CN111647946A - Method for preparing high-quality crystal by rotating magnetic field - Google Patents
Method for preparing high-quality crystal by rotating magnetic field Download PDFInfo
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- CN111647946A CN111647946A CN202010557846.0A CN202010557846A CN111647946A CN 111647946 A CN111647946 A CN 111647946A CN 202010557846 A CN202010557846 A CN 202010557846A CN 111647946 A CN111647946 A CN 111647946A
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- 239000013078 crystal Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000005204 segregation Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000002834 transmittance Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 19
- 239000010453 quartz Substances 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 229910052733 gallium Inorganic materials 0.000 abstract 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052787 antimony Inorganic materials 0.000 abstract 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052738 indium Inorganic materials 0.000 abstract 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000008646 thermal stress Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 229910005542 GaSb Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
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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
-
- 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
-
- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
-
- 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
- C30B30/00—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions
- C30B30/04—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions using magnetic fields
Abstract
The invention discloses a method for preparing a high-quality antimony-indium-gallium crystal by using a rotating magnetic field. High-purity gallium (Ga), high-purity indium (In) and high-purity antimony (Sb) are filled into a high-purity quartz crucible according to a certain molar ratio, and the high-purity quartz crucible is placed into a polycrystalline synthesis furnace to synthesize GaInSb polycrystalline ingots In advance after vacuum tube sealing treatment. And placing the GaInSb polycrystal material in a rotating magnetic field crystal growth furnace with five sections of independent heating temperature control devices to perform GaInSb crystal growth. The prepared GaInSb crystal has the advantages of small In element segregation, uniform distribution and less defects such as dislocation and the like. The invention uses the Rotating Magnetic Field (RMF) -moving heater method (THM) to prepare the GaInSb crystal, has simple operation and lower cost, can effectively inhibit the segregation of In element In the GaInSb crystal and reduce dislocation In the crystal, and can be used for preparing high-quality GaInSb crystal.
Description
Technical Field
The invention belongs to the technical field of semiconductor single crystal materials and preparation thereof, and particularly relates to a preparation method of a GaInSb crystal with low segregation and low dislocation density.
Background
The semiconductor material has a resistivity of 107Ω·cm～10-3Material between Ω · cm. Semiconductor materials are largely classified into two types, one is an elemental semiconductor material typified by a silicon single crystal, and the other is a compound semiconductor material. At this stage, the compound semiconductor material mainly includes a group III-V compound semiconductor material and a group II-VI compound semiconductor material. GaInSb belongs to a typical III-V compound semiconductor material and can be considered as a pseudo-binary solid solution material formed from GaSb and InSb.
The GaInSb crystal has the advantages that the forbidden band width Eg and the lattice constant of the GaInSb crystal can be changed along with the change of the In component concentration, and further can be better matched with the lattice constant of other ternary or quaternary solid solution materials, so that the lattice mismatch degree of the GaInSb crystal as a substrate material is reduced, and the GaInSb crystal material can better meet the performance requirements of different devices.
Although the GaInSb crystal material has the advantages that other III-V group compound semiconductor materials cannot be substituted, the preparation of the GaInSb crystal has the following difficulties:
(1) for ternary solid solution materials, the In component In the GaInSb crystal has a greater tendency to segregate. As can be seen from the phase diagram of GaSb-InSb, an incompatible component region exists between GaSb and InSb in the reaction process, and components in the GaInSb crystal are non-uniformly distributed. Currently, the equilibrium segregation coefficient of In GaInSb crystals is about 0.2. In the crystal growth process, the non-uniform distribution of In element can form overcooling of components at a solid-liquid interface, thereby influencing the quality of crystals.
(2) The dislocation density in GaInSb crystals is large. The dislocations are mainly caused by thermal stress in the crystal growth process, and under the action of the thermal stress, the dislocations move and proliferate. However, in the actual crystal growth process, the shape of the solid-liquid interface is difficult to control, and once the appearance instability occurs at the growth interface, stress is introduced into the crystal, so that the number of defects such as dislocation and the like in the crystal is rapidly increased.
At present, the processes for preparing GaInSb crystals mainly include a Vertical bridgman Method (Vertical bridgman Method), a Czochralski Method (Czochralski), a moving Heater Method (Vertical Heater Method), and a Vertical Gradient solidification Method (Vertical Gradient solidification). The sunken solid-liquid interface usually introduces larger thermal stress in the process of directional solidification and crystallization of the melt, and the thermal stress is the main reason for generating defects such as dislocation, twin crystal, microcrack and the like in the crystal. Therefore, the appearance and stability of the solid-liquid interface directly affect the quality of the crystal during the crystal growth process. However, in the process of preparing GaInSb crystals by using the above four conventional processes, natural convection due to concentration difference and temperature difference in a high-temperature melt is always present, and it is difficult to maintain the morphology of a solid-liquid interface in a flat or slightly convex shape. Therefore, the GaInSb crystal prepared by the traditional crystal growth method has larger In element segregation and more defects such as dislocation and the like.
Disclosure of Invention
The invention aims to provide a preparation method of high-quality GaInSb crystal aiming at the problems commonly existing in the traditional crystal growth process. The GaInSb crystal prepared by the method has low In component segregation and less defects such as dislocation.
A method for preparing low segregation and low dislocation density GaInSb crystal by a rotating magnetic field comprises the following steps: high-purity raw materials used for crystal growth are filled into a high-purity quartz crucible according to a certain proportion, and the synthesis of GaInSb polycrystal ingots is carried out after the vacuum pumping and tube sealing treatment. And (3) placing the pre-synthesized polycrystals in a rotating magnetic field crystal growth furnace, and performing GaInSb crystal growth after adjusting the frequency and the strength of a rotating magnetic field.
In the step, the purity of the high-purity raw material is 99.999-99.9999%, and the purity of the high-purity quartz crucible is 99.9-99.999%.
The vacuum degree range in the step is 10Pa to 10Pa-3Pa。
In the step, the synthesis temperature of the GaInSb polycrystal ingot is 700-900 ℃, and the synthesis reaction time is 4-16 h.
The temperature range of the GaInSb crystal growth in the step is 600-800 ℃, and the temperature gradient is 5-10 ℃/cm.
In the step, the growth rate of the GaInSb crystal is 0.5 mm/h-2 mm/h, and the rotation rate of the crucible is 1 r/min-20 r/min.
The annealing rate after the growth of the GaInSb crystal is finished in the step is 30-120 ℃/h.
The frequency of the rotating magnetic field in the step is 0 Hz-100 Hz, and the intensity of the rotating magnetic field is 0 mT-30 mT.
Drawings
Fig. 1 is an appearance map of a GaInSb crystal prepared by the present invention and a GaInSb wafer sample map after slicing treatment. The GaInSb crystal has smooth appearance, no pits and higher flatness.
FIG. 2 is a schematic diagram showing the crystal growth principle of the Rotating Magnetic Field (RMF) -moving heater method (THM) used in the present invention.
Fig. 3 is a graph showing the relationship between the In concentration In the GaInSb crystal prepared according to the present invention and the radial position.
Fig. 4 is a graph showing the relationship between the concentration of In element In the GaInSb crystal prepared according to the present invention and the change In the axial position.
Fig. 5 is a graph showing the effect of the rotating magnetic field on the carrier concentration of the GaInSb crystal in the present invention.
Fig. 6 is a graph showing the effect of the rotating magnetic field on the resistivity of the GaInSb crystal in the present invention.
FIG. 7 is a graph showing the effect of a rotating magnetic field on the infrared transmittance of a GaInSb crystal in the present invention.
Fig. 8 is a dislocation distribution diagram of GaInSb crystals prepared under different rotating magnetic field frequencies and intensities according to the present invention.
Note: s0 in the figure is a GaInSb crystal prepared in an environment where a rotating magnetic field is not applied.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting, and are not intended to limit the scope of the invention.
The first embodiment is as follows:
the crucible used for GaInSb crystal growth is a high-purity quartz crucible, and the used raw materials are high-purity Ga, high-purity In and high-purity Sb. The three raw materials are strictly loaded into a high-purity quartz crucible with the diameter of 25mm and the length of 500mm according to the proportion, and the opening of the crucible is sealed by a rubber plug and then is vacuumized. Putting the quartz crucible filled with the raw materials into a polycrystal synthesis furnace for polycrystal ingot synthesis, and fully reacting and synthesizing for 12 hours at 850 ℃. And placing the pre-synthesized polycrystalline ingot into a rotating magnetic field crystal growth furnace with 5 sections of independent temperature control intervals to perform GaInSb crystal growth. The temperature gradient in the crystal growth process is 5 ℃/cm, the growth rate is 1mm/h, the frequency of the rotating magnetic field is fixed at 50Hz, and the GaInSb crystal growth experiment is carried out under the conditions that the magnetic field intensity is 5mT, 15mT and 25mT in sequence. In addition, GaInSb crystals were prepared without applying a rotating magnetic field to facilitate comparison of the final experimental results.
Example two:
three high-purity raw materials used for GaInSb crystal growth are strictly loaded into a quartz crucible according to the proportion, vacuumized and sealed, placed in a polycrystal synthesis furnace for polycrystalline ingot synthesis, and fully reacted and synthesized for 12 hours at 850 ℃. And placing the pre-synthesized polycrystalline material in a rotating magnetic field crystal growth furnace with 5 sections of independent heating temperature control devices to perform GaInSb crystal growth. The temperature gradient in the crystal growth process is 5 ℃/cm, the growth rate is 1mm/h, the strength of the rotating magnetic field is fixed to be 25mT, and the crystal growth is carried out under the conditions that the magnetic field frequency is 10Hz, 30Hz and 50Hz in sequence.
Claims (5)
1. A preparation method of low dislocation and low segregation GaInSb crystal is characterized by comprising the following steps: in the process of growing the GaInSb crystal by applying the rotating magnetic field to the moving heater method, the GaInSb crystal with low segregation and low dislocation density is prepared by changing the frequency and the strength of the rotating magnetic field.
2. The low segregation, low dislocation density GaInSb crystal of claim 1, wherein: dislocation density in GaInSb crystal is 103～104。
3. The low segregation, low dislocation density GaInSb crystal of claim 1, wherein: the radial segregation of the In element In the GaInSb crystal is In the range of 0.363 mol%/mm to 0.157 mol%/mm, and the axial segregation of the In element is In the range of 0.251 mol%/mm to 0.096 mol%/mm.
4. The GaInSb crystal with low segregation and low dislocation density as claimed in claim 1, wherein the electrical properties of the GaInSb crystal are significantly improved, the carrier mobility of the crystal is at 1.407 × 103cm2(Vs)～1.902×103cm2In the interval of (Vs), the resistivity of the crystal is at 1.047 × 10-3Ω·cm～1.788×10-3In the range of omega cm.
5. The low segregation, low dislocation density GaInSb crystal of claim 1, wherein: the infrared transmittance of the GaInSb crystal increases. The infrared transmittance of the crystal is 36-39%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010557846.0A CN111647946A (en) | 2020-06-18 | 2020-06-18 | Method for preparing high-quality crystal by rotating magnetic field |
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| CN202010557846.0A CN111647946A (en) | 2020-06-18 | 2020-06-18 | Method for preparing high-quality crystal by rotating magnetic field |
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Application publication date: 20200911 |