CN104328498A - Automatic integrated control process for sapphire single crystal growth - Google Patents
Automatic integrated control process for sapphire single crystal growth Download PDFInfo
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- CN104328498A CN104328498A CN201410696057.XA CN201410696057A CN104328498A CN 104328498 A CN104328498 A CN 104328498A CN 201410696057 A CN201410696057 A CN 201410696057A CN 104328498 A CN104328498 A CN 104328498A
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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
- C30B15/20—Controlling or regulating
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Abstract
The invention relates to an automatic integrated control process for sapphire single crystal growth. The process comprises the following steps: mounting a weighing sensor and a temperature sensor on a sapphire growth furnace, automatically reading the actual crystal weight obtained by the weighing sensor, comparing crystal growth curve parameters introduced into the system, and adjusting the output power, so that the aim of controlling automatic crystal growth is achieved; performing automatic regulation and control by utilizing the mounted temperature sensor, a water flow sensor and a water pressure transducer to realize automatic integrated control of parameters such as water temperature, water pressure, pulling rate and rotating speed needed by sapphire crystal growth, so that stable crystal growth is guaranteed, and the crystal quality is improved. Meanwhile, according to the designed special man-machine operating system, the operability of equipment can be obviously improved, the dependence of the original sapphire growth on a human body is reduced, lots of manpower and material resources are saved, and the production cost is reduced.
Description
Technical field
The present invention relates to a kind of Sapphire Crystal Growth automatization Comprehensive Control technique, belong to technical field of crystal growth.
Background technology
Sapphire single-crystal has that the transparency is good, physical strength is high, chemical stability is excellent and the heat-conductive characteristic superior over-all properties such as good, and first it has the hardness of superelevation and extremely low frictional coefficient, and nature is only second to diamond; It has high optical transmittance in ultra wide wave band (300nm ~ 5000nm); Sapphire single-crystal also has excellent antiacid caustic corrosion ability, even all cannot be etched under molten state, therefore sapphire single-crystal just arises at the historic moment as the commercial applications of high-end photoelectron material under general soda acid normal temperature.
The crystal growth of current sapphire crystal especially more than 80 feather weight, large to Personnel Dependence degree, and growth furnace operation interface is complicated, automation degree of equipment is low, the operation of tyro's GPRS whole plant at least needs 3-6 month, most crystal growing furnace needs operator with the naked eye to observe, for a long time facing to high-temperature fusant, very large to the eyesight influence of operator.For overcoming the above problems, existing part Chang Jing producer research and development automated control technology carries out long crystalline substance at present, but Automated condtrol precision is general not high, and there is only part stage (seeding and shouldering stage except) and adopt Automated condtrol, or only for the problem of Automated condtrol technique of heating and cooling power and the setting of crystal weight two parameter, systematically do not carry out the automatization integrated control method of crystal growth.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of Sapphire Crystal Growth automatization Comprehensive Control technique is provided, realize the automatization Comprehensive Control of crystal growth, and control accuracy is high.
According to technical scheme provided by the invention, a kind of Sapphire Crystal Growth automatization Comprehensive Control technique, it is characterized in that: on sapphire growth furnace, install LOAD CELLS, temperature sensor, water flow sensor, hydraulic pressure transmitter, LOAD CELLS, temperature sensor, water flow sensor are all connected with operating system with hydraulic pressure transmitter; Specific embodiment is as follows:
(1) feed: high-purity mangesium oxide aluminum feedstock is put into crucible, crucible is put into sapphire and generate stove, closed furnace door;
(2) heat up: carry out taking out rough vacuum operation, when vacuum tightness reaches 1 ~ 1.5 × 10
-3during Pa, proceed to pumping high vacuum operation; When vacuum tightness reaches 2 ~ 8 × 10
-3during Pa, start heating system, control output rating to increase with the speed of 0.1 ~ 0.5kW/h, last 20 ~ 30h, when detecting that in-furnace temperature reaches 2050 DEG C, stop increasing output rating, in 3 ~ 5 hours crucibles, raw material is fused into high temperature solution completely, then keeps melt temperature to stablize 4 ~ 6 hours;
(3) seeding: under shake seed crystal contact liquid level, keep in-furnace temperature, and control variable power at ± 1 ~ 5kW, controlling crystalline style lift velocity is 500-1000r/h, and speed of rotation is 200-500r/h, seed crystal is pulled out thin neck that length is 30-40mm;
(4) shouldering, isodiametric growth: in shouldering, isodiametric growth process, operating system compares the time every a unit, compare crystal actual growth weight and theoretical growth weight, the ratio according to crystal actual growth weight and theoretical growth weight carries out lift adjustment to the temperature in stove; Automatically adjust crystalline style, burner hearth water temperature and pull rate according to residing Different growth phases, to meet the thermograde required for crystal growth simultaneously; Concrete technology optimum configurations is:
A, shouldering stage, it is 3 ~ 5 minutes that unit compares the time, and now crystalline style water temperature controls at 35 ~ 40 DEG C, and burner hearth water temperature controls at 30 ~ 35 DEG C, and pull rate controls at 1-1.5mm/h;
In the described shouldering stage: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, operating system controls to keep constant temperature after power rises 0.3 ~ 0.6kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0kW/h < rate of temperature fall≤0.3kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.3kW/h < rate of temperature fall≤0.6kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.6kW/h < rate of temperature fall≤1kW/h;
B, isometrical early stage, it is 5 ~ 15 minutes that unit compares the time, and now crystalline style water temperature controls at 40 ~ 45 DEG C, and burner hearth water temperature controls at 35 ~ 40 DEG C, and pull rate controls at 0.8-1.2mm/h;
In described isometrical early stage: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, operating system controls to keep constant temperature after power rises 0.4 ~ 0.8kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0kW/h < rate of temperature fall≤0.3kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.3kW/h < rate of temperature fall≤0.5kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.5kW/h < rate of temperature fall≤0.8kW/h;
C, isometrical later stage, it is 15 ~ 30 minutes that unit compares the time, and now crystalline style water temperature controls at 45 ~ 50 DEG C, and burner hearth water temperature controls at 40 ~ 45 DEG C, and pull rate controls at 0.4-0.8mm/h;
The described isometrical later stage refers to that the ratio of real crystal weight and original charge weight is 50% ~ 95%; When the ratio of real crystal weight and original charge weight is 50% ~ 80%, the method of operating system heating and cooling adjustment is: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, and operating system controls to keep constant temperature after power rises 0.5 ~ 1kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0kW/h < rate of temperature fall≤0.2kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.2kW/h < rate of temperature fall≤0.4kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.4kW/h < rate of temperature fall≤0.6kW/h;
When the ratio of real crystal weight and original charge weight is 80% ~ 90%, the method of operating system heating and cooling adjustment is: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, and operating system controls to keep constant temperature after power rises 0.5 ~ 1kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is less than 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.1kW/h < rate of temperature fall≤0.3kW/h;
When the ratio of real crystal weight and original charge weight is 90% ~ 95%, keep power constant, continue to mention crystal after 2 ~ 3 hours and enter ending;
(5) finish up, anneal: above shake crystalline style 10 ~ 20mm, after making crystal depart from liquid level, enter the cooling down stage, automatic inflating after completing, terminate growth.
Further, in whole process of growth, hydraulic pressure remains on 0.12 ~ 0.18MPa.
Further, the described shouldering stage refers to that real crystal weight is 0 ~ 15% of original charge weight.
Further, described operating system compares the time every a unit, compares a crystal actual growth weight and theoretical growth weight, and according to the ratio of crystal actual growth weight with theoretical growth weight, adjusts a power.
Beneficial effect of the present invention:
The present invention by installing LOAD CELLS, temperature sensor on sapphire growth furnace, the crystal actual weight that automatic reading LOAD CELLS claims, the crystal growth parameter of curve imported in comparison system, adjustment output rating reaches the object controlling crystal automatization growth, and utilize temperature sensor, water flow sensor and the hydraulic pressure transmitter installed to carry out auto-control, realize water temperature hydraulic pressure needed for sapphire crystal growth, the isoparametric automatization Comprehensive Control of pulling rate rotating speed, ensure that the stable growth of crystal, improve crystal mass.Meanwhile, the special man-machine operation system of design can significantly improve operation of equipment, reduces the dependency of original sapphire growth to people, saves a large amount of manpower and materials, reduces production cost.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment one: a kind of Sapphire Crystal Growth automatization Comprehensive Control technique, sapphire growth furnace is installed LOAD CELLS (weight precision is 100,000/), temperature sensor (temperature-controlled precision is 0.1 DEG C), water flow sensor, hydraulic pressure transmitter, LOAD CELLS, temperature sensor, water flow sensor is all connected with operating system with hydraulic pressure transmitter, operating system reads the crystal actual weight that LOAD CELLS claims, contrast crystal growth curve, adjustment output rating, temperature and discharge, make crystal according to given process automatic growth, specific embodiment is as follows:
(1) feed: high-purity mangesium oxide aluminum feedstock is put into crucible, crucible is put into sapphire and generate stove, closed furnace door;
(2) heat up: start the operating system, carry out taking out rough vacuum operation, when vacuum tightness reaches 1 × 10
-3during Pa, proceed to pumping high vacuum operation; When vacuum tightness reaches 2 × 10
-3during Pa, start heating system, control output rating to increase with the speed of 0.1kW/h, last 30h, when detecting that in stove, (mouth of pot position) temperature reaches 2050 DEG C, stop increasing output rating, in 3 hours crucibles, raw material is fused into high temperature solution completely, then keeps melt temperature to stablize 4 hours;
(3) seeding: under shake seed crystal contact liquid level, keep in-furnace temperature, and control variable power at ± 1kW, controlling crystalline style lift velocity is 500r/h, and speed of rotation is 200r/h, seed crystal is pulled out thin neck that length is 30mm;
(4) shouldering, isodiametric growth: enter after seeding terminates and automatically control process of growth, now operating system enters Full-automatic monitoring state; In shouldering, isodiametric growth process, operating system compares the time every a unit, and according to crystal actual growth weight and the theoretical ratio growing weight, carry out lift adjustment to the temperature in stove, concrete inflation method is as shown in table 1; Automatically adjust crystalline style, burner hearth water temperature and pull rate according to residing Different growth phases, to meet the thermograde required for crystal growth simultaneously; Concrete technology optimum configurations is:
A, shouldering stage (crystal weight is 0 ~ 15% of charge weight), it is 5 minutes that unit compares the time, needs larger thermograde, and now crystalline style water temperature controls at 40 DEG C, and burner hearth water temperature controls at 35 DEG C, and pull rate controls at 1.5mm/h;
In the described shouldering stage: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, operating system controls to keep constant temperature after power rises 0.3kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.1kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.4kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.7kW/h;
B, isometrical early stage, it is 5 minutes that unit compares the time, and now crystalline style water temperature controls at 40 DEG C, and burner hearth water temperature controls at 35 DEG C, and pull rate controls at 1.2mm/h;
In described isometrical early stage: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, operating system controls to keep constant temperature after power rises 0.4kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.1kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.4kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.6kW/h;
C, isometrical later stage, it is 15 minutes that unit compares the time, and now crystalline style water temperature controls at 45 DEG C, and burner hearth water temperature controls at 40 DEG C, and pull rate controls at 0.8mm/h;
The described isometrical later stage refers to that the ratio of real crystal weight and original charge weight is 50% ~ 95%; When the ratio of real crystal weight and original charge weight is 50% ~ 80%, the method of operating system heating and cooling adjustment is: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, and operating system controls to keep constant temperature after power rises 0.5kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.1kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.3kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.5kW/h;
When the ratio of real crystal weight and original charge weight is 80% ~ 90%, the method of operating system heating and cooling adjustment is: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, and operating system controls to keep constant temperature after power rises 0.5kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is less than 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.2kW/h;
When the ratio of real crystal weight and original charge weight is 90% ~ 95%, keep power constant, continue to mention crystal after 2 hours and enter ending;
Heating and cooling method in step (4) shouldering isodiametric growth process is as shown in table 1:
Table 1
(5) finish up, anneal: above shake crystalline style 10mm, after making crystal depart from liquid level, enter the cooling down stage, automatic inflating after completing, terminate growth.
For controlling the stability of water temperature, in whole process of growth, system controls within hydraulic pressure remains on 0.12MPa automatically.
Embodiment two: a kind of Sapphire Crystal Growth automatization Comprehensive Control technique, sapphire growth furnace is installed LOAD CELLS (weight precision is 100,000/), temperature sensor (temperature-controlled precision is 0.1 DEG C), water flow sensor, hydraulic pressure transmitter, LOAD CELLS, temperature sensor, water flow sensor is all connected with operating system with hydraulic pressure transmitter, operating system reads the crystal actual weight that LOAD CELLS claims, contrast crystal growth curve, adjustment output rating, temperature and discharge, make crystal according to given process automatic growth, specific embodiment is as follows:
(1) feed: high-purity mangesium oxide aluminum feedstock is put into crucible, crucible is put into sapphire and generate stove, closed furnace door;
(2) heat up: start the operating system, carry out taking out rough vacuum operation, when vacuum tightness reaches 1.5 × 10
-3during Pa, proceed to pumping high vacuum operation; When vacuum tightness reaches 8 × 10
-3during Pa, start heating system, control output rating to increase with the speed of 0.5kW/h, last 20h, when detecting that in stove, (mouth of pot position) temperature reaches 2050 DEG C, stop increasing output rating, in 5 hours crucibles, raw material is fused into high temperature solution completely, then keeps melt temperature to stablize 6 hours;
(3) seeding: under shake seed crystal contact liquid level, keep in-furnace temperature, and control variable power at ± 5kW, controlling crystalline style lift velocity is 1000r/h, and speed of rotation is 500r/h, seed crystal is pulled out thin neck that length is 40mm;
(4) shouldering, isodiametric growth: enter after seeding terminates and automatically control process of growth, now operating system enters Full-automatic monitoring state; In shouldering, isodiametric growth process, operating system compares the time every a unit, and according to crystal actual growth weight and the theoretical ratio growing weight, carry out lift adjustment to the temperature in stove, concrete inflation method is as shown in table 1; Automatically adjust crystalline style, burner hearth water temperature and pull rate according to residing Different growth phases, to meet the thermograde required for crystal growth simultaneously; Concrete technology optimum configurations is:
A, shouldering stage, it is 5 minutes that unit compares the time, and now crystalline style water temperature controls at 40 DEG C, and burner hearth water temperature controls at 35 DEG C, and pull rate controls at 1mm/h;
In the described shouldering stage: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, operating system controls to keep constant temperature after power rises 0.6kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.3kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.6kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 1kW/h;
B, isometrical early stage, it is 15 minutes that unit compares the time, and now crystalline style water temperature controls at 45 DEG C, and burner hearth water temperature controls at 40 DEG C, and pull rate controls at 0.8mm/h;
In described isometrical early stage: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, operating system controls to keep constant temperature after power rises 0.4 ~ 0.8kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.3kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.5kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.8kW/h;
C, isometrical later stage, it is 30 minutes that unit compares the time, and now crystalline style water temperature controls at 50 DEG C, and burner hearth water temperature controls at 45 DEG C, and pull rate controls at 0.4mm/h;
The described isometrical later stage refers to that the ratio of real crystal weight and original charge weight is 50% ~ 95%; When the ratio of real crystal weight and original charge weight is 50% ~ 80%, the method of operating system heating and cooling adjustment is: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, and operating system controls to keep constant temperature after power rises 1kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.2kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.4kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.6kW/h;
When the ratio of real crystal weight and original charge weight is 80% ~ 90%, the method of operating system heating and cooling adjustment is: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, and operating system controls to keep constant temperature after power rises 0.5 ~ 1kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is less than 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.3kW/h;
When the ratio of real crystal weight and original charge weight is 90% ~ 95%, keep power constant, continue to mention crystal after 3 hours and enter ending;
(5) finish up, anneal: above shake crystalline style 20mm, after making crystal depart from liquid level, enter the cooling down stage, automatic inflating after completing, terminate growth.
For controlling the stability of water temperature, in whole process of growth, system controls within hydraulic pressure remains on 0.18MPa automatically.
Embodiment three: a kind of Sapphire Crystal Growth automatization Comprehensive Control technique, sapphire growth furnace is installed LOAD CELLS (weight precision is 100,000/), temperature sensor (temperature-controlled precision is 0.1 DEG C), water flow sensor, hydraulic pressure transmitter, LOAD CELLS, temperature sensor, water flow sensor is all connected with operating system with hydraulic pressure transmitter, operating system reads the crystal actual weight that LOAD CELLS claims, contrast crystal growth curve, adjustment output rating, temperature and discharge, make crystal according to given process automatic growth, specific embodiment is as follows:
(1) feed: high-purity mangesium oxide aluminum feedstock is put into crucible, crucible is put into sapphire and generate stove, closed furnace door;
(2) heat up: start the operating system, carry out taking out rough vacuum operation, when vacuum tightness reaches 1.2 × 10
-3during Pa, proceed to pumping high vacuum operation; When vacuum tightness reaches 5 × 10
-3during Pa, start heating system, control output rating to increase with the speed of 0.4kW/h, last 25h, when detecting that in stove, (mouth of pot position) temperature reaches 2050 DEG C, stop increasing output rating, in 4 hours crucibles, raw material is fused into high temperature solution completely, then keeps melt temperature to stablize 5 hours;
(3) seeding: under shake seed crystal contact liquid level, keep in-furnace temperature, and control variable power at ± 4kW, controlling crystalline style lift velocity is 600r/h, and speed of rotation is 300r/h, seed crystal is pulled out thin neck that length is 35mm;
(4) shouldering, isodiametric growth: enter after seeding terminates and automatically control process of growth, now operating system enters Full-automatic monitoring state; In shouldering, isodiametric growth process, operating system compares the time every a unit, and according to crystal actual growth weight and the theoretical ratio growing weight, carry out lift adjustment to the temperature in stove, concrete inflation method is as shown in table 1; Automatically adjust crystalline style, burner hearth water temperature and pull rate according to residing Different growth phases, to meet the thermograde required for crystal growth simultaneously; Concrete technology optimum configurations is:
A, shouldering stage, it is 4 minutes that unit compares the time, and now crystalline style water temperature controls at 36 DEG C, and burner hearth water temperature controls at 32 DEG C, and pull rate controls at 1.2mm/h;
In the described shouldering stage: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, operating system controls to keep constant temperature after power rises 0.5kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.2kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.5kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.8kW/h;
B, isometrical early stage, it is 10 minutes that unit compares the time, and now crystalline style water temperature controls at 42 DEG C, and burner hearth water temperature controls at 36 DEG C, and pull rate controls at 1mm/h;
In described isometrical early stage: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, operating system controls to keep constant temperature after power rises 0.6kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.2kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.4kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.7kW/h;
C, isometrical later stage, it is 20 minutes that unit compares the time, and now crystalline style water temperature controls at 46 DEG C, and burner hearth water temperature controls at 42 DEG C, and pull rate controls at 0.6mm/h;
The described isometrical later stage refers to that the ratio of real crystal weight and original charge weight is 50% ~ 95%; When the ratio of real crystal weight and original charge weight is 50% ~ 80%, the method of operating system heating and cooling adjustment is: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, and operating system controls to keep constant temperature after power rises 0.8kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.1kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.3kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.5kW/h;
When the ratio of real crystal weight and original charge weight is 80% ~ 90%, the method of operating system heating and cooling adjustment is: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, and operating system controls to keep constant temperature after power rises 0.6kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is less than 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.2kW/h;
When the ratio of real crystal weight and original charge weight is 90% ~ 95%, keep power constant, continue to mention crystal after 2.5 hours and enter ending;
(5) finish up, anneal: above shake crystalline style 15mm, after making crystal depart from liquid level, enter the cooling down stage, automatic inflating after completing, terminate growth.
For controlling the stability of water temperature, in whole process of growth, system controls within hydraulic pressure remains on 0.16MPa automatically.
Claims (4)
1. a Sapphire Crystal Growth automatization Comprehensive Control technique, it is characterized in that: on sapphire growth furnace, install LOAD CELLS, temperature sensor, water flow sensor, hydraulic pressure transmitter, LOAD CELLS, temperature sensor, water flow sensor are all connected with operating system with hydraulic pressure transmitter; Specific embodiment is as follows:
(1) feed: high-purity mangesium oxide aluminum feedstock is put into crucible, crucible is put into sapphire and generate stove, closed furnace door;
(2) heat up: carry out taking out rough vacuum operation, when vacuum tightness reaches 1 ~ 1.5 × 10
-3during Pa, proceed to pumping high vacuum operation; When vacuum tightness reaches 2 ~ 8 × 10
-3during Pa, start heating system, control output rating to increase with the speed of 0.1 ~ 0.5kW/h, last 20 ~ 30h, when detecting that in-furnace temperature reaches 2050 DEG C, stop increasing output rating, in 3 ~ 5 hours crucibles, raw material is fused into high temperature solution completely, then keeps melt temperature to stablize 4 ~ 6 hours;
(3) seeding: under shake seed crystal contact liquid level, keep in-furnace temperature, and control variable power at ± 1 ~ 5kW, controlling crystalline style lift velocity is 500-1000r/h, and speed of rotation is 200-500r/h, seed crystal is pulled out thin neck that length is 30-40mm;
(4) shouldering, isodiametric growth: in shouldering, isodiametric growth process, operating system compares the time every a unit, compare crystal actual growth weight and theoretical growth weight, the ratio according to crystal actual growth weight and theoretical growth weight carries out lift adjustment to the temperature in stove; Automatically adjust crystalline style, burner hearth water temperature and pull rate according to residing Different growth phases, to meet the thermograde required for crystal growth simultaneously; Concrete technology optimum configurations is:
A, shouldering stage, it is 3 ~ 5 minutes that unit compares the time, and now crystalline style water temperature controls at 35 ~ 40 DEG C, and burner hearth water temperature controls at 30 ~ 35 DEG C, and pull rate controls at 1-1.5mm/h;
In the described shouldering stage: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, operating system controls to keep constant temperature after power rises 0.3 ~ 0.6kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0kW/h < rate of temperature fall≤0.3kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.3kW/h < rate of temperature fall≤0.6kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.6kW/h < rate of temperature fall≤1kW/h;
B, isometrical early stage, it is 5 ~ 15 minutes that unit compares the time, and now crystalline style water temperature controls at 40 ~ 45 DEG C, and burner hearth water temperature controls at 35 ~ 40 DEG C, and pull rate controls at 0.8-1.2mm/h;
In described isometrical early stage: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, operating system controls to keep constant temperature after power rises 0.4 ~ 0.8kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0kW/h < rate of temperature fall≤0.3kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.3kW/h < rate of temperature fall≤0.5kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.5kW/h < rate of temperature fall≤0.8kW/h;
C, isometrical later stage, it is 15 ~ 30 minutes that unit compares the time, and now crystalline style water temperature controls at 45 ~ 50 DEG C, and burner hearth water temperature controls at 40 ~ 45 DEG C, and pull rate controls at 0.4-0.8mm/h;
The described isometrical later stage refers to that the ratio of real crystal weight and original charge weight is 50% ~ 95%; When the ratio of real crystal weight and original charge weight is 50% ~ 80%, the method of operating system heating and cooling adjustment is: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, and operating system controls to keep constant temperature after power rises 0.5 ~ 1kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is 80% ~ 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0kW/h < rate of temperature fall≤0.2kW/h; When crystal actual growth weight is 50% ~ 80% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.2kW/h < rate of temperature fall≤0.4kW/h; When crystal actual growth weight is less than 50% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.4kW/h < rate of temperature fall≤0.6kW/h;
When the ratio of real crystal weight and original charge weight is 80% ~ 90%, the method of operating system heating and cooling adjustment is: when crystal actual growth weight is greater than 120% with the theoretical ratio growing weight, and operating system controls to keep constant temperature after power rises 0.5 ~ 1kW; When crystal actual growth weight is 100% ~ 120% with the theoretical ratio growing weight, operating system keeps constant temperature constant; When crystal actual growth weight is less than 100% with the theoretical ratio growing weight, operating system is lowered the temperature until next unit compares the time with 0.1kW/h < rate of temperature fall≤0.3kW/h;
When the ratio of real crystal weight and original charge weight is 90% ~ 95%, keep power constant, continue to mention crystal after 2 ~ 3 hours and enter ending;
(5) finish up, anneal: above shake crystalline style 10 ~ 20mm, after making crystal depart from liquid level, enter the cooling down stage, automatic inflating after completing, terminate growth.
2. Sapphire Crystal Growth automatization Comprehensive Control technique as claimed in claim 1, is characterized in that: in whole process of growth, hydraulic pressure remains on 0.12 ~ 0.18MPa.
3. Sapphire Crystal Growth automatization Comprehensive Control technique as claimed in claim 1, is characterized in that: the described shouldering stage refers to that real crystal weight is 0 ~ 15% of original charge weight.
4. Sapphire Crystal Growth automatization Comprehensive Control technique as claimed in claim 1, it is characterized in that: described operating system compares the time every a unit, a relatively crystal actual growth weight and theoretical growth weight, and according to crystal actual growth weight and the theoretical ratio growing weight, adjust a power.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104775152A (en) * | 2015-03-16 | 2015-07-15 | 内蒙古京晶光电科技有限公司 | Automatic growth control method of sapphire (80-150 kg) monocrystalline |
| CN104988577A (en) * | 2015-07-14 | 2015-10-21 | 福建汇晶光电科技有限公司 | Sapphire automatic control system and control method |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003052175A1 (en) * | 2001-12-19 | 2003-06-26 | Mark Fielker | 'waterfall' production equipment for crystal growth |
| CN101220503A (en) * | 2007-09-18 | 2008-07-16 | 山东大学 | Integration type programmable crystal growth control system |
| RU2341593C1 (en) * | 2007-03-21 | 2008-12-20 | Михаил Демьянович Скубилин | Device for crystallisation of leucosapphire melt |
| CN101824649A (en) * | 2010-04-30 | 2010-09-08 | 中山大学 | Growth early-stage control method of automatic photoelectric crystal furnace |
| CN202072794U (en) * | 2011-05-17 | 2011-12-14 | 江苏清能电源有限公司 | Full-digital energy-saving single crystal growth power supply for solar energy and control device |
| CN202323109U (en) * | 2011-11-18 | 2012-07-11 | 无锡鼎晶光电科技有限公司 | Weighing device for sapphire single crystal furnace |
| CN102691098A (en) * | 2012-05-30 | 2012-09-26 | 苏州晶昇光电科技有限公司 | Growing method of sapphire crystal prepared by Kyropoulos method |
| CN103060913A (en) * | 2013-01-24 | 2013-04-24 | 天通控股股份有限公司 | Growth method of large-scale sapphire crystal |
| CN202975709U (en) * | 2012-12-18 | 2013-06-05 | 西安西光机械制造有限公司 | Digital control system for sapphire crystal growth furnace |
| CN103710745A (en) * | 2013-12-26 | 2014-04-09 | 南京晶升能源设备有限公司 | Method for automatically controlling growth of 85-120kg sapphire crystals |
-
2014
- 2014-11-26 CN CN201410696057.XA patent/CN104328498B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003052175A1 (en) * | 2001-12-19 | 2003-06-26 | Mark Fielker | 'waterfall' production equipment for crystal growth |
| RU2341593C1 (en) * | 2007-03-21 | 2008-12-20 | Михаил Демьянович Скубилин | Device for crystallisation of leucosapphire melt |
| CN101220503A (en) * | 2007-09-18 | 2008-07-16 | 山东大学 | Integration type programmable crystal growth control system |
| CN101824649A (en) * | 2010-04-30 | 2010-09-08 | 中山大学 | Growth early-stage control method of automatic photoelectric crystal furnace |
| CN202072794U (en) * | 2011-05-17 | 2011-12-14 | 江苏清能电源有限公司 | Full-digital energy-saving single crystal growth power supply for solar energy and control device |
| CN202323109U (en) * | 2011-11-18 | 2012-07-11 | 无锡鼎晶光电科技有限公司 | Weighing device for sapphire single crystal furnace |
| CN102691098A (en) * | 2012-05-30 | 2012-09-26 | 苏州晶昇光电科技有限公司 | Growing method of sapphire crystal prepared by Kyropoulos method |
| CN202975709U (en) * | 2012-12-18 | 2013-06-05 | 西安西光机械制造有限公司 | Digital control system for sapphire crystal growth furnace |
| CN103060913A (en) * | 2013-01-24 | 2013-04-24 | 天通控股股份有限公司 | Growth method of large-scale sapphire crystal |
| CN103710745A (en) * | 2013-12-26 | 2014-04-09 | 南京晶升能源设备有限公司 | Method for automatically controlling growth of 85-120kg sapphire crystals |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016082361A1 (en) * | 2014-11-26 | 2016-06-02 | 元亮科技有限公司 | Sapphire single crystal growth plc closed loop control method |
| CN104775152B (en) * | 2015-03-16 | 2017-06-30 | 内蒙古京晶光电科技有限公司 | A kind of automatic growth control method of 80 150kg jewel monocrystalline |
| CN104775152A (en) * | 2015-03-16 | 2015-07-15 | 内蒙古京晶光电科技有限公司 | Automatic growth control method of sapphire (80-150 kg) monocrystalline |
| CN104988577A (en) * | 2015-07-14 | 2015-10-21 | 福建汇晶光电科技有限公司 | Sapphire automatic control system and control method |
| CN106801251B (en) * | 2015-11-26 | 2019-04-16 | 中国科学院沈阳科学仪器股份有限公司 | A kind of ending of kyropoulos growing large-size crystal takes off crucible technique and its application |
| CN106801251A (en) * | 2015-11-26 | 2017-06-06 | 中国科学院沈阳科学仪器股份有限公司 | A kind of ending of kyropoulos growing large-size crystal takes off crucible technique and its application |
| CN105648521B (en) * | 2016-01-26 | 2018-10-30 | 中山大学 | A kind of growing method and equipment |
| CN105568369B (en) * | 2016-01-26 | 2018-10-30 | 中山大学 | A kind of lower crystal method for method of crystal growth by crystal pulling and automatic lower brilliant equipment |
| CN105648521A (en) * | 2016-01-26 | 2016-06-08 | 中山大学 | Crystal growth method and device |
| CN105568369A (en) * | 2016-01-26 | 2016-05-11 | 中山大学 | Crystal feeding method for Czochralski method crystal growth and automatic crystal feeding equipment |
| CN110344108A (en) * | 2019-08-21 | 2019-10-18 | 眉山博雅新材料有限公司 | Upper lifting vacuum drying oven |
| CN112442736A (en) * | 2020-11-11 | 2021-03-05 | 银川隆基光伏科技有限公司 | Silicon rod drawing system |
| CN112725883A (en) * | 2020-12-24 | 2021-04-30 | 宁夏富乐德石英材料有限公司 | Method for controlling tail length of monocrystalline silicon and ending method of monocrystalline furnace |
| CN112725883B (en) * | 2020-12-24 | 2022-03-22 | 宁夏盾源聚芯半导体科技股份有限公司 | Method for controlling tail length of monocrystalline silicon and ending method of monocrystalline furnace |
| CN113344439A (en) * | 2021-06-29 | 2021-09-03 | 蓝思系统集成有限公司 | Crystal growth control method, device and system and readable storage medium |
| CN113344439B (en) * | 2021-06-29 | 2024-04-26 | 蓝思系统集成有限公司 | Crystal growth control method, device and system and readable storage medium |
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