CN108360061A - The method of continuous VGF crystal growths is rotated after a kind of horizontal injection synthesis - Google Patents
The method of continuous VGF crystal growths is rotated after a kind of horizontal injection synthesis Download PDFInfo
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- CN108360061A CN108360061A CN201711295536.0A CN201711295536A CN108360061A CN 108360061 A CN108360061 A CN 108360061A CN 201711295536 A CN201711295536 A CN 201711295536A CN 108360061 A CN108360061 A CN 108360061A
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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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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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
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Abstract
The present invention provides a kind of method that continuous VGF crystal growths are rotated after horizontal injection synthesis, belong to semiconductor crystal synthesis and growing technology field, the technical solution adopted is that after being synthesized by the direct horizontal injection of Volatile Elements and simple metal element, further by the whole slowly rotation of rotating odd even stock control furnace body, rotation is with continuous VGF crystal growths after realizing Opacity in lens, to prepare high-purity compound semiconductor crystal, seed crystal is melted by simple metal before avoiding VGF crystal growths, this method step is succinct, device structure is simple, it is easy to operate and control, be conducive to the industrialization production of semiconductor crystal.
Description
Technical field
The present invention relates to the device and method of semiconductor crystal synthesis and growth, and in particular to after a kind of horizontal injection synthesis
The method for rotating continuous VGF crystal growths is particularly suitable for the semiconductor that indium phosphide, gallium phosphide etc. carry volatile element synthesis
The VGF crystal growths of crystalline material.
Background technology
Compound semiconductor is widely used in electronics industry, is important compound semiconductor materials.For example, InP, GaP,
GaAs etc..Contain volatile element in being formed due to element, synthetic method has horizontal proliferation synthesizes and injection synthesizes etc..Its crystal
Growing method has LEC (Liquid Encapsulated Czochralski：Liquid seal straight pull) method, VGF (Vertical
gradient freezing：Vertical gradient solidification) method etc., since LEC methods need equipment cost higher, crystal stress is larger,
Dislocation density is high, and crystal growth technique is complicated, is unfavorable for growing the large-sized monocrystalline of high quality, therefore, applies at present more
It is VGF methods.
Use AT＆T Labs of the U.S. and the eighties in last century VGF methods to prepare III-V compound for the first time, this method be by
Container equipped with indium phosphide polycrystal raw material is vertically arranged in the relevant temperature gradient position set in stove, and container surroundings are distributed with red
Phosphorus slowly crystallizes from lower end thereof and is extended to the growing method of upper one end after polycrystal raw material fine melt.VGF methods
The speed of growth is slower, temperature gradient very little, therefore stress suffered by crystal is smaller, it is possible to it is relatively low to grow dislocation density
Crystalline material.But this method needs seed crystal being first placed in crucible before crystal growth.If connected after being synthesized to realization
Continuous VGF crystal growths are with regard to relatively difficult, because needing seed crystal to be in direct contact with simple metal in this way, in high temperature simple metal melt
In, compound seed crystal by Melt molten that simple metal is either synthesizing or can be eaten away.In order to protect seed crystal, need in advance
It is put into polycrystal material in crucible and is melted by cumbersome temperature control program to protect seed crystal not to be synthesized process, but meeting in this way
Cause the crystalline material purity of synthesis to reduce, and leads to synthetic crystal growth course time-consuming, process complexity is cumbersome, volatile
Accidentally, it is difficult to which industrialization and grown on larger scale seriously hinder the application development of semiconductor crystalline material.
Invention content
The present invention is that VGF crystal growths need to be put into polycrystal material, growth course before need to synthesizing after solving current injection method synthesis
Very complicated, the big technical problem of industrialization difficulty provide the side that continuous VGF crystal growths are rotated after a kind of horizontal injection synthesis
Method further controls furnace body after the direct horizontal injection synthesis using Volatile Elements and simple metal element by rotating mechanism
Whole slowly rotation, continuous VGF crystal growths avoid to prepare high-purity compound semiconductor crystal after realizing Opacity in lens
Seed crystal is melted by simple metal before VGF growths, and this method step is succinct, device structure is simple, is easy to operate and control, and is conducive to half
The industrialization production of conductor crystal.
The technical solution adopted by the present invention is：The method of continuous VGF crystal growths, base are rotated after a kind of horizontal injection synthesis
In including furnace body, the Opacity in lens growing system being located in furnace chamber and its mating heating system, temp measuring system, heat-insulation system
Equipment with continuous VGF crystal growths are rotated after the injection synthesis of control system, it is critical that the Opacity in lens growing system
It is equipped with the crucible of seed crystal accommodating chamber including side and is arranged in the horizontal side of crucible and the volatilization member that communicates therewith by injection pipe
Plain carrier, the furnace body the described method comprises the following steps with rotating mechanism is arranged with：
Stock and device assembly：By volatile element be packed into volatile element carrier in and seal, by seed crystal, metallic element and
Boron oxide is placed in crucible, and volatile element carrier and crucible are positioned in furnace chamber together；Control metallic element and volatile element
The compound melt liquid level of formation is less than seed crystal accommodating chamber, and sealed compound melt and liquid level are higher than seed crystal appearance after boron oxide fusing
Receive chamber；
Furnace body is sealed, protective gas is filled with after vacuumizing；
Heating makes metallic element and boron oxide melt；
Heating makes volatile element pass through injection pipe and enters metallic element melt, injection synthesis compound melt；
After synthesis, furnace body is rotated to vertical state, the temperature point of adjustment crucible region by rotating mechanism
Cloth realizes continuous VGF crystal growths after synthesis.
Further, the stepIt is the member that will first volatilize that middle volatile element carrier and crucible, which are positioned at together in furnace chamber,
The injection pipe of plain carrier stretches into crucible, is then put into together equipped in exhaust outlet sealed compartment, then sealed compartment is positioned at stove
Intracavitary.
Further, the stepMiddle heating makes metallic element and boron oxide melt the required temperature controlled：Make gold
The temperature for belonging to element is higher than 30-70 DEG C of melting point compound, while the temperature for making seed crystal accommodate cavity region is less than melting point compound 5-
15℃。
Further, the stepWhen middle heating makes volatile element pass through injection pipe to enter metallic element melt, heating
The condition of the reached temperature of volatile element is to ensure that the pressure in volatile element carrier is higher than the dissociation pressure of compound melt.
Further, the stepAfter middle synthesis, compound melt is cooled to higher than compound first
5-20 DEG C of fusing point, the interface temperature for controlling the seed crystal accommodating chamber side of compound melt liquid level and crucible are higher than compound crystalline temperature
3-5 DEG C of range, while seed crystal accommodating chamber regional temperature being kept to stablize.
Further, the stepAfter middle furnace body rotates state in a vertical shape, compound melt is stood into 10-30min.
Further, the stepMiddle speed of rotation control is in 20-40 °/h；Seed crystal accommodating chamber is kept in rotary course
Regional temperature is stablized；After rotation to vertical state, the Temperature Distribution of adjustment crucible region is by temp measuring system and control
The coordination of system controls, and establishes temperature gradient in the interface and compound melt of seed crystal and compound melt contacts, realizes injection
Continuous VGF crystal growths after synthesis.Further, in the equipment of the injection synthesis rotation VGF crystal growths, rotating mechanism knot
Structure includes driving motor and the retarder that is connect with driving motor output shaft, and the reducer output shaft is by shaft coupling and stove
Body rotates axis connection, and furnace body is limited by furnace body rotary shaft on holder.
Further, in the equipment that continuous VGF crystal growths are rotated after the injection synthesis, the injection pipe end back of the body
From or tilting far from volatile element carrier, be in 60 ° of -85 ° of angles with volatile element carrier.
Further, in the equipment that continuous VGF crystal growths are rotated after the injection synthesis, in the heating system structure
Multistage heating device including being set in Opacity in lens growing system periphery；The heat-insulation system structure includes being set in heating system
Muff outside system；The temp measuring system structure includes being respectively used to measure seed crystal in crystal growing crucible to accommodate alveolus
Domain, the thermocouple a of crystal growth zone and volatile element carrier regional temperature, thermocouple c and/or thermocouple d and/or thermoelectricity
Even e, thermocouple b.
In above-mentioned technical proposal, a kind of method that continuous VGF crystal growths are rotated after horizontal injection synthesis is provided, accordingly
A kind of equipment of horizontal injection synthesis rotation VGF crystal growths is provided, the device structure includes furnace body, the furnace chamber of furnace body
Opacity in lens growing system is inside located, Opacity in lens growing system is mating to be provided with heating system, temp measuring system, heat-insulation system
And control system, it is critical that the mating rotating mechanism being provided with for its rotation of furnace body, has rotary freedom；The crystalline substance
Body synthesis growing system includes crucible and volatile element carrier, and crucible side is equipped with seed crystal accommodating chamber, crucible and volatilization member
The position relationship of both plain carriers is placed for horizontal alignment, wherein the funnel-form of similar placement of droping to the ground when crucible is horizontal positioned,
Structure includes the seed crystal accommodating chamber of horizontal strip, the synthesis being connect with seed crystal accommodating chamber and crystal growth portion, injection insertion hole；
Volatile element carrier is provided with injection pipe, and injection pipe passes through injection to be inserted into hole and stretches in crucible.
Based on above equipment, the method that continuous VGF crystal growths are rotated after level injection synthesis includes the following steps：
Stock and device assembly：By volatile element be packed into volatile element carrier in and seal, by seed crystal, metallic element and
Protective agent such as boron oxide are placed in crucible, and the injection pipe of volatile element carrier is inserted into crucible, then carries volatile element
Device and crucible are positioned in furnace chamber together；The amount that each material is controlled when stock is as follows：The amount of metallic element is height after heating fusing
Degree is in seed crystal accommodating chamber hereinafter, not contacted with seed crystal；Height is higher than seed crystal accommodating chamber after protective agent boron oxide melted by heat is complete, from
And seed crystal is covered, metallic element melt is entered by injection pipe after volatile element is heated, injection is synthetically formed compound melt, changes
Polymer melt liquid level is less than seed crystal accommodating chamber height, it is ensured that is not contacted with seed crystal.It heats molten metal element melt and waves
Send out and form compound melt after element evaporation, after protective agent such as boron oxide fusing can sealed compound melt and liquid level be higher than seed crystal
Accommodating chamber；
Furnace body is sealed, furnace body is vacuumized, is generally evacuated to 10-3Pa is then charged with protective gas, can be inertia
Gas, such as nitrogen, argon gas, when need to generally control synthesis and crystal growth protective gas pressure be more than compound melt from
Decompression；
Heating makes metallic element and boron oxide melt, and general control heating temperature range is to ensure metallic element in the step
Temperature reach above 30-70 DEG C of the fusing point of compound, while make seed crystal accommodate cavity region temperature be less than melting point compound 5-
15 DEG C, boron oxide sealing metal element melt and seed crystal after fusing；
Heating makes volatile element pass through injection pipe and enters metallic element melt, level injection synthesis compound melt, heating
In the process, the temperature of volatile element region to be detected accurately and is controlled in time, in order to control the injection of volatile element
Rate；
After synthesis, furnace body is rotated to vertical state, the temperature point of adjustment crucible region by rotating mechanism
Cloth establishes temperature gradient, after carrying out injection synthesis in the interface and compound melt of seed crystal and compound melt contacts
Rotate continuous VGF crystal growths.
The beneficial effects of the invention are as follows：The present invention is laid out volatile element in furnace body by ingenious setting rotating mechanism, science
The positional structure of support container and crucible controls the change in location of volatile element support container and crucible, realizes horizontal injection
Continuous vertical gradient crystal growth is rotated after synthesis；Horizontal injection synthesis provided by the invention rotates continuous VGF crystal growths
Method and its corollary equipment, simplify technique, and seed crystal is melted by simple metal before avoiding VGF growths；This method step is succinct, easy
In operation and control, apparatus structure is simple, easily operated, and synthesized semiconductor crystal controlled shape, quality are uniform, are conducive to
Realize the industrialization production of semiconductor crystal.
Description of the drawings
Fig. 1 is overall structure diagram of the present apparatus furnace body on holder；
Long crucible structure schematic diagram when Fig. 2 is horizontally arranged for the present apparatus；
Fig. 3 is the schematic diagram that the present apparatus is horizontally arranged stock stage Opacity in lens growing system；
Fig. 4 is the schematic diagram that the present apparatus is horizontally arranged synthesis phase Opacity in lens growing system；
The schematic diagram of Opacity in lens growing system after Fig. 5 synthesizes for the present apparatus is horizontal positioned；
Fig. 6 is the schematic diagram of VGF crystal growth phase Opacity in lens growing systems after present apparatus rotation is vertical；
In figure, 1, thermocouple c；2, thermal insulation board；3, multistage heating device；4, thermocouple b；5, load compartment；5-1, sealing cover, 5-1-1, exhaust
Hole；6, volatile element carrier；7, volatile element；8, injection pipe；9, crucible；9-1, seed crystal accommodating chamber；9-2, synthesis and crystal
Growing part；Hole is inserted into 9-3, injection；10, metallic element；11, boron oxide；12：Thermocouple e；13, thermocouple d；14, thermocouple a；15, seed
It is brilliant；16, crucible supporting；17, furnace body；17-1, furnace body rotary shaft；17-2, holder；18：Muff.
Specific implementation mode
It is given birth to below by way of continuous VGF crystal is rotated after the specific embodiment horizontal injection synthesis that the present invention will be described in detail provides
Long method and its corollary equipment, in order to understand, but the invention is not limited in any way, one of ordinary skill in the art according to
The improvement modification or similar replacement that technical solution is carried out, should all be included in the protection scope of the present invention.
Apparatus embodiments
Equipment the present embodiment provides continuous VGF crystal growths are rotated after a kind of horizontal injection synthesis, referring to Fig. 1, device structure
Include furnace body 17, the Opacity in lens growing system that is located in the furnace chamber of furnace body 17 and its mating heating system, thermometric system
System and heat-insulation system, furnace body 17 set Packed lid, form seal cavity, synthesis and crystal growth system are equipped in furnace body 17
System, heating system are located at Opacity in lens growing system periphery, and for accurately being heated to each section, the present embodiment is using multistage
Heater 3；Heat-insulation system setting is in heating system outer layer, and the present embodiment is using muff 18, for being given birth to Opacity in lens
Long system integral heat insulation；Temp measuring system can be multiple thermocouples, and dispersion or interspersed setting in Opacity in lens growing system and add
In hot systems or heat-insulation system structure, for each section the real time measure temperature in Opacity in lens growing system, in the present embodiment,
The temp measuring system structure include be respectively used to measure crucible 9 in seed crystal accommodating chamber 9-1 regional temperatures thermocouple a 14,
It is synthesized with the thermocouple c 1 and thermocouple d 13 and thermocouple e 12 of crystal growth portion 9-2 regional temperatures, for surveying for measuring
Determine the thermocouple b 4 of 6 regional temperature of volatile element carrier；Control system is used for receiving and transmitting signal, and Comprehensive Control coordinates heating system
System, temp measuring system and heat-insulation system etc..Key Design as this equipment, which is that the furnace body 17 is mating, is provided with rotating mechanism,
To realize the rotation of furnace body 17, positioning and connection relation, rotating mechanism optional conventional rotation of the furnace body 17 with rotating mechanism
Turn, in the present embodiment, referring to Fig. 1, furnace body 17 is limited by furnace body rotary shaft 17-1 on holder 17-2, the rotating mechanism
The retarder for including driving motor and being connect with driving motor output shaft, the reducer output shaft is by shaft coupling and stove
Body rotary shaft 17-1 connections, to control the rotation of furnace body 17.The Opacity in lens growing system includes that crucible 9 and setting exist
The volatile element carrier 6 of its horizontal side, wherein the funnel-form of similar placement of droping to the ground when crucible 9 is horizontally arranged, shape referring to
Fig. 2, structure include be arranged the horizontal rectangular-shape of side or cylindric etc. seed crystal accommodating chamber 9-1, with seed crystal accommodating chamber
The synthesis of 9-1 connections is inserted into hole 9-3 with crystal growth portion 9-2, injection, and injection insertion tube 9-3 is located at synthesis and crystal growth portion
The top or end of 9-2, after diameter need to ensure synthesis, compound melt height is less than injection insertion tube 9-3's
Lower edge flows out crucible 9 to which compound melt will not occur from injection insertion tube 9-3；Volatile element carrier 6 is provided with note
Enter pipe 8, injection pipe 8 passes through injection to be inserted into hole 9-3 and stretches in crucible 9, and the volatile element 7 in volatile element carrier 6 is heated
The metal bath entered in crucible 9, with crucible 9 by injection pipe 8 can realize horizontal injection synthesis；After synthesis, whirler
Structure makes furnace body 17 by rotating horizontally as vertical state（As shown in Figure 6）, the Temperature Distribution of each heat affected zone is adjusted, ensures that seed crystal holds
The temperature of intracavitary received is less than the fusing point of seed crystal 15 and adjusts the Temperature Distribution of each heat affected zone again after furnace body 17 is in vertical
Ensure that the compound melt in crucible 9 is contacted with seed crystal 15 and realizes vertical gradient crystal growth.
To avoid the rotation of furnace body 17 that the compound melt in crucible 9 is caused to pour in down a chimney to volatile element carrier 6, the note
Enter that 8 end of pipe deviates from or tilting is far from volatile element carrier 6, as shown in figure 3, injection pipe 8 can be bending shape, latter end portion
Point tilting is far from volatile element carrier 6, it is preferable that end segment parts deviate volatile element carrier 6 and with its lateral edge line
In 60 ° of -85 ° of angles.
More specifically, to be further ensured that the stability of synthesis and crystal growth system, the synthesis and crystal growth
Further include the load compartment 5 for loading the crucible 9 and volatile element carrier 6 in system, referring to Fig. 3 to Fig. 6, load compartment 5 can be
Quartz, silicon carbide, boron nitride or ceramic material, the load compartment 5 mating setting sealing cover 5-1, sealing cover 5-1 are equipped with exhaust
Mouth 5-1-1.When assembling device, the injection that the injection pipe 8 of volatile element carrier 6 is inserted into crucible 9 is inserted into the 9-3 of hole, volatilization
Thermal insulation board 2 in 9 middle pad of element carrier 6 and crucible, is then put into togerther load compartment 5 by volatile element carrier 6 and crucible 9
In, then sealing cover 5-1 is installed, sealing cover 5-1 and 5 fixed seal connection of load compartment are made, at this point, outer layer muff 18 is to sealing
Lid 5-1 has further position-limiting action, can effectively prevent sealing cover 5-1 and loosens, load compartment when exhaust outlet 5-1-1 is for balancing synthesis
Air pressure in 5 is formed after volatile element injection metal bath can be discharged in compound melt process, and pressure increases in load compartment 5
Generated excessive gas.
It is separated by thermal insulation board 2 between the crucible 9 and volatile element carrier 6, on the one hand the setting of thermal insulation board 2 separates
Crucible 9 and volatile element carrier 6, avoid temperature from interacting；On the other hand, after furnace body 17 rotates state in a vertical shape, every
Hot plate 2 is supported on the upper surface of crucible 9, avoids volatile element carrier 6 and surprisingly falls into crucible 9.
9 mating setting crucible supporting 16 of the crucible, whole to seed crystal accommodating chamber 9-1 and crucible 9 have support and protection
Effect.
Based on above equipment, method of the invention is described in detail with following embodiment.
Synthetic method embodiment 1 --- the synthesis of inp semiconductor material
Stock and device assembly are carried out first：As shown in figure 3, by volatile element 7（The present embodiment is red phosphorus）It is assemblied in and waves
It in hair element carrier 6 and seals, by the seed crystal 15 of indium phosphide, metallic element 10（The present embodiment is pure indium metal）Together with doping
Agent（High purity sulphur or high purity iron）And boron oxide 11 is placed in 9 in crucible, then inserts the injection pipe 8 of volatile element carrier 6
The injection for entering crucible 9 is inserted into the 9-3 of hole, volatile element carrier 6 and synthesis among crystal growing crucible 9 with thermal insulation board 2 every
It opens, is then put into volatile element carrier 6, crucible 9 and thermal insulation board 2 between the two in sealed compartment together, then by sealed compartment
Entirety is put into furnace chamber, and the sealed compartment in the present embodiment selects load compartment 5, and 5 mating setting sealing cover 5-1 of load compartment is to form
Sealed compartment, the mode that is tightly connected are welding or suit sealing etc..Load pure indium metal amount be ensure indium fusing after the completion of not with
Seed crystal 15 contacts, and ensures to cover seed crystal 15 after boron oxide 11 has melted, while ensureing that the indium-phosphorus formed after synthesis is molten
Body is not contacted with seed crystal 15.
Furnace body is sealed, is evacuated to 10-3Pa, is filled with protective gas nitrogen 1.5-1.8MPa, and guarantee is synthesized
It is 3.0-4.0MPa with protective gas pressure when crystal growth（More than the dissociation pressure 2.75MPa of indium phosphide near fusing point）.
Then control multistage heating device 3 heats 9 region of crucible, makes 10 temperature of metallic element higher than change
Close 30-70 DEG C of object fusing point, temperature is too low will to influence injection combined coefficient, and temperature is excessively high will to lead to pressure needed for synthetic ratio melt
Power is excessively high, by control system and thermocouple e and/or thermocouple c and/or thermocouple d, ensures the metallic element 10 in crucible 9
（Pure indium）Temperature reach 1112 DEG C（The fusing point of compound indium phosphide is 1062 DEG C）, while making the regions seed crystal accommodating chamber 9-1
Temperature is less than 5-15 DEG C of melting point compound, and the present embodiment always by the cooperation of thermocouple e and control system and heating system, is about controlled
Galvanic couple e temperature is heated at 1050 DEG C.Boron oxide 11 is heated to become melt, seals pure indium melt and seed crystal 15.
Multistage heating device 3 is controlled again to heat 6 region of volatile element carrier, makes the locations thermocouple b
Domain temperature control is at 800 DEG C or so.At this point, the dissociation pressure of red phosphorus is higher than atmosphere pressures（3.0-4.0MPa）, the heated volatilization of red phosphorus,
Phosphorus gas is injected into 7 melt of metallic element（Pure indium melt）In, as shown in Figure 4.It is overflowed after being injected due to volatile element 7, quartz
Pressure in load compartment 5 can increase, and extra gas can pass through the exhaust outlet 5-1-1 discharges on load compartment 5；With synthesis into
Row, the volume of compound melt is continuously increased, at this time seed crystal 15 will not with compound melt contacts, as shown in Figure 5.
After synthesis, cool down to compound melt region, until thermocouple a and/or thermocouple c and/or
Thermocouple d temperature is 1062 DEG C or more 10 DEG C, controls thermocouple b, the temperature of thermocouple d is thermocouple b >=thermocouple d>1062
DEG C, at the same ensure the regions seed crystal accommodating chamber 9-1 thermocouple e it is temperature-resistant；Then, by entire furnace body 17 with 30 °/h
Speed slowly melt is stood 10-30 minute to vertical state by rotation so that the boron oxide in injection pipe 8 and melt instillation
In synthesis and crystal growth portion 9-2, guarantee thermocouple e temperature is constant during this, and control multistage heating device 3 is in seed crystal 15 and change
Temperature gradient is established in the interface of polymer melt contact and compound melt, control electric thermo-couple temperature height relationship is thermocouple b
>Thermocouple c>Thermocouple e>Thermocouple d>Thermocouple a, at this point, ensure solid liquid interface temperature gradient in 5K/mm or so, then
VGF crystal growths are carried out, as shown in fig. 6, obtaining inp semiconductor monocrystal material.
The carrier concentration for mixing sulphur indium phosphide crystal prepared：≥1×1018cm-3；Mobility：≥1000 cm2V-1S-1；
Resistivity：（0.1-6）×10-3Ω·cm；Dislocation density<1000/cm2。
The mobility for mixing iron indium phosphide crystal prepared：≥1000 cm2V-1S-1；Resistivity：1×107Ω cm dislocations are close
Degree<5000/cm2。
The synthesis of synthetic method embodiment 2 --- GaP semiconductor material
Stock and device assembly are carried out first：As shown in figure 3, by volatile element 7（Red phosphorus）It is assemblied in volatile element carrying
It in device 6 and seals, by the seed crystal 15 of gallium phosphide, metallic element 10（Pure gallium metal）Together with dopant（High purity sulphur or high purity zinc）
And boron oxide 11 is placed in crucible 9, and the injection pipe 8 of volatile element carrier 6 is then inserted into synthesis and crystal growing crucible 9
Injection be inserted into hole 9-3 in, volatile element carrier 6 is separated among crucible 9 with thermal insulation board 2, then carries volatile element
Device 6, crucible 9 and thermal insulation board 2 are put into load compartment 5, sealing cover 5-1 and load compartment 5 are assembled together, and be integrally put into furnace chamber
It is interior.The amount for loading pure gallium metal is to ensure not contact with seed crystal 15 after the completion of gallium fusing, and ensure to want after boron oxide 11 has melted
Seed crystal 15 is covered, while ensureing that the gallium-phosphorus melt formed after synthesis is not contacted with seed crystal 15.
Furnace body is sealed, is evacuated to 10-3Pa, is filled with 3 MPa of protective gas, and guarantee carries out synthesis and crystal growth
When protective gas pressure be 5.0MPa.
Then control multistage heating device 3 heats 9 region of crucible, passes through control system and thermocouple a
And/or thermocouple c and/or thermocouple d, ensure the metallic element 7 in crucible 9（Pure gallium）Temperature reach 1526 DEG C（Compound
The fusing point of gallium phosphide is 1476 DEG C, above 50 DEG C）, while ensureing the regions seed crystal accommodating chamber 9-1（Thermocouple e）Temperature
Degree is about controlled less than the fusing point of compound at 1465 DEG C.Boron oxide 11 is heated to become melt, seals pure gallium melt and seed crystal 15.
Multistage heating device 3 is controlled again to heat 6 region of volatile element carrier, makes the locations thermocouple b
Domain temperature control is at 900 DEG C or so.At this point, the dissociation pressure of red phosphorus is higher than atmosphere pressures（5.0MPa）, the heated volatilization of red phosphorus, phosphorus gas
Body is injected into 7 melt of metallic element（Pure gallium melt）In, as shown in Figure 4.It is overflowed after being injected due to volatile element 7, quartz loads
Pressure in cabin 5 can increase, and extra gas can pass through the exhaust outlet 5--1-1 discharges of load compartment 5；With the progress of synthesis, change
The volume of polymer melt is continuously increased, at this time seed crystal 15 will not with compound melt contacts, as shown in Figure 5.
After synthesis, cool down to compound melt region, until thermocouple a and/or thermocouple c and/or
Thermocouple d temperature is 1476 DEG C or more 10 DEG C, controls thermocouple b, the temperature of thermocouple d is thermocouple b >=thermocouple d>1476
DEG C, at the same ensure the regions seed crystal accommodating chamber 9-1 thermocouple e it is temperature-resistant；Then, by entire furnace body 17 with 35 °/h
Speed slowly melt is stood 20 minutes to vertical state by rotation so that it is molten that the boron oxide in injection pipe 8 instills compound
In body, guarantee thermocouple e temperature is constant during this, and control multistage heating device 3 is on the boundary of seed crystal 15 and compound melt contacts
Temperature gradient is established in face and compound melt, control electric thermo-couple temperature height relationship is thermocouple b>Thermocouple c>Thermocouple e
>Thermocouple d>Thermocouple a, at this point, the temperature gradient for ensureing solid liquid interface carries out VGF crystal growths, obtain in 5K/mm or so
Gallium phosphide semiconductor monocrystal material.
The carrier concentration for mixing sulphur GaP crystal prepared：（1-8）×1017cm-3；The cm of mobility >=1002V-1S-1；
Dislocation density<5000/cm2。
The carrier concentration for mixing zinc GaP crystal prepared：（5-200）×1017cm-3；The cm of mobility >=252V-1S-1；
Dislocation density<5000/cm2。
In summary content, it is known that the method for continuous VGF crystal growths is rotated after horizontal injection synthesis provided by the invention
And its corollary equipment simplifies technique, avoids VGF without being put into polycrystal material after injection method synthesizes, before VGF crystal growths
Seed crystal 15 is melted by simple metal before growth；Method and step is succinct, is easy to operate and control, and apparatus structure is simple, easily operated, institute
The semiconductor crystal controlled shape of synthesis, quality are uniform, are advantageously implemented the industrialization production of semiconductor crystal.
Claims (10)
1. rotating the method for continuous VGF crystal growths after a kind of horizontal injection synthesis, it is based on including furnace body（17）, be located in furnace chamber
The injection synthesis of interior Opacity in lens growing system and its mating heating system, temp measuring system, heat-insulation system and control system
The equipment of continuous VGF crystal growths is rotated afterwards, which is characterized in that the Opacity in lens growing system includes that side holds equipped with seed crystal
Receive chamber（9-1）Crucible（9）With setting in crucible（9）Horizontal side and by injection pipe（8）The volatile element communicated therewith is held
Carry device（6）, the furnace body（17）With rotating mechanism is arranged with, the described method comprises the following steps：
Stock and device assembly：By volatile element（7）It is packed into volatile element carrier（6）It is interior and seal, by seed crystal（15）、
Metallic element（10）And boron oxide（11）It is placed in crucible（9）It is interior, volatile element carrier（6）And crucible（9）It is positioned at stove together
Intracavitary；Control metallic element（10）With volatile element（7）The compound melt liquid level of formation is less than seed crystal accommodating chamber（9-1）, oxygen
Change boron（11）Sealed compound melt and liquid level are higher than seed crystal accommodating chamber after fusing（9-1）；
Seal furnace body（17）, protective gas is filled with after vacuumizing；
Heating makes metallic element（10）And boron oxide（11）Fusing；
Heating makes volatile element（7）Pass through injection pipe（8）Into metallic element（10）Melt, injection synthesis compound melt；
After synthesis, by rotating mechanism by furnace body（17）Rotation adjusts crucible to vertical state（9）Region
Temperature Distribution realizes continuous VGF crystal growths after synthesis.
2. according to the method described in claim 1, it is characterized in that, the stepMiddle volatile element carrier（6）And crucible
（9）Be positioned at together in furnace chamber is first by volatile element carrier（6）Injection pipe（8）Stretch into crucible（9）It is interior, then put together
Enter to be equipped with exhaust outlet（5-1-1）In sealed compartment, then sealed compartment is positioned in furnace chamber.
3. according to the method described in claim 1, it is characterized in that, the stepMiddle heating makes metallic element（10）And oxidation
Boron（11）Melting the required temperature controlled is：Make metallic element（7）Temperature be higher than 30-70 DEG C of melting point compound, while making seed
Brilliant accommodating chamber（9-1）The temperature in region is less than 5-15 DEG C of melting point compound.
4. according to the method described in claim 1, it is characterized in that, the stepMiddle heating makes volatile element（7）Pass through note
Enter pipe（8）Into metallic element（10）When melt, volatile element is heated（7）The condition of reached temperature is to ensure that volatile element is held
Carry device（6）Interior pressure is higher than the dissociation pressure of compound melt.
5. according to any methods of claim 1-4, which is characterized in that the stepIt is right first after middle synthesis
Compound melt is cooled to higher than 5-20 DEG C of melting point compound, and compound melt liquid level and crucible are controlled（9）Seed crystal hold
Receive chamber（9-1）The interface temperature of side is higher than 3-5 DEG C of compound crystalline temperature, while keeping seed crystal accommodating chamber（9-1）Regional temperature
Stablize.
6. according to the method described in claim 1, it is characterized in that, the stepMiddle furnace body（17）Rotate state in a vertical shape
Afterwards, compound melt is stood into 10-30min.
7. according to any methods of claim 1-4, which is characterized in that the stepMiddle speed of rotation control is in 20-
40°/h；Seed crystal accommodating chamber is kept in rotary course（9-1）Regional temperature is stablized；After rotation to vertical state, crucible is adjusted（9）
The Temperature Distribution of region is controlled by the coordination of temp measuring system and control system, in seed crystal and compound melt contacts
Temperature gradient is established in interface and compound melt, realizes continuous VGF crystal growths after injection synthesis.
8. according to the method described in claim 1, it is characterized in that, rotating continuous VGF crystal growths after injection synthesis
In equipment, rotating mechanism structure includes driving motor and the retarder that is connect with driving motor output shaft, and the retarder is defeated
Shaft is by shaft coupling and furnace body rotary shaft（17-1）Connection, furnace body（17）By furnace body rotary shaft（17-1）Limit is in holder
（17-2）On.
9. according to the method described in claims 1 or 2 or 8, which is characterized in that the injection synthesizes continuous VGF crystal growths
In equipment, the injection pipe（8）End deviates from or tilting is far from volatile element carrier（6）, with volatile element carrier（6）
In 60 ° of -85 ° of angles.
10. according to the method described in claims 1 or 2 or 8, which is characterized in that rotate continuous VGF crystal after the injection synthesis
In the equipment of growth, the heating system structure includes being set in the multistage heating device of Opacity in lens growing system periphery（3）；
The heat-insulation system structure includes the muff being set in outside heating system；The temp measuring system structure includes using respectively
In measurement crystal growing crucible（9）Interior seed crystal accommodating chamber（9-1）Region, synthesis and crystal growth portion（9-2）Region and volatilization member
Plain carrier（6）The thermocouple a of regional temperature（14）, thermocouple c（1）And/or thermocouple d（13）And/or thermocouple e（12）、
Thermocouple b（4）.
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| CN201711295536.0A CN108360061B (en) | 2017-12-08 | 2017-12-08 | The method of continuous VGF crystal growth is rotated after a kind of horizontal injection synthesis |
| US16/475,842 US10519563B2 (en) | 2017-12-08 | 2017-12-11 | Device and method for continuous VGF crystal growth through rotation after horizontal injection synthesis |
| PCT/CN2017/115469 WO2019109367A1 (en) | 2017-12-08 | 2017-12-11 | Device and method for rotational and continuous crystal growth by vgf process after horizontal injection and synthesis |
| JP2019541269A JP6837566B2 (en) | 2017-12-08 | 2017-12-11 | Rotational continuous VGF crystal growth apparatus and method after horizontal injection synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117626407A (en) * | 2024-01-26 | 2024-03-01 | 常州臻晶半导体有限公司 | System for efficiently growing silicon carbide single crystal by liquid phase method and working method thereof |
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