CN114232069B - Group II element doped GaAs monocrystalline silicon and preparation method thereof - Google Patents
Group II element doped GaAs monocrystalline silicon and preparation method thereof Download PDFInfo
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- C30B11/06—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt at least one but not all components of the crystal composition being added
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Abstract
The application relates to the technical field of GaAs single crystal silicon, and particularly discloses a group II element doped GaAs single crystal silicon and a preparation method thereof. A kind ofThe preparation method of the GaAs single crystal silicon doped with the II group elements comprises the following steps: s1: synthesizing a GaAs polycrystal by adopting a horizontal directional solidification method; s2: cleaning a crucible and a quartz ampoule for later use; s3: fixing GaAs seed crystals in a crucible seed crystal groove, adding GaAs polycrystal and a dopant into a crucible, wherein the dopant is at least one of Zn, Cd, Be and Mg; s4: adding a proper amount of B into the crucible2O3Sealing, namely placing the crucible into a quartz ampoule, and placing the sealed quartz ampoule into a growth furnace after the vacuum degree is qualified; s5: and slowly cooling after the growth is finished by adopting a VGF growth process. The group II element doped GaAs single crystal silicon has excellent electrical properties.
Description
Technical Field
The application relates to the technical field of GaAs single crystal preparation, in particular to a GaAs single crystal doped with II-group elements and a preparation method thereof.
Background
Gallium arsenide (gallium arsenide), chemical formula GaAs. Dark gray solid, melting point 1238 ℃. It is stable in air at temperatures below 600 deg.C and is not attacked by non-oxidizing acids.
Gallium arsenide is an important semiconductor material, belongs to III-V group compound semiconductors, belongs to a zinc blende type lattice structure, has a lattice constant of 5.65 x 10 < -10 > m, a melting point of 1238 ℃ and a forbidden band width of 1.4 electron volts. Gallium arsenide has entered practical use in 1964, and gallium arsenide can be made into semi-insulating high-resistance materials with resistivity higher than that of silicon and germanium by more than 3 orders of magnitude, and is used for manufacturing integrated circuit substrates, infrared detectors, gamma photon detectors, and the like. The electron mobility of the material is 5-6 times higher than that of silicon, so that the material is applied to the aspects of manufacturing microwave devices and high-speed digital circuits. The semiconductor device made of gallium arsenide has the advantages of good high-frequency, high-temperature and low-temperature performances, low noise, strong radiation resistance and the like. It can also be used to make transfer device-body effect device.
The current gallium arsenide mainstream preparation process comprises the following steps: liquid sealed Czochralski method (LEC), horizontal Brillouin method (HB), vertical Brillouin method (VB), and vertical gradient freeze method (VGF). The gallium arsenide monocrystal with high purity can be prepared by adopting the process, and the gallium arsenide chip is prepared by cutting, polishing and other processes. In addition, in the growth preparation process of the gallium arsenide crystal, proper dopant can be added to control and improve the electrical property of the gallium arsenide crystal, so that different use requirements are met. For example, chinese patent application publication No. CN111893571A discloses a process for growing a gallium arsenide-doped single crystal, in which Si is doped in two links of polycrystalline synthesis and single crystal growth to allow Si to enter gallium arsenide and occupy space effectively, C, Al or Ti is placed in a quartz tube to absorb oxygen in the quartz tube during the growth of the single crystal, so as to control the oxygen content in the single crystal and realize selective adsorption of impurities, thereby improving the performance of the gallium arsenide single crystal.
Aiming at the doped gallium arsenide single crystal, the doping element type and the doping mode are single, and the electrical property of the doped gallium arsenide single crystal is poor.
Disclosure of Invention
In order to prepare a doped GaAs single crystal with excellent electrical properties, the application provides a group II element doped GaAs single crystal silicon and a preparation method thereof.
In a first aspect, the present application provides a method for preparing a group ii element-doped GaAs monocrystalline silicon, which adopts the following technical scheme:
a preparation method of a group II element doped GaAs monocrystalline silicon comprises the following steps:
s1: synthesizing GaAs polycrystal by adopting a horizontal directional solidification method, and cleaning and drying the GaAs polycrystal for later use;
s2: cleaning a crucible and a quartz ampoule for later use;
s3: fixing GaAs seed crystals in a crucible seed crystal groove, adding GaAs polycrystal and a doping agent into a crucible, wherein the mass ratio of the GaAs polycrystal to the doping agent is 1 (0.0025-0.0925), and the doping agent is at least one of Zn, Cd, Be and Mg;
s4: adding a proper amount of B into the crucible2O3Sealing, namely placing the crucible into a quartz ampoule, vacuumizing until the vacuum degree is more than 0.003Pa, sealing the quartz ampoule, and placing the sealed quartz ampoule into a growth furnace after the vacuum degree is qualified;
S5: adopting a VGF method growth process, controlling the vertical temperature gradient of the growth furnace to be 2-3 ℃/cm, and slowly cooling after the growth is finished.
By adopting the technical scheme, one or more of group II elements Zn, Cd, Be and Mg are doped with GaAs, so that on one hand, the doping concentration is adjusted and optimized to inhibit dislocation proliferation, the yield stress of the crystal is enhanced, and plastic deformation is not easy to generate, so that dislocation is not easy to introduce to obtain low-dislocation single crystals; on the other hand, the doped second phase can be formed after the II group element is doped, so that uniform and reasonable occupation is formed in the GaAs crystal, the structural property and the electrical property of the GaAs are improved, and the GaAs crystal has higher carrier concentration and lower dislocation density.
Preferably, in the step S3, the fitting equation of the control curve of the vertical temperature gradient is y = (0.128-m) x + (5.9-n) x +1252, wherein the ordinate is temperature in degrees celsius, the abscissa is distance in cm, and the abscissa is set vertically upward with the seed crystal position as the starting point.
By adopting the technical scheme, the temperature environment for single crystal growth is controlled according to a more proper temperature gradient, the probability of dislocation and point defects generated in the process of converting a melt into a crystal is greatly reduced, a single crystal is formed in a better growth state, and the electrical property of the GaAs single crystal is improved.
Preferably, m is in the range of (0-0.06) and n is in the range of (0.3-0.5).
By adopting the technical scheme, the numerical ranges of the parameters m and n are optimized and adjusted, the conformity of the gradient temperature field in the single crystal growth process is improved, and the probability of defects, dislocation, stacking faults and particle structures is reduced.
Preferably, the origin coordinate of the fitting equation is (0, 1230- > 1235).
By adopting the technical scheme, the initial temperature of the bottom of the crystal growth is tested and adjusted, the probability of segregation phenomenon in the crystal growth process is reduced, and the crystal growth state is good.
Preferably, R of the fitting equation2In the range of 0.5-0.68.
By adopting the technical scheme, the correlation coefficient of the fitting equation is adjusted and optimized, and the fitting degree of the gradient temperature field is improved in the controllable range of the temperature control device, so that the gradient temperature field is more suitable for the growth of the GaAs crystal.
Further preferably, the dopant consists of Be and Zn according to the molar ratio of (2-5) to (1-3).
By adopting the technical scheme, the doping type and the doping proportion of the II-group element are adjusted and optimized, the electrical property of GaAs is further improved, lower dislocation density is obtained, and the mechanical property of the crystal is improved.
Further preferably, in step S3, the GaAs polycrystal is sliced into GaAs polycrystal sheets, then a plurality of grooves are cut on the surfaces of the GaAs polycrystal sheets, then the dopant is filled and fixed in the grooves to form a GaAs polycrystal mixed material, and finally the GaAs polycrystal mixed material is placed in the crucible.
By adopting the technical scheme, the dopant and the GaAs polycrystal are subjected to melting growth together in the crucible in a filling and fixing mode, the distribution uniformity of the dopant in the crystal is improved, dopant atoms are easier to embed into a GaAs crystal lattice, the deposition amount of the dopant to the bottom of the crucible can be reduced, the interference of the dopant to the growth process of the surface of the seed crystal is reduced, and the crystal quality is improved.
Further preferably, the seed crystal size is phi 6 x 20 mm-phi 7.5 x 30 mm.
By adopting the technical scheme, the seed crystals with different sizes are optimized and tested, and the seed crystals with proper sizes are selected, so that the interface potential barrier is lower when the GaAs and II group element melt is converted into the crystal, and the crystal production process is more stable and uniform.
Preferably, the GaAs seed crystal direction is < 111 > B.
By adopting the technical scheme, the crystal orientation of the GaAs seed crystal is adjusted and optimized, and the generation of stray crystal nuclei in the crystal growth process is inhibited, so that the growth process of the single crystal is more stable, and the dislocation density of the single crystal is reduced.
Preferably, the growth speed of the group II element doped GaAs single crystal silicon is 2-2.5 mm/h.
By adopting the technical scheme, the growth speed of the crystal is adjusted, the probability of segregation in the crystal production process is reduced, and the quality of the crystal is further improved.
Preferably, the dopant in the step S3 is ultrasonically cleaned for 20-35min by a cleaning solution before being added into the crucible, and then cleaned and dried by ultrapure water.
Through adopting above-mentioned technical scheme, utilize ultrapure water's strong polarity and strong permeability, clean the impurity on dopant surface for the dopant is purer, reduces the pollution of impurity to the GaAs single crystal, reduces the dislocation because of impurity causes, promotes the crystal quality.
Further preferably, the ultrapure water cleaning solution comprises the following components in percentage by mass: 1-3.5% ammonia water, and the balance ultrapure water.
By adopting the technical scheme, under the strong polarity and strong permeation environment of ultrapure water, the ion pair dissociated by the ammonia water peels off and removes the oxide film and the pollutant on the surface of the dopant, so that the purity of the dopant is further improved, and the quality and the electrical property of the crystal are improved.
In a second aspect, the present application provides a group ii element-doped GaAs single crystal silicon, which is prepared by the above method for preparing a group ii element-doped GaAs single crystal silicon.
In summary, the present application has the following beneficial effects:
1. as the GaAs crystal is doped by adopting the II group elements and the proper doping proportion and doping type are selected, the GaAs crystal with good mechanical property and excellent electrical property is obtained.
2. In the method, the production process parameters of the crystal are optimized and adjusted, and the high-quality GaAs crystal with low dislocation is obtained by selecting a proper production temperature gradient and a filling doping mode.
3. The group II element doped GaAs monocrystalline silicon prepared by the production method has lower dislocation density and better electrical property.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials of the examples and comparative examples of the present application are generally commercially available unless otherwise specified.
Examples
Example 1
The group II element-doped GaAs single crystal silicon of the present example was prepared by the following preparation method:
s1: respectively cleaning a quartz vessel, an annular quartz boat and a quartz tank by using aqua regia and deionized water, removing dirt and impurities stained on the surface, then putting a simple substance Ga with the purity of 7N into the quartz vessel, putting the quartz vessel at the center of the quartz tank, then putting a simple substance As with the purity of 7N into the annular quartz boat, putting the annular quartz boat outside the quartz vessel and concentrically arranging the annular quartz boat and the quartz vessel, and simultaneously controlling the molar ratio of Ga to As to be 1: 1.02; then sealing the quartz pot and putting the quartz pot into a horizontal directional solidification furnace, wherein the horizontal directional solidification furnace consists of three temperature control regions, namely a high temperature region, a medium temperature region and a low temperature region from the center of the quartz pot to the outside in sequence, the temperature of the high temperature region is 1256 ℃, the temperature of the medium temperature region is 785 ℃, the temperature of the low temperature region is 635 ℃, reacting until the simple substance As is completely evaporated, then cooling the low temperature region at the speed of 5 ℃/h, cooling the medium temperature region at the speed of 8 ℃/h, and cooling the high temperature region at the speed of 10 ℃/h until the horizontal directional solidification furnace is cooled to the room temperature to obtain GaAs polycrystal;
S2: respectively cleaning the PBN crucible, the quartz ampoule and the quartz cap by using aqua regia and deionized water, and drying for later use;
s3: fixing the GaAs seed crystal with the diameter less than 511 & gt direction and the diameter of 6 multiplied by 20mm in a PBN crucible seed crystal groove, adding GaAs polycrystal and a doping agent into the PBN crucible, wherein the mass ratio of the GaAs polycrystal to the doping agent is 1:0.0025, the doping agent is simple substance Zn, and the purity of the simple substance Zn is 7N;
s4: adding a proper amount of anhydrous B into a PBN crucible2O3Sealing, namely putting the PBN crucible into a quartz ampoule, vacuumizing until the vacuum degree is more than 0.003Pa, welding and sealing a quartz cap and the quartz ampoule after the vacuum degree is qualified, and then putting into a growth furnace;
s5: adopting a VGF method growth process, controlling the vertical temperature gradient of a growth furnace to be 2 ℃/cm, the temperature of the growth furnace to be 1285 ℃, the growth speed to be 2mm/h, and slowly cooling after the growth is finished.
Example 2
The group ii element-doped GaAs single-crystal silicon of the present example is different from example 1 in that: step S1, respectively cleaning a quartz vessel, an annular quartz boat and a quartz tank by using aqua regia and deionized water, removing dirt and impurities stained on the surface, then placing the simple substance Ga with the purity of 7N into the quartz vessel, placing the quartz vessel at the center of the quartz tank, then placing the simple substance As with the purity of 7N into the annular quartz boat, placing the annular quartz boat outside the quartz vessel and concentrically arranging the annular quartz boat and the quartz vessel, and simultaneously controlling the molar ratio of Ga to As to be 1: 1.05; then sealing the quartz pot and putting the quartz pot into a horizontal directional solidification furnace, wherein the horizontal directional solidification furnace consists of three temperature control regions, namely a high temperature region, a medium temperature region and a low temperature region from the center of the quartz pot to the outside in sequence, the temperature of the high temperature region is 1260 ℃, the temperature of the medium temperature region is 790 ℃, the temperature of the low temperature region is 640 ℃, reacting until the simple substance As is completely evaporated, then cooling the low temperature region at the speed of 8 ℃/h, cooling the medium temperature region at the speed of 12 ℃/h, and cooling the high temperature region at the speed of 15 ℃/h until the horizontal directional solidification furnace is cooled to the room temperature to obtain GaAs polycrystal; in step S5, a VGF growth process is adopted, the vertical temperature gradient of the growth furnace is controlled to be 3 ℃/cm, the temperature of the growth furnace is 1285 ℃, the growth rate is 2mm/h, and the growth is completed by slow cooling, and the rest is the same as in example 1.
Example 3
The group ii element-doped GaAs single-crystal silicon of the present example is different from example 1 in that: step S1, respectively cleaning a quartz vessel, an annular quartz boat and a quartz tank by using aqua regia and deionized water, removing dirt and impurities stained on the surface, then placing the simple substance Ga with the purity of 7N into the quartz vessel, placing the quartz vessel at the center of the quartz tank, then placing the simple substance As with the purity of 7N into the annular quartz boat, placing the annular quartz boat outside the quartz vessel and concentrically arranging the annular quartz boat and the quartz vessel, and simultaneously controlling the molar ratio of Ga to As to be 1: 1.035; then sealing the quartz pot and putting the quartz pot into a horizontal directional solidification furnace, wherein the horizontal directional solidification furnace consists of three temperature control regions, namely a high temperature region, a medium temperature region and a low temperature region from the center of the quartz pot to the outside in sequence, the temperature of the high temperature region is 1258 ℃, the temperature of the medium temperature region is 788 ℃, the temperature of the low temperature region is 638 ℃, reacting until the simple substance As is completely evaporated, then cooling the low temperature region at the speed of 6.5 ℃/h, cooling the medium temperature region at the speed of 10 ℃/h, cooling the high temperature region at the speed of 12 ℃/h until the horizontal directional solidification furnace is cooled to the room temperature, and obtaining GaAs polycrystal; in step S5, a VGF growth process is adopted, the vertical temperature gradient of the growth furnace is controlled to be 2.35 ℃/cm, the temperature of the growth furnace is 1285 ℃, the growth rate is 2mm/h, and the growth is performed by slow cooling after the growth is completed, and the rest is the same as that in example 1.
Example 4
The group ii element-doped GaAs single-crystal silicon of this example is different from example 3 in that: in step S3, the dopant is elemental Be, the purity of the elemental Be is 7N, and the rest is the same as in example 3.
Example 5
The group ii element-doped GaAs single-crystal silicon of this example is different from example 3 in that: in step S3, the dopant is elemental Cd, the purity of the elemental Cd is 7N, and the rest is the same as in example 3.
Example 6
The group ii element-doped GaAs single-crystal silicon of this example is different from example 3 in that: in step S3, the GaAs poly crystal to dopant mass ratio was 1:0.0925, and the rest was the same as in example 3.
Example 7
The group ii element-doped GaAs single-crystal silicon of this example is different from example 3 in that: in step S3, the mass ratio of GaAs poly to dopant was 1:0.0575, and the rest was the same as in example 3.
Example 8
The group ii element-doped GaAs single-crystal silicon of the present example is different from example 7 in that: in step S3, the dopant is composed of elemental Be and elemental Zn in a molar ratio of 2:1, the purity of elemental Zn is 7N, the purity of elemental Be is 7N, and the rest is the same as in example 7.
Example 9
The group ii element-doped GaAs single-crystal silicon of the present example is different from example 7 in that: in step S3, the dopant is composed of elemental Be and elemental Zn in a molar ratio of 5:3, the purity of elemental Zn is 7N, the purity of elemental Be is 7N, and the rest is the same as in example 7.
Example 10
The group ii element-doped GaAs single-crystal silicon of the present example is different from example 7 in that: in step S3, the dopant is composed of elemental Be and elemental Zn at a molar ratio of 3:1.25, the purity of elemental Zn is 7N, the purity of elemental Be is 7N, and the rest is the same as in example 7.
Example 11
The group ii element-doped GaAs single crystal silicon of this example differs from example 10 in that: in step S3, the GaAs polycrystal is sliced into GaAs polycrystal sheets under the protection of inert gas, then a plurality of grooves are cut on the surface of the GaAs polycrystal sheets, the grooves have a size of 5mm × 1.5mm × 0.5mm, then the dopant is filled and fixed in the grooves to prepare a GaAs polycrystal mixed material, and finally the GaAs polycrystal mixed material is placed in a crucible, the rest being the same as in example 10.
Example 12
The group ii element-doped GaAs single-crystal silicon of this example differs from example 11 in that: in step S3, the seed crystal size was 7X 25mm, and the rest was the same as in example 11.
Example 13
The group ii element-doped GaAs single-crystal silicon of this example differs from example 11 in that: in step S3, the seed crystal size was 7.5X 30mm, and the rest was the same as in example 11.
Example 14
The group ii element-doped GaAs single-crystal silicon of this example differs from example 12 in that: in step S3, the GaAs seed crystal direction was < 111 > B, and the rest was the same as in example 12.
Example 15
The group ii element-doped GaAs single-crystal silicon of this example differs from example 14 in that: in step S3, the growth rate was 2.5mm/h, and the rest was the same as in example 14.
Example 16
The group ii element-doped GaAs single-crystal silicon of this example differs from example 15 in that: in step S3, the fitting equation of the control curve of the vertical temperature gradient is y =0.128x +5.6x +1252, R2=0.5, wherein the ordinate is temperature (° c), the abscissa is distance (cm), the abscissa is set vertically upward with the seed crystal position as the starting point, and the origin is (0,1230), and the rest is the same as in example 15.
Example 17
The group ii element-doped GaAs single-crystal silicon of this example differs from example 15 in that: in step S3, fitting equation of control curve of vertical temperature gradientBeing y =0.122x +5.4x +1252, R2=0.6, wherein the ordinate is temperature (° c), the abscissa is distance (cm), the abscissa is set vertically upward with the seed crystal position as the starting point, and the origin is (0,1230), and the rest is the same as in example 15.
Example 18
The group ii element-doped GaAs single-crystal silicon of this example differs from example 15 in that: in step S3, the fitting equation of the control curve of the vertical temperature gradient is y =0.122x +5.4x +1252, R 2=0.68, wherein the ordinate is temperature (° c), the abscissa is distance (cm), the abscissa is set vertically upward with the seed crystal position as the starting point, and the origin is (0,1235), and the rest is the same as in example 15.
Example 19
The group ii element-doped GaAs single-crystal silicon of this example differs from example 15 in that: in step S3, the fitting equation of the control curve of the vertical temperature gradient is y =0.128x +5.52x +1252, R2=0.68, wherein the ordinate is temperature (° c), the abscissa is distance (cm), the abscissa is set vertically upward with the seed crystal position as the starting point, and the origin is (0,1235), and the rest is the same as in example 15.
Example 20
The group ii element-doped GaAs single-crystal silicon of this example differs from example 19 in that: in step S3, the dopant was previously subjected to ultrasonic cleaning for 30min with a cleaning liquid which was an aqueous hydrogen peroxide solution, and then cleaned and dried with ultrapure water, the rest being the same as in example 19.
Comparative example
Comparative example 1
The group ii element-doped GaAs single-crystal silicon of this comparative example is different from example 1 in that: step S1, respectively cleaning a quartz tube and a quartz boat by using aqua regia and deionized water, removing dirt and impurities stained on the surface, then placing the simple substance Ga with the purity of 7N into a quartz dish, placing the quartz dish on one side of the quartz tube, then placing the simple substance As with the purity of 7N into the other side of the quartz tube, and simultaneously controlling the molar ratio of Ga to As to be 1: 1.02; and then sealing the quartz tube and putting the quartz tube into a horizontal directional solidification furnace, wherein the horizontal directional solidification furnace consists of three temperature control regions, a high temperature region, a medium temperature region and a low temperature region are sequentially arranged from the side of the quartz tube filled with the simple substance Ga to the side filled with the simple substance As, the temperature of the high temperature region is 1256 ℃, the temperature of the medium temperature region is 785 ℃, the temperature of the low temperature region is 635 ℃ after the reaction is finished until the simple substance As is evaporated, then cooling the low temperature region at the speed of 5 ℃/h, cooling the medium temperature region at the speed of 8 ℃/h, and cooling the high temperature region at the speed of 10 ℃/h until the horizontal directional solidification furnace is cooled to the room temperature to obtain the GaAs polycrystal.
Comparative example 2
The group ii element-doped GaAs single-crystal silicon of this comparative example is different from example 1 in that: the molar ratio of Ga to As in step S1 was 1:1, and the rest was the same As in example 1.
Comparative example 3
The group ii element-doped GaAs single-crystal silicon of this comparative example is different from example 3 in that: in step S3, the dopant is elemental In, the purity of the elemental In is 7N, and the rest is the same as In example 3.
Comparative example 4
The group ii element-doped GaAs single-crystal silicon of this comparative example is different from example 3 in that: in step S3, the mass ratio of GaAs poly to dopant was 1:0.15, and the rest was the same as in example 3.
Comparative example 5
The group ii element-doped GaAs single-crystal silicon of this comparative example is different from example 7 in that: in step S3, the dopant is composed of elemental Be and elemental Zn at a molar ratio of 1:1, the purity of elemental Zn is 7N, the purity of elemental Be is 7N, and the rest is the same as in example 7.
Comparative example 6
The group ii element-doped GaAs single-crystal silicon of this comparative example is different from example 11 in that: in step S3, the seed crystal size was 5X 15mm, and the rest was the same as in example 11.
Comparative example 7
The group ii element-doped GaAs single-crystal silicon of this comparative example is different from example 12 in that: in step S3, the GaAs seed direction is < 100 >, and the rest is the same as that of example 12.
Comparative example 8
The group ii element-doped GaAs single-crystal silicon of this comparative example is different from example 14 in that: in step S3, the growth rate was 1.8mm/h, and the rest was the same as in example 14.
Comparative example 9
The group ii element-doped GaAs single-crystal silicon of this comparative example is different from example 16 in that: in step S3, the dopant was previously subjected to ultrasonic cleaning with an absolute ethyl alcohol solution for 30min, and then cleaned and dried with ultrapure water in step S3, the rest being the same as in example 16.
Performance test
Detection method
(1) The group II element-doped GaAs single-crystal silicon of examples 1 to 20 and comparative examples 1 to 9 were tested for dislocation density at different portions of the ingot in accordance with national Standard GB/T8760-.
TABLE 1 EXAMPLES 1-20 dislocation Density test data for group II doped GaAs Single Crystal silicon of comparative examples 1-9
| Serial number | Head dislocation Density (cm)-2） | Dislocation Density in the middle (cm)-2） | Tail dislocation density (cm)-2） |
| Example 1 | 410 | 460 | 550 |
| Example 2 | 430 | 490 | 600 |
| Example 3 | 400 | 450 | 520 |
| Example 4 | 420 | 470 | 570 |
| Example 5 | 450 | 500 | 630 |
| Example 6 | 440 | 490 | 590 |
| Example 7 | 390 | 430 | 510 |
| Example 8 | 380 | 420 | 500 |
| Example 9 | 360 | 400 | 490 |
| Example 10 | 350 | 380 | 470 |
| Example 11 | 330 | 350 | 450 |
| Example 12 | 310 | 330 | 410 |
| Example 13 | 320 | 340 | 430 |
| Example 14 | 280 | 310 | 380 |
| Example 15 | 300 | 320 | 400 |
| Example 16 | 250 | 280 | 350 |
| Example 17 | 240 | 270 | 340 |
| Example 18 | 220 | 250 | 310 |
| Example 19 | 230 | 260 | 330 |
| Example 20 | 230 | 250 | 320 |
| Comparative example 1 | 1320 | 1430 | 1550 |
| Comparative example 2 | 950 | 1050 | 1170 |
| Comparative example 3 | 550 | 630 | 710 |
| Comparative example 4 | 460 | 510 | 600 |
| Comparative example 5 | 400 | 460 | 530 |
| Comparative example 6 | 340 | 370 | 460 |
| Comparative example 7 | 510 | 600 | 690 |
| Comparative example 8 | 410 | 480 | 550 |
| Comparative example 9 | 250 | 270 | 350 |
(2) Ingots of group ii element-doped GaAs single crystals of examples 1 to 20 comparative examples 1 to 9 were cut into head and tail samples, the head sample being 10% of the length of the ingot (from the seed crystal) and the tail sample being 85 to 90% of the length of the ingot (from the seed crystal), and then the head and tail samples were subjected to Hall electrical property tests, the results of which are shown in table 2.
TABLE 2 EXAMPLES 1-20 comparative examples 1-9 group II doped GaAs Single Crystal silicon Electrical test data
| Serial number | Head carrier concentration (cm)-3） | Tail carrier concentration (cm)-3） |
| Example 1 | 5.15×1017 | 0.23×1018 |
| Example 2 | 6.36×1017 | 1.08×1018 |
| Example 3 | 8.16×1017 | 1.86×1018 |
| Example 4 | 3.2×1017 | 1.31×1018 |
| Example 5 | 1.15×1017 | 0.81×1018 |
| Example 6 | 7.09×1017 | 1.57×1018 |
| Example 7 | 1.35×1018 | 2.69×1018 |
| Example 8 | 1.91×1018 | 2.97×1018 |
| Example 9 | 2.05×1018 | 3.19×1018 |
| Example 10 | 2.55×1018 | 3.61×1018 |
| Example 11 | 2.75×1018 | 4.83×1018 |
| Example 12 | 2.92×1018 | 5.15×1018 |
| Example 13 | 2.52×1018 | 4.68×1018 |
| Example 14 | 3.26×1018 | 5.75×1018 |
| Example 15 | 3.01×1018 | 5.32×1018 |
| Example 16 | 4.86×1018 | 6.85×1018 |
| Example 17 | 5.03×1018 | 7.17×1018 |
| Example 18 | 5.15×1018 | 7.6×1018 |
| Example 19 | 5.08×1018 | 7.25×1018 |
| Example 20 | 5.05×1018 | 7.21×1018 |
| Comparative example 1 | 0.15×1017 | 5.23×1017 |
| Comparative example 2 | 2.06×1017 | 0.12×1018 |
| Comparative example 3 | 1.03×1017 | 0.56×1018 |
| Comparative example 4 | 3.09×1017 | 1.02×1018 |
| Comparative example 5 | 1.26×1018 | 2.05×1018 |
| Comparative example 6 | 1.89×1018 | 3.75×1018 |
| Comparative example 7 | 2.76×1018 | 4.19×1018 |
| Comparative example 8 | 3.85×1018 | 5.13×1018 |
| Comparative example 9 | 4.83×1018 | 6.72×1018 |
Analytical examples 1-3 and comparative example 1,Compared with the comparative example 2, and tables 1 and 2 are combined, the annular quartz boat is selected to bear the simple substance As, in the synthesis process of the GaAs polycrystal, As steam can be fully and uniformly contacted with Ga, and the formed GaAs polycrystal has better quality; in addition, the molar ratio of Ga to As is adjusted to further control the proportion of Ga to As in the GaAs polycrystal, so that the dislocation density of a finally prepared crystal ingot can be controlled below 600, and the highest carrier concentration can reach 1.86 multiplied by 1018。
Analyzing examples 4-5, examples 6-7, examples 8-10, comparative examples 3-5 in combination with tables 1 and 2, it can be seen that adjusting and optimizing the composition and ratio of the doping elements, and the mass ratio of the dopant to the GaAs polycrystal improves the doping state of the doping elements in the GaAs crystal, further reduces the dislocation density of the GaAs ingot to 470 or less, and increases the carrier concentration up to 3.61 × 1018The prepared GaAs crystal has better electrical property.
Analyzing the example 11 and combining tables 1 and 2, it can be seen that mixing the dopant with the GaAs polycrystal in a filling manner can greatly improve the distribution uniformity of the dopant during the growth of the GaAs crystal, and further reduce the dislocation density of the GaAs crystal to below 450.
Analyzing examples 12-13, example 14, example 15, comparative examples 6-8 and combining table 1 and table 2, it can be seen that the size of the seed crystal is further optimized, so that the growth state of the GaAs crystal is better, and the dislocation density is reduced from 450 to 410; when the seed crystal direction is less than 111 and more than B, the dislocation density is further reduced by 11.6 percent; in addition, the growth speed of the GaAs crystal is optimized, the crystal growth state is improved, and the dislocation density is found to be increased when the growth speed is 2.5mm/h, so that the quality of the GaAs crystal is better when the production speed is 2 mm/h.
As can be seen by analyzing examples 16 to 19 in combination with tables 1 and 2, when the synthesis is carried out with a more reasonable vertical temperature gradient distribution, the GaAs crystal of example 18 is reduced by 21% in the head dislocation density as compared with example 15, and the carrier concentration is reduced from 5.32X 1018Lifting to 7.6X 1018The obtained GaAs crystal has better electrical property.
It can be seen from analysis example 20 and comparative example 9 and from tables 1 and 2 that after the dopant is washed with the ultrapure water cleaning solution containing hydrogen peroxide, the impurity concentration in the dopant is further reduced, and the quality of the GaAs crystal is improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (6)
1. A preparation method of a group II element doped GaAs single crystal is characterized by comprising the following steps:
s1: synthesizing a GaAs polycrystal by adopting a horizontal directional solidification method, and cleaning and drying the GaAs polycrystal for later use;
s2: cleaning a crucible and a quartz ampoule for later use;
s3: fixing GaAs seed crystals in a crucible seed crystal groove, adding GaAs polycrystal and a doping agent into a crucible, wherein the mass ratio of the GaAs polycrystal to the doping agent is 1 (0.0025-0.0925), and the doping agent is at least one of Zn, Cd, Be and Mg;
s4: adding a proper amount of B into the crucible2O3Sealing, namely placing the crucible into a quartz ampoule, vacuumizing until the vacuum degree is more than 0.003Pa, sealing the quartz ampoule, and placing the sealed quartz ampoule into a growth furnace after the vacuum degree is qualified;
s5: adopting a VGF method growth process, controlling the vertical temperature gradient of the growth furnace to be 2-3 ℃/cm, and slowly cooling after the growth is finished to obtain the product; wherein the fitting equation of the control curve of the vertical temperature gradient is y = (0.128-m) x + (5.9-n) x +1252, wherein the ordinate is the temperature in the unit of ℃, and the abscissa is the distance in the unit of cm, and the abscissa is set vertically upward with the seed crystal position as the starting point.
2. The method of producing a group ii element-doped GaAs single crystal according to claim 1, wherein m is in the range of (0-0.06) and n is in the range of (0.3-0.5).
3. The method of producing a group ii element-doped GaAs single crystal according to claim 2, wherein the growth rate of the group ii element-doped GaAs single crystal is 2 to 2.5 mm/h.
4. The method for preparing a group II element-doped GaAs single crystal according to claim 1, wherein the GaAs seed crystal direction is < 111 > B.
5. The method of producing a group II element-doped GaAs single crystal according to claim 4, wherein the dopant in step S3 is ultrasonically cleaned with a cleaning solution for 20 to 35min before being charged into the crucible, and then cleaned with ultrapure water and dried.
6. A group II element-doped GaAs single crystal produced by the method for producing a group II element-doped GaAs single crystal according to any one of claims 1 to 5.
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