CN116288251A - Tubular variable-temperature boron diffusion deposition process - Google Patents
Tubular variable-temperature boron diffusion deposition process Download PDFInfo
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- CN116288251A CN116288251A CN202211562108.0A CN202211562108A CN116288251A CN 116288251 A CN116288251 A CN 116288251A CN 202211562108 A CN202211562108 A CN 202211562108A CN 116288251 A CN116288251 A CN 116288251A
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000009792 diffusion process Methods 0.000 title claims abstract description 45
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 44
- 238000005137 deposition process Methods 0.000 title claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 50
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 230000008021 deposition Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000151 deposition Methods 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 239000010703 silicon Substances 0.000 claims description 25
- 235000012431 wafers Nutrition 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 12
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000003574 free electron Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/28—Deposition of only one other non-metal element
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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Abstract
The invention discloses a tubular variable-temperature boron diffusion deposition process, and belongs to the technical field of solar cells. The method adopts a multi-step through source deposition process and a variable-temperature push junction process to realize the boron diffusion process; the method specifically comprises 7 steps of nitrogen introduction into a boat, pre-oxidation treatment, multi-step source deposition, variable-temperature junction pushing, high-temperature oxidation, cooling oxidation, nitrogen introduction out of the boat, and the 7 steps are completed under different temperature conditions. The boron diffusion process is processed by a variable temperature process, so that the defect that the interface area is easy to have uneven diffusion is overcome; meanwhile, the multi-step through source deposition mode is adopted, so that the interface uniformity of boron diffusion deposition is well repaired, and the conversion efficiency of the battery is improved while the boron diffusion uniformity is optimized.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a tubular variable-temperature boron diffusion deposition process.
Background
The heart of the solar cell is a PN junction. The silicon crystal is characterized in that atoms are connected together by covalent bonds, and 4 valence electrons of the silicon atoms and 4 adjacent atoms form 4 pairs of common electron pairs. Such a common pair of electrons is referred to as a "covalent bond". After the silicon wafer is doped with boron, since the outermost layer of boron atoms has 3 valence electrons, there must be a vacancy in one valence bond due to the absence of one electron, which is called a "hole". Such a semiconductor relying on hole conduction is called a hole type semiconductor, abbreviated as P type semiconductor. Similarly, the outermost layer of the phosphorus (P) atom has five valence electrons, only four of which participate in covalent bonds, and the other of which is not at valence bonds, becomes free electrons, and the semiconductor doped with phosphorus plays a role in conduction, mainly the free electrons provided by phosphorus, and the semiconductor which relies on electron conduction is called an electronic type semiconductor, abbreviated as an N-type semiconductor.
If the N-type silicon wafer is placed in a quartz furnace tube, the silicon wafer is heated to a certain temperature, and a boron-containing compound is introduced to decompose boron on the surface of the silicon wafer, cover the surface of the silicon wafer and permeate and diffuse into the silicon wafer. The P type is formed on the surface with boron penetration, the original N type is formed on the surface without penetration, and the required PN junction is formed in the silicon wafer, namely the diffusion is carried out, and the purpose of the diffusion is to manufacture the PN junction. The process of using boron trichloride as a doping source to diffuse the N-type substrate silicon wafer is called a boron diffusion process, and the process commonly adopted in the boron diffusion process in the prior art is a constant temperature push-junction process, so that the defect that the interface area is easy to have uneven diffusion can be caused.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a tubular variable-temperature boron diffusion deposition process, which overcomes the defect that the interface area is easy to have uneven diffusion by variable-temperature process treatment in the boron diffusion process; meanwhile, the multi-step through source deposition mode is adopted, so that the interface uniformity of boron diffusion deposition is well repaired, and the conversion efficiency of the battery is improved while the boron diffusion uniformity is optimized.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a tubular variable-temperature boron diffusion deposition process adopts a combination of a multi-step through source deposition process and a variable-temperature push-junction process to realize a boron diffusion process.
The tubular variable-temperature boron diffusion deposition process comprises the following steps of: depositing according to the conditions of the temperature of 860 ℃, the nitrogen flow of 3000sccm, the oxygen flow of 2000sccm and the boron trichloride flow of 300sccm, wherein the first deposition time is 300s; depositing according to the conditions of 870 ℃ of temperature, 4000sccm of nitrogen flow, 3000sccm of oxygen flow and 200sccm of boron trichloride flow, wherein the second deposition time is 240s; and (3) performing deposition according to the conditions of the temperature of 880 ℃, the nitrogen flow of 5000sccm, the oxygen flow of 4000sccm and the boron trichloride flow of 100sccm, wherein the deposition time in the third step is 180 seconds.
The tubular variable-temperature boron diffusion deposition process comprises the following steps of: pushing knots according to the conditions of the temperature of 930-990 ℃ and the nitrogen flow of 6000sccm and the oxygen flow of 2000sccm, wherein the temperature is increased by 10 ℃ every 300s, and the total pushing knot time is 2100s. According to the time gradient, the time of each step is gradually decreased, the temperature is gradually increased, the temperature changing effect is achieved, and the silicon wafer after the process has better sheet resistance uniformity.
The tubular variable-temperature boron diffusion deposition process comprises the following steps of:
(1) Introducing nitrogen into the boat, placing the quartz boat filled with the silicon wafers on silicon carbide slurry, conveying the silicon carbide slurry into a furnace tube, and ensuring that the inside of the tube is in a positive pressure state;
(2) Pre-oxidation treatment, heating to an oxidation temperature, and oxidizing under a certain flow of nitrogen and oxygen;
(3) The multi-step deposition of the through source,
(4) The temperature is changed to push the knot,
(5) High-temperature oxidation is carried out according to the temperature of 1040 ℃ and under the condition of certain nitrogen and oxygen flow;
(6) Cooling and oxidizing, and oxidizing under the condition of certain nitrogen and oxygen flow according to the temperature of 800 ℃;
(7) Introducing nitrogen, discharging the boat, placing the quartz boat of the silicon wafer after the process treatment on the silicon carbide slurry, discharging the silicon wafer from the furnace tube, and ensuring that the inside of the tube is in a positive pressure state.
The tube type variable-temperature boron diffusion deposition process comprises the following steps that (1) the boat feeding temperature is 780-800 ℃, the boat feeding speed is 150mm/s, the positive pressure state in the tube is ensured according to the nitrogen flow of 10000sccm, and the boat feeding time is 720s.
The tubular variable-temperature boron diffusion deposition process comprises the following steps of (2) maintaining the boat carrying temperature at 840-850 ℃, heating to 860 ℃ at the speed of 20 ℃/min for oxidation, and oxidizing according to the conditions of 3000sccm of nitrogen flow and 2000sccm of oxygen flow for 300s.
The tubular variable-temperature boron diffusion deposition process comprises the following steps of (5) oxidizing under the conditions of 2000sccm of nitrogen flow and 18000sccm of oxygen flow for 7200s.
The tubular variable-temperature boron diffusion deposition process comprises the following steps of (6) oxidizing under the conditions of 5000sccm of nitrogen flow and 10000sccm of oxygen flow, wherein the temperature is reduced by 20 ℃ every 300s, and the total oxidizing time is 3900s.
The tube type variable-temperature boron diffusion deposition process comprises the following steps of (7) keeping the boat outlet temperature at 780-800 ℃, keeping the boat outlet speed at 150mm/s, and ensuring that the inside of the tube is in a positive pressure state according to the nitrogen flow of 10000sccm, wherein the boat outlet time is 720s.
The beneficial effects are that: compared with the prior art, the invention has the advantages that:
according to the invention, a variable-temperature junction pushing process is adopted, the gradient of boron trichloride during deposition is reduced, the service life of carriers in a silicon wafer is prolonged, the non-uniformity of the diffused sheet resistance is reduced, the low-efficiency discreteness of a finished battery is reduced, and the contrast electrical performance parameters are improved, so that the battery efficiency is improved.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Example 1
A tubular variable-temperature boron diffusion deposition process comprises the following specific implementation processes:
introducing nitrogen into the boat, placing the quartz boat filled with the silicon wafers on silicon carbide slurry, keeping the boat feeding temperature at 780-800 ℃, feeding the quartz boat into a furnace tube at a speed of 150mm/s for preparation process, and ensuring that the inside of the tube is in a positive pressure state according to the nitrogen flow of 10000sccm, wherein the boat feeding time is 720s.
And (3) performing pre-oxidation treatment, namely keeping the boat carrying temperature at 840-850 ℃, heating to 860 ℃ at the speed of 20 ℃/min for oxidation, and performing oxidation according to the conditions of 3000sccm of nitrogen flow and 2000sccm of oxygen flow for 300s.
And (3) performing multi-step through source deposition according to the conditions of the temperature of 860 ℃, the nitrogen flow rate of 3000sccm, the oxygen flow rate of 2000sccm and the boron trichloride flow rate of 300sccm, wherein the deposition time of the first step is 300s. And performing deposition according to the conditions of 870 ℃ and nitrogen flow 4000sccm and oxygen flow 3000sccm and boron trichloride flow 200sccm, wherein the deposition time is 240s in the second step. And (3) performing deposition according to the conditions of the temperature of 880 ℃, the nitrogen flow of 5000sccm, the oxygen flow of 4000sccm and the boron trichloride flow of 100sccm, wherein the deposition time in the third step is 180 seconds.
And (4) changing the temperature and pushing the knot, wherein the knot is pushed according to the conditions that the temperature is 930-990 ℃, the nitrogen flow is 6000sccm, the oxygen flow is 2000sccm, the temperature is increased by 10 ℃ every 300s, and the total knot pushing time is 2100s.
And (5) high-temperature oxidation, wherein the oxidation is carried out according to the conditions of 1040 ℃ of nitrogen flow rate 2000sccm and 18000sccm of oxygen flow rate, and the oxidation time is 7200s.
And (6) cooling and oxidizing, wherein the oxidizing is carried out according to the conditions of 800 ℃ of temperature, 5000sccm of nitrogen flow and 10000sccm of oxygen flow, the temperature is reduced by 20 ℃ every 300s, and the total oxidizing time is 3900s.
And (7) introducing nitrogen and discharging the boat, placing the quartz boat of the silicon wafer after the process treatment on silicon carbide slurry, keeping the boat discharging temperature at 780-800 ℃, discharging the silicon wafer from a furnace tube at a speed of 150mm/s, and ensuring that the inside of the tube is in a positive pressure state according to the nitrogen flow of 10000sccm, wherein the boat discharging time is 720s.
Comparative example 1
The specific flow of the traditional boron diffusion process is as follows:
introducing nitrogen into the boat, placing the quartz boat filled with the silicon wafers on silicon carbide slurry, keeping the boat feeding temperature at 780-800 ℃, feeding the quartz boat into a furnace tube at a speed of 150mm/s for preparation process, and ensuring that the inside of the tube is in a positive pressure state according to the nitrogen flow of 10000sccm, wherein the boat feeding time is 720s.
And (3) performing pre-oxidation treatment, namely keeping the boat carrying temperature at 840-850 ℃, heating to 860 ℃ at the speed of 20 ℃/min for oxidation, and performing oxidation according to the conditions of 3000sccm of nitrogen flow and 2000sccm of oxygen flow for 300s.
And (3) single-step through source deposition, wherein the deposition is carried out according to the conditions of the temperature of 870 ℃, the nitrogen flow of 9000sccm, the oxygen flow of 6000sccm and the boron trichloride flow of 300sccm, and the deposition time is 6000s.
And (4) pushing the knot at constant temperature, namely heating to 990 ℃ in a vacuum state for 1800 seconds, and pushing the knot under the conditions of 6000sccm of nitrogen flow and 2000sccm of oxygen flow, wherein the temperature is increased by 10 ℃ every 300 seconds, and the total knot pushing time is 2100 seconds.
And (5) high-temperature oxidation, wherein the oxidation is carried out according to the conditions of 1040 ℃ of nitrogen flow rate 2000sccm and 18000sccm of oxygen flow rate, and the oxidation time is 7200s.
And (6) cooling and oxidizing, wherein the oxidizing is carried out according to the conditions of 800 ℃ of temperature, 5000sccm of nitrogen flow and 10000sccm of oxygen flow, the temperature is reduced by 20 ℃ every 300s, and the total oxidizing time is 3900s.
And (7) introducing nitrogen and discharging the boat, placing the quartz boat of the silicon wafer after the process treatment on silicon carbide slurry, keeping the boat discharging temperature at 780-800 ℃, discharging the silicon wafer from a furnace tube at a speed of 150mm/s, and ensuring that the inside of the tube is in a positive pressure state according to the nitrogen flow of 10000sccm, wherein the boat discharging time is 720s.
TABLE 1 uniformity comparison of silicon wafers produced using conventional boron diffusion process and temperature varying boron diffusion process
| Project | Uniformity in sheet (%) |
| Traditional boron diffusion process | 5.6 |
| Variable-temperature pushing and knotting process | 4.5 |
TABLE 2 comparison of sheet resistance data for silicon wafers produced by conventional boron diffusion process and temperature varying boron diffusion process
Wherein the data unit in the table is Ω.
In the traditional boron diffusion process, when the square resistance reaches 141.7 ohms, the on-chip uniformity STD is 5.6%; when the sheet resistance value of the variable temperature boron diffusion process reaches 141 ohms, the sheet uniformity STD is 4.5%; compared with the variable temperature boron diffusion process, the uniformity of the variable temperature boron diffusion process is smaller, the finished product finished by the process is more concentrated in discreteness, and the conversion efficiency is better.
Claims (9)
1. A tubular variable-temperature boron diffusion deposition process is characterized in that a multi-step through source deposition process and a variable-temperature push junction process are combined to realize a boron diffusion process.
2. The tubular variable temperature boron diffusion deposition process of claim 1, wherein the multi-step through-source deposition process is: depositing according to the conditions of the temperature of 860 ℃, the nitrogen flow of 3000sccm, the oxygen flow of 2000sccm and the boron trichloride flow of 300sccm, wherein the first deposition time is 300s; depositing according to the conditions of 870 ℃ of temperature, 4000sccm of nitrogen flow, 3000sccm of oxygen flow and 200sccm of boron trichloride flow, wherein the second deposition time is 240s; and (3) performing deposition according to the conditions of the temperature of 880 ℃, the nitrogen flow of 5000sccm, the oxygen flow of 4000sccm and the boron trichloride flow of 100sccm, wherein the deposition time in the third step is 180 seconds.
3. The tubular variable temperature boron diffusion deposition process of claim 1, wherein the variable temperature push junction process is: pushing knots according to the conditions of the temperature of 930-990 ℃ and the nitrogen flow of 6000sccm and the oxygen flow of 2000sccm, wherein the temperature is increased by 10 ℃ every 300s, and the total pushing knot time is 2100s.
4. A tubular variable temperature boron diffusion deposition process according to any one of claims 1 to 3, comprising the steps of:
(1) Introducing nitrogen into the boat, placing the quartz boat filled with the silicon wafers on silicon carbide slurry, conveying the silicon carbide slurry into a furnace tube, and ensuring that the inside of the tube is in a positive pressure state;
(2) Pre-oxidation treatment, heating to an oxidation temperature, and oxidizing under a certain flow of nitrogen and oxygen;
(3) Multi-step source deposition;
(4) Changing the temperature and pushing the knot;
(5) High-temperature oxidation is carried out according to the temperature of 1040 ℃ and under the condition of certain nitrogen and oxygen flow;
(6) Cooling and oxidizing, and oxidizing under the condition of certain nitrogen and oxygen flow according to the temperature of 800 ℃;
(7) Introducing nitrogen, discharging the boat, placing the quartz boat of the silicon wafer after the process treatment on the silicon carbide slurry, discharging the silicon wafer from the furnace tube, and ensuring that the inside of the tube is in a positive pressure state.
5. The process according to claim 4, wherein the temperature of the boat fed in step (1) is 780-800 ℃, the boat feeding rate is 150mm/s, and the positive pressure state in the tube is ensured according to the nitrogen flow of 10000sccm, and the boat feeding time is 720s.
6. The process according to claim 4, wherein the temperature of the carrier is kept at 840-850 ℃ and the carrier is heated to 860 ℃ at 20 ℃/min for oxidation, and the oxidation is performed under conditions of 3000sccm nitrogen flow and 2000sccm oxygen flow for 300s.
7. The process of claim 4, wherein the oxidation is performed in step (5) at a nitrogen flow rate of 2000sccm and an oxygen flow rate of 18000sccm for 7200s.
8. The process of claim 4, wherein the oxidation is performed at a nitrogen flow rate of 5000sccm and an oxygen flow rate of 10000sccm in step (6), the temperature is reduced by 20 ℃ per 300s, and the total oxidation time is 3900s.
9. The process according to claim 4, wherein the temperature of the discharge boat is 780-800 ℃ and the discharge speed is 150mm/s, and the positive pressure state in the tube is ensured according to the nitrogen flow of 10000sccm, and the discharge time is 720s.
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