CN102534771A - Method for growing gallium phosphide single crystals - Google Patents
Method for growing gallium phosphide single crystals Download PDFInfo
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- CN102534771A CN102534771A CN2010106226234A CN201010622623A CN102534771A CN 102534771 A CN102534771 A CN 102534771A CN 2010106226234 A CN2010106226234 A CN 2010106226234A CN 201010622623 A CN201010622623 A CN 201010622623A CN 102534771 A CN102534771 A CN 102534771A
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Abstract
The invention relates to a method for growing gallium phosphide single crystals. The method comprises the following steps of: preparing materials, charging, vacuumizing, filling gas, heating for dissolving, welding seed crystals, seeding, shouldering, removing a floating needle for the first time, removing the floating needle for the second time, performing equal-diameter control, and ending, wherein gallium phosphide polycrystals, a floating boat, a doping agent and boron oxide are put into a crucible in the material preparation process, the floating boat is made of silicon nitride and has the internal diameter of phi20 to 80mm, and pressure is controlled to be 1.0 to 5.0MPa (absolute pressure) after a hearth is filled with nitrogen. The method has the advantages that: the diameter of the crystals is controlled by the floating boat, the density of the floating boat is between the density of the boron oxide and the density of gallium phosphide, the floating boat can float on a melting surface of the gallium phosphide, and the diameter is slightly influenced by the ascending or descending of a solid liquid interface in the floating boat due to temperature change, so the diameter of the crystals can be well controlled by controlling the rotating speed of the floating boat, the gallium phosphide single crystals with the size of 1 to 3 inches are grown, the yield of the single crystals is improved, the crystallization quality of the single crystals is high, and a mobility index in electrical parameters can stably reach 130-140cm<2>/v.s.
Description
Technical field
The present invention relates to a kind of compound semiconductor single crystal growth technique, specifically, relate to a kind of monocrystal of gallium phosphide growth method.
Background technology
The monocrystal of gallium phosphide material can be used for making general red, yellow, green LED, has low current, the high efficiency characteristics of luminescence, is one of main raw of visible light LED.Simultaneously; The monocrystal of gallium phosphide material also can be used as the bonding material of high brightness LED, make quaternary LED crystal grain by original single face luminous become six luminous, its luminosity improves more than 60%; And eliminated former GaAs substrate absorption energy, the life-span of having improved LED.
At present, the growth method of monocrystal of gallium phosphide has high pressure single crystal growing furnace hydraulic seal vertical pulling method, VGF, vertical bridgman method.Modern semiconductors industrial production monocrystal of gallium phosphide all is in the high pressure synthetic furnace, adopts the synthetic gallium phosphide polycrystal of directional solidification processes, and the high pressure single crystal growing furnace of packing into after suitably handling carries out crystal-pulling.This method is called for short high pressure LEC method high-pressure liquid encapsulation pulling method.And adopt VGF, vertical bridgman method to prepare the low-dislocation-density monocrystal of gallium phosphide, but be not used for industrial production.
LEC method suitability for industrialized production gallium phosphide is adopted in the whole world now, and single crystal diameter is main with 50mm, adopt X-ray scanning and weighing method to wait usually and control crystal diameter, but the monocrystal of gallium phosphide diameter that adopts this method to make is inhomogeneous.Owing to receive very big thermal stresses in the crystal growing process, cause producing higher dislocation desity in addition, cause the growing single-crystal difficulty, especially along with the single crystal diameter size increases, single crystal growing is just difficult more, and it is lower that yield rate becomes.
Summary of the invention
The object of the present invention is to provide a kind of monocrystal of gallium phosphide growth method, adopt this method can control crystal diameter preferably, the crystal boundary diameter is even, can improve working (machining) efficiency and higher yield rate is arranged.
In order to achieve the above object, the present invention has adopted following technical scheme:
High-pressure liquid encapsulation pulling method, 1～3 inch monocrystal of gallium phosphide of can growing are adopted in this monocrystal of gallium phosphide growth.
Single crystal diameter control uses the pontoon material to be silicon nitride (Si
3N
4), the pontoon internal diameter is φ 20～80mm.
The growth method of this monocrystal of gallium phosphide, it may further comprise the steps: get the raw materials ready, shove charge vacuumizes, inflates; Temperature increasing for melting materials, seed crystal welding, seeding, shouldering, float needle one takes off, and float needle two takes off; Diameter control, ending in procedure for preparation, is placed with gallium phosphide polycrystal, pontoon, doping agent and boron oxide in the crucible; Described pontoon material is a silicon nitride, the internal diameter φ 20～80mm of pontoon, and the pressure-controlling behind the burner hearth inflated with nitrogen is in 1.0～5.0MPa (absolute pressure.
In the described temperature increasing for melting materials operation, rotate seed rod with 1-30 rev/min speed, with 5-50 rev/min speed counter-rotation crucible pole; The seeding operation is the cooling seeding, and rate of temperature fall is controlled at 0.03～2.0 ℃/min, when the solid phase of seeing solid-liquid interface is grown up, begins to lift, and pull rate is controlled at 1～15mm/h.
Differential weight shows that increasing crucible when 0.1～1.5g/min is above rises progressively to 0.2～1.8mm/hr, along with the crystalline adjustment temperature of growing up is controlled the pontoon rotating speed, so that the pontoon rotating speed is at the uniform velocity slack-off, reaches the purpose of controlling the crystalline speed of growth,
When the pontoon rotating speed reaches 2.0～5.0 seconds/stable earlier temperature once when changeing, accomplish run-bake-needle fault for the first time; Control pontoon rotating speed reaches 2.5～6.0 seconds/more than changeing, accomplishes run-bake-needle fault for the second time.
In the diameter control operation, steadily control the pontoon rotating speed 2.5～6.0 seconds/change with the control crystal diameter, when boat changes cooling when accelerating, heat up when boat changes when slowing down, temperature rate is controlled at 0.03～3.0 ℃/min.
Before crystal growth finishes, heat up, make the pontoon rotating speed reach 2.0～4.0 seconds/commentaries on classics, crucible changes, the crucible liter when time at the bottom of the pontoon contact crucible stops, and begins to fall the crucible position of crucible when getting back to seeding.
The present invention has following characteristics:
1. because the present invention adopts pontoon control crystal diameter; Pontoon density is between boron oxide and gallium phosphide; Can float on the gallium phosphide melt face; Temperature variation causes that the interior solid-liquid interface of pontoon rises or decline is less to diameter influences, therefore can better control crystal diameter through control pontoon rotating speed, grows 1～3 inch monocrystal of gallium phosphide.
2. because the present invention adopts suitable pulling rate, crucible raising speed rate and rate of temperature fall in technological process, help single crystal growing, reduce dislocation desity, improve the monocrystalline yield rate.
Monocrystal of gallium phosphide growth method of the present invention adopts pontoon control crystal diameter, 1～3 inch monocrystal of gallium phosphide of growing preferably.In the crystal pulling process, adopt suitable process method, help improving the monocrystalline yield rate.The crystal boundary diameter is even, and this handicraft product quality is reached advanced world standards in addition, and the monocrystalline crystalline quality is higher, and electrical parameter such as mobility index can be stablized and reach 130～140cm
2/ v.s.
Description of drawings
Fig. 1 is the FB(flow block) of monocrystal of gallium phosphide growth method of the present invention.
Embodiment
Monocrystal of gallium phosphide growth method employing equipment of the present invention is the high pressure single crystal growing furnace, and single crystal diameter control uses the pontoon material to be silicon nitride, and the pontoon internal diameter is φ 20～80mm.
With specific embodiment the present invention is further specified below:
Embodiment 1:
1. preparation work: boron oxide is carried out vacuum hydro-extraction, with cleaning with deionized water behind the chloroazotic acid corrosion gallium phosphide polycrystal, handle behind the quartz apparatus and spend dried up cleaning with chloroazotic acid.
2. get the raw materials ready: will corrode 1.0 kilograms of gallium phosphide polycrystals that cleaned quartz crucible of packing into, be that the pontoon of φ 30mm is put in crucible central authorities with internal diameter, puts into doping agent sulphur 40mg, and the 200g boron oxide that will smash is again put into crucible.
3. shove charge: install seed crystal, cross bar, float needle, camera lens, mix up the verticality of crucible pole, configure graphite heater and heat preservation member, the quartz crucible that installs polycrystal is placed in the graphite crucible wall, the sealing body of heater with dial indicator.
4. extract the air in the burner hearth out with vacuum pump, last air pressure is less than 400Pa.In burner hearth, charge into high pure nitrogen then and reach 1.5Mpa, inspection furnace sealing property.
5. temperature increasing for melting materials: temperature is raised to 1620 ℃ the gallium phosphide polycrystal material melted.Speed with 10 rev/mins forwards seed rod to, with 20 rev/mins speed counter-rotation crucible pole.
6. seed crystal welding: make seed crystal contact melt after the abundant preheating of seed crystal, when seed crystal with after melt contact, adjust temperature according to the aperture that produces, the aperture of solid-liquid interface is stablized.
7. seeding: begin the seeding of lowering the temperature stable after touching 5 minutes, rate of temperature fall is controlled at 0.1～1.0 ℃/min, when the solid phase of seeing solid-liquid interface is grown up, begins to lift, and pull rate is 9mm/h.Crystal growth characteristic in the close observation shouldering process is if monocrystalline then continues pulling crystal.As do not have the then timely melt back of need of monocrystalline characteristic, repeat above-mentioned seeding process.
8. shouldering: increase the crucible liter when differential weight shows 0.9g/min and progressively arrive 0.5mm/hr.Along with the crystalline adjustment temperature of growing up is controlled the pontoon rotating speed, so that the pontoon rotating speed is at the uniform velocity slack-off, reach the purpose of the control crystalline speed of growth, accomplish crystal shouldering process.
9. float needle one takes off: when the pontoon rotating speed reaches 2.8 seconds/stable earlier temperature once when changeing, accomplish run-bake-needle fault for the first time.
10. float needle two takes off: control pontoon rotating speed reaches 4.2 seconds/changes the completion run-bake-needle fault second time.
11. diameter control: steadily control the pontoon rotating speed 3.6 seconds/turn left rightly with the control crystal diameter, suitably lower the temperature when boat changes when accelerating, suitably heat up when slowing down when boat changes, temperature rate is controlled at 0.03～1.5 ℃/min.
12. ending: before crystal growth finishes, suitably heat up, make the pontoon rotating speed reach 3.0 seconds/commentaries on classics.Crucible changes, the crucible liter when time at the bottom of the pontoon contact crucible stops, and begins to fall the crucible position of crucible when getting back to seeding.Make crystal break away from melt and disengaging boron oxide lentamente then, more than crystal leaves boron oxide 30mm, stop; Progressively cooling, venting makes the boron oxide foaming with the whole removals of burner hearth internal gas pressure in the time of 1300 ℃; Continue to drop to normal temperature again.
13. through detecting, the monocrystalline carrier concentration is (1.5～4.0) * 10
17Cm
-3, dislocation desity EPD＜5 * 10
5Cm
-2
Embodiment 2:
1. preparation work: boron oxide is carried out vacuum hydro-extraction, with cleaning with deionized water behind the chloroazotic acid corrosion gallium phosphide polycrystal, handle behind the quartz apparatus and spend dried up cleaning with chloroazotic acid.
2. get the raw materials ready: will corrode 1.5 kilograms of gallium phosphide polycrystals that cleaned quartz crucible of packing into, be that the pontoon of φ 45mm is put in crucible central authorities with internal diameter, puts into doping agent sulphur 80mg, and the 400g boron oxide that will smash is again put into crucible.
3. shove charge: install seed crystal, cross bar, float needle, camera lens, mix up the verticality of crucible pole, configure graphite heater and heat preservation member, the quartz crucible that installs polycrystal is placed in the graphite crucible wall, the sealing body of heater with dial indicator.
4. extract the air in the burner hearth out with vacuum pump, last air pressure is less than 450Pa.In burner hearth, charge into high pure nitrogen then and reach 2.0Mpa, inspection furnace sealing property.
5. temperature increasing for melting materials: temperature is raised to 1680 ℃ the gallium phosphide polycrystal material melted.Speed with 8 rev/mins forwards seed rod to, with 15 rev/mins speed counter-rotation crucible pole.
6. seed crystal welding: make seed crystal contact melt after the abundant preheating of seed crystal, when seed crystal with after melt contact, adjust temperature according to the aperture that produces, the aperture of solid-liquid interface is stablized.
7. seeding: begin the seeding of lowering the temperature stable after touching 15 minutes, rate of temperature fall is controlled at 0.03～0.3 ℃/min, when the solid phase of seeing solid-liquid interface is grown up, begins to lift, and pull rate is 4mm/h.Crystal growth characteristic in the close observation shouldering process is if monocrystalline then continues pulling crystal.As do not have the then timely melt back of need of monocrystalline characteristic, repeat above-mentioned seeding process.
8. shouldering: increase the crucible liter when differential weight shows 0.2g/min and progressively arrive 0.9mm/hr.Along with the crystalline adjustment temperature of growing up is controlled the pontoon rotating speed, so that the pontoon rotating speed is at the uniform velocity slack-off, reach the purpose of the control crystalline speed of growth, accomplish crystal shouldering process.
9. float needle one takes off: when the pontoon rotating speed reaches 2.5 seconds/stable earlier temperature once when changeing, accomplish run-bake-needle fault for the first time.
10. float needle two takes off: control pontoon rotating speed reaches 2.8 seconds/changes the completion run-bake-needle fault second time.
11. diameter control: steadily control the pontoon rotating speed 3.4 seconds/turn left rightly with the control crystal diameter, suitably lower the temperature when boat changes when accelerating, suitably heat up when slowing down when boat changes, temperature rate is controlled at 0.1～1.0 ℃/min.
12. ending: before crystal growth finishes, suitably heat up, make the pontoon rotating speed reach 3.2 seconds/commentaries on classics.Crucible changes, the crucible liter when time at the bottom of the pontoon contact crucible stops, and begins to fall the crucible position of crucible when getting back to seeding.Make crystal break away from melt and disengaging boron oxide lentamente then, more than crystal leaves boron oxide 45mm, stop; Progressively cooling, venting makes the boron oxide foaming with the whole removals of burner hearth internal gas pressure in the time of 1100 ℃; Continue to drop to normal temperature again.
13. through detecting, the monocrystalline carrier concentration is (3.0～8.0) * 10
17Cm
-3, dislocation desity EPD＜4 * 10
5Cm
-2
Embodiment 3:
1. preparation work: boron oxide is carried out vacuum hydro-extraction, with cleaning with deionized water behind the chloroazotic acid corrosion gallium phosphide polycrystal, handle behind the quartz apparatus and spend dried up cleaning with chloroazotic acid.
2. get the raw materials ready: will corrode 2.0 kilograms of gallium phosphide polycrystals that cleaned quartz crucible of packing into, be that the pontoon of φ 55mm is put in crucible central authorities with internal diameter, puts into doping agent tellurium 900mg, and the 500g boron oxide that will smash is again put into crucible.
3. shove charge: install seed crystal, cross bar, float needle, camera lens, mix up the verticality of crucible pole, configure graphite heater and heat preservation member, the quartz crucible that installs polycrystal is placed in the graphite crucible wall, the sealing body of heater with dial indicator.
4. extract the air in the burner hearth out with vacuum pump, last air pressure is less than 300Pa.In burner hearth, charge into high pure nitrogen then and reach 3.5Mpa, inspection furnace sealing property.
5. temperature increasing for melting materials: temperature is raised to 1820 ℃ the gallium phosphide polycrystal material melted.Speed with 15 rev/mins forwards seed rod to, with 40 rev/mins speed counter-rotation crucible pole.
6. seed crystal welding: make seed crystal contact melt after the abundant preheating of seed crystal, when seed crystal with after melt contact, adjust temperature according to the aperture that produces, the aperture of solid-liquid interface is stablized.
7. seeding: begin the seeding of lowering the temperature stable after touching 25 minutes, rate of temperature fall is controlled at 1.0～1.5 ℃/min, when the solid phase of seeing solid-liquid interface is grown up, begins to lift, and pull rate is 12mm/h.Crystal growth characteristic in the close observation shouldering process is if monocrystalline then continues pulling crystal.As do not have the then timely melt back of need of monocrystalline characteristic, repeat above-mentioned seeding process.
8. shouldering: increase the crucible liter when differential weight shows 1.0g/min and progressively arrive 1.5mm/hr.Along with the crystalline adjustment temperature of growing up is controlled the pontoon rotating speed, so that the pontoon rotating speed is at the uniform velocity slack-off, reach the purpose of the control crystalline speed of growth, accomplish crystal shouldering process.
9. float needle one takes off: when the pontoon rotating speed reaches 2.6 seconds/stable earlier temperature once when changeing, accomplish run-bake-needle fault for the first time.
10. float needle two takes off: control pontoon rotating speed reaches 4.7 seconds/changes the completion run-bake-needle fault second time.
11. diameter control: steadily control the pontoon rotating speed 4.5 seconds/turn left rightly with the control crystal diameter, suitably lower the temperature when boat changes when accelerating, suitably heat up when slowing down when boat changes, temperature rate is controlled at 1.0～1.5 ℃/min.
12. ending: before crystal growth finishes, suitably heat up, make the pontoon rotating speed reach 3.2 seconds/commentaries on classics.Crucible changes, the crucible liter when time at the bottom of the pontoon contact crucible stops, and begins to fall the crucible position of crucible when getting back to seeding.Make crystal break away from melt and disengaging boron oxide lentamente then, more than crystal leaves boron oxide 60mm, stop; Progressively cooling, venting makes the boron oxide foaming with the whole removals of burner hearth internal gas pressure in the time of 600 ℃; Continue to drop to normal temperature again.
13. through detecting, the monocrystalline carrier concentration is (1.0～6.0) * 10
17Cm
-3, dislocation desity EPD＜3.5 * 10
5Cm
-2
Embodiment 4:
1. preparation work: boron oxide is carried out vacuum hydro-extraction, with cleaning with deionized water behind the chloroazotic acid corrosion gallium phosphide polycrystal, handle behind the quartz apparatus and spend dried up cleaning with chloroazotic acid.
2. get the raw materials ready: will corrode 2.5 kilograms of gallium phosphide polycrystals that cleaned quartz crucible of packing into, be that the pontoon of φ 60mm is put in crucible central authorities with internal diameter, puts into doping agent tellurium 1050mg, and the 600g boron oxide that will smash is again put into crucible.
3. shove charge: install seed crystal, cross bar, float needle, camera lens, mix up the verticality of crucible pole, configure graphite heater and heat preservation member, the quartz crucible that installs polycrystal is placed in the graphite crucible wall, the sealing body of heater with dial indicator.
4. extract the air in the burner hearth out with vacuum pump, last air pressure is less than 250Pa.In burner hearth, charge into high pure nitrogen then and reach 4.5Mpa, inspection furnace sealing property.
5. temperature increasing for melting materials: temperature is raised to 1750 ℃ the gallium phosphide polycrystal material melted.Speed with 25 rev/mins forwards seed rod to, with 20 rev/mins speed counter-rotation crucible pole.
6. seed crystal welding: make seed crystal contact melt after the abundant preheating of seed crystal, when seed crystal with after melt contact, adjust temperature according to the aperture that produces, the aperture of solid-liquid interface is stablized.
7. seeding: begin the seeding of lowering the temperature stable after touching 5 minutes, rate of temperature fall is controlled at 1.0～2.0 ℃/min, when the solid phase of seeing solid-liquid interface is grown up, begins to lift, and pull rate is 6mm/h.Crystal growth characteristic in the close observation shouldering process is if monocrystalline then continues pulling crystal.As do not have the then timely melt back of need of monocrystalline characteristic, repeat above-mentioned seeding process.
8. shouldering: increase the crucible liter when differential weight shows 0.4g/min and progressively arrive 1.0mm/hr.Along with the crystalline adjustment temperature of growing up is controlled the pontoon rotating speed, so that the pontoon rotating speed is at the uniform velocity slack-off, reach the purpose of the control crystalline speed of growth, accomplish crystal shouldering process.
9. float needle one takes off: when the pontoon rotating speed reaches 3.5 seconds/stable earlier temperature once when changeing, accomplish run-bake-needle fault for the first time.
10. float needle two takes off: control pontoon rotating speed reaches 3.0 seconds/changes the completion run-bake-needle fault second time.
11. diameter control: steadily control the pontoon rotating speed 2.8 seconds/turn left rightly with the control crystal diameter, suitably lower the temperature when boat changes when accelerating, suitably heat up when slowing down when boat changes, temperature rate is controlled at 0.05～0.5 ℃/min.
12. ending: before crystal growth finishes, suitably heat up, make the pontoon rotating speed reach 2.0 seconds/commentaries on classics.Crucible changes, the crucible liter when time at the bottom of the pontoon contact crucible stops, and begins to fall the crucible position of crucible when getting back to seeding.Make crystal break away from melt and disengaging boron oxide lentamente then, more than crystal leaves boron oxide 80mm, stop; Progressively cooling, venting makes the boron oxide foaming with the whole removals of burner hearth internal gas pressure in the time of 700 ℃; Continue to drop to normal temperature again.
13. through detecting, the monocrystalline carrier concentration is (1.5～5.5) * 10
17Cm
-3, dislocation desity EPD＜4.5 * 10
5Cm
-2
Embodiment 5:
1. preparation work: boron oxide is carried out vacuum hydro-extraction, with cleaning with deionized water behind the chloroazotic acid corrosion gallium phosphide polycrystal, handle behind the quartz apparatus and spend dried up cleaning with chloroazotic acid.
2. get the raw materials ready: will corrode 3.0 kilograms of gallium phosphide polycrystals that cleaned quartz crucible of packing into, be that the pontoon of φ 80mm is put in crucible central authorities with internal diameter, puts into doping agent sulphur 400mg, and the 800g boron oxide that will smash is again put into crucible.
3. shove charge: install seed crystal, cross bar, float needle, camera lens, mix up the verticality of crucible pole, configure graphite heater and heat preservation member, the quartz crucible that installs polycrystal is placed in the graphite crucible wall, the sealing body of heater with dial indicator.
4. extract the air in the burner hearth out with vacuum pump, last air pressure is less than 200Pa.In burner hearth, charge into high pure nitrogen then and reach 4.0Mpa, inspection furnace sealing property.
5. temperature increasing for melting materials: temperature is raised to 1900 ℃ the gallium phosphide polycrystal material melted.Speed with 5 rev/mins forwards seed rod to, with 50 rev/mins speed counter-rotation crucible pole.
6. seed crystal welding: make seed crystal contact melt after the abundant preheating of seed crystal, when seed crystal with after melt contact, adjust temperature according to the aperture that produces, the aperture of solid-liquid interface is stablized.
7. seeding: begin the seeding of lowering the temperature stable after touching 5 minutes, rate of temperature fall is controlled at 0.1～2.0 ℃/min, when the solid phase of seeing solid-liquid interface is grown up, begins to lift, and pull rate is 15mm/h.Crystal growth characteristic in the close observation shouldering process is if monocrystalline then continues pulling crystal.As do not have the then timely melt back of need of monocrystalline characteristic, repeat above-mentioned seeding process.
8. shouldering: increase the crucible liter when differential weight shows 1.5g/min and progressively arrive 1.8mm/hr.Along with the crystalline adjustment temperature of growing up is controlled the pontoon rotating speed, so that the pontoon rotating speed is at the uniform velocity slack-off, reach the purpose of the control crystalline speed of growth, accomplish crystal shouldering process.
9. float needle one takes off: when the pontoon rotating speed reaches 5.0 seconds/stable earlier temperature once when changeing, accomplish run-bake-needle fault for the first time.
10. float needle two takes off: control pontoon rotating speed reaches 6.0 seconds/changes the completion run-bake-needle fault second time.
11. diameter control: steadily control the pontoon rotating speed 5.5 seconds/turn left rightly with the control crystal diameter, suitably lower the temperature when boat changes when accelerating, suitably heat up when slowing down when boat changes, temperature rate is controlled at 0.3～3.0 ℃/min.
12. ending: before crystal growth finishes, suitably heat up, make the pontoon rotating speed reach 4.0 seconds/commentaries on classics.Crucible changes, the crucible liter when time at the bottom of the pontoon contact crucible stops, and begins to fall the crucible position of crucible when getting back to seeding.Make crystal break away from melt and disengaging boron oxide lentamente then, more than crystal leaves boron oxide 100mm, stop; Progressively cooling, venting makes the boron oxide foaming with the whole removals of burner hearth internal gas pressure in the time of 500 ℃; Continue to drop to normal temperature again.
13. through detecting, the monocrystalline carrier concentration is (2.5～5.0) * 10
18Cm
-3, dislocation desity EPD＜6 * 10
5Cm
-2
Claims (6)
1. the growth method of a monocrystal of gallium phosphide, it is characterized in that: it may further comprise the steps: get the raw materials ready, shove charge vacuumizes, inflates; Temperature increasing for melting materials, seed crystal welding, seeding, shouldering, float needle one takes off, and float needle two takes off; Diameter control, ending in procedure for preparation, is placed with gallium phosphide polycrystal, pontoon, doping agent and boron oxide in the crucible; Described pontoon material is a silicon nitride, the internal diameter φ 20～80mm of pontoon, and the pressure-controlling behind the burner hearth inflated with nitrogen is in 1.0～5.0MPa (absolute pressure.
2. the growth method of a kind of monocrystal of gallium phosphide according to claim 1 is characterized in that: in the described temperature increasing for melting materials operation, rotate seed rod with 1-30 rev/min speed, with 5-50 rev/min speed counter-rotation crucible pole; The seeding operation is the cooling seeding, and rate of temperature fall is controlled at 0.03～2.0 ℃/min, when the solid phase of seeing solid-liquid interface is grown up, begins to lift, and pull rate is controlled at 1～15mm/h.
3. the growth method of a kind of monocrystal of gallium phosphide according to claim 1 and 2; It is characterized in that: differential weight shows that increasing crucible when 0.1～1.5g/min is above rises progressively to 0.2～1.8mm/hr; Along with crystalline grow up the adjustment temperature control the pontoon rotating speed; So that the pontoon rotating speed is at the uniform velocity slack-off, reach the purpose of the control crystalline speed of growth
4. according to the growth method of claim 1 or 2 or 3 described a kind of monocrystal of gallium phosphide, it is characterized in that:, accomplish run-bake-needle fault for the first time when the pontoon rotating speed reaches 2.0～5.0 seconds/stable earlier temperature once when changeing; Control pontoon rotating speed reaches 2.5～6.0 seconds/more than changeing, accomplishes run-bake-needle fault for the second time.
5. according to the growth method of claim 1 or 2 or 3 or 4 described a kind of monocrystal of gallium phosphide; It is characterized in that: in the diameter control operation; Steadily control pontoon rotating speed 2.5～6.0 seconds/change with the control crystal diameter; Lower the temperature when boat changes when accelerating, heat up when boat changes when slowing down, temperature rate is controlled at 0.03～3.0 ℃/min.
6. the growth method of a kind of monocrystal of gallium phosphide according to claim 1; It is characterized in that: before crystal growth finishes, heat up; Make the pontoon rotating speed reach 2.0～4.0 seconds/commentaries on classics, crucible changes, the crucible liter when time at the bottom of the pontoon contact crucible stops, and begins to fall the crucible position of crucible when getting back to seeding.
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| CN108166061A (en) * | 2017-12-25 | 2018-06-15 | 云南北方昆物光电科技发展有限公司 | A kind of method for reducing Insb Single Crystals dislocation |
| CN108166060A (en) * | 2017-12-25 | 2018-06-15 | 云南北方昆物光电科技发展有限公司 | A kind of indium antimonide<211>The preparation method of direction monocrystalline |
| CN108502929A (en) * | 2018-05-03 | 2018-09-07 | 武汉轻工大学 | A method of preparing electron level nanometer titanium dioxide molybdenum powder |
| CN116121867A (en) * | 2023-02-01 | 2023-05-16 | 有研国晶辉新材料有限公司 | Preparation method of optical grade gallium phosphide single crystal |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108166061A (en) * | 2017-12-25 | 2018-06-15 | 云南北方昆物光电科技发展有限公司 | A kind of method for reducing Insb Single Crystals dislocation |
| CN108166060A (en) * | 2017-12-25 | 2018-06-15 | 云南北方昆物光电科技发展有限公司 | A kind of indium antimonide<211>The preparation method of direction monocrystalline |
| CN107955971A (en) * | 2017-12-27 | 2018-04-24 | 有研光电新材料有限责任公司 | Shouldering method in Horizontal Bridgman Method arsenide gallium monocrystal pulling process |
| CN108502929A (en) * | 2018-05-03 | 2018-09-07 | 武汉轻工大学 | A method of preparing electron level nanometer titanium dioxide molybdenum powder |
| CN116121867A (en) * | 2023-02-01 | 2023-05-16 | 有研国晶辉新材料有限公司 | Preparation method of optical grade gallium phosphide single crystal |
| CN116121867B (en) * | 2023-02-01 | 2023-08-15 | 有研国晶辉新材料有限公司 | Preparation method of optical grade gallium phosphide single crystal |
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