CN114606573A - Environment-friendly boron diffusion source formula - Google Patents
Environment-friendly boron diffusion source formula Download PDFInfo
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- CN114606573A CN114606573A CN202210053500.6A CN202210053500A CN114606573A CN 114606573 A CN114606573 A CN 114606573A CN 202210053500 A CN202210053500 A CN 202210053500A CN 114606573 A CN114606573 A CN 114606573A
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- ethylene glycol
- silicon wafer
- boron
- ethyl ether
- glycol ethyl
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 87
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 57
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 109
- 239000010703 silicon Substances 0.000 claims abstract description 109
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000000243 solution Substances 0.000 claims abstract description 70
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims abstract description 47
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000005530 etching Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 235000012431 wafers Nutrition 0.000 claims description 94
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 84
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 238000005498 polishing Methods 0.000 claims description 25
- 239000010453 quartz Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 16
- 238000007789 sealing Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 206010053615 Thermal burn Diseases 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003190 viscoelastic substance Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims 4
- 238000009472 formulation Methods 0.000 claims 4
- 239000000203 mixture Substances 0.000 claims 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000007517 polishing process Methods 0.000 abstract 1
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical group BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000005247 gettering Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005389 semiconductor device fabrication Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
- C30B31/06—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous 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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
-
- 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
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
- C30B31/06—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state
- C30B31/16—Feed and outlet means for the gases; Modifying the flow of the gases
- C30B31/165—Diffusion sources
-
- 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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
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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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/005—Oxydation
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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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/2225—Diffusion sources
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
- H01L21/2251—Diffusion into or out of group IV semiconductors
- H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
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Abstract
The invention discloses an environment-friendly boron diffusion source formula which comprises the following raw materials in parts by weight: ethylene glycol ethyl ether; boron trioxide; the method comprises the following steps of preparing boron trioxide/ethylene glycol ethyl ether solution from boron trioxide and ethylene glycol ethyl ether, preparing aluminum nitrate/ethylene glycol ethyl ether solution from aluminum nitrate and ethylene glycol ethyl ether, and preparing a boron diffusion liquid source from the boron trioxide/ethylene glycol ethyl ether solution, the aluminum nitrate/ethylene glycol ethyl ether solution and alumina powder. According to the environment-friendly boron diffusion source formula, the silicon wafer is sequentially subjected to surface corrosion, surface oxidation, drying and polishing processes, the silicon wafer is placed into an etching solution of a hydrofluoric acid/nitric acid/water mixed solution system for reaction, and then the silicon wafer is placed into an alkali solution for reaction at normal temperature, so that the surface concentration of the silicon wafer after diffusion is high, the problem of low surface concentration caused by the boron absorption effect of silicon dioxide after boron diffusion is solved, the uniformity of the silicon wafer after boron diffusion is good, and the problem of low single boron diffusion source cannot occur.
Description
Technical Field
The invention relates to the technical field of boron diffusion, in particular to an environment-friendly boron diffusion source formula.
Background
The boron diffusion process is to incorporate a certain amount of boron impurities into the silicon wafer crystal to change the original electrical properties of the silicon wafer. Boron diffusion is an important doping process in the field of silicon-based semiconductor device fabrication. The sources used to effect boron diffusion are, in physical form, gaseous, liquid and solid sources.
The gaseous source generally selects boron chloride with strong gettering performance, which can ensure that the silicon wafer has a longer minority carrier lifetime, but the boron chloride has a stronger bond strength and needs higher decomposition energy, the temperature for realizing boron diffusion reaches over 960 ℃, heat loss is easily caused to devices, an auxiliary vacuum pump is required under low-pressure conditions, and the preparation cost is higher; the liquid source is boron bromide, and the temperature is required to be above 950 ℃ and the gaseous BCl is required to obtain the diffusion thin layer sheet resistance of 150 omega/sq in a conventional mode3With liquid BBr3Reacting with oxygen at high temperature to generate boron oxide (B)2O3) Deposited on the surface of a silicon wafer due to B2O3The silicon dioxide is liquid at the diffusion temperature, the uniformity of the silicon dioxide is poor, and the surface concentration is low due to the boron absorption effect of the silicon dioxide after boron diffusion.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an environment-friendly boron diffusion source formula, which has the advantage of good uniformity and can perform diffusion at low temperature.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: an environment-friendly boron diffusion source formula comprises the following raw materials in parts by weight: ethylene glycol Ether (C)44H10O2) (ii) a Boron trioxide (B)2O3) (ii) a Aluminum nitrate (Al (NO)3）3) And alumina (Al)2O3）。
Preferably, the preparation method of the boron diffusion source comprises the following steps:
s1: preparing a diboron trioxide/ethylene glycol ether solution, taking diboron trioxide: ethylene glycol ethyl ether =120 g: 400mL, placing 800mL of ground bottle pad filter paper on a stirrer, pouring ethylene glycol ethyl ether, starting the stirrer, observing that the center of the bottle has a vortex, weighing boron trioxide according to the required proportion by using an electronic scale, slowly pouring the boron trioxide along the edge of the ground bottle, covering a bottle cap after the bottle body does not scald hands, stirring for 5-6 hours, closing the stirrer, and sealing the boron trioxide/ethylene glycol ethyl ether solution.
S2: preparing an aluminum nitrate/ethylene glycol ether solution, taking aluminum nitrate: ethylene glycol ethyl ether =5 g: 50mL, placing filter paper below a ground bottle on a stirrer, pouring ethylene glycol ethyl ether, starting the stirrer, weighing aluminum nitrate, slowly pouring while attaching to the ground bottle, grinding a bottle cap to form a half cover, covering the bottle cap after the bottle body is not scalded, stirring for 1-2 hours, closing the stirrer, and sealing the aluminum nitrate/ethylene glycol ethyl ether solution.
S3: preparing a boron diffusion liquid source, taking a boron trioxide/ethylene glycol ether solution: aluminum nitrate/ethylene glycol ethyl ether solution: alumina powder =50 mL: 6mL of: 2g, putting the ground bottle on a stirrer, measuring the filtered diboron trioxide/ethylene glycol ether solution and the filtered aluminum nitrate/ethylene glycol ether solution, slowly pouring the filtered diboron trioxide/ethylene glycol ether solution and the filtered aluminum nitrate/ethylene glycol ether solution into the ground bottle, opening the stirrer, pouring weighed alumina powder (4N: 5N = 1: 3), covering a bottle cap, and stirring for 10-15 minutes for use.
S4: preparing a silicon wafer, sequentially carrying out four procedures of surface corrosion, surface oxidation, drying and polishing on the silicon wafer to obtain the silicon wafer, putting the silicon wafer into an etching solution of a hydrofluoric acid/nitric acid/water mixed solution system for reaction for 0.5-2min, increasing the sheet resistance by 10-20 omega/sq, putting the silicon wafer into an alkali solution for reaction for 5-20s at normal temperature, putting the silicon wafer into a mixed acid solution for cleaning for 1-5min until the surface is completely hydrophobic, and finally cleaning and drying the silicon wafer by using deionized water.
S5: loading the silicon wafers obtained in the step S4 into a diffusion quartz boat, slowly feeding the quartz boat loaded with the silicon wafers into a diffusion quartz tube at the temperature of 600-700 ℃ under the nitrogen atmosphere, sealing the orifice of the diffusion quartz tube to ensure the temperature in the diffusion quartz tube to be stable, completing boat feeding, gradually heating to 800-1000 ℃, performing diffusion under the nitrogen atmosphere, introducing oxygen in the process, completing temperature rise diffusion, gradually cooling to 600-700 ℃ after the temperature rise diffusion is finished, then slowly outputting the quartz boat loaded with the silicon wafers, cooling and taking out the boat, and completing the diffusion of boron into silicon.
Preferably, the error of the electronic scale is within +/-0.01, the diboron trioxide/ethylene glycol ethyl ether solution is required to be precipitated for more than 6 hours before use so as to be used, the aluminum nitrate/ethylene glycol ethyl ether solution is required to be precipitated for 1 hour before use so as to be used, the prepared boron diffusion liquid source is required to be used up within 12 hours, and the prepared boron diffusion liquid source is required to be in a stirring state all the time in the use process.
Preferably, the silicon wafer in S4 is one of P-type silicon, N-type silicon or polycrystalline silicon wafer.
Preferably, the preparation of the silicon wafer in the S4 comprises the following specific steps:
s4-1: surface corrosion: and carrying out surface corrosion operation on the silicon wafer, removing the cutting damage layer on the surface of the silicon wafer, and processing the surface of the silicon wafer into a specific pattern.
S4-2: surface oxidation: and oxidizing the surface of the silicon wafer to improve the surface hydrophilicity of the silicon wafer.
S4-3: and (3) drying: and drying the silicon wafer to fully volatilize the solvent in the surface source of the silicon wafer.
S4-4: polishing: and (3) polishing the surface to be diffused of the silicon wafer by using a low-elasticity material polishing disc rotating at a high speed or a soft elastic or viscoelastic material polishing disc rotating at a low speed and adding a polishing agent.
(III) advantageous effects
Compared with the prior art, the invention provides an environment-friendly boron diffusion source formula, which has the following beneficial effects:
1. according to the environment-friendly boron diffusion source formula, the silicon wafer is prefabricated and subjected to four processes of surface corrosion, surface oxidation, drying and polishing in sequence to obtain the silicon wafer, so that the silicon wafer has good uniformity after boron diffusion, and the problem of low boron diffusion source at a single position is solved.
2. According to the formula of the environment-friendly boron diffusion source, a silicon wafer is placed in an etching solution of a hydrofluoric acid/nitric acid/water mixed solution system for reaction, then the silicon wafer is placed in an alkali solution for reaction at normal temperature, the silicon wafer is placed in a mixed acid solution for cleaning until the surface is completely hydrophobic, and finally deionized water is used for cleaning and drying, so that the surface concentration of the silicon wafer after diffusion is high, and the problem of low surface concentration caused by the boron absorption effect of silicon dioxide after boron diffusion is solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
an environment-friendly boron diffusion source formula comprises the following raw materials in parts by weight: ethylene glycol Ether (C)44H10O2) (ii) a Boron trioxide (B)2O3) (ii) a Aluminum nitrate (Al (NO)3）3) And alumina (Al)2O3）。
The preparation method of the boron diffusion source comprises the following steps:
s1: preparing boron trioxide/ethylene glycol ether solution, taking boron trioxide: ethylene glycol ethyl ether =120 g: 400mL, placing 800mL of ground bottle pad filter paper on a stirrer, pouring ethylene glycol ethyl ether, starting the stirrer, observing that the center of the bottle has a vortex, weighing boron trioxide according to the required proportion by using an electronic scale, slowly pouring the boron trioxide close to the edge of the ground bottle, covering a bottle cap after the bottle body does not scald the hand, stirring for 5 hours, closing the stirrer, and sealing the boron trioxide/ethylene glycol ethyl ether solution.
S2: preparing an aluminum nitrate/ethylene glycol ether solution, taking aluminum nitrate: ethylene glycol ethyl ether =5 g: 50mL, placing filter paper below a ground bottle on a stirrer, pouring ethylene glycol ethyl ether, starting the stirrer, weighing aluminum nitrate, slowly pouring while attaching to the ground bottle, grinding a bottle cap to form a half cover, covering the bottle cap after the bottle body is not scalded, stirring for 1-2 hours, closing the stirrer, and sealing the aluminum nitrate/ethylene glycol ethyl ether solution.
S3: preparing a boron diffusion liquid source, taking a boron trioxide/ethylene glycol ether solution: aluminum nitrate/ethylene glycol ethyl ether solution: alumina powder =50 mL: 6mL of: 2g, placing the ground bottle on a stirrer, measuring the filtered diboron trioxide/ethylene glycol ether solution and the filtered aluminum nitrate/ethylene glycol ether solution, slowly pouring the filtered diboron trioxide/ethylene glycol ether solution and the filtered aluminum nitrate/ethylene glycol ether solution into the ground bottle, opening the stirrer, pouring weighed alumina powder (4N: 5N = 1: 3), covering a bottle cap, and stirring for 10 minutes for use.
S4: preparing a silicon wafer, sequentially carrying out four procedures of surface corrosion, surface oxidation, drying and polishing on the silicon wafer to obtain the silicon wafer, putting the silicon wafer into an etching solution of a hydrofluoric acid/nitric acid/water mixed solution system for reaction for 1min, increasing the sheet resistance by 10 omega/sq, putting the silicon wafer into an alkali solution for reaction for 10S at normal temperature, putting the silicon wafer into a mixed acid solution for cleaning for 2min until the surface is completely hydrophobic, finally cleaning with deionized water and drying, wherein the silicon wafer in S4 is N-type silicon.
The preparation of the silicon wafer in S4 comprises the following specific steps:
s4-1: surface corrosion: and carrying out surface corrosion operation on the silicon wafer, removing the cutting damage layer on the surface of the silicon wafer, and processing the surface of the silicon wafer into a specific pattern.
S4-2: surface oxidation: and oxidizing the surface of the silicon wafer to improve the surface hydrophilicity of the silicon wafer.
S4-3: and (3) drying: and drying the silicon wafer to fully volatilize the solvent in the surface source of the silicon wafer.
S4-4: polishing: and (3) polishing the surface to be diffused of the silicon wafer by using a low-elasticity material polishing disc rotating at a high speed or a soft elastic or viscoelastic material polishing disc rotating at a low speed and adding a polishing agent.
S5: loading the silicon wafers obtained in the step S4 into a diffusion quartz boat, slowly feeding the quartz boat loaded with the silicon wafers into a diffusion quartz tube at the temperature of 700 ℃ and under the nitrogen atmosphere, sealing the tube opening of the diffusion quartz tube to ensure the temperature in the diffusion quartz tube to be stable, completing boat feeding, gradually raising the temperature to 1000 ℃, performing diffusion in the nitrogen atmosphere, introducing oxygen in the process, completing temperature rise diffusion, gradually lowering the temperature to 700 ℃ after the temperature rise diffusion is finished, then slowly outputting the quartz boat loaded with the silicon wafers, and performing temperature reduction and boat discharging to complete the diffusion of boron into silicon.
The error of the electronic scale is within +/-0.01, the diboron trioxide/ethylene glycol ethyl ether solution is required to be precipitated for more than 6 hours before use and can be used, the aluminum nitrate/ethylene glycol ethyl ether solution is required to be precipitated for 1 hour before use and can be used, the prepared boron diffusion liquid source is required to be used up within 12 hours, and the boron diffusion liquid source is required to be in a stirring state all the time in the use process.
Example two:
an environment-friendly boron diffusion source formula comprises the following raw materials in parts by weight: ethylene glycol Ether (C)44H10O2) (ii) a Boron trioxide (B)2O3) (ii) a Aluminum nitrate (Al (NO)3）3) And alumina (Al)2O3）。
The preparation method of the boron diffusion source comprises the following steps:
s1: preparing boron trioxide/ethylene glycol ether solution, taking boron trioxide: ethylene glycol ethyl ether =120 g: 400mL, placing 800mL of ground bottle pad filter paper on a stirrer, pouring ethylene glycol ethyl ether, starting the stirrer, observing that the center of the bottle has a vortex, weighing boron trioxide according to the required proportion by using an electronic scale, slowly pouring the boron trioxide close to the edge of the ground bottle, covering a bottle cap after the bottle body does not scald the hand, stirring for 6 hours, closing the stirrer, and sealing the boron trioxide/ethylene glycol ethyl ether solution.
S2: preparing an aluminum nitrate/ethylene glycol ether solution, taking aluminum nitrate: ethylene glycol ethyl ether =5.2 g: 56mL, placing filter paper below a ground bottle on a stirrer, pouring ethylene glycol ethyl ether, starting the stirrer, weighing aluminum nitrate, slowly pouring while attaching to the ground bottle, grinding a bottle cover half cover, covering the bottle cover after the bottle body is not scalded, stirring for 1-2 hours, closing the stirrer, and sealing the aluminum nitrate/ethylene glycol ethyl ether solution.
S3: preparing a boron diffusion liquid source, taking a boron trioxide/ethylene glycol ether solution: aluminum nitrate/ethylene glycol ethyl ether solution: alumina powder =46 mL: 5.7 mL: 3g, placing the ground bottle on a stirrer, measuring the filtered diboron trioxide/ethylene glycol ether solution and the filtered aluminum nitrate/ethylene glycol ether solution, slowly pouring the filtered diboron trioxide/ethylene glycol ether solution and the filtered aluminum nitrate/ethylene glycol ether solution into the ground bottle, opening the stirrer, pouring weighed alumina powder (4N: 5N = 1.2: 2.7), covering a bottle cap, and stirring for 15 minutes for use.
S4: preparing a silicon wafer, sequentially carrying out four procedures of surface corrosion, surface oxidation, drying and polishing on the silicon wafer to obtain the silicon wafer, putting the silicon wafer into an etching solution of a hydrofluoric acid/nitric acid/water mixed solution system for reaction for 1min, increasing the sheet resistance by 20 omega/sq, putting the silicon wafer into an alkali solution for reaction for 10S at normal temperature, putting the silicon wafer into a mixed acid solution for cleaning for 2min until the surface is completely hydrophobic, finally cleaning with deionized water and drying, wherein the silicon wafer in S4 is P-type silicon.
The preparation of the silicon wafer in S4 comprises the following specific steps:
s4-1: surface corrosion: and carrying out surface corrosion operation on the silicon wafer, removing the cutting damage layer on the surface of the silicon wafer, and processing the surface of the silicon wafer into a specific pattern.
S4-2: surface oxidation: and oxidizing the surface of the silicon wafer to improve the surface hydrophilicity of the silicon wafer.
S4-3: and (3) drying: and drying the silicon wafer to fully volatilize the solvent in the surface source of the silicon wafer.
S4-4: polishing: and (3) polishing the surface to be diffused of the silicon wafer by using a low-elasticity material polishing disc rotating at a high speed or a soft elastic or viscoelastic material polishing disc rotating at a low speed and adding a polishing agent.
S5: loading the silicon wafers obtained in the step S4 into a diffusion quartz boat, slowly feeding the quartz boat loaded with the silicon wafers into a diffusion quartz tube at the temperature of 650 ℃ under the nitrogen atmosphere, sealing the tube opening of the diffusion quartz tube to ensure the temperature in the diffusion quartz tube to be stable, completing boat feeding, gradually raising the temperature to 900 ℃, performing diffusion in the nitrogen atmosphere, introducing oxygen in the process, completing temperature rise diffusion, gradually lowering the temperature to 650 ℃ after the temperature rise diffusion is finished, slowly outputting the quartz boat loaded with the silicon wafers, and performing temperature lowering to take out the quartz boat, thereby completing the diffusion of boron into silicon.
The error of the electronic scale is within +/-0.01, the diboron trioxide/ethylene glycol ethyl ether solution is required to be precipitated for more than 6 hours before use and can be used, the aluminum nitrate/ethylene glycol ethyl ether solution is required to be precipitated for 1 hour before use and can be used, the prepared boron diffusion liquid source is required to be used up within 12 hours, and the boron diffusion liquid source is required to be in a stirring state all the time in the use process.
Respectively carrying out diffusion in S5 on the boron diffusion sources prepared in the first embodiment and the second embodiment, wherein after the diffusion, as the more phosphorus is doped into the N-type silicon wafer, the more free electrons are, the stronger the conductive capability is, and the lower the resistivity is; the more boron is doped into the P-type silicon wafer, the more holes generated by silicon replacement are increased, the stronger the conductivity is, and the lower the resistivity is, so that the first embodiment uses the N-type silicon wafer and uses diboron trioxide to prepare the boron diffusion source, and therefore the first embodiment is the best embodiment of the scheme.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. An environment-friendly boron diffusion source formula is characterized by comprising the following raw materials in parts by weight: ethylene glycol Ether (C)44H10O2) (ii) a Boron trioxide (B)2O3) (ii) a Aluminum nitrate (Al (NO)3）3) And alumina (Al)2O3）。
2. The environmental boron diffusion source formulation of claim 1, wherein: the preparation method of the boron diffusion source comprises the following steps:
s1: preparing boron trioxide/ethylene glycol ether solution, taking boron trioxide: ethylene glycol ethyl ether =120 g: 400mL, placing 800mL of ground bottle pad filter paper on a stirrer, pouring ethylene glycol ethyl ether, starting the stirrer, observing that the center of the bottle has a vortex, weighing boron trioxide according to the required proportion by using an electronic scale, slowly pouring the boron trioxide along the edge of the ground bottle, covering a bottle cap after the bottle body does not scald hands, stirring for 5-6 hours, closing the stirrer, and sealing the boron trioxide/ethylene glycol ethyl ether solution;
s2: preparing an aluminum nitrate/ethylene glycol ether solution, taking aluminum nitrate: ethylene glycol ethyl ether =5 g: 50mL, placing filter paper below a ground bottle on a stirrer, pouring ethylene glycol ethyl ether, starting the stirrer, weighing aluminum nitrate, slowly pouring along the ground bottle, grinding a bottle cover half cover, covering the bottle cover after the bottle body is not scalded, stirring for 1-2 hours, closing the stirrer, and sealing the aluminum nitrate/ethylene glycol ethyl ether solution;
s3: preparing a boron diffusion liquid source, taking a boron trioxide/ethylene glycol ether solution: aluminum nitrate/ethylene glycol ethyl ether solution: alumina powder =50 mL: 6mL of: 2g, putting the ground bottle on a stirrer, measuring the filtered diboron trioxide/ethylene glycol ethyl ether solution and the filtered aluminum nitrate/ethylene glycol ethyl ether solution, slowly pouring the filtered diboron trioxide/ethylene glycol ethyl ether solution and the filtered aluminum nitrate/ethylene glycol ethyl ether solution into the ground bottle, opening the stirrer, pouring weighed alumina powder (4N: 5N = 1: 3), covering a bottle cap, and stirring for 10-15 minutes for use;
s4: preparing a silicon wafer, sequentially carrying out four procedures of surface corrosion, surface oxidation, drying and polishing on the silicon wafer to obtain the silicon wafer, putting the silicon wafer into an etching solution of a hydrofluoric acid/nitric acid/water mixed solution system for reaction for 0.5-2min, increasing the sheet resistance by 10-20 omega/sq, putting the silicon wafer into an alkali solution for reaction for 5-20s at normal temperature, putting the silicon wafer into a mixed acid solution for cleaning for 1-5min until the surface is completely hydrophobic, and finally cleaning and drying the silicon wafer by using deionized water;
s5: loading the silicon wafers obtained in the step S4 into a diffusion quartz boat, slowly feeding the quartz boat loaded with the silicon wafers into a diffusion quartz tube at the temperature of 600-700 ℃ under the nitrogen atmosphere, sealing the orifice of the diffusion quartz tube to ensure the temperature in the diffusion quartz tube to be stable, completing boat feeding, gradually heating to 800-1000 ℃, performing diffusion under the nitrogen atmosphere, introducing oxygen in the process, completing temperature rise diffusion, gradually cooling to 600-700 ℃ after the temperature rise diffusion is finished, then slowly outputting the quartz boat loaded with the silicon wafers, cooling and taking out the boat, and completing the diffusion of boron into silicon.
3. The environmental boron diffusion source formulation of claim 2, wherein: the error of the electronic scale in the S1 is within plus or minus 0.01, the diboron trioxide/ethylene glycol ethyl ether solution is required to be precipitated for more than 6 hours before use and can be used, the aluminum nitrate/ethylene glycol ethyl ether solution is required to be precipitated for 1 hour before use and can be used, the prepared boron diffusion liquid source is required to be used up within 12 hours, and the boron diffusion liquid source is required to be in a stirring state all the time in the use process.
4. The environmental boron diffusion source formulation of claim 1, wherein: the silicon wafer in the S4 is one of P-type silicon, N-type silicon or polycrystalline silicon wafer.
5. The environmental boron diffusion source formulation of claim 1, wherein: the preparation of the silicon wafer in the S4 comprises the following specific steps:
s4-1: surface corrosion: carrying out surface corrosion operation on the silicon wafer, removing a cutting damage layer on the surface of the silicon wafer, and processing the surface of the silicon wafer into a specific pattern;
s4-2: surface oxidation: oxidizing the surface of the silicon wafer to improve the surface hydrophilicity of the silicon wafer;
s4-3: and (3) drying: drying the silicon wafer to fully volatilize the solvent in the surface source of the silicon wafer;
s4-4: polishing: and (3) polishing the surface to be diffused of the silicon wafer by using a low-elasticity material polishing disc rotating at a high speed or a soft elastic or viscoelastic material polishing disc rotating at a low speed and adding a polishing agent.
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| CN111370304A (en) * | 2018-12-25 | 2020-07-03 | 天津环鑫科技发展有限公司 | Boron-aluminum source and configuration method thereof |
| CN111370303A (en) * | 2018-12-25 | 2020-07-03 | 天津环鑫科技发展有限公司 | Boron-aluminum source for diffusion and configuration method thereof |
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| JP2002299274A (en) * | 2001-04-02 | 2002-10-11 | Sanken Electric Co Ltd | Manufacturing method for semiconductor device |
| CN102074464A (en) * | 2010-12-09 | 2011-05-25 | 西安卫光科技有限公司 | Boron-aluminum process for high-power transistor chip |
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