CN114420550A - Preparation method of composite antimony diffusion source and semiconductor doping processing method - Google Patents
Preparation method of composite antimony diffusion source and semiconductor doping processing method Download PDFInfo
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- CN114420550A CN114420550A CN202210000074.XA CN202210000074A CN114420550A CN 114420550 A CN114420550 A CN 114420550A CN 202210000074 A CN202210000074 A CN 202210000074A CN 114420550 A CN114420550 A CN 114420550A
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- antimony
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- diffusion source
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- butyl alcohol
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 90
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 65
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000004065 semiconductor Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000003672 processing method Methods 0.000 title abstract description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 238000000137 annealing Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000005468 ion implantation Methods 0.000 description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005389 semiconductor device fabrication Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L21/2252—Diffusion into or out of group IV semiconductors using predeposition of impurities into the semiconductor surface, e.g. from a gaseous phase
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a preparation method of a composite antimony diffusion source and a semiconductor doping processing method, 1, 20-22 parts of tetraethoxysilane and 35-40 parts of ethanol are uniformly mixed and heated to 60-65 ℃ according to the mass parts; 2, adding 3-5 parts of water by mass, preserving heat at 60-65 ℃ for 2-3h, and cooling to room temperature; 3, uniformly mixing 3-15 parts of n-butyl alcohol and 1-5 parts of antimony pentachloride in parts by mass, introducing sufficient ammonia gas, filtering, precipitating and collecting filtrate to obtain n-butyl alcohol antimony, wherein the mass part of the n-butyl alcohol is 3 times that of the antimony pentachloride; and 4, adding the n-butyl alcohol antimony prepared in the step 3 into the mixed liquid prepared in the step 2, and stirring for 2-3 hours to obtain the antimony-butyl alcohol. The method for doping and processing the semiconductor comprises the following steps: 1, uniformly coating the composite antimony diffusion source on the surface of a silicon wafer; 2, pre-baking and heating the silicon wafer to enable the composite antimony diffusion source to form a solidified film layer; and 3, moving the silicon wafer into a diffusion furnace for thermal diffusion. The precise control of the antimony doping concentration is realized by controlling the film thickness and the content of antimony in the diffusion source.
Description
Technical Field
The invention belongs to the technical field of composite antimony diffusion source processing methods and semiconductor processing, and particularly relates to a preparation method of a composite antimony diffusion source and a semiconductor doping processing method.
Background
Diffusion sources are an essential microelectronic chemical in the doping process of semiconductor device fabrication. According to the difference of doping sources used in different doping processes, the doping processes are mainly divided into two types: thermal diffusion and ion implantation.
The ion implantation is to bombard the surface of a silicon wafer by high-energy ion beams, impurity ions are implanted into bulk silicon at a doping window, and the impurity ions are shielded by a protective layer on the surface of the silicon in other regions which do not need to be doped, so that the selective doping is completed. In the ion implantation process, ionized impurity ions are accelerated by an electrostatic field and hit the surface of a silicon wafer, and the implantation dosage can be strictly controlled by measuring the ion current.
The ion implantation is usually shallow in depth and high in concentration, and annealing and redistribution processes must be performed. Since ions can cause extensive damage to the crystal lattice after entering the silicon crystal, annealing is performed after ion implantation in order to recover the crystal lattice damage. While annealing, the impurities are redistributed within the silicon body, and if necessary, a subsequent high temperature treatment may be performed to obtain the desired junction depth. The process is complex and cannot meet the processing requirement of products with large junction depth at one time.
In addition, the ion implanter technology is always mastered in an external enterprise, so that the problems of high equipment price, limited purchase and the like are prominent. Particularly, for some semiconductor manufacturing facilities during the separation period, the cost of using the ion implanter for the production period is too high, and the production efficiency is low due to the limited number of devices, and the product supply is tense.
Thermal diffusion doping means that impurity atoms are diffused from an impurity source with high concentration into bulk silicon to form a certain distribution by utilizing diffusion movement of molecules at high temperature.
Thermal diffusion is typically carried out in two steps: predeposition and redistribution. The predeposition is to diffuse a doped window on a silicon wafer by using an impurity source, such as a boron source, a phosphorus source and the like, at a high temperature to form a thin impurity layer with high concentration at the window. This is a diffusion process for a constant surface source. The redistribution is a diffusion process for limiting a surface source, and is a process for diffusing the impurity layer formed by predeposition into bulk silicon at high temperature by using the surface impurity layer as an impurity source, wherein the redistribution time is usually longer, and certain impurity distribution and junction depth can be formed on a silicon substrate through redistribution.
However, the thermal diffusion doping process has a significant disadvantage in that the concentration of impurities cannot be precisely controlled, and thus the produced circuit may be different from the designed circuit.
Compared with ion implantation, the thermal diffusion process is simple to operate, and the requirements on equipment and environment are relatively low. The production and manufacturing cost is low, so that the method is favored by some manufacturers.
Antimony sources are the most commonly used impurity sources for buried layer diffusion in bipolar integrated circuits. Antimony sources have a lower diffusion coefficient and a lower vapor pressure than other impurities (e.g., arsenic) and thus have less out-diffusion during subsequent heat treatment. The lateral diffusion is small, which is beneficial to improving the integration level, and the epitaxial layer has small self-doping. Is favorable for thin epitaxy and low-resistance epitaxy and is convenient for manufacturing high-speed circuits.
The conventional antimony source mainly comprises stibium hydride, antimony pentachloride, antimony trioxide and the like. Wherein, the stibium hydride is mainly used for the ion implantation technology, and the antimony pentachloride and the antimony trioxide are mainly used for thermal diffusion. In thermal diffusion, antimony pentachloride is colorless liquid, has strong hygroscopicity, and is fuming when exposed in air. Therefore, the diffusion system should be kept airtight during application to prevent moisture absorption. The diffusion mode of antimony trioxide and antimony pentachloride is almost the same, nitrogen is used as carrier gas to bring the impurity source into the diffusion furnace for diffusion, and the biggest defect of the diffusion process is that the amount of the impurity source brought into the diffusion furnace cannot be accurately controlled, so that the non-uniformity of diffusion concentration is caused.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a composite antimony diffusion source and a semiconductor doping processing method, and the preparation method of the diffusion source and the semiconductor doping processing method can realize the accurate control of the antimony doping concentration by controlling the film thickness and the content of antimony in the composite antimony diffusion source. The diffusion process does not need the participation of an ion implanter, reduces the capital investment of the equipment, is simple to operate, completes the whole diffusion process in the diffusion furnace once, does not need secondary annealing, can meet the processing requirement of products with large junction depth, and improves the production efficiency.
In order to solve the technical problem, the invention is solved by the following technical scheme: a preparation method of a composite antimony diffusion source comprises the following steps: 1, uniformly mixing 20-22 parts of ethyl orthosilicate and 35-40 parts of ethanol according to the mass parts, and heating to 60-65 ℃; 2, adding 3-5 parts of water by mass into the mixed solution prepared in the step 1, preserving the heat at the temperature of 60-65 ℃ for 2-3h, and cooling to room temperature; 3, uniformly mixing 3-15 parts of n-butyl alcohol and 1-5 parts of antimony pentachloride in parts by mass, introducing sufficient ammonia gas, filtering, precipitating and collecting filtrate to obtain n-butyl alcohol antimony, wherein the mass part of the n-butyl alcohol is 3 times that of the antimony pentachloride; and 4, adding the n-butyl alcohol antimony prepared in the step 3 into the mixed liquid prepared in the step 2, and stirring for 2-3 hours to obtain the antimony-butyl alcohol. The preparation method of the diffusion source can realize the accurate control of the doping concentration of the antimony by controlling the content of the antimony in the composite antimony diffusion source. The diffusion process does not need the participation of an ion implanter, reduces the capital investment of the equipment, is simple to operate, completes the whole diffusion process in the diffusion furnace once, does not need secondary annealing, can meet the processing requirement of products with large junction depth, and improves the production efficiency.
In the above technical solution, preferably, the method further comprises a step 5 of filtering the mixed solution obtained in the step 4 by using a filter element with a pressure of 0.5 μm.
In the above technical solution, preferably, the whole process of step 3 is performed under nitrogen protection.
The method for preparing the composite antimony diffusion source for semiconductor doping processing comprises the following steps: 1, uniformly coating a composite antimony diffusion source on the surface of a silicon wafer; 2, pre-baking and heating the silicon wafer to enable the composite antimony diffusion source to form a solidified film layer; and 3, moving the silicon wafer into a diffusion furnace for thermal diffusion. The method for using the composite antimony diffusion source for semiconductor doping processing can realize accurate control of antimony doping concentration by controlling the film thickness of the composite antimony diffusion source. The diffusion process does not need the participation of an ion implanter, reduces the capital investment of the equipment, is simple to operate, completes the whole diffusion process in the diffusion furnace once, does not need secondary annealing, can meet the processing requirement of products with large junction depth, and improves the production efficiency.
Preferably, in the step 1, the composite antimony diffusion source is coated by a spin coater.
Compared with the prior art, the invention has the following beneficial effects: the preparation method of the diffusion source and the method for using the composite antimony diffusion source in semiconductor doping processing can realize accurate control of antimony doping concentration by controlling the content of antimony in the composite antimony diffusion source and controlling the film thickness of the composite antimony diffusion source. The diffusion process does not need the participation of an ion implanter, reduces the capital investment of the equipment, is simple to operate, completes the whole diffusion process in the diffusion furnace once, does not need secondary annealing, can meet the processing requirement of products with large junction depth, and improves the production efficiency.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments below: example 1, first, a composite antimony diffusion source was prepared, comprising the steps of: 1, uniformly mixing 20 parts of ethyl orthosilicate and 35 parts of ethanol according to the mass parts, and heating to 60 ℃; 2, adding 3 parts of water into the mixed solution prepared in the step 1 by mass, preserving the heat at the temperature of 60-65 ℃ for 2 hours, and cooling to room temperature; 3, uniformly mixing 3 parts of n-butyl alcohol and 1 part of antimony pentachloride in parts by mass, introducing enough ammonia gas, filtering, precipitating and collecting filtrate to obtain n-butyl alcohol antimony, wherein the step is carried out under the protection of nitrogen; and 4, adding the n-butyl alcohol antimony prepared in the step 3 into the mixed liquid prepared in the step 2, and stirring for 2 hours to obtain the antimony-butyl alcohol. In other embodiments, step 5 may also be included, and the mixed solution obtained in step 4 is filtered by using a filter element pressure of 0.5 μm. The viscosity of the product can meet the coating requirement, and the content of antimony can meet the requirement of doping processing.
The method for using the prepared composite antimony diffusion source in semiconductor doping processing comprises the following steps: 1, uniformly coating the prepared composite antimony diffusion source on the surface of a silicon wafer by using a spin coater, wherein the coating thickness can be adjusted according to the content of antimony required in the diffusion process; 2, pre-baking and heating the silicon wafer through an electric heating plate to enable the coated composite antimony diffusion source to form a solidified film layer; 3, placing the preheated silicon chip stack in a quartz boat, and placing the quartz boat in a diffusion furnace for thermal diffusion; and 4, discharging to finish the doping processing.
Embodiment 2, first, a composite antimony diffusion source is prepared, and the specific steps are as follows: 1, uniformly mixing 22 parts of tetraethoxysilane and 40 parts of ethanol according to the mass parts, and heating to 65 ℃; 2, adding 5 parts of water by mass into the mixed solution prepared in the step 1, preserving the heat at 65 ℃ for 3 hours, and cooling to room temperature; uniformly mixing 15 parts of n-butyl alcohol and 5 parts of antimony pentachloride in parts by mass, introducing sufficient ammonia gas, filtering, precipitating and collecting filtrate to obtain n-butyl alcohol antimony, wherein the step is carried out under the protection of nitrogen; and 4, adding the n-butyl alcohol antimony prepared in the step 3 into the mixed liquid prepared in the step 2, and stirring for 3 hours to obtain the antimony-butyl alcohol. In other embodiments, step 5 may also be included, and the mixed solution obtained in step 4 is filtered by using a filter element pressure of 0.5 μm. The viscosity of the product can meet the coating requirement, and the content of antimony can meet the requirement of doping processing.
The method for using the prepared composite antimony diffusion source in semiconductor doping processing comprises the following steps: 1, uniformly coating the prepared composite antimony diffusion source on the surface of a silicon wafer by using a spin coater, wherein the coating thickness can be adjusted according to the content of antimony required in the diffusion process; 2, pre-baking and heating the silicon wafer through an electric heating plate to enable the coated composite antimony diffusion source to form a solidified film layer; 3, placing the preheated silicon chip stack in a quartz boat, and placing the quartz boat in a diffusion furnace for thermal diffusion; and 4, discharging to finish the doping processing.
The preparation method of the composite antimony diffusion source and the semiconductor doping processing method in the two embodiments can realize accurate control of antimony doping concentration by controlling the film thickness and the content of antimony in the composite antimony diffusion source, are more environment-friendly, do not need an ion implanter to participate in the diffusion process, reduce the capital investment of the equipment, are simple to operate, complete the whole diffusion process in a diffusion furnace at one time, do not need secondary annealing, can meet the processing requirement of large junction depth products, and improve the production efficiency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.
Claims (5)
1. The preparation method of the composite antimony diffusion source is characterized by comprising the following steps of: 1, uniformly mixing 20-22 parts of ethyl orthosilicate and 35-40 parts of ethanol according to the mass parts, and heating to 60-65 ℃; 2, adding 3-5 parts of water by mass into the mixed solution prepared in the step 1, preserving the heat at the temperature of 60-65 ℃ for 2-3h, and cooling to room temperature; 3, uniformly mixing 3-15 parts of n-butyl alcohol and 1-5 parts of antimony pentachloride in parts by mass, introducing sufficient ammonia gas, filtering, precipitating and collecting filtrate to obtain n-butyl alcohol antimony, wherein the mass part of the n-butyl alcohol is 3 times that of the antimony pentachloride; and 4, adding the n-butyl alcohol antimony prepared in the step 3 into the mixed liquid prepared in the step 2, and stirring for 2-3 hours to obtain the antimony-butyl alcohol.
2. The method of claim 1, further comprising a step 5 of filtering the mixed solution obtained in the step 4 with a filter element pressure of 0.5 μm.
3. The method for preparing a composite antimony diffusion source as claimed in claim 1, wherein the whole process of step 3 is performed under nitrogen protection.
4. A method for preparing the composite antimony diffusion source according to claim 1, wherein the composite antimony diffusion source is used for semiconductor doping processing, and the method comprises the following steps: 1, uniformly coating a composite antimony diffusion source on the surface of a silicon wafer; 2, pre-baking and heating the silicon wafer to enable the composite antimony diffusion source to form a solidified film layer; and 3, moving the silicon wafer into a diffusion furnace for thermal diffusion.
5. The method for doping semiconductor according to claim 4, wherein in step 1, the composite antimony diffusion source is coated by a spin coater.
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