CN113957537A - Growth device and method for rapidly growing low-dislocation gallium arsenide single crystal by combining VB method and VGF method - Google Patents
Growth device and method for rapidly growing low-dislocation gallium arsenide single crystal by combining VB method and VGF method Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 52
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001218 Gallium arsenide Inorganic materials 0.000 title claims abstract description 36
- 239000010453 quartz Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 17
- 239000003708 ampul Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052810 boron oxide Inorganic materials 0.000 claims description 12
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000011081 inoculation Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 235000012431 wafers Nutrition 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 238000013473 artificial intelligence Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/42—Gallium arsenide
-
- 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
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
- C30B13/16—Heating of the molten zone
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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
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
- C30B13/28—Controlling or regulating
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Abstract
The invention discloses a growth device for rapidly growing low-dislocation gallium arsenide single crystals by combining a VB method and a VGF method, which consists of a furnace body, a graphite base, a PBN crucible and a lifting device; the furnace body comprises 6 heating areas and 6 temperature control devices for controlling the temperature of the heating areas, and the furnace body sequentially comprises a first area, a second area, a third area, a fourth area, a fifth area and a sixth area from bottom to top; the graphite base is arranged on the ground through the supporting base; the PBN crucible is arranged in a quartz ampoule which is arranged on a graphite base; the lifting device is connected with the furnace body and can pull the furnace body to be lifted at a certain pulling speed; a quartz cover is arranged between the furnace body and the PBN crucible and connected with the supporting base. The method can not only grow the crystal with ultra-low dislocation, but also shorten the shouldering time by 20 percent and shorten the equal-diameter growth time by 50 percent, thereby greatly improving the growth efficiency.
Description
Technical Field
The patent technology belongs to the field of compound semiconductor crystal growth, and particularly relates to a growth device and a method for rapidly growing low-dislocation gallium arsenide single crystals by combining a VB method and a VGF method.
Background
In the current artificial intelligence, 5G communication and the rapid development of outer space, gallium arsenide materials play more and more important roles, and especially infrared/infrared photoelectric devices, solar devices, microwave devices and the like play more and more important roles. With the increasing integration level of gallium arsenide ICs and the need to reduce cost, the general trend of gallium arsenide development is towards large diameter, long size, uniformity and consistency of electrical parameters, so the requirements for product batch consistency are more stringent. The current industry has the problems that the crystal length is generally less than 150mm, and once the crystal length is longer, the dislocation density is obviously improved, and the edge dislocation density is serious. Meanwhile, the ratio of the double crystals influencing the yield is large, and the qualification rate is influenced.
At present, the gallium arsenide single crystal shouldering method is generally adopted in a VGF method, but the VB method and the VGF method are combined for shouldering, so that ultra-low dislocation crystals can be grown, and compared with the traditional shouldering time of about 62-83 hours, the shouldering time of the gallium arsenide single crystal shouldering method is at least shortened by about 20%. The traditional constant-diameter VB walking speed is about 1.4-1.7 mm/h, the constant-diameter pulling speed of the constant-diameter VB walking device is 2.5-3.0 mm/h, the constant-diameter growth time is shortened by about 50%, and the growth efficiency is greatly improved. The diameter of the commonly used seed is about 5-6 mm, and the adoption of the coarse seed crystal has the advantages of effectively avoiding the interference of the formation of the bicrystal and bearing larger material weight, thereby improving the production efficiency. The traditional support systems are all made of refractory materials, and the graphite support system is beneficial to release of crystallization latent heat, and can particularly increase the cooling of the center of a melt so as not to cause the shape of a solid-liquid interface to be too concave. In addition, the graphite support system can also slow down the crystallization speed of the melt edge, inhibit impurities from transferring to the edge and inhibit the dense formation of edge dislocation.
Disclosure of Invention
Objects of the invention
The invention aims to provide a growth device and a method for rapidly growing low-dislocation gallium arsenide single crystals by combining a VB method and a VGF method, which shorten the time for heating and melting materials and shouldering so as to improve the production efficiency.
(II) technical scheme
In order to solve the problems, the invention provides a growth device for rapidly growing low-dislocation gallium arsenide single crystals by combining a VB method and a VGF method, which is characterized by comprising a furnace body, a graphite base, a PBN crucible and a lifting device; the furnace body comprises 6 heating areas and 6 temperature control devices for controlling the temperature of the heating areas, and the furnace body sequentially comprises a first area, a second area, a third area, a fourth area, a fifth area and a sixth area from bottom to top; the graphite base is arranged on the ground through the supporting base; the PBN crucible is arranged in a quartz ampoule which is arranged on a graphite base; the lifting device is connected with the furnace body and can pull the furnace body to be lifted at a certain pulling speed; a quartz cover is arranged between the furnace body and the PBN crucible and connected with the supporting base.
Furthermore, temperature measuring thermocouples are respectively arranged in the first zone, the second zone, the third zone, the fourth zone, the fifth zone and the sixth zone; temperature thermocouples are respectively arranged at the head and the tail of the seed crystal of the PBN crucible, the tail end of the shouldering part and the tail of the crystal growth.
Furthermore, the temperature thermocouple adopts an R-type thermocouple.
According to another aspect of the invention, a method for rapidly growing low-dislocation gallium arsenide single crystal by combining VB method and VGF method comprises the following steps:
step 1, charging and thermocouple: respectively loading seed crystals, boron oxide, arsenic particles and gallium arsenide return materials with silicon wafers into a PBN crucible, putting the PBN crucible into a quartz tube, vacuumizing and sealing the quartz tube, so that the gallium arsenide return materials in the crucible correspond to the third region;
9, when the temperature is lower than 80 ℃, opening the furnace to take out the crystal, and putting the crystal into hot methanol to soak so as to separate the gallium arsenide crystal from the PBN crucible; and cutting the test piece from the head and the tail of the crystal, and testing the carrier concentration, the mobility, the resistivity and the dislocation density of the gallium arsenide.
(III) advantageous effects
The technical scheme of the invention has the following beneficial technical effects: the adoption of the VB method and the VGF method combined shouldering can not only grow ultra-low dislocation crystals, but also shorten the shouldering time by 20 percent and shorten the equal-diameter growth time by 50 percent, thereby greatly improving the growth efficiency. The adoption of the 15mm coarse seed crystal can not only effectively avoid the interference of the formation of double crystals, but also bear larger material weight, thereby improving the production efficiency. The graphite support system is beneficial to releasing crystallization latent heat, and particularly can increase the cooling of the melt center so as not to cause the shape of a solid-liquid interface to be too concave. In addition, the graphite support system can also slow down the crystallization speed of the melt edge, inhibit impurities from transferring to the edge and inhibit the dense formation of edge dislocation.
Drawings
FIG. 1 is the structure diagram of the growth device for fast growing low dislocation gallium arsenide single crystal by combining VB method and VGF method.
Fig. 2 is a schematic view of the charging of the present invention.
1. A support base; 2. measuring the temperature 1; 3. measuring the temperature 2; 4. measuring the temperature 3; 5. 4, measuring the temperature; 6. measuring the temperature 5; 7. 6, measuring the temperature; 8. a graphite base; 9. a quartz ampoule; PBN crucible; 11. a gallium arsenide melt; 12. a first region; 13. a second region; 14. a third region; 15. a fourth region; 16. a fifth region; 17. a sixth zone; 18. a quartz cover; 19. a monocrystalline silicon wafer; 20. returning the small round cakes; 21. trapezoidal returning; 22. arsenic particles; 23. seed crystal; 25. boron oxide; 26. feeding back a small end; 27. and (5) returning the big round cakes.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
As shown in figure 1, a growth device for rapidly growing low-dislocation gallium arsenide single crystals by combining a VB method and a VGF method is provided, and is characterized by comprising a furnace body, a graphite base 8, a PBN crucible 10 and a lifting device; the furnace body comprises 6 heating areas and 6 temperature control devices for controlling the temperature of the heating areas, and the furnace body sequentially comprises a first area 12, a second area 13, a third area 14, a fourth area 15, a fifth area 16 and a sixth area 17 from bottom to top; the graphite base 8 is arranged on the ground through the supporting base 1; the PBN crucible 10 is arranged in the quartz ampoule 9, and the quartz ampoule 9 is arranged on the graphite base 8; the lifting device is connected with the furnace body and can pull the furnace body to be lifted at a certain pulling speed; a quartz cover 18 is arranged between the furnace body and the PBN crucible 10, and the quartz cover 18 is connected with the supporting base 1.
Preferably, the first zone 12, the second zone 13, the third zone 14, the fourth zone 15, the fifth zone 16 and the sixth zone 17 are respectively provided with a temperature measuring thermocouple; the head and the tail of the seed crystal of the PBN crucible 10, the tail end of the shoulder part and the tail of the crystal growth are respectively provided with a temperature thermocouple.
Preferably, the temperature thermocouple is an R-type thermocouple.
As shown in fig. 2, a growth method for rapidly growing low dislocation gallium arsenide single crystal by combining VB method and VGF method is provided, which comprises the following steps:
(1) charging and thermocouple:
a seed crystal 23 with the crystal orientation (100) to (111) of 2 degrees and the diameter of 15mm, a small-end return material 26, arsenic particles 22, boron oxide 22, a trapezoidal return material 21, 4 small-cake return materials 20 and a large-cake return material 27 are loaded into a PBN crucible 10 according to the drawing of figure 2, wherein the total weight of the materials is 10kg, the boron oxide is 36g, the arsenic is 5.6g and the silicon is 1.16g, and after the materials are loaded, a hydrogen-oxygen flame seal tube is utilized to load the materials into a single crystal furnace.
(2) Preheating of crucible and boron oxide:
the heater is started to heat up to 300 ℃ after half an hour, the temperature is kept for 4 hours, the temperature is measured at 1 and 382.3 ℃, the temperature is measured at 2 and 387.5 ℃, the temperature is measured at 3 and 395.1 ℃, the temperature is measured at 5 and 402.2 ℃, the temperature is measured at 7 and 399.8 ℃, and the temperature is measured at 8 and 385.9 ℃. The temperature was maintained for 4 hours.
(3) Material loading:
heating to 950 ℃ in a first area, 1030 ℃ in a second area, 1180 ℃ in a third area, 1185 ℃ in a fourth area, 1218 ℃ in a fifth area and 1220 ℃ in a sixth area, and keeping the program for 16 hours to ensure that the No. 1 monitoring thermocouple reaches 1216-1218 ℃; the No. 2 monitoring thermocouple reaches 1220-1232 ℃; the No. 3 monitoring thermocouple reaches 1236-1242 ℃; the number 5 monitoring thermocouple reaches 1249-1250 ℃; the No. 7 monitoring thermocouple reaches 1242-1245 ℃; the No. 6 monitoring thermocouple reaches 1215-1220 ℃; in the temperature rising process, nitrogen is introduced into the quartz tube 3, and the gas is automatically discharged; then keeping the temperature for 8-10h to melt gallium arsenide polycrystal at the lower part of the crucible.
(4) Digestion of bottoms and preparation before inoculation
Heating to the temperature of 990 ℃, 1090 ℃, 1177 ℃, 1185 ℃, 1218 ℃ and 1220 ℃ in the first zone, keeping the temperature for 4 hours, measuring 1 at 1226.1 ℃, 2 at 1242 ℃, 3 at 1251 ℃, 5 at 1253 ℃, 7 at 1254.2 ℃ and 8 at 1254.5 ℃, and jumping to the next step after the curve is stabilized;
(5) inoculating seed crystals:
after 5 hours, firstly lowering the temperature by about 2.5 ℃ in a VGF mode to perform recrystallization after seed crystal remelting;
(6) shouldering:
cooling to 980 ℃, 1078 ℃, 1173 ℃, 1184 ℃, 1218 ℃, 1220 ℃ in the first zone, and 1218 ℃ in the sixth zone within 12 hours at a drawing speed of 0-1.5 mm/h; cooling to 960 ℃ of the first zone, 1063 ℃ of the second zone, 1172 ℃ of the third zone, 1182 ℃ of the fourth zone, 1218 ℃ of the fifth zone, 1220 ℃ of the sixth zone within 18 hours, wherein the pulling speed is 1.5-2.5 mm/h;
finally, the temperature is reduced to 960 ℃ of the first zone, 1063 ℃ of the second zone, 1171 ℃ of the third zone, 1181 ℃ of the fourth zone, 1218 ℃ of the fifth zone, 1220 ℃ of the sixth zone within 18 hours, and the pulling speed is 2.5-3.5 mm/h;
(7) and (3) isometric growth:
and continuing to perform the procedure and the drawing speed at the same time, wherein the drawing speed is 2.5-3.5 mm/h, and performing equal-diameter growth until ending.
(8) And cooling annealing and large temperature reduction are carried out.
(9) When the temperature is lower than 80 ℃, the furnace can be opened to take out the crystal, and the crystal is put into hot methanol to be soaked so that the gallium arsenide crystal is separated from the PBN crucible. And cutting the test piece from the head and the tail of the crystal, and testing the carrier concentration, the mobility, the resistivity and the dislocation density of the gallium arsenide. As a result, as shown in Table 1, the head-to-tail mean dislocations were 1cm each-1And 2cm-1Maximum point dislocations are less than 1000cm-1。
| Position of | Average EPD (cm)-1） | Maximum point EPD (cm)-1） | Resistivity of | Concentration of carriers | Mobility ratio |
| Head (H) | 1 | 39 | 2.86E-03 | 1.01E+18 | 2190 |
| Tail (T) | 2 | 709 | 1.20E-03 | 3.46E+18 | 1507 |
TABLE 1
In another embodiment, the method comprises the following steps:
(1) charging and thermocouple:
a seed crystal 23 with the crystal orientation (100) to (111) of 2 degrees and the diameter of 6mm, a small-end return material 26, arsenic particles 22, boron oxide 25, a trapezoidal return material 21, 4 small round cake return materials 20 and a large round cake return material 27 are loaded into a PBN crucible 10 according to the drawing of figure 2, wherein the total weight of the materials is 10kg, the weight of the boron oxide 25 is 36g, the weight of the arsenic 22 is 5.6g, the weight of a monocrystalline silicon piece 19 is 1.16g, and the loaded materials are loaded into a monocrystalline furnace by using an oxyhydrogen flame seal tube.
(2) Preheating of crucible and boron oxide:
the heater is started to heat up to 300 ℃ after half an hour, the temperature is kept for 4 hours, the temperature is measured at 1 and 382.3 ℃, the temperature is measured at 2 and 387.5 ℃, the temperature is measured at 3 and 395.1 ℃, the temperature is measured at 5 and 402.2 ℃, the temperature is measured at 7 and 399.8 ℃, and the temperature is measured at 8 and 385.9 ℃. The advantage of maintaining the temperature for 4 hours is to allow the crucible and the boron oxide to be preheated.
(3) Material loading:
heating to 950 ℃ in a first area, 1030 ℃ in a second area, 1180 ℃ in a third area, 1185 ℃ in a fourth area, 1218 ℃ in a fifth area and 1220 ℃ in a sixth area, and keeping the program for 16 hours to ensure that the No. 1 monitoring thermocouple reaches 1216-1218 ℃; the No. 2 monitoring thermocouple reaches 1220-1232 ℃; the No. 3 monitoring thermocouple reaches 1236-1242 ℃; the number 5 monitoring thermocouple reaches 1249-1250 ℃; no. 7 monitoring thermocouple 9 reaches 1242-1245 ℃; the No. 6 monitoring thermocouple reaches 1215-1220 ℃; in the temperature rising process, nitrogen is introduced into the quartz tube 3, and the gas is automatically discharged; then keeping the temperature for 8-10h to melt gallium arsenide polycrystal at the lower part of the crucible.
(4) Bottom material melting and preparation before inoculation:
heating to the temperature of 990 ℃, 1090 ℃, 1177 ℃, 1185 ℃, 1218 ℃ and 1220 ℃ in the first zone, keeping the temperature for 2 hours, measuring 1 at 1226.1 ℃, 2 at 1242 ℃, 3 at 1251 ℃, 5 at 1253 ℃, 7 at 1254.2 ℃ and 8 at 1254.5 ℃, and jumping to the next step after the curve is stabilized;
(5) inoculating seed crystals:
after 5 hours, firstly lowering the temperature by about 2.5 ℃ in a VGF mode to perform recrystallization after seed crystal remelting;
(6) shouldering:
cooling to 980 ℃, 1078 ℃, 1173 ℃, 1184 ℃, 1218 ℃, 1220 ℃ in the first zone, and 1218 ℃ in the sixth zone within 12 hours at a drawing speed of 0-1.5 mm/h; cooling to 960 ℃ of the first zone, 1063 ℃ of the second zone, 1172 ℃ of the third zone, 1182 ℃ of the fourth zone, 1218 ℃ of the fifth zone, 1220 ℃ of the sixth zone within 18 hours, wherein the pulling speed is 1.5-2.5 mm/h;
finally, the temperature is reduced to 960 ℃ of the first zone, 1063 ℃ of the second zone, 1171 ℃ of the third zone, 1181 ℃ of the fourth zone, 1218 ℃ of the fifth zone, 1220 ℃ of the sixth zone within 18 hours, and the pulling speed is 2.5-3.5 mm/h;
(7) and (3) isometric growth:
and continuing to perform the procedure and the drawing speed at the same time, wherein the drawing speed is 2.5-3.5 mm/h, and performing equal-diameter growth until ending.
(8) And cooling annealing and large temperature reduction are carried out.
(9) When the temperature is lower than 80 ℃, the furnace can be opened to take out the crystal, and the crystal is put into hot methanol to be soaked so that the gallium arsenide crystal is separated from the PBN crucible. And cutting the test piece from the head and the tail of the crystal, and testing the carrier concentration, the mobility, the resistivity and the dislocation density of the gallium arsenide. As a result, as shown in Table 2, the head-to-tail mean dislocations were 10cm each-1And 27cm-1Maximum point dislocations are less than 1000cm-1。
| Position of | Average EPD (cm)-1） | Maximum point EPD (cm)-1） | Resistivity of | Concentration of carriers | Mobility ratio |
| Head (H) | 10 | 88 | 3.21E-03 | 8.62E+17 | 2257 |
| Tail (T) | 27 | 709 | 1.23E-03 | 3.12E+18 | 1627 |
TABLE 2
The crystal growth procedure is shown in the following table:
| Step | Time | first region | Second region | Third zone | Fourth zone | Fifth zone | The sixth zone | Pulling speed (mm/h) |
| 1 | 0:30 | 300 | 300 | 300 | 300 | 300 | 300 | |
| 2 | 4:00 | 300 | 300 | 300 | 300 | 300 | 300 | |
| 3 | 4:00 | 860 | 960 | 1170 | 1170 | 1170 | 1120 | |
| 4 | 6:00 | 950 | 1030 | 1180 | 1185 | 1218 | 1220 | |
| 5 | 2:00 | 990 | 1090 | 1180 | 1185 | 1218 | 1220 | |
| 6 | 5:00 | 990 | 1090 | 1177 | 1185 | 1218 | 1220 | |
| 7 | 12:00 | 980 | 1078 | 1173 | 1184 | 1218 | 1220 | 0～1.5 |
| 8 | 18:00 | 960 | 1063 | 1172 | 1182 | 1218 | 1220 | 1.5～2.5 |
| 9 | 18:00 | 960 | 1063 | 1171 | 1181 | 1218 | 1220 | 2.5～3.5 |
| 10 | 30:00 | 960 | 1063 | 1170 | 1180 | 1218 | 1220 | 2.5～3.5 |
| 11 | 30:00 | 960 | 1063 | 1170 | 1180 | 1218 | 1220 | 2.5～3.5 |
TABLE 3
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (4)
1. A VB method combines the growth device of the gallium arsenide monocrystal of fast growth low dislocation with VGF method, characterized by, it is made up of furnace body, graphite base, PBN crucible and hoisting device; the furnace body comprises 6 heating areas and 6 temperature control devices for controlling the temperature of the heating areas, and the furnace body sequentially comprises a first area, a second area, a third area, a fourth area, a fifth area and a sixth area from bottom to top; the graphite base is arranged on the ground through the supporting base; the PBN crucible is arranged in a quartz ampoule which is arranged on a graphite base; the lifting device is connected with the furnace body and can pull the furnace body to be lifted at a certain pulling speed; a quartz cover is arranged between the furnace body and the PBN crucible and connected with the supporting base.
2. The growth device for rapidly growing the low-dislocation gallium arsenide single crystal by combining the VB method and the VGF method as claimed in claim 1, wherein the first region, the second region, the third region, the fourth region, the fifth region and the sixth region are respectively provided with a temperature measuring thermocouple; temperature thermocouples are respectively arranged at the head and the tail of the seed crystal of the PBN crucible, the tail end of the shouldering part and the tail of the crystal growth.
3. The growth device for rapidly growing the low-dislocation gallium arsenide single crystal by combining the VB method and the VGF method as claimed in claim 2, wherein the temperature thermocouple is an R-type thermocouple.
4. A method for rapidly growing low-dislocation gallium arsenide single crystal by combining VB method and VGF method comprises the following steps:
step 1, charging and thermocouple: respectively loading seed crystals, boron oxide, arsenic particles and gallium arsenide return materials with silicon wafers into a PBN crucible, putting the PBN crucible into a quartz tube, vacuumizing and sealing the quartz tube, so that the gallium arsenide return materials in the crucible correspond to the third region;
step 2, preheating the crucible and boron oxide: starting a heater to heat up, heating to 300 ℃ after half an hour, and keeping for 4 hours;
step 3, melting the upper material: heating to 950 deg.C in the first zone, 1030 deg.C in the second zone, 1180 deg.C in the third zone, 1185 deg.C in the fourth zone, 1218 deg.C in the fifth zone, and 1220 deg.C in the sixth zone, and maintaining the program for 16 hr; in the temperature rising process, nitrogen is introduced into the quartz tube 3, and the gas is automatically discharged; then keeping the temperature for 8-10h to melt gallium arsenide polycrystal at the lower part of the crucible;
step 4, preparing a bottom material and before inoculation: heating to the temperature of 990 ℃ in the first zone, 1090 ℃ in the second zone, 1177 ℃ in the third zone, 1185 ℃ in the fourth zone, 1218 ℃ in the fifth zone and 1220 ℃ in the sixth zone, then preserving the heat of the coarse seed crystal for 4 hours, and preserving the heat of the fine seed crystal for 2 hours;
step 5, inoculating seed crystals: after 5 hours, firstly reducing the temperature by about 2-3 ℃ to perform recrystallization after seed crystal remelting;
step 6, shouldering: cooling to 980 ℃, 1078 ℃, 1173 ℃, 1184 ℃, 1218 ℃, 1220 ℃ in the first zone, and 1218 ℃ in the sixth zone within 12 hours at a drawing speed of 0-1.5 mm/h; cooling to 960 ℃ of the first zone, 1063 ℃ of the second zone, 1172 ℃ of the third zone, 1182 ℃ of the fourth zone, 1218 ℃ of the fifth zone, 1220 ℃ of the sixth zone within 18 hours, wherein the pulling speed is 1.5-2.5 mm/h; finally, the temperature is reduced to 960 ℃ of the first zone, 1063 ℃ of the second zone, 1171 ℃ of the third zone, 1181 ℃ of the fourth zone, 1218 ℃ of the fifth zone, 1220 ℃ of the sixth zone within 18 hours, and the pulling speed is 2.5-3.5 mm/h;
step 7, isometric growth: drawing at a speed of 2.5-3.5 mm/h for isometric growth ending;
step 8, performing cooling annealing and large cooling;
9, when the temperature is lower than 80 ℃, opening the furnace to take out the crystal, and putting the crystal into hot methanol to soak so as to separate the gallium arsenide crystal from the PBN crucible; and cutting the test piece from the head and the tail of the crystal, and testing the carrier concentration, the mobility, the resistivity and the dislocation density of the gallium arsenide.
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| CN115029783A (en) * | 2022-05-09 | 2022-09-09 | 云南鑫耀半导体材料有限公司 | Indium arsenide single crystal growth method based on combination of VB method and VGF method |
| CN115771996A (en) * | 2022-11-18 | 2023-03-10 | 云南中科鑫圆晶体材料有限公司 | Vacuum sealing and welding method of oversized-diameter quartz tube for VGF crystal growth |
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| CN109252220A (en) * | 2018-12-04 | 2019-01-22 | 中国电子科技集团公司第四十六研究所 | A kind of VGF/VB arsenide gallium monocrystal furnace structure and growing method |
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| CN105803515A (en) * | 2014-12-29 | 2016-07-27 | 有研光电新材料有限责任公司 | New process for gallium arsenide single crystal growth by VGF |
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| CN115029783A (en) * | 2022-05-09 | 2022-09-09 | 云南鑫耀半导体材料有限公司 | Indium arsenide single crystal growth method based on combination of VB method and VGF method |
| CN115029783B (en) * | 2022-05-09 | 2023-10-03 | 云南鑫耀半导体材料有限公司 | Indium arsenide monocrystal growth method based on VB method and VGF method |
| CN114808130A (en) * | 2022-05-10 | 2022-07-29 | 云南鑫耀半导体材料有限公司 | Charging method for growing single crystal by indium phosphide polycrystal material VGF or VB method |
| CN114808130B (en) * | 2022-05-10 | 2023-12-12 | 云南鑫耀半导体材料有限公司 | Charging method for growing single crystal by indium phosphide polycrystal material VGF or VB method |
| CN115771996A (en) * | 2022-11-18 | 2023-03-10 | 云南中科鑫圆晶体材料有限公司 | Vacuum sealing and welding method of oversized-diameter quartz tube for VGF crystal growth |
| CN115771996B (en) * | 2022-11-18 | 2024-03-22 | 云南中科鑫圆晶体材料有限公司 | Vacuum seal welding method of oversized-diameter quartz tube for VGF crystal growth |
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