CN109112631A - A kind of sapphire C is to long crystal method - Google Patents
A kind of sapphire C is to long crystal method Download PDFInfo
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- CN109112631A CN109112631A CN201811267589.6A CN201811267589A CN109112631A CN 109112631 A CN109112631 A CN 109112631A CN 201811267589 A CN201811267589 A CN 201811267589A CN 109112631 A CN109112631 A CN 109112631A
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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
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/20—Aluminium oxides
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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
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Abstract
This application provides a kind of sapphire C to long crystal method, the method is long brilliant using " pagoda type " seeding and " sitting pot " mode, the bubble range that can reduce at the top of sapphire crystal and the defects of crystal dislocation can be cut off, and it can reduce the risk being broken when pot is glued in bottom to the fracture of pulling rate seed crystal or collet, to improve crystal quality, the utilization rate of crystal is improved.
Description
Technical field
The invention belongs to the technical fields of Sapphire Crystal Growth, in particular to are suitable for large-size sapphire in single crystal growing furnace
C is to long crystal method.
Background technique
Sapphire (α-Al2O3) have the characteristics that high rigidity, high intensity, corrosion-resistant, high light transmission rate, from France in 1890
Since scientist Vinal is prepared for sapphire crystal for the first time, the technology of preparing of synthetic sapphire crystal has obtained quick hair
Exhibition, crystal quality are continuously improved, and application field is also widened significantly.Currently, sapphire is widely used in civilian and military
Etc. every field.In civil field, sapphire is used for abrasion-proof structure, medical material, high temperature window, microelectronic industry substrate material
Material, laser host material, optical prism, mobile phone window etc.；In military field, wave transparent of the sapphire as high-speed aircraft and guided missile
The fields such as optronics mast of window, photoelectric nacelle, submarine.The application field constantly expanded constantly proposes sapphire material newly to want
Ask, except high rigidity, high intensity, it is wear-resistant in addition to, also require sapphire that there are the property such as low stress, high optical perfection, major diameter
Energy.Therefore, growing low cost, large scale, high quality becomes artificial synthesized sapphire trend.
Artificial synthesized sapphire, that is, the method for growing sapphire crystal mainly includes vertical pulling method (cz), heat-exchanging method
(HEM), the terraced method (TGT) of temperature and kyropoulos (Kyropoulos) etc..Wherein, vertical pulling method and the terraced method of temperature are mainly used for growing 100kg
Sapphire crystal below；And heat-exchanging method is easy to cause crystalline substance since molybdenum crucible is different from the thermal expansion coefficient of sapphire single-crystal
Thermal stress is easily generated at body and crucible EDGE CONTACT, and then easily causes cracking outside monocrystalline.Therefore, growing large-size is blue precious at present
Stone mainly uses kyropoulos, and the crystal defect of such method growth is few, dislocation density is low.
The fast development of LED technology based on Sapphire Substrate occupies 90% or more the share in LED substrate market, to 6 English
The demand of the very little and above sapphire substrate sheet is increasing.Since c-plane sapphire crystal and III/V and II/VI compounds of group are thin
There is the lattice mismatch rate of very little between film (such as GaN film), for example, the lattice mismatch rate between c-plane sapphire and GaN film is only
It is 17%, therefore, LED field is often using c-plane sapphire as GaN film epitaxially grown layer.
For sapphire, C is big to long brilliant large scale, the sapphire difficulty of high-quality of obtaining, in general, C is to growth
Sapphire crystal weight is small, is commonly 80kg or less.Specifically, C is bigger than other directions to long Jingjing lattice deformation extent, due to indigo plant
The anisotropy of gem crystal, any heterogeneous nucleation easily generate parasitic defect.In addition, there are dislocation defects also can for seed crystal itself
It is genetic in grown crystal.It is theoretical according to Burgers vector conservation, if dislocation intersects with growth interface, in growth course
In with interface displacement, will lead to the extension of dislocation, dislocation line has special topological property, in the dislocation of C axis direction, Neng Gouyan
C plane of crystal is reached, for C to long crystalline substance as more and more Interfacial Dislocations lines can be accumulated constantly, crystal dislocation also can be higher and higher,
C is easiest to the problem of low angle boundary and big angle crystal boundary occur to long crystalline substance.
Compared to C to long crystalline substance, A is more easy to long crystalline substance, therefore, sapphire of the current country's outgrowth for LED substrate
Mostly using A to long brilliant, C is to the mode for drawing stick.But since A to long brilliant crystal top is also easy to produce taper bubble column, bottom is easy
It generates and is buckled to bowl-shape bubble cloud, laterally drawing stick causes stock utilization low, as depicted in figs. 1 and 2, utilization of the A to growth crystal
Rate is low, and only 37.5%.Identical size identical weight sapphire crystal is according to C to long crystalline substance, then utilization rate of crystal can be promoted to
56.5%, that is, it is 1.5 times that A draws to long crystalline substance stick amount that C, which draws stick amount to long crystalline substance, so that C to the long brilliant utilization rate of crystal obtained significantly
It is promoted.
Since C currently on the market is mainly 80kg or less crystal to growth technique, the growth of large-size crystals is also immature,
Moreover, the problem of C low angle boundary and big angle crystal boundary easily occurs to long crystalline substance, influences the utilization rate of crystal.Therefore, exploitation one is needed
It kind can weaken the sapphire C of low angle boundary and big angle crystal boundary problem to growing method.
Summary of the invention
The application provides a kind of sapphire C to long crystal method, and the method is using " pagoda type " seeding and " sitting pot " mode
It is long brilliant, the bubble range that can reduce at the top of sapphire crystal and the defects of crystal dislocation can be cut off, and can reduce bottom
The risk being broken when viscous pot to the fracture of pulling rate seed crystal or collet improves the utilization rate of crystal to improve crystal quality.
Method provided by the present application the following steps are included:
Step 1, the crucible equipped with alumina raw material is put into furnace chamber, rear material is vacuumized to furnace chamber, obtains aluminium oxide
Molten soup；
Step 2, seed crystal is put into the molten soup of the aluminium oxide, it is default every mentioning seed crystal first first prefixed time interval wink
Highly, until the crystal diameter is preset diameters；
Step 3, pulling rate is reduced to 0, when crystal weight is the first preset weight ratio of charge, mentions crystal second wink
Preset height, and increase heating power, heating power is gradually decreased after increasing heating power, the long brilliant speed for controlling crystal is less than
Default long speed；
Step 4, when crystal weight is greater than the second preset weight ratio, being averaged in the crystal nearest 24 hours is calculated
Long speed v calculates remaining growth time h using following formula I according to the average length speed v, also, continues to cool down with current range of decrease rate
H hours:
H=Δ w/v Formulas I
Wherein, h indicates remaining growth time,
Δ w indicates the weight of the molten soup of remaining aluminium oxide,
V indicates the average long speed in the crystal nearest 24 hours；
Step 5, the position of crystal is adjusted according to the weight of crystal, until crystal weight is stable to default within a preset time
Weight range.
In a kind of achievable mode, in step 1, the purity of the alumina raw material is 5N or more, is taken out to furnace chamber
Vacuum degree is lower than 1e-4Pa after vacuum.
In a kind of achievable mode, in step 1, the material includes following sub-step:
Sub-step 1 is kept the temperature under target power to the oxidation according to predetermined power raising speed increased wattage to target power
Aluminum feedstock is molten soup state；
Sub-step 2, the architecture heat preservation that sub-step 1 is obtained monitor the state of the alumina raw material, such as during incubation
There is crystal precipitation in the molten soup of aluminium oxide described in fruit, then continues to increase power, system is kept the temperature again after increasing power.
In a kind of achievable mode, in sub-step 1, the raising speed increased wattage is the base in existing increased wattage
Increase 500w/h~1000w/h on plinth.
In a kind of achievable mode, in step 1, the crucible that alumina raw material is housed is being put into furnace chamber it
Before, it further include examining seed crystal with the presence or absence of defect, the defect includes: bubble, twin and crackle.
In a kind of achievable mode, in step 2, seed crystal is put into during the molten soup of the aluminium oxide described in monitoring
The state of the molten soup of aluminium oxide and seed crystal lifts the seed crystal if the seed crystal lower end is rounded；And/or the if oxygen
Change and precipitated crystal in the molten soup of aluminium, then increases power.
In a kind of achievable mode, in step 2, first prefixed time interval is 0.5~15min, preferably
It is 0.1~5mm, preferably 0.5~2mm for 1~10min and/or first preset height；And/or the preset diameters are
30~150mm, preferably 60~100mm.
In a kind of achievable mode, in step 3, the preset weight ratio is 8wt%~15wt%；And/or institute
Stating the second preset height is 2~5mm.
In a kind of achievable mode, in step 4, the preset weight ratio be the charge 70wt%~
80wt%.
In a kind of achievable mode, in steps of 5, the preset time is 8~12h；And/or the preset weight
Range is the alumina raw material charge ± 0.5~2kg, such as ± 1kg.
Method provided by the present application uses " pagoda type " seeding mode, and the method can effectively reduce top bubble range,
Simultaneously by proposing cutting sapphire crystal dislocation wink the defects of, to improve sapphire crystal quality and utilization rate.Meanwhile this Shen
The pulling rate of seed crystal is reduced to 0 in the expansion shoulder stage by the scheme that please be provided, and makes that free convection is presented in long crystal furnace, to keep sapphire brilliant
Transverse temperature gradient and longitudinal temperature gradient tend towards stability when body is grown, to reduce the sapphire due to caused by thermal perturbation
Thermal stress in crystal, and then the generation of dislocation, low angle boundary and big angle crystal boundary in sapphire crystal is reduced, reduce the wind of cracking
Long brilliant quality is improved, and brilliant intracorporal remnants are reduced by the design of reasonable radial symmetry gradient and transverse temperature gradient in danger
Stress realizes that the C of large-size sapphire is brilliant to length.In addition, the application uses " sitting pot " mode growing sapphire crystal, to subtract
Few later period ending bottom is buckled to the formation of bowl-shape bubble, compared with tradition proposes de- ending mode to pulling rate, side provided by the present application
Method is reduced during growing large-size sapphire crystal since the fracture of seed crystal caused by pot is glued in crystal bottom or collet is disconnected
The risk split.Further, the change adjust automatically pulling rate that the application weighs when annealing stage is according to annealing, is moved back to realize
The automation control in fiery stage reduces and manually guards risk that is improper and that overweight caused seed crystal or seedholder fracture occur.
Detailed description of the invention
Fig. 1 shows A and draws bar mode schematic diagram to growing sapphire crystal；
Fig. 2 shows C to draw bar mode schematic diagram to growing sapphire crystal.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The technical solution of the application described below.
The present invention, which is directed to, carries out deficiency of the sapphire C to crystal growing technology using kyropoulos, proposes a kind of novel sapphire C
To crystal growing technology, it can be achieved that large scale (e.g., 200kg or more) sapphire C is brilliant to length.Sapphire C provided by the present application to
Long crystal method the following steps are included:
Step 1, the crucible equipped with alumina raw material is put into furnace chamber, rear material is vacuumized to furnace chamber, obtains aluminium oxide
Molten soup.
It in the present embodiment, further include that inspection seed crystal is before the crucible that alumina raw material is housed is put into furnace chamber
No existing defects, the defect include: bubble, twin and crackle.Specifically, polariscope and strong photoelectric inspection can be used, see
It surveys with the presence or absence of bubble, twin and crackle etc. inside seed crystal, if the qualified seed crystal of the unqualified timely replacement of discovery seed crystal, to avoid seed
Transgranular there are excessive defects to be genetic in grown crystal, influences crystal quality.
In the present embodiment, the purity of the alumina raw material is 5N (i.e. 99.999%) or more, using such high-purity
Alumina raw material can reduce the defect of sapphire crystal obtained from source.
Crucible equipped with high-purity mangesium oxide aluminum feedstock is packed into sapphire furnace cavity, the sapphire furnace can be existing skill
Any one sapphire furnace in art, the sapphire furnace preoperation inspection its thermal field, heat protection screen, temperature sensor etc. whether just
Often, temperature deficiency or the unexpected generation of cooling etc. suddenly during sapphire crystal growth are avoided, sapphire crystal life is caused
Long failure.When sapphire furnace inspection finishes thing, closing furnace chamber is vacuumized.
In the present embodiment, make in furnace chamber vacuum degree lower than after 1e-4Pa after vacuumizing to furnace chamber, it is believed that take out true
Sky is completed.Then start material program.
In a kind of achievable mode, the material includes following sub-step:
Sub-step 1, according to predetermined power raising speed increased wattage to target power, heat preservation is until the oxygen under target power
Change aluminum feedstock is molten soup state.
In the present embodiment, the predetermined power raising speed can be determined according to aluminium oxide charge, it is specifically as follows 3~
10kw/h, preferably 5~7kw/h, e.g., for the charge of 400kg, the predetermined power can be 5.33kw/h, for small
The charge of amount can suitably reduce power raising speed.
Applicants have discovered that since alumina raw material is different from the expansion rate of crucible, specifically, the expansion speed of aluminium oxide
Rate is big, and the expansion rate of crucible is small, therefore, if predetermined power raising speed is excessive, will lead to aluminium oxide and overruns expansion, and then lead
Crucible is caused to be cracked, therefore, in the present embodiment, predetermined power raising speed selects 3~10kw/h.
In the present embodiment, the target power can also be determined according to aluminium oxide charge, it is specifically as follows 100~
150kw can suitably reduce target power for a small amount of charges for example, can be 120kw for the charge of 400kg.
Sub-step 2, the architecture heat preservation that sub-step 1 is obtained monitor the state of the alumina raw material, such as during incubation
There is crystal precipitation in the molten soup of aluminium oxide described in fruit, then continues to increase power, system is kept the temperature again after increasing power.
In the present embodiment, after being raised to target temperature by system and form molten soup, preparation system is kept the temperature, and every
The state of (such as 1 hour) observation system e.g., goes out if it find that precipitating crystal in the molten soup of aluminium oxide on molten soup surface for a period of time
Phenomena such as now floating brilliant or molding, then increase the heating power of system, and molten soup is made to restore molten condition.Continuous monitoring 5~10 is small
When, the molten soup of aluminium oxide is persistently kept molten by, then transfers seed crystal into molten soup.
Step 2, seed crystal is put into the molten soup of the aluminium oxide, it is default every mentioning seed crystal first first prefixed time interval wink
Highly, until the crystal diameter is preset diameters.
In the present embodiment, the molten soup of the aluminium oxide and seed are monitored during seed crystal being put into the molten soup of the aluminium oxide
Brilliant state shows that molten soup temperature is excessively high, seed crystal melts in the molten soup, and loses work if the seed crystal lower end is rounded
For the effect of growing sapphire crystal seed, therefore, it is necessary to lift the seed crystal to disengage it from the molten soup of aluminium oxide, and to the aluminium oxide
Molten soup cools down.Applicants have discovered that after the seed crystal is lifted to seed crystal bottom end and molten soup surface at a distance of 20~30mm,
Seed crystal will not be influenced by molten soup temperature again.In the case, operator can according to seed crystal by roasting position, seed crystal end situation,
Situations such as liquid stream form, to reduce heating power, so that can be kept molten by will not baking seed crystal for the molten soup.
Since the temperature of seed crystal itself is far below the temperature of the molten soup of aluminium oxide, moreover, generalling use the types of cooling such as water cooling
Seed crystal is set to be held in lower temperature, therefore, if during transferring seed crystal, if be precipitated in the molten soup of the aluminium oxide brilliant
Body such as aoxidizes aluminium surface and floating brilliant or molding occurs, then needs to increase heating power, the alumina solution is made to keep molten
State, to guarantee the best in quality of sapphire crystal.
It is constantly debugging repeatedly to suitable temperature, decentralization seed crystal and molten soup welding.After seed crystal and molten soup welding, institute
Stating system reduces heating power according to the specific range of decrease, and the specific range of decrease can be adjusted according to the speed of growth of crystal.
In the present embodiment, first prefixed time interval is 0.5~15min, preferably 1~10min；Described first
Preset height is 0.1~5mm, preferably 0.5~2mm.
Applicants have discovered that being conducive to pull out matter when the seed crystal grows 0.5~15min in the molten soup of the aluminium oxide
High brilliant disk is measured, the easy roastingization seed crystal if growth time is too long；And if growth time is too short, it can be washed due to seed crystal and not done
Only, finally obtained sapphire crystal is caused the defects of hollow, to deviate occur.When seed crystal is grown in the molten soup of the aluminium oxide
When 0.5~15min, seed crystal can not only be washed in crystalline substance completely by lifting the seed crystal upwards, and can be prolonged using reduction seed crystal is mentioned wink
The dislocation got off is stretched, the brilliant knot of high quality is obtained.
Applicant have also found that 0.1~5mm, especially 0.5~2mm are lifted every time, so that sapphire crystal is detached from molten soup
Part encounter quenching, so that the defects of making crystal dislocation that may be present in sapphire crystal, is cut off with quenching, from
And improve the quality of sapphire crystal.
The preset diameters are 30~150mm, preferably 60~100mm, when the sapphire crystal growth to the diameter
When, that is, facilitate operator to observe the form of sapphire crystal, thus monitoring growth process, be also convenient for the sapphire crystal later period after
Continuous growth.
Applicants have discovered that if process generally described above 20~50 times repeatedly, sapphire can be made brilliant using general seed crystal
Body diameter reaches about 60~100mm.
This such seeding methods provided by the present application can effectively reduce top bubble range, and can cut off crystal
The defects of dislocation, improves the product quality of sapphire crystal.
Step 3, pulling rate is reduced to 0, when crystal weight is the first preset weight ratio of charge, mentions crystal second wink
Preset height, and increase heating power, heating power is gradually decreased after increasing heating power, the long brilliant speed for controlling crystal is less than
Default long speed.
After the diameter of sapphire crystal reaches preset diameters, pulling rate is reduced to 0, that is, no longer lifting seed crystal, specific
The range of decrease reduces heating power, makes sapphire crystal carry out expanding shoulder growth, it is raw that the specific range of decrease can expand shoulder according to sapphire crystal
Long speed and adjust.
During expanding shoulder growth, sapphire crystal is voluntarily grown up, and in the process, monitors sapphire crystal
Weight can recognize according to charge and crucible diameter when the weight of sapphire crystal is 8wt%~15wt% of charge
It is completed to expand shoulder.
In the present embodiment, it completes after expanding shoulder, mentions 2~5mm of seed crystal wink, completion turns shoulder, and anti-rotation stop shoulder glues pot.
Further, after wink mentions, increase heating power, optionally, heating power increases by 400~800W, to prevent from expanding
Crystal block section glues pot when shoulder, increases heating power, makes viscous pot partial melting.
After increasing heating power, 0 is remained to the pulling rate of sapphire crystal, that is, sapphire crystal is not lifted,
Sapphire crystal is set to carry out isodiametric growth, maintaining the heating power range of decrease at this time is to expand the specific range of decrease of shoulder growth phase.
In the present embodiment, during sapphire crystal isodiametric growth, heating power is gradually decreased, to control sapphire
The long speed of crystal is between 1.5kg/h~3kg/h.
Applicants have discovered that the sapphire crystal bubble grown increases when the long speed of sapphire crystal is greater than 3kg/h
Add, cracking risk increase, influences utilization rate of crystal；When long speed is less than 1.5kg/h, grows back and melt line increase, influence crystal and take
Material rate, meanwhile, growth cycle increases, and energy consumption is larger.Therefore, the long speed of the present embodiment control sapphire crystal 1.5kg/h~
Between 3kg/h.
In the present embodiment, the range of decrease of temperature in growth furnace, optionally, institute are controlled by controlling the range of decrease of heating power
The range of decrease for stating heating power is 10~80w/h, thus
Step 4, when crystal weight is greater than the second preset weight ratio, being averaged in the crystal nearest 24 hours is calculated
Long speed v calculates remaining growth time h using following formula I according to the average length speed v, also, continues to cool down with current range of decrease rate
H hours:
H=Δ w/v Formulas I
Wherein, h indicates remaining growth time,
Δ w indicates the weight of the molten soup of remaining aluminium oxide, is specifically as follows oxygen aluminum feedstock charge and subtracts sapphire crystal weight
The difference of amount；
V indicates the average long speed in the crystal nearest 24 hours.
In the present embodiment, the second preset weight ratio is 70wt%~80wt% of the charge.For example, such as
Fruit charge is 400kg, then when the weight of sapphire crystal is 350kg, it is believed that the long speed inaccuracy calculated by weighing, then
It needs to calculate remaining growth time by above-mentioned Formulas I.
Applicants have discovered that sapphire crystal isodiametric growth stage, the especially later period of isodiametric growth, in nearest 24
The speed of growth is almost stablized constant, therefore, can estimate the remaining speed of growth according to nearest 24 hours average speed, then benefit
Remaining growth time is calculated with alumina raw material surplus, can relatively accurately estimate remaining growth time, so as to
The time for sitting pot growth is enough better grasped, the quality of sapphire crystal is improved.
In the present embodiment step 4, after the growth time of sapphire crystal reaches the time h of estimation, sapphire is reduced
Heating power, carry out annealing stage, that is, step 5.
Step 5, the position of crystal is adjusted according to the weight of crystal, until crystal weight is stable to default within a preset time
Weight range.
In the present embodiment, the position of the crystal refers to the relative position of sapphire crystal Yu the molten soup of aluminium oxide, that is, is
Lifting upwards, or decentralization.
In the present embodiment, the annealing stage control annealing time is 150h~200h, that is, is reduced to from current power
Power is 0, and total time used is 150h~200h,
Since the application is by the way of " sitting pot " growth, the sapphire crystal described in annealing stage may be due to
It is more than charge that bottom, which glues crucible and its weight is shown, when the weight of sapphire crystal is more than the 5wt% of charge, is needed
Transfer sapphire crystal；It again may be since in decentralization process, crystal bottom, which touches crucible, causes the weight of sapphire crystal aobvious
Show lower than charge, as the 5wt% for weighing less than charge of sapphire crystal, needs to stop to transfer sapphire crystal.
In the present embodiment, the preset time is 8~12h, such as 10h；The preset weight range is the aluminium oxide
Raw material charge ± 0.5~2kg, such as ± 1kg.That is, regardless of whether annealing is completed, as long as the weight of the sapphire crystal exists
± 0.5~2kg of charge is stable in 8~12h, i.e., it is believed that sapphire crystal has taken off pot, after the completion of to be annealed
Take out crystal.
Method provided by the present application is by the design of reasonable radial symmetry gradient and transverse temperature gradient to reduce crystal
Interior residual stress realizes that the C of large-size sapphire is brilliant to length to the design of crystal growing technology by C.
Embodiment
Embodiment 1
1. seed crystal detects: after getting seed crystal, with polariscope and strong photoelectric inspection, observe inside seed crystal with the presence or absence of bubble,
Twin and crackle etc., if the qualified seed crystal of the unqualified timely replacement of discovery seed crystal, to avoid there are excessive defects to be genetic in seed crystal
In grown crystal, crystal quality is influenced.
2. charging: using purity for the high-purity mangesium oxide aluminum feedstock 450kg of 5N, be placed in crucible, crucible is packed into blue
Jewel is grown in furnace cavity, and whether thermal field, heat protection screen, temperature sensor for checking growth furnace etc. be normal, is closed furnace chamber and is taken out very
It is empty.
3. material: when the vacuum degree of growth furnace reaches 1e-4pa, completion is vacuumized, starts automatic material program, wherein
Material power rises to 120kw with the rate of 5.33kw/h.
4. seeding: the liquid-flow state of the observation molten soup of growth furnace internal oxidition aluminium, on top, molten soup is 2050 DEG C of decentralization seed crystals,
During seed crystal decline, not by roasting circle, the liquid level of the molten soup of aluminium oxide does not also occur floating crystalline substance for seed crystal lower end.Every 10min wink mentions seed crystal
2mm is mentioned 40 times or so altogether, sapphire crystal diameter about 60mm obtained.
5. expanding shoulder growth: 0 will be reduced to the pulling rate of seed crystal, completed as the 8wt% of sapphire crystal weight to charge
Expand shoulder.It mentions seed crystal 2mm wink at this time, increases heating power 400w.
6. isodiametric growth: the control power range of decrease is 10~80w/h, so that controlling long speed is 1.5kg/h.
7. finishing phase: keeping being 0 to the pulling rate of seed crystal, using " sitting pot " mode growing sapphire crystal.Claim in crystal
It weighs to after 350kg, calculates average long speed v=2.4kg/h interior for 24 hours before this, calculate remaining growth time h=Δ w/v=50/
2.4=20.8h.
8. annealing stage: when showing that weight is more than the 5% of charge, transferring crystal automatically；When display weighs less than dress
Doses 5% when, stop decentralization.Until the display weight of crystal is stablized in 10h to charge ± 1kg, it is believed that crystal takes off pot,
Crystal annealing is completed in control annealing total time in 150h~200h, takes out crystal.
Comparative example
1 traditional scheme C of comparative example is to preparing sapphire crystal
Alumina raw material described in this comparative example in embodiment alumina raw material used and dosage it is all the same, the seed crystal
Also suitable with seed crystal used in embodiment 1.
Method used in this comparative example is specific as follows:
1. seed crystal detects: after getting seed crystal, with polariscope and strong photoelectric inspection, observe inside seed crystal with the presence or absence of bubble,
Twin and crackle etc., if the qualified seed crystal of the unqualified timely replacement of discovery seed crystal, to avoid there are excessive defects to be genetic in seed crystal
In grown crystal, crystal quality is influenced.
2. charging: using purity for the high-purity mangesium oxide aluminum feedstock 200kg of 5N, be placed in crucible, crucible is packed into blue
Jewel is grown in furnace cavity, and whether thermal field, heat protection screen, temperature sensor for checking growth furnace etc. be normal, is closed furnace chamber and is taken out very
It is empty.
3. material: when the vacuum degree of growth furnace reaches 1e-4pa, completion is vacuumized, starts automatic material program, wherein
Material power rises to 95kw with the rate of 4.4kw/h.
4. seeding: the liquid-flow state of the observation molten soup of growth furnace internal oxidition aluminium, on top, molten soup is 2050 DEG C of decentralization seed crystals,
During seed crystal decline, not by roasting circle, the liquid level of the molten soup of aluminium oxide does not also occur floating crystalline substance for seed crystal lower end.Seed crystal is transferred, crystalline substance, seed are washed
Crystalline substance insertion liquid level 15mm is hereinafter, complete seeding with 0.1mm/h pulling rate.
5. expanding shoulder growth: the pulling rate 0.15mm/h to seed crystal completes to expand shoulder when sapphire crystal weight is 18.5kg.
6. isodiametric growth: the control power range of decrease is 10~80w/h, so that controlling long speed is 1.3kg/h.
7. finishing phase: pulling rate being changed to 0.3mm/h, when crystal weight is constant within 5h, it is believed that crystal takes off pot at this time.
8. annealing stage: increasing the range of decrease, crystal annealing is completed in 150h.
The performance of sapphire crystal made from the embodiment of the present application 1 and comparative example 1 is detected respectively, as a result as shown in table 1 below:
Sapphire crystal performance comparison result made from the different preparation methods of table 1
By above-mentioned table 1 it is found that being compared with the traditional method, using method provided by the present application as C to growth made from indigo plant
Gem crystal, crystal defect significantly reduce, and dislocation density is substantially reduced, and utilization rate of crystal dramatically increases.
Combine detailed description and exemplary example that the application is described in detail above, but these explanations are simultaneously
It should not be understood as the limitation to the application.It will be appreciated by those skilled in the art that without departing from the application spirit and scope,
A variety of equivalent substitution, modification or improvements can be carried out to technical scheme and embodiments thereof, these each fall within the application
In the range of.The protection scope of the application is determined by the appended claims.
Claims (10)
1. a kind of sapphire C is to long crystal method, which is characterized in that the described method comprises the following steps:
Step 1, the crucible equipped with alumina raw material is put into furnace chamber, rear material is vacuumized to furnace chamber, obtains the molten soup of aluminium oxide；
Step 2, seed crystal is put into the molten soup of the aluminium oxide, it is default high every mentioning seed crystal first first prefixed time interval wink
Degree, until the crystal diameter is preset diameters；
Step 3, pulling rate is reduced to 0, when crystal weight is the first preset weight ratio of charge, it is default mentions crystal second wink
Highly, and increase heating power, gradually decrease heating power after increasing heating power, the long brilliant speed for controlling crystal, which is less than, to be preset
Long speed；
Step 4, when crystal weight is greater than the second preset weight ratio, the average long speed in the crystal nearest 24 hours is calculated
V calculates remaining growth time h using following formula I according to the average length speed v, also, small with the current range of decrease rate h that continues to cool down
When:
H=Δ w/v Formulas I
Wherein, h indicates remaining growth time,
Δ w indicates the weight of the molten soup of remaining aluminium oxide,
V indicates the average long speed in the crystal nearest 24 hours；
Step 5, the position of crystal is adjusted according to the weight of crystal, until crystal weight is stable to preset weight within a preset time
Range.
2. the method according to claim 1, wherein in step 1,
The purity of the alumina raw material is 5N or more,
Rear vacuum degree is vacuumized lower than 1e-4Pa to furnace chamber.
3. method according to claim 1 or 2, which is characterized in that in step 1, the material includes following sub-step:
Sub-step 1, according to predetermined power raising speed increased wattage to target power, heat preservation is former to the aluminium oxide under target power
Material is molten soup state；
Sub-step 2, the architecture heat preservation that sub-step 1 is obtained monitor the state of the alumina raw material during incubation, if institute
Stating in the molten soup of aluminium oxide has crystal precipitation, then continues to increase power, keep the temperature again to system after increasing power.
4. method according to any one of claims 1 to 3, which is characterized in that in sub-step 1,
The predetermined power raising speed is 3~10kw/h；And/or
In sub-step 2, when continuing to increase power, the raising speed of power is 500w/h~1000w/h.
5. method according to any one of claims 1 to 4, which is characterized in that in step 1, aluminium oxide original will be housed
It further include examining seed crystal with the presence or absence of defect, the defect includes: bubble, twin and splits before the crucible of material is put into furnace chamber
Line.
6. method according to any one of claims 1 to 5, which is characterized in that in step 2,
The state that the molten soup of the aluminium oxide and seed crystal are monitored during seed crystal is put into the molten soup of the aluminium oxide, if described
Seed crystal lower end is rounded, then lifts the seed crystal；If precipitated crystal in the molten soup of aluminium oxide, increase power.
7. method according to any one of claims 1 to 6, which is characterized in that in step 2,
First prefixed time interval is that first prefixed time interval is 0.5~15min, preferably 1~10min；With/
Or
First preset height is 0.1~5mm, preferably 0.5~2mm；And/or
The preset diameters are 30~150mm, preferably 60~100mm.
8. method according to any one of claims 1 to 7, which is characterized in that in step 3,
First preset weight ratio is 8wt%~15wt%；And/or
Second preset height is 2~5mm.
9. method according to any one of claims 1 to 8, which is characterized in that in step 4, second preset weight
Ratio is 70wt%~80wt% of the charge.
10. method according to any one of claims 1 to 9, which is characterized in that in steps of 5,
The preset time is 8~12h；And/or
The preset weight range is the alumina raw material charge ± 0.5~2kg.
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|---|---|---|---|---|
| CN103103604A (en) * | 2013-01-24 | 2013-05-15 | 天通控股股份有限公司 | Manufacturing method of large-size C-oriented sapphire crystals |
| JP2013209257A (en) * | 2012-03-30 | 2013-10-10 | Sumco Corp | Sapphire single crystal and method for producing the same |
| CN105671630A (en) * | 2015-12-17 | 2016-06-15 | 南京晶升能源设备有限公司 | Ending method for growth of sapphire crystal through kyropoulos method and growth method |
| CN108315812A (en) * | 2018-05-10 | 2018-07-24 | 内蒙古恒嘉晶体材料有限公司 | A kind of method of kyropoulos growing sapphire crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013209257A (en) * | 2012-03-30 | 2013-10-10 | Sumco Corp | Sapphire single crystal and method for producing the same |
| CN103103604A (en) * | 2013-01-24 | 2013-05-15 | 天通控股股份有限公司 | Manufacturing method of large-size C-oriented sapphire crystals |
| CN105671630A (en) * | 2015-12-17 | 2016-06-15 | 南京晶升能源设备有限公司 | Ending method for growth of sapphire crystal through kyropoulos method and growth method |
| CN108315812A (en) * | 2018-05-10 | 2018-07-24 | 内蒙古恒嘉晶体材料有限公司 | A kind of method of kyropoulos growing sapphire crystal |
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