand 125g that is doped with earth alkali metal barium 1600ppm of model h, evenly put into the wall portion internal surface of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 150 μ m) that internal surface is doped with barium, compare with comparative example, the assay result sees table 2.
Embodiment 9
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation; Through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then, so in mould moment form the electric arc of＞2000 ℃ the condition of high temperature; Slowly silica sand is melted into the quartz crucible matrix; After treating quartz crucible matrix melt molding, adjustment commissioning pipe position is with the natural siliceous sand that is doped with earth alkali metal barium 1800ppm of model i and the mixed sand 167g of synthetic quartz sand; Evenly put into whole internal surfaces of quartz glass crucible base body with 100g/ minute speed; Wait to feed intake and finish and after fusion accomplishes, after the cooling crucible is taken out, make the quartz glass crucibles of the Clear coating (theoretic throat is 100 μ m) that internal surface is doped with barium; Compare with comparative example, the assay result sees table 2.
Embodiment 10
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation, through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding after; Adjustment commissioning pipe position; With the mixed sand 83g of the synthetic quartz sand that is doped with earth alkali metal barium 2000ppm of model j, evenly put into whole internal surfaces of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 50 μ m) that internal surface is doped with barium, compare with comparative example, the assay result sees table 2.
Embodiment 11
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation, through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding after; Adjustment commissioning pipe position; With the synthetic quartz sand 334g that is doped with earth alkali metal barium 400ppm of model k, evenly put into whole internal surfaces of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 200 μ m) that internal surface is doped with barium, compare with comparative example 4, the assay result sees table 2.
Embodiment 12
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation, through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding after; Adjustment commissioning pipe position; With the natural siliceous sand 167g that is doped with earth alkali metal barium 1200ppm of model 1, evenly put into whole internal surfaces of quartz glass crucible base body with 100g/ minute speed, wait to feed intake and finish and after fusion accomplishes; After the cooling crucible is taken out; Make the quartz glass crucibles of the Clear coating (theoretic throat is 100 μ m) that internal surface is doped with barium, compare with comparative example, the assay result sees table 2.
Comparative example 1:
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation; Through centrifugal action this natural siliceous sand is formed the quartz crucible shape; Electrode to mould top feeds strong current then, so in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into quartz crucible; Take out the cooling back, obtains not having the common quartz crucible of surface-treated.
Comparative example 2:
The natural siliceous sand of 25Kg is put into 20 inches crucible dies of rotation, this natural siliceous sand is formed the quartz crucible shape through centrifugal action.Electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding; Take out the cooling back; Obtain not having the common quartz crucible matrix of surface-treated, then on whole internal surfaces of quartz crucible matrix, evenly spray 100g concentration and be 1.5% barium hydroxide solution; And, make the quartz glass crucibles that internal surface is coated with barium at 200 ℃ times dry 2 hours.
Comparative example 3:
The natural siliceous sand of 25Kg is put into 20 inches crucible dies of rotation, this natural siliceous sand is formed the quartz crucible shape through centrifugal action.Electrode to the mould top feeds strong current then; And then in mould moment form the electric arc of＞2000 ℃ the condition of high temperature, slowly silica sand is melted into the quartz crucible matrix, treat quartz crucible matrix melt molding; Take out the cooling back; Obtain not having the common quartz crucible matrix of surface-treated, then on the bottom interior surface of quartz crucible matrix, evenly spraying contains the toluene solution that 100g concentration is 1.5% isovaleric acid barium; And, make the quartz glass crucibles that internal surface is coated with barium at 800 ℃ times dry 3 hours.
Comparative example 4
The natural siliceous sand of 25Kg is put in 20 inches crucible dies of rotation; Through centrifugal action this natural siliceous sand is formed the quartz crucible shape, the electrode to the mould top feeds strong current then, so in mould moment form the electric arc of＞2000 ℃ the condition of high temperature; Slowly silica sand is melted into the quartz crucible matrix; After treating quartz crucible matrix melt molding, adjustment commissioning pipe position is with the synthetic quartz sand 334g that is doped with earth alkali metal barium 150ppm; Evenly put into whole internal surfaces of quartz glass crucible base body with 100g/ minute speed; Wait to feed intake and finish and after fusion accomplishes, after the cooling crucible is taken out, make the quartz glass crucibles of the Clear coating (theoretic throat is 200 μ m) that internal surface is doped with barium.
In order to characterize the contrast properties that quartz crucible of the present invention and internal surface apply baric solution coatings crucible; The characterizing method that adopts respectively is: (1) uses pressure to be the high pressure water washing inner surface of crucible of 0.2MPa 25 minutes, the amount of contrast flushing front and back inner surface of crucible per surface area metal remained oxide compound; (2) after concentration is to soak 5 minutes in 10% the HF acid, clean inner surface of crucible with pure water again, the amount of inner surface of crucible per surface area metal remained oxide compound before and after the 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 the mass ratio that the quality of dislocation-free single crystal accounts for the interior polysilicon of crucible of packing into) of the silicon single crystal that several kinds of crucibles draw out.Test result is as shown in table 2 below.
Table 2
Claims (10)
1. quartz glass crucibles; Said quartz glass crucibles comprises crucible base; It is characterized in that being coated with the Clear coating that theoretic throat is 50～500 μ m on the internal surface of crucible base of said quartz glass crucibles; Said Clear coating is to prepare through the silica sand that fusion is doped with alkali earth metal; Said silica sand is natural siliceous sand, synthetic quartz sand or both mixing with arbitrary proportion; Said alkali earth metal is meant magnesium elements, barium element, strontium element or calcium constituent; Said alkali earth metal comes from the mixture of salt arbitrary proportion of alkali and earth alkali metal of salt or earth alkali metal of alkali, the earth alkali metal of barium oxide, earth alkali metal, and the mass content of alkali earth metal is 400～2000ppm in the said silica sand that is doped with alkali earth metal, and said internal surface is meant the bottom interior surface of crucible base, the wall portion internal surface of crucible base or whole internal surfaces of crucible base.
2. quartz glass crucibles as claimed in claim 1; It is characterized in that described Clear coating through when preparing quartz glass crucible base body with crucible die, treat the crucible base melt molding after, receiving electrode feeds strong current on described crucible die again; And then in described mould moment form the electric arc of the condition of high temperature; Drop into the silica sand that is doped with alkali earth metal then equably, after high-temperature fusion, be coated in the internal surface of quartz glass crucible base body, obtain described Clear coating.
3. quartz glass crucibles as claimed in claim 2 is characterized in that said crucible base is to be made by the natural siliceous sand fusion.
4. quartz glass crucibles as claimed in claim 1, the theoretic throat that it is characterized in that described Clear coating are 50～100 μ m.
5. quartz glass crucibles as claimed in claim 1, the mass content that it is characterized in that being doped with alkali earth metal in the silica sand of alkali earth metal is 800～1200ppm.
6. quartz glass crucibles as claimed in claim 1 is characterized in that the alkali of said earth alkali metal is following one or more mixing: Marinco H, hydrated barta, strontium hydroxide or calcium hydroxide; The salt of said earth alkali metal is earth alkali metal inorganic salt and/or earth alkali metal organic salt, and said earth alkali metal inorganic salt are one or more the mixing in following: MeX
n, n is 1 or 2, 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
-The time, n=2; X is CO
3 2-, SiO
3 2-Or C
2O
4 2-The time, n=1; Said earth alkali metal organic salt is one or more the mixing in following: (R)
2M, wherein M is Mg, Ba, Sr or Ca, R is C
mH
2m+1COO, the integer of m=3～8.
7. quartz glass crucibles as claimed in claim 5; It is characterized in that the said silica sand that is doped with alkali earth metal can obtain by following method: it is 0.01～50% solution that the mixture of the salt arbitrary proportion of the alkali of the salt of the alkali of barium oxide, earth alkali metal, earth alkali metal or earth alkali metal and earth alkali metal is mixed with the quality percentage composition; Join in the silica sand; Said silica sand is natural siliceous sand, synthetic quartz sand or both mixing with arbitrary proportion; Fully mix; Descended dry 1～10 hour at 50～1000 ℃ then, obtain being doped with the silica sand of alkali earth metal, make the mass content 400～2000ppm of alkali earth metal in silica sand.
8. quartz glass crucibles as claimed in claim 1 is characterized in that said quartz glass crucibles makes according to following method:
(1) mixture of the salt arbitrary proportion of the alkali of the salt of the alkali of barium oxide, earth alkali metal, earth alkali metal or earth alkali metal and earth alkali metal being mixed with the quality percentage composition is 0.01～50% solution; Join in the silica sand; Said silica sand is natural siliceous sand, synthetic quartz sand or both mixing with arbitrary proportion; Fully mix; Descended dry 1～10 hour at 50～1000 ℃ then, obtain being doped with the silica sand of alkali earth metal, make the quality percentage composition 400～2000ppm of alkali earth metal in silica sand; The alkali of said earth alkali metal is following one or more mixing: Marinco H, hydrated barta, strontium hydroxide or calcium hydroxide;
The salt of said earth alkali metal is earth alkali metal inorganic salt and/or earth alkali metal organic salt, and said earth alkali metal inorganic salt are one or more the mixing in following: MeX
n, n is 1 or 2, 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
-The time, n=2; X is CO
3 2-, SiO
3 2-Or C
2O
4 2-The time, n=1; Said earth alkali metal organic salt is one or more the mixing in following: (R)
2M, wherein M is Mg, Ba, Sr or Ca, R is C
mH
2m+1COO, the integer of m=3～8;
(2) natural siliceous sand is put into the crucible die of rotation; Said natural siliceous sand forms the crucible shape under centrifugal action; Electrode to crucible die top feeds the electric arc that strong current forms the condition of high temperature more than 2000 ℃ then, lentamente natural siliceous sand is melted and forms crucible base, treat the crucible base melt molding after; The silica sand that is doped with alkali earth metal that step (1) is obtained; Evenly put into the internal surface of crucible base with 50～100g/ minute speed, said 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, feeds intake to finish and after fusion accomplishes; Take out the cooling back, promptly makes said quartz glass crucibles; The quality consumption m of the said silica sand that is doped with alkali earth metal is with the area S of thickness b that estimates Clear coating and the internal surface of estimating to apply; Calculate according to formula m=K * S * b * ρ; Wherein K is a different size diameter crucible experience factor; K=1.2～1.8, ρ is the density that is doped with the silica sand of alkali earth metal, the thickness b of said expectation Clear coating is 50～500 μ m.
9. quartz glass crucibles as claimed in claim 8, the alkali that it is characterized in that said earth alkali metal is hydrated barta; Said earth alkali metal inorganic salt are barium carbonate or barium silicate, and said earth alkali metal organic salt is barium stearate or isocaprylic acid barium.
10. quartz glass crucibles as claimed in claim 9 is characterized in that the quality percentage composition of said alkali earth metal in silica sand is 800～1200ppm, and the thickness b of said expectation Clear coating is 50～100 μ m.
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| CN2010105220283 | 2010-10-27 | ||
| CN201010591172 | 2010-12-16 | ||
| CN201010591172.2 | 2010-12-16 | ||
| CN2010105911722 | 2010-12-16 | ||
| CN201110040454.8A CN102453956B (en) | 2010-10-27 | 2011-02-18 | A kind of quartz glass crucibles and preparation method thereof |
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|---|---|---|---|---|
| CN110709539A (en) * | 2017-05-02 | 2020-01-17 | 胜高股份有限公司 | Quartz glass crucible and method for producing same |
| CN114436506A (en) * | 2021-12-27 | 2022-05-06 | 深圳市众诚达应用材料科技有限公司 | Glass powder smelting method |
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| CN103641300B (en) * | 2013-11-26 | 2016-01-13 | 连云港市盛昌照明电器有限公司 | High purity quartz preparation method and for cryogenic heat exchanger silica tube and preparation 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110709539A (en) * | 2017-05-02 | 2020-01-17 | 胜高股份有限公司 | Quartz glass crucible and method for producing same |
| CN110709539B (en) * | 2017-05-02 | 2022-03-15 | 胜高股份有限公司 | Quartz glass crucible and method for producing same |
| CN114436506A (en) * | 2021-12-27 | 2022-05-06 | 深圳市众诚达应用材料科技有限公司 | Glass powder smelting 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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| Publication number | Publication date |
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| WO2012055195A1 (en) | 2012-05-03 |
| CN102453956B (en) | 2016-03-23 |
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Effective date of registration: 20161226 Address after: 750000 Yinchuan economic and Technological Development Zone, Guangming West Road, No. 23, No. Patentee after: Ferrotec (Ningxia) Advanced Quartz Material Co., Ltd. Address before: 310053 Binjiang District, Zhejiang Province, Hangzhou Road, No. 668 Patentee before: Advanced Quartz Material (Hangzhou) Co., Ltd. |
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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. |
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