CN103556223B - A kind of method of growing large-size and square sapphire single-crystal - Google Patents
A kind of method of growing large-size and square sapphire single-crystal Download PDFInfo
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Abstract
The method of a kind of growing large-size of the present invention and square sapphire single-crystal, relate to the monocrystal material of the oxide compound of aluminium, using in the round outside but spuare inside shape i.e. cylindrical internal space of its outside surface is trapezoidal pyramidal, the special copple of the bore of the end mouth of internal space trapezoidal pyramidal is greater than with the bore suitable for reading of internal space trapezoidal pyramidal, adopt the technique of top seeding crystallographic orientation, growth has the rectangular parallelepiped of particular crystal plane orientation or the sapphire crystal of square shape, overcome homogeneity and stability that conventional growth method can not ensure growth interface, cause crystal mass not high, simultaneously due to the anisotropy of its growth velocity, easily there is larger thermal stresses and the poor many defects of cracked and perfection of crystal in crystal growing process.
Description
Technical field
Technical scheme of the present invention relates to the monocrystal material of the oxide compound of aluminium, specifically a kind of method of growing large-size and square sapphire single-crystal.
Background technology
Sapphire single-crystal has excellent optics, mechanics, calorifics, dielectric, radioprotective and corrosion resistant performance, be a kind of crystal of high comprehensive performance, be widely used in semiconductor material with wide forbidden band as the substrate of gan, aerospace, military infrared optical window and femto-second laser substrate material field.Along with the fast development in semiconductor lighting market, sapphire single-crystal material is proposed to the requirements at the higher level of large size, high quality and low cost.In recent years, Apple starts extensively to adopt sapphire material in smart mobile phone field, and comprise mobile phone camera minute surface, sapphire HOME key minute surface and Sapphire mobile phone cover plate, widened sapphire Application Areas further, the market space is opened further.
Traditional sapphire production method, as the complex process of EFG technique (EFG), kyropoulos (KY) and crystal pulling method (CZ), length consuming time, production cost is high.Because the sapphire single-crystal crystal of growth is round, need to require to drill through plug from the side according to special crystal orientation, the utilization ratio of crystal is less than 30%, and utilization ratio is lower, causes cost very high.The crucible of traditional sapphire production method application is cylindrical crucible, is conducive to growth and has specific symmetry axis system crystal.Because traditional sapphire single-crystal generally adopts A axial growth, and A is to non-sapphire symmetry axis, and therefore conventional growth method can not ensure homogeneity and the stability of growth interface, causes crystal mass not high.Simultaneously due to the anisotropy of its growth velocity, easily there is larger thermal stresses and cracked in crystal growing process, perfection of crystal is poor.
In prior art, CN201310113549 discloses a kind of growth method of large size c orientation sapphire single-crystal, CN201310112926 discloses a kind of new method for producing of c orientation sapphire single-crystal, above-mentioned two kinds of methods crystal in process of growth contacts with crucible all the time, the thermal expansivity of crystal and crucible is inconsistent, and crystal stress concentration can be made even to ftracture; CN201310026250 reports large size C to sapphire crystal manufacture method, aforesaid method complex process, can not solve C easily produces technical barrier from low angle boundary to crystal growth.The crystal weight that prior art is produced is all at 70 ~ 80Kg, and complex manufacturing, during consumption energy consumption, can not produce more than the large size of 100Kg and the high perfect sapphire crystal of utilization ratio.
Summary of the invention
Technical problem to be solved by this invention is: a kind of method providing growing large-size and square sapphire single-crystal, using is the special copple that round outside but spuare inside shape and top bore are greater than bottom bore, adopt the technique of top seeding crystallographic orientation, growth has the rectangular parallelepiped of particular crystal plane orientation or the sapphire crystal of square shape, overcome homogeneity and stability that conventional growth method can not ensure growth interface, cause crystal mass not high, simultaneously due to the anisotropy of its growth velocity, easily there is larger thermal stresses and the poor many defects of cracked and perfection of crystal in crystal growing process.
The present invention solves this technical problem adopted technical scheme: a kind of method of growing large-size and square sapphire single-crystal, and step is:
A. growing large-size and square sapphire single-crystal crystal growing furnace used
The formation of growing large-size and square sapphire single-crystal crystal growing furnace used comprises top water-cooled copper dish, miramint seed rod, top heat protection screen, sidewall of the furnace body water-cooled copper, square seed crystal, steel body of heater, middle part tungsten net well heater, middle part molybdenum sheet heat protection screen, special copple, bottom tungsten net well heater, bottom molybdenum sheet heat protection screen, tungsten support bar, bottom water-cooled copper dish, special copple lid and top tungsten net well heater, top water-cooled copper dish is positioned at the top of top heat protection screen, miramint seed rod passes the circular hole of top heat protection screen and special copple lid, the top of special copple is positioned at bottom miramint seed rod, miramint seed rod upper contact top water-cooled copper dish, top tungsten net well heater and middle part tungsten net well heater are between the sidewall and middle part molybdenum sheet heat protection screen of special copple, bottom tungsten net well heater is between the bottom of special copple and bottom molybdenum sheet heat protection screen, special copple is placed on tungsten support bar, contact with bottom water-cooled copper dish bottom tungsten support bar, sidewall of the furnace body water-cooled copper is positioned at steel furnace interior, wherein special copple is round outside but spuare inside shape, namely its outside surface is cylindrical, internal space is trapezoidal pyramidal, the shape suitable for reading of this crucible appearance is circular, the shape suitable for reading of internal space trapezoidal pyramidal is square, the shape of the bottom of this crucible appearance is circular, the shape of the end mouth of internal space trapezoidal pyramidal is square, the bore suitable for reading of internal space trapezoidal pyramidal is greater than the bore of the end mouth of internal space trapezoidal pyramidal, internal surface four side of this crucible internal space is isosceles trapezoid, the junction of the stepped inner surface adjacent side of internal space is the chamfering circular arc seamlessly transitted, the outside of this crucible bottom and the junction of crucible outer side are the chamfering circular arc seamlessly transitted, top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater are collectively referred to as well heater, the shape of well heater is corresponding with columned special copple outside surface.
B. operation steps
The first step, the arrangement of sapphire single-crystal seed crystal
Be A face by upper surface, the rectangular-shaped sapphire single-crystal seed crystal tungsten filament in side leptoprosopy to be C face and wide of side be M face ties up on miramint seed rod;
Second step, adding of raw material
The high purity aluminium oxide crystal block raw material reaching 99.999% is joined in the special copple of growing large-size described in A and square sapphire single-crystal crystal growing furnace used, this special copple is put into the desired location of growing large-size described in A and square sapphire single-crystal crystal growing furnace used;
3rd step, the melting of raw material
Above-mentioned crystal growing furnace is evacuated to 1.33 × 10
-4pa ~ 1.06 × 10
-4pa, the special copple in the crystal growing furnace of heating described in A, to add the high purity aluminium oxide crystal block raw material in special copple in melting second step;
4th step, seeding and the growth of brilliant neck
Said miramint seed rod in the decline the first step, makes the surface of the liquation of bottom surface contact the 3rd step gained of sapphire single-crystal seed crystal, starts seeding, wait crystal growth to proceed to next step to 200g ~ 230g;
5th step, shouldering and isodiametric growth
Reduce the power of top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater, solid-liquid interface is passed with steady speed, make isodiametric growth of crystal, during Deng crystal growth to 2kg ~ 2.5kg, miramint seed rod rotates and stops, observe crystal by view port, ensure the consistence of sapphire crystal face and crucible inner face;
6th step, ending and annealing
After treating that the crystal growth of the 5th step is complete, with the speed of 0.2mm/h ~ 0.5mm/h lift miramint seed rod, crystal is separated with crucible, then three-step annealing is divided, its processing sequence is: first arrange top tungsten net well heater, the power of middle part tungsten net well heater and bottom tungsten net well heater is respectively 22000W ~ 21000W, 52000W ~ 51000W and 17000W ~ 16000W, the power of top and middle part well heater is made to drop to 20380W ~ 19380W respectively in 30 hours, 48760W ~ 47760W, keep this heater power 5 hours, then this top tungsten net well heater is made, the power of middle part tungsten net well heater and bottom tungsten net well heater three well heaters dropped to 12580W ~ 11580W respectively in 20 hours, 27760W ~ 26760W and 11000W ~ 10000W, keep this heater power 3 hours, be filled with argon gas simultaneously, then these three heater powers are made all to be reduced to 0W respectively in 30 hours, complete three steps and divide step annealing.
7th step, gets crystalline substance
After the 6th step has operated, be filled with argon gas, when waiting the air pressure in crystal growing furnace the same with normal atmosphere, crystalline substance is got in blow-on, i.e. obtained large size and square sapphire single-crystal.
The method of above-mentioned a kind of growing large-size and square sapphire single-crystal, the cylindrical height of outer surface of described special copple is 180 ~ 520mm, and described outer surface shape suitable for reading is circular outside diameter is 140 ~ 450mm.
The method of above-mentioned a kind of growing large-size and square sapphire single-crystal, the length of side of the oblique waist of the trapezoidal pyramidal of the internal space of described special copple is 165 ~ 490mm, the shape suitable for reading of internal space trapezoidal pyramidal is the square length of side is 80 ~ 300mm, and the shape of the end mouth of internal space trapezoidal pyramidal is the square length of side is 70 ~ 250mm.
The method of above-mentioned a kind of growing large-size and square sapphire single-crystal, the shape of the shape suitable for reading of the internal space trapezoidal pyramidal of described special copple and the end mouth of internal space trapezoidal pyramidal is rectangle or simultaneously square simultaneously.
The method of above-mentioned a kind of growing large-size and square sapphire single-crystal, the crucible bottom thickness of described special copple is 10 ~ 30mm.
The method of above-mentioned a kind of growing large-size and square sapphire single-crystal, described special copple is the molybdenum crucible made of powder metallurgical technique or tungsten crucible.
The method of above-mentioned a kind of growing large-size and square sapphire single-crystal, the internal surface of described special copple has carried out polished finish.
The method of above-mentioned a kind of growing large-size and square sapphire single-crystal, involved starting material are all obtained by known approach, and involved equipment and operating procedure are known by those skilled in the art and grasp.
The invention has the beneficial effects as follows: compared with prior art, its outstanding substantive distinguishing features and marked improvement are in the present invention:
(1) by top seeding technique, ensure crystal seed hereditary property, improve crystal mass;
(2) after seeding completes, wait sapphire single-crystal to grow to 2kg ~ 2.5kg size and stop the rotation, make it according to sapphire each crystal orientation habit free growth;
(3) special copple outer shape is circular, and the shape of top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater three well heaters is also circular, ensures the relatively stable and homogeneity of the warm field of Sapphire Crystal Growth room;
(4) special copple interior shape is rectangular trapezoidal pyramidal or square trapezoidal pyramidal, by the positive action of crucible, the differentiation of restriction crystal shape, adopt the technique of top seeding crystallographic orientation, ensure the consistence of sapphire crystal face and crucible inner face, growth has the rectangular parallelepiped of particular crystal plane orientation or the sapphire crystal of square shape, significantly improves more than the utilization ratio to 60% of crystal.Utilize the characteristic that sapphire single-crystal anisotropy and A face, M face are different with each of C face growth velocity simultaneously, balance sapphire single-crystal because of with crucible thermal mismatching and the thermal stresses that causes, reduce the microdefects such as dislocation, and prevent the germinating of crackle in sapphire single-crystal, improve crystal mass and yield rate.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the main pseudosection of growing large-size and square sapphire single-crystal crystal growing furnace used.
Fig. 2 is the side cut away view of special copple.
The top plan of Fig. 3 to be the shape suitable for reading of internal space trapezoidal pyramidal be rectangular special copple.
The top plan of Fig. 4 to be the shape suitable for reading of internal space trapezoidal pyramidal be foursquare special copple.
In figure, 1. top water-cooled copper dish, 2. miramint seed rod, 3. top heat protection screen, 4. sidewall of the furnace body water-cooled copper, 5. square seed crystal, 6. steel body of heater, 7. tungsten net well heater in the middle part of, 8. molybdenum sheet heat protection screen in the middle part of, 9. special copple, 10. tungsten net well heater bottom, molybdenum sheet heat protection screen bottom 11., 12. tungsten support bars, water-cooled copper dish bottom 13., 14. special copple lids, 15. top tungsten net well heaters, 16. outer surfaces are suitable for reading, 17. seamlessly transit chamfering circular arc a, 18. rectangle limits, 19. square limits, the outer surface of 20. crucibles, 21. crucible bottom, 22. seamlessly transit chamfering circular arc b, the end mouth of 23. internal space trapezoidal pyramidal, the internal surface of 24. internal spaces, 25. internal space trapezoidal pyramidal suitable for reading.
Embodiment
Embodiment illustrated in fig. 1ly show, the formation of growing large-size of the present invention and square sapphire single-crystal crystal growing furnace used comprises top water-cooled copper dish 1, miramint seed rod 2, top heat protection screen 3, sidewall of the furnace body water-cooled copper 4, square seed crystal 5, steel body of heater 6, middle part tungsten net well heater 7, middle part molybdenum sheet heat protection screen 8, special copple 9, bottom tungsten net well heater 10, bottom molybdenum sheet heat protection screen 11, tungsten support bar 12, bottom water-cooled copper dish 13, special copple lid 14, top tungsten net well heater 15, wherein, top water-cooled copper dish 1 is positioned at the top of top heat protection screen 3, miramint seed rod 2 passes the circular hole of top heat protection screen 3 and special copple lid 14, the top of special copple 9 is positioned at bottom miramint seed rod 2, be used for fixing seed crystal 5, miramint seed rod 2 upper contact top water-cooled copper dish 1 is with cooled, top tungsten net well heater 15 and middle part tungsten net well heater 7 are between the sidewall and middle part molybdenum sheet heat protection screen 8 of special copple 9, bottom tungsten net well heater 10 is between the bottom of special copple 9 and bottom molybdenum sheet heat protection screen 11, special copple 9 is placed on tungsten support bar 12, contact for strengthening heat radiation bottom tungsten support bar 12 with bottom water-cooled copper dish 13, it is inner that sidewall of the furnace body water-cooled copper 3 is positioned at steel body of heater 6, and the sidewall being used for strengthening steel body of heater 6 dispels the heat, wherein special copple 9 is in round outside but spuare inside shape, namely the outer surface 20 of this crucible is cylindrical, the shape of crucible bottom 21 outside surface is circular, internal space is trapezoidal pyramidal, the shape of outer surface suitable for reading 16 is circular, internal space trapezoidal pyramidal suitable for reading 25 shape be square, the shape of the end mouth 23 of internal space trapezoidal pyramidal is square, internal space trapezoidal pyramidal suitable for reading 25 bore be greater than the bore of the end mouth 23 of internal space trapezoidal pyramidal, internal surface 24 4 side of internal space is isosceles trapezoid, the junction of each isosceles trapezoid internal surface adjacent side of the internal surface 24 of internal space is the chamfering circular arc a17 seamlessly transitted, junction between the outer surface of crucible and crucible bottom outside surface is for seamlessly transitting chamfering circular arc b22, top tungsten net well heater 15, middle part tungsten net well heater 7 and bottom tungsten net well heater 10 are collectively referred to as well heater, the shape of well heater is corresponding with columned special copple 9 outside surface.
Embodiment illustrated in fig. 2ly to show, junction between the outer surface 20 of the cylindrical crucible of special copple 9 of the present invention and crucible bottom 21 outside surface is for seamlessly transitting chamfering circular arc b22, the internal space formed by the internal surface 24 of internal space is trapezoidal pyramidal, is greater than the bore of the end mouth 23 of internal space trapezoidal pyramidal in figure with the bore of suitable for reading 25 of the internal space trapezoidal pyramidal of dotted line sign.
Embodiment illustrated in fig. 3ly to show, suitable for reading 25 of the internal space trapezoidal pyramidal of special copple 9 of the present invention is rectangle, the shape of outer surface suitable for reading 16 is circular, the junction of each isosceles trapezoid internal surface adjacent side of internal space is for seamlessly transitting chamfering circular arc a17, and the shape suitable for reading of internal space trapezoidal pyramidal is rectangle limit 18.
Embodiment illustrated in fig. 4ly to show, suitable for reading 25 of the internal space trapezoidal pyramidal of special copple 9 of the present invention is square, the shape of outer surface suitable for reading 16 is circular, the junction of each isosceles trapezoid internal surface adjacent side of internal space is for seamlessly transitting chamfering circular arc a17, and the shape suitable for reading of internal space trapezoidal pyramidal is square limit 19.
Embodiment 1
A. growing large-size and square sapphire single-crystal crystal growing furnace used
Embodiment forms the present embodiment growing large-size used and square sapphire single-crystal crystal growing furnace used as shown in Figure 1, wherein the cylindrical height of outer surface 20 of the crucible of special copple 9 is 180mm, the shape of described outer surface suitable for reading 16 is circular outside diameter is 140mm, the length of side of the oblique waist of the trapezoidal pyramidal of internal space is 165mm, internal space trapezoidal pyramidal suitable for reading 25 shape be the rectangular long length of side be 90mm and the broadside length of side be 80mm, the shape of the end mouth 23 of internal space trapezoidal pyramidal is the rectangular long length of side be 80mm and the broadside length of side is 70mm, the shape of suitable for reading 25 of internal space trapezoidal pyramidal and the shape of the end mouth 23 of internal space trapezoidal pyramidal are rectangle simultaneously, crucible bottom 21 thickness is 10mm, the tungsten crucible that special copple 9 is made for powder metallurgical technique, the internal surface of special copple 9 has carried out polished finish.
B. operation steps
The first step, the arrangement of sapphire single-crystal seed crystal
Be A face by upper surface, the rectangular-shaped sapphire single-crystal seed crystal tungsten filament in side leptoprosopy to be C face and wide of side be M face ties up on miramint seed rod;
Second step, adding of raw material
The high purity aluminium oxide crystal block raw material reaching 99.999% is joined in the special copple of growing large-size described in A and square sapphire single-crystal crystal growing furnace used, this special copple is put into the desired location of growing large-size described in A and square sapphire single-crystal crystal growing furnace used;
3rd step, the melting of raw material
Above-mentioned crystal growing furnace is evacuated to 10
-4pa, arranges the special copple in the above-mentioned crystal growing furnace of heater power programmed heating, to add the high purity aluminium oxide crystal block raw material in special copple in melting second step;
4th step, seeding and the growth of brilliant neck
Said miramint seed rod in the decline the first step, makes the surface of the liquation of bottom surface contact the 3rd step gained of sapphire single-crystal seed crystal, starts seeding, wait crystal growth to proceed to next step to 200g;
5th step, shouldering and isodiametric growth
Reduce the power of top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater, solid-liquid interface is passed with steady speed, make isodiametric growth of crystal, during Deng crystal growth to 2kg, miramint seed rod rotates and stops, observe crystal by view port, ensure the consistence of sapphire crystal face and crucible inner face;
6th step, ending and annealing
After treating that the crystal growth of the 5th step is complete, with 0.2mm/h speed lift miramint seed rod, crystal is separated with crucible, then three-step annealing is divided, its processing sequence is: first arrange top tungsten net well heater, the power of middle part tungsten net well heater and bottom tungsten net well heater is respectively 22000W, 52000W and 17000W, the power of top and middle part well heater is made to drop to 20380W respectively in 30 hours, 48760W, keep this heater power 5 hours, then this top tungsten net well heater is made, the power of middle part tungsten net well heater and bottom tungsten net well heater three well heaters dropped to 12580W respectively in 20 hours, 27760W and 11000W, keep this heater power 3 hours, be filled with argon gas simultaneously, then these three heater powers are made all to be reduced to 0W respectively in 30 hours, complete three-step annealing,
7th step, gets crystalline substance
After the 6th step has operated, be filled with argon gas, when waiting the air pressure in crystal growing furnace the same with normal atmosphere, crystalline substance is got in blow-on, i.e. obtained large size and square sapphire single-crystal.
Embodiment 2
A. growing large-size and square sapphire single-crystal crystal growing furnace used
Embodiment forms the present embodiment growing large-size used and square sapphire single-crystal crystal growing furnace used as shown in Figure 1, wherein the cylindrical height of outer surface 20 of the crucible of special copple 9 is 350mm, the shape of described outer surface suitable for reading 16 is circular outside diameter is 290mm, the length of side of the oblique waist of the trapezoidal pyramidal of internal space is 300mm, internal space trapezoidal pyramidal suitable for reading 25 shape be the rectangular long length of side be 210mm and the broadside length of side be 190mm, the shape of the end mouth 23 of internal space trapezoidal pyramidal is the rectangular long length of side be 180mm and the broadside length of side is 160mm, the shape of suitable for reading 25 of internal space trapezoidal pyramidal and the shape of the end mouth 23 of internal space trapezoidal pyramidal are rectangle simultaneously, crucible bottom 21 thickness is 15mm, the tungsten crucible that special copple 9 is made for powder metallurgical technique, the internal surface of special copple 9 has carried out polished finish.
B. operation steps
The first step, the arrangement of sapphire single-crystal seed crystal
Be A face by upper surface, the rectangular-shaped sapphire single-crystal seed crystal tungsten filament in side leptoprosopy to be C face and wide of side be M face ties up on miramint seed rod;
Second step, adding of raw material
The high purity aluminium oxide crystal block raw material reaching 99.999% is joined in the special copple of growing large-size described in A and square sapphire single-crystal crystal growing furnace used, this special copple is put into the desired location of growing large-size described in A and square sapphire single-crystal crystal growing furnace used;
3rd step, the melting of raw material
Above-mentioned crystal growing furnace is evacuated to 10
-4pa, arranges the special copple in the above-mentioned crystal growing furnace of heater power programmed heating, to add the high purity aluminium oxide crystal block raw material in special copple in melting second step;
4th step, seeding and the growth of brilliant neck
Said miramint seed rod in the decline the first step, makes the surface of the liquation of bottom surface contact the 3rd step gained of sapphire single-crystal seed crystal, starts seeding, wait crystal growth to proceed to next step to 215g;
5th step, shouldering and isodiametric growth
Reduce the power of top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater, solid-liquid interface is passed with steady speed, make isodiametric growth of crystal, during Deng crystal growth to 2.2kg, miramint seed rod rotates and stops, observe crystal by view port, ensure the consistence of sapphire crystal face and crucible inner face;
6th step, ending and annealing
After treating that the crystal growth of the 5th step is complete, with 0.35mm/h speed lift miramint seed rod, crystal is separated with crucible, then three-step annealing is divided, its processing sequence is: first arrange top tungsten net well heater, the power of middle part tungsten net well heater and bottom tungsten net well heater is respectively 21800W, 51800W and 16800W, the power of top and middle part well heater is made to drop to 20180W respectively in 30 hours, 48560W, keep this heater power 5 hours, then this top tungsten net well heater is made, the power of middle part tungsten net well heater and bottom tungsten net well heater three well heaters was dropping to 12380W respectively in 20 hours, 27560W and 10800W, keep this heater power 3 hours, be filled with argon gas simultaneously, then these three heater powers are made all to be reduced to 0W respectively in 30 hours, complete three-step annealing,
7th step, gets crystalline substance
After the 6th step has operated, be filled with argon gas, when waiting the air pressure in crystal growing furnace the same with normal atmosphere, crystalline substance is got in blow-on, i.e. obtained large size and square sapphire single-crystal.
Embodiment 3
A. growing large-size and square sapphire single-crystal crystal growing furnace used
Embodiment forms the present embodiment growing large-size used and square sapphire single-crystal crystal growing furnace used as shown in Figure 1, wherein the cylindrical height of outer surface 20 of the crucible of special copple 9 is 520mm, the shape of described outer surface suitable for reading 16 is circular outside diameter is 450mm, the length of side of the oblique waist of the trapezoidal pyramidal of internal space is 490mm, internal space trapezoidal pyramidal suitable for reading 25 shape be the rectangular long length of side be 300mm and the broadside length of side be 280mm, the shape of the end mouth 23 of internal space trapezoidal pyramidal is the rectangular long length of side be 250mm and the broadside length of side is 220mm, the shape of suitable for reading 25 of internal space trapezoidal pyramidal and the shape of the end mouth 23 of internal space trapezoidal pyramidal are rectangle simultaneously, crucible bottom 21 thickness is 30mm, the tungsten crucible that special copple 9 is made for powder metallurgical technique, the internal surface of special copple 9 has carried out polished finish.
B. operation steps
The first step, the arrangement of sapphire single-crystal seed crystal
Be A face by upper surface, the rectangular-shaped sapphire single-crystal seed crystal tungsten filament in side leptoprosopy to be C face and wide of side be M face ties up on miramint seed rod;
Second step, adding of raw material
The high purity aluminium oxide crystal block raw material reaching 99.999% is joined in the special copple of growing large-size described in A and square sapphire single-crystal crystal growing furnace used, this special copple is put into the desired location of growing large-size described in A and square sapphire single-crystal crystal growing furnace used;
3rd step, the melting of raw material
Above-mentioned crystal growing furnace is evacuated to 10
-4pa, arranges the special copple in the above-mentioned crystal growing furnace of heater power programmed heating, to add the high purity aluminium oxide crystal block raw material in special copple in melting second step;
4th step, seeding and the growth of brilliant neck
Said miramint seed rod in the decline the first step, makes the surface of the liquation of bottom surface contact the 3rd step gained of sapphire single-crystal seed crystal, starts seeding, wait crystal growth to proceed to next step to 230g;
5th step, shouldering and isodiametric growth
Reduce the power of top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater, solid-liquid interface is passed with steady speed, make isodiametric growth of crystal, during Deng crystal growth to 2.5kg, miramint seed rod rotates and stops, observe crystal by view port, ensure the consistence of sapphire crystal face and crucible inner face;
6th step, ending and annealing
After treating that the crystal growth of the 5th step is complete, with 0.5mm/h speed lift miramint seed rod, crystal is separated with crucible, then three-step annealing is divided, its processing sequence is: first arrange top tungsten net well heater, the power of middle part tungsten net well heater and bottom tungsten net well heater is respectively 21600W, 51600W and 16600W, the power of top and middle part well heater is made to drop to 19980W respectively in 30 hours, 48360W, keep this heater power 5 hours, then this top tungsten net well heater is made, the power of middle part tungsten net well heater and bottom tungsten net well heater three well heaters was dropping to 12180W respectively in 20 hours, 27360W and 10600W, keep this heater power 3 hours, be filled with argon gas simultaneously, then these three heater powers are made all to be reduced to 0W respectively in 30 hours, complete three-step annealing,
7th step, gets crystalline substance
After the 6th step has operated, be filled with argon gas, when waiting the air pressure in crystal growing furnace the same with normal atmosphere, crystalline substance is got in blow-on, i.e. obtained large size and square sapphire single-crystal.
Embodiment 4
A. growing large-size and square sapphire single-crystal crystal growing furnace used
Embodiment forms the present embodiment growing large-size used and square sapphire single-crystal crystal growing furnace used as shown in Figure 1, wherein the cylindrical height of outer surface 20 of the crucible of special copple 9 is 180mm, the shape of described outer surface suitable for reading 16 is circular outside diameter is 140mm, the length of side of the oblique waist of the trapezoidal pyramidal of internal space is 165mm, internal space trapezoidal pyramidal suitable for reading 25 shape be the foursquare length of side be 80mm, the shape of the end mouth 23 of internal space trapezoidal pyramidal is the foursquare length of side is 70mm, the shape of suitable for reading 25 of internal space trapezoidal pyramidal and the shape of the end mouth 23 of internal space trapezoidal pyramidal are square simultaneously, crucible bottom 21 thickness is 10mm, the tungsten crucible that special copple 9 is made for powder metallurgical technique, the internal surface of special copple 9 has carried out polished finish.
B. operation steps
The first step, the arrangement of sapphire single-crystal seed crystal
Be A face by upper surface, the rectangular-shaped sapphire single-crystal seed crystal tungsten filament in side leptoprosopy to be C face and wide of side be M face ties up on miramint seed rod;
Second step, adding of raw material
The high purity aluminium oxide crystal block raw material reaching 99.999% is joined in the special copple of growing large-size described in A and square sapphire single-crystal crystal growing furnace used, this special copple is put into the desired location of growing large-size described in A and square sapphire single-crystal crystal growing furnace used;
3rd step, the melting of raw material
Above-mentioned crystal growing furnace is evacuated to 10
-4pa, arranges the special copple in the above-mentioned crystal growing furnace of heater power programmed heating, to add the high purity aluminium oxide crystal block raw material in special copple in melting second step;
4th step, seeding and the growth of brilliant neck
Said miramint seed rod in the decline the first step, makes the surface of the liquation of bottom surface contact the 3rd step gained of sapphire single-crystal seed crystal, starts seeding, wait crystal growth to proceed to next step to 200g;
5th step, shouldering and isodiametric growth
Reduce the power of top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater, solid-liquid interface is passed with steady speed, make isodiametric growth of crystal, during Deng crystal growth to 2kg, miramint seed rod rotates and stops, observe crystal by view port, ensure the consistence of sapphire crystal face and crucible inner face;
6th step, ending and annealing
After treating that the crystal growth of the 5th step is complete, with 0.5mm/h speed lift miramint seed rod, crystal is separated with crucible, then three-step annealing is divided, its processing sequence is: first arrange top tungsten net well heater, the power of middle part tungsten net well heater and bottom tungsten net well heater is respectively 21400W, 51400W and 16400W, the power of top and middle part well heater is made to drop to 19780W respectively in 30 hours, 48160W, keep this heater power 5 hours, then this top tungsten net well heater is made, the power of middle part tungsten net well heater and bottom tungsten net well heater three well heaters dropped to 11980W respectively in 20 hours, 27160W and 10400W, keep this heater power 3 hours, be filled with argon gas simultaneously, then these three heater powers are made all to be reduced to 0W respectively in 30 hours, complete three-step annealing,
7th step, gets crystalline substance
After the 6th step has operated, be filled with argon gas, when waiting the air pressure in crystal growing furnace the same with normal atmosphere, crystalline substance is got in blow-on, i.e. obtained large size and square sapphire single-crystal.
Embodiment 5
A. growing large-size and square sapphire single-crystal crystal growing furnace used
Embodiment forms the present embodiment growing large-size used and square sapphire single-crystal crystal growing furnace used as shown in Figure 1, wherein the cylindrical height of outer surface 20 of the crucible of special copple 9 is 350mm, the shape of described outer surface suitable for reading 16 is circular outside diameter is 300mm, the length of side of the oblique waist of the trapezoidal pyramidal of internal space is 330mm, internal space trapezoidal pyramidal suitable for reading 25 shape be the foursquare length of side be 190mm, the shape of the end mouth 23 of internal space trapezoidal pyramidal is the foursquare length of side is 160mm, the shape of suitable for reading 25 of internal space trapezoidal pyramidal and the shape of the end mouth 23 of internal space trapezoidal pyramidal are square simultaneously, crucible bottom 21 thickness is 15mm, the tungsten crucible that special copple 9 is made for powder metallurgical technique, the internal surface of special copple 9 has carried out polished finish.
B. operation steps
The first step, the arrangement of sapphire single-crystal seed crystal
Be A face by upper surface, the rectangular-shaped sapphire single-crystal seed crystal tungsten filament in side leptoprosopy to be C face and wide of side be M face ties up on miramint seed rod;
Second step, adding of raw material
The high purity aluminium oxide crystal block raw material reaching 99.999% is joined in the special copple of growing large-size described in A and square sapphire single-crystal crystal growing furnace used, this special copple is put into the desired location of growing large-size described in A and square sapphire single-crystal crystal growing furnace used;
3rd step, the melting of raw material
Above-mentioned crystal growing furnace is evacuated to 1.2 × 10
-4pa, arranges the special copple in the above-mentioned crystal growing furnace of heater power programmed heating, to add the high purity aluminium oxide crystal block raw material in special copple in melting second step;
4th step, seeding and the growth of brilliant neck
Said miramint seed rod in the decline the first step, makes the surface of the liquation of bottom surface contact the 3rd step gained of sapphire single-crystal seed crystal, starts seeding, wait crystal growth to proceed to next step to 215g;
5th step, shouldering and isodiametric growth
Reduce the power of top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater, solid-liquid interface is passed with steady speed, make isodiametric growth of crystal, during Deng crystal growth to 2.2kg, miramint seed rod rotates and stops, observe crystal by view port, ensure the consistence of sapphire crystal face and crucible inner face;
6th step, ending and annealing
After treating that the crystal growth of the 5th step is complete, with 0.3mm/h speed lift miramint seed rod, crystal is separated with crucible, then three-step annealing is divided, its processing sequence is: first arrange top tungsten net well heater, the power of middle part tungsten net well heater and bottom tungsten net well heater is respectively 21200W, 51200W and 16200W, the power of top and middle part well heater is made to drop to 19580W respectively in 30 hours, 47960W, keep this heater power 5 hours, then this top tungsten net well heater is made, the power of middle part tungsten net well heater and bottom tungsten net well heater three well heaters was dropping to 11780W respectively in 20 hours, 26960W and 10200W, keep this heater power 3 hours, be filled with argon gas simultaneously, then these three heater powers are made all to be reduced to 0W respectively in 30 hours, complete three-step annealing,
7th step, gets crystalline substance
After the 6th step has operated, be filled with argon gas, when waiting the air pressure in crystal growing furnace the same with normal atmosphere, crystalline substance is got in blow-on, i.e. obtained large size and square sapphire single-crystal.
Embodiment 6
A. growing large-size and square sapphire single-crystal crystal growing furnace used
Embodiment forms the present embodiment growing large-size used and square sapphire single-crystal crystal growing furnace used as shown in Figure 1, wherein the cylindrical height of outer surface 20 of the crucible of special copple 9 is 520mm, the shape of described outer surface suitable for reading 16 is circular outside diameter is 450mm, the length of side of the oblique waist of the trapezoidal pyramidal of internal space is 490mm, internal space trapezoidal pyramidal suitable for reading 25 shape be the foursquare length of side be 300mm, the shape of the end mouth 23 of internal space trapezoidal pyramidal is the foursquare length of side is 250mm, the shape of suitable for reading 25 of internal space trapezoidal pyramidal and the shape of the end mouth 23 of internal space trapezoidal pyramidal are square simultaneously, crucible bottom 21 thickness is 30mm, the tungsten crucible that special copple 9 is made for powder metallurgical technique, the internal surface of special copple 9 has carried out polished finish.
B. operation steps
The first step, the arrangement of sapphire single-crystal seed crystal
Be A face by upper surface, the rectangular-shaped sapphire single-crystal seed crystal tungsten filament in side leptoprosopy to be C face and wide of side be M face ties up on miramint seed rod;
Second step, adding of raw material
The high purity aluminium oxide crystal block raw material reaching 99.999% is joined in the special copple of growing large-size described in A and square sapphire single-crystal crystal growing furnace used, this special copple is put into the desired location of growing large-size described in A and square sapphire single-crystal crystal growing furnace used;
3rd step, the melting of raw material
Above-mentioned crystal growing furnace is evacuated to 1.2 × 10
-4pa, arranges the special copple in the above-mentioned crystal growing furnace of heater power programmed heating, to add the high purity aluminium oxide crystal block raw material in special copple in melting second step;
4th step, seeding and the growth of brilliant neck
Said miramint seed rod in the decline the first step, makes the surface of the liquation of bottom surface contact the 3rd step gained of sapphire single-crystal seed crystal, starts seeding, wait crystal growth to proceed to next step to 230g;
5th step, shouldering and isodiametric growth
Reduce the power of top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater, solid-liquid interface is passed with steady speed, make isodiametric growth of crystal, during Deng crystal growth to 2.5kg, miramint seed rod rotates and stops, observe crystal by view port, ensure the consistence of sapphire crystal face and crucible inner face;
6th step, ending and annealing
After treating that the crystal growth of the 5th step is complete, with 0.5mm/h speed lift miramint seed rod, crystal is separated with crucible, then three-step annealing is divided, its processing sequence is: first arrange top tungsten net well heater, the power of middle part tungsten net well heater and bottom tungsten net well heater is respectively 21000W, 51000W and 16000W, the power of top and middle part well heater is made to drop to 19380W respectively in 30 hours, 47760W, keep this heater power 5 hours, then this top tungsten net well heater is made, the power of middle part tungsten net well heater and bottom tungsten net well heater three well heaters dropped to 11580W respectively in 20 hours, 26760W and 10000W, keep this heater power 3 hours, be filled with argon gas simultaneously, then these three heater powers are made all to be reduced to 0W respectively in 30 hours, complete three-step annealing,
7th step, gets crystalline substance
After the 6th step has operated, be filled with argon gas, when waiting the air pressure in crystal growing furnace the same with normal atmosphere, crystalline substance is got in blow-on, i.e. obtained large size and square sapphire single-crystal.
Starting material involved by above-described embodiment are all obtained by known approach, and involved equipment and operating procedure are known by those skilled in the art and grasp.
Claims (3)
1. a method for growing large-size and square sapphire single-crystal, is characterized in that step is:
A. growing large-size and square sapphire single-crystal crystal growing furnace used
The formation of growing large-size and square sapphire single-crystal crystal growing furnace used comprises top water-cooled copper dish, miramint seed rod, top heat protection screen, sidewall of the furnace body water-cooled copper, square seed crystal, steel body of heater, middle part tungsten net well heater, middle part molybdenum sheet heat protection screen, special copple, bottom tungsten net well heater, bottom molybdenum sheet heat protection screen, tungsten support bar, bottom water-cooled copper dish, special copple lid and top tungsten net well heater, top water-cooled copper dish is positioned at the top of top heat protection screen, miramint seed rod passes the circular hole of top heat protection screen and special copple lid, the top of special copple is positioned at bottom miramint seed rod, miramint seed rod upper contact top water-cooled copper dish, top tungsten net well heater and middle part tungsten net well heater are between the sidewall and middle part molybdenum sheet heat protection screen of special copple, bottom tungsten net well heater is between the bottom of special copple and bottom molybdenum sheet heat protection screen, special copple is placed on tungsten support bar, contact with bottom water-cooled copper dish bottom tungsten support bar, sidewall of the furnace body water-cooled copper is positioned at steel furnace interior, wherein special copple is round outside but spuare inside shape, namely its outside surface is cylindrical, internal space is trapezoidal pyramidal, the shape suitable for reading of this crucible appearance is circular, the shape suitable for reading of internal space trapezoidal pyramidal is square, the shape of the bottom of this crucible appearance is circular, the shape of the end mouth of internal space trapezoidal pyramidal is square, the bore suitable for reading of internal space trapezoidal pyramidal is greater than the bore of the end mouth of internal space trapezoidal pyramidal, internal surface four side of this crucible internal space is isosceles trapezoid, the junction of the stepped inner surface adjacent side of internal space is the chamfering circular arc seamlessly transitted, the outside of this crucible bottom and the junction of crucible outer side are the chamfering circular arc seamlessly transitted, top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater are collectively referred to as well heater, the shape of well heater is corresponding with columned special copple outside surface,
B. operation steps
The first step, the arrangement of sapphire single-crystal seed crystal
Be A face by upper surface, the rectangular-shaped sapphire single-crystal seed crystal tungsten filament in side leptoprosopy to be C face and wide of side be M face ties up on miramint seed rod;
Second step, adding of raw material
The high purity aluminium oxide crystal block raw material reaching 99.999% is joined in the special copple of growing large-size described in A and square sapphire single-crystal crystal growing furnace used, this special copple is put into the desired location of growing large-size described in A and square sapphire single-crystal crystal growing furnace used;
3rd step, the melting of raw material
Above-mentioned crystal growing furnace is evacuated to 1.33 × 10
-4pa ~ 1.06 × 10
-4pa, the special copple in the crystal growing furnace of heating described in A, to add the high purity aluminium oxide crystal block raw material in special copple in melting second step;
4th step, seeding and the growth of brilliant neck
Said miramint seed rod in the decline the first step, makes the surface of the liquation of bottom surface contact the 3rd step gained of sapphire single-crystal seed crystal, starts seeding, wait crystal growth to proceed to next step to 200g ~ 230g;
5th step, shouldering and isodiametric growth
Reduce the power of top tungsten net well heater, middle part tungsten net well heater and bottom tungsten net well heater, solid-liquid interface is passed with steady speed, make isodiametric growth of crystal, during Deng crystal growth to 2kg ~ 2.5kg, miramint seed rod rotates and stops, observe crystal by view port, ensure the consistence of sapphire crystal face and crucible inner face;
6th step, ending and annealing
After treating that the crystal growth of the 5th step is complete, with the speed of 0.2mm/h ~ 0.5mm/h lift miramint seed rod, crystal is separated with crucible, then three-step annealing is divided, its processing sequence is: first arrange top tungsten net well heater, the power of middle part tungsten net well heater and bottom tungsten net well heater is respectively 22000W ~ 21000W, 52000W ~ 51000W and 17000W ~ 16000W, the power of top and middle part well heater is made to drop to 20380W ~ 19380W respectively in 30 hours, 48760W ~ 47760W, keep this heater power 5 hours, then this top tungsten net well heater is made, the power of middle part tungsten net well heater and bottom tungsten net well heater three well heaters dropped to 12580W ~ 11580W respectively in 20 hours, 27760W ~ 26760W and 11000W ~ 10000W, keep this heater power 3 hours, be filled with argon gas simultaneously, then these three heater powers are made all to be reduced to 0W respectively in 30 hours, complete three steps and divide step annealing,
7th step, gets crystalline substance
After the 6th step has operated, be filled with argon gas, when waiting the air pressure in crystal growing furnace the same with normal atmosphere, crystalline substance is got in blow-on, i.e. obtained large size and square sapphire single-crystal;
The cylindrical height of outer surface of described special copple is 180 ~ 520mm, and described outer surface shape suitable for reading is circular outside diameter is 140 ~ 450mm; The length of side of the oblique waist of the trapezoidal pyramidal of the internal space of described special copple is 165 ~ 490mm, the shape suitable for reading of internal space trapezoidal pyramidal is the square length of side is 80 ~ 300mm, and the shape of the end mouth of internal space trapezoidal pyramidal is the square length of side is 70 ~ 250mm; The shape of the shape suitable for reading of the internal space trapezoidal pyramidal of described special copple and the end mouth of internal space trapezoidal pyramidal is rectangle or simultaneously square simultaneously; The crucible bottom thickness of described special copple is 10 ~ 30mm.
2. according to the method for the said a kind of growing large-size of claim 1 and square sapphire single-crystal, it is characterized in that: described special copple is the molybdenum crucible made of powder metallurgical technique or tungsten crucible.
3., according to the method for the said a kind of growing large-size of claim 1 and square sapphire single-crystal, it is characterized in that: the internal surface of described special copple has carried out polished finish.
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