CN115117201B - Silicon wafer phosphorus or boron doping method - Google Patents
Silicon wafer phosphorus or boron doping method Download PDFInfo
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- CN115117201B CN115117201B CN202210731224.4A CN202210731224A CN115117201B CN 115117201 B CN115117201 B CN 115117201B CN 202210731224 A CN202210731224 A CN 202210731224A CN 115117201 B CN115117201 B CN 115117201B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 78
- 239000010703 silicon Substances 0.000 title claims abstract description 78
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 58
- 239000011574 phosphorus Substances 0.000 title claims abstract description 58
- 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
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000009792 diffusion process Methods 0.000 claims abstract description 81
- 239000007789 gas Substances 0.000 claims abstract description 40
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 17
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 12
- 238000002161 passivation Methods 0.000 description 12
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 10
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000005641 tunneling Effects 0.000 description 6
- 229920005591 polysilicon Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000005360 phosphosilicate glass Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- 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
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02046—Dry cleaning only
- H01L21/02049—Dry cleaning only with gaseous HF
-
- 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
- H01L21/223—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 gaseous phase
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- Engineering & Computer Science (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
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Abstract
The invention relates to the technical field of solar cells, and particularly discloses a silicon wafer phosphorus or boron doping method. The method comprises the following steps: sending the silicon wafer into a diffusion tube in nitrogen atmosphere to finish boat feeding; vacuumizing the diffusion tube, and introducing hydrogen halide gas at the temperature of 300-700 ℃ to clean the silicon wafer, wherein the hydrogen halide is HBr or HI; vacuumizing the diffusion tube, and introducing oxygen and a doping source to perform phosphorus doping or boron doping; evacuating the diffusion tube, then N 2 And cooling in the atmosphere, and taking out of the boat to obtain the phosphorus doped or boron doped silicon wafer. The invention cleans the silicon wafer in the diffusion tube by utilizing the hydrogen halide gas, and completes the cleaning and doping in the same system, thereby fundamentally solving the problem that the silicon wafer contaminates impurities in the air before phosphorus diffusion or boron diffusion.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a silicon wafer phosphorus or boron doping method.
Background
The solar cell is a semiconductor device for directly converting solar light energy into electric energy, and the power generation principle is based on the photovoltaic effect of a semiconductor PN junction. The N-type topcon battery is characterized in that an ultrathin tunneling oxide layer and a high-doped polycrystalline silicon thin layer are respectively prepared on the front side and the back side of the battery, and a passivation contact structure is formed by the ultrathin tunneling oxide layer and the high-doped polycrystalline silicon thin layer, so that metal contact composite current is greatly reduced, and the conversion efficiency of the battery is improved. At present, after the tunneling oxidation passivation layer is prepared in LPCVD equipment, the silicon wafer is directly transferred to a high-temperature diffusion furnace for phosphorus doping or boron doping. When the preparation of the tunneling oxidation passivation layer is finished, the polysil layer is exposed in the air, so that impurities in the air are easily polluted, and the performance of the silicon wafer is influenced, which is unavoidable; when high-temperature phosphorus doping or boron doping is carried out later, impurities can enter the silicon wafer under the high-temperature condition, so that the quality of the silicon wafer is influenced, and the conversion efficiency of the battery is influenced.
To avoid the influence of impurities, the polysilicon film can be cleaned by HCl solution, but the following problems still exist: if the matched cleaning equipment comprising acid washing, water washing and drying is required to be added, the manufacturing cost is greatly increased; if the HCl solution is volatile and corrosive, professional personnel are required to operate the HCl solution so as to ensure the personal safety of the staff; if the surface of the silicon wafer is cleaned by the HCl solution, the silicon wafer still needs to be operated before entering a high-temperature diffusion furnace, and the risk of contaminating impurities in the air exists, so that the problem cannot be fundamentally avoided. Therefore, a method for fundamentally solving the problem that the silicon wafer contaminates impurities in the air before phosphorus diffusion or boron diffusion is needed to be searched, and the method has important significance in improving the qualification rate of the silicon wafer and the conversion efficiency of a battery.
Disclosure of Invention
Aiming at the problem that the existing silicon wafer is easy to pollute impurities in air before phosphorus diffusion or boron diffusion, the invention provides a method for doping silicon wafer phosphorus or boron, which is characterized in that hydrogen halide gas is used for cleaning the silicon wafer in a diffusion tube, and cleaning and doping are completed in the same system, so that the problem that the silicon wafer is polluted with impurities in air before phosphorus diffusion or boron diffusion is fundamentally solved.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
a method for phosphorus or boron doping of a silicon wafer, the method comprising the steps of:
step one, sending a silicon wafer into a diffusion tube under the nitrogen atmosphere to finish boat feeding;
step two, vacuumizing the diffusion tube, and introducing hydrogen halide gas at the temperature of 300-700 ℃ to clean the silicon wafer, wherein the hydrogen halide is HBr or HI;
step three, vacuumizing the diffusion tube, and introducing oxygen and a doping source to perform phosphorus doping or boron doping;
step four, vacuumizing the diffusion tube, and then carrying out vacuum pumping on the diffusion tube in N 2 And cooling in the atmosphere, and taking out of the boat to obtain the phosphorus doped or boron doped silicon wafer.
Compared with the prior art, the silicon wafer phosphorus or boron doping method provided by the application has the following advantages:
the method utilizes HBr or HI gas with stronger binding capacity with metal in the diffusion tube to clean the silicon wafer at the temperature of 300-700 ℃, can ensure the cleaning, can avoid the contamination on the silicon wafer from entering the silicon wafer or causing the defect of the silicon wafer, then carries out subsequent oxidation and doping, realizes the completion of the cleaning of the silicon wafer and the doping of elements in the same system, fundamentally solves the problem that the silicon wafer contaminates impurities in the air before phosphorus diffusion or boron diffusion, and does not need to add additional process equipment and professionals, thereby completing the cleaning process with extremely low cost.
According to the method, the HBr or HI gas is decomposed into the simple substance Br or the simple substance I at the temperature of 300-700 ℃, so that the contamination on the surface of the silicon wafer is cleaned by the simple substance Br or the simple substance I before being diffused into the silicon wafer, an excellent surface cleaning effect is achieved, toxic and side effects cannot be generated after the HBr or HI gas is decomposed, and the problem of threat to safety and health of workers is avoided.
The diffusion tube is a core component of the high-temperature diffusion furnace and is used for realizing phosphorus doping or boron doping of the silicon wafer.
Optionally, the flow rate of the hydrogen halide gas is 500sccm to 2000sccm.
Optionally, the cleaning time is 5-15 min.
The preferable gas flow and cleaning time can ensure that the contamination on the surface of the silicon wafer can be treated cleanly, and the waste of resources can not be caused.
Optionally, the vacuum degree formed by vacuumizing is 80-150 mbar.
Optionally, the process conditions of the phosphorus doping are as follows: the oxygen flow is 100 sccm-500 sccm, the phosphorus source flow is 200 sccm-1000 sccm, the temperature is 750 ℃ to 900 ℃, the power-on time is 15 min-25 min, and the propulsion time is 15 min-30 min.
Preferred phosphorus sources are compounds commonly used in the art for phosphorus doping, such as phosphorus oxychloride and the like.
The preferable process parameters of phosphorus doping enable phosphorus elements decomposed by the phosphorus source to be uniformly dispersed on the surface of the silicon wafer, so that uniform phosphorus doping is formed.
Optionally, the process conditions of boron doping are: the oxygen flow is 300 sccm-800 sccm, the boron source flow is 100 sccm-500 sccm, the temperature is 900-1050 ℃, the power-on time is 8-20 min, and the propulsion time is 30-100 min.
Preferred boron sources are compounds commonly used in the art for boron doping, such as boron tribromide, boron trichloride, and the like.
The optimized technological parameters of boron doping enable boron elements decomposed by a boron source to be uniformly dispersed on the surface of the silicon wafer, so that uniform boron doping is formed.
Optionally, the middle part of the side wall of the diffusion tube is symmetrically provided with a first air inlet tube and a second air inlet tube for introducing hydrogen halide gas, the lower part and the upper part of the side wall are respectively provided with a third air inlet tube and a fourth air inlet tube for introducing the hydrogen halide gas, and the third air inlet tube and the fourth air inlet tube are in central symmetrical distribution.
The diffusion tube is provided with four air inlet tubes for realizing the introduction of hydrogen halide, so that the hydrogen halide gas is rapidly and uniformly distributed in the diffusion tube, and the aim of rapidly cleaning the surface of the silicon wafer is fulfilled.
Optionally, the ratio of the inlet flow rates of the first inlet pipe, the second inlet pipe, the third inlet pipe and the fourth inlet pipe is 1.5-2.5:1.5-2.5:0.5-1.5:0.5-1.5.
Further optionally, the ratio of the intake flows of the first intake pipe, the second intake pipe, the third intake pipe and the fourth intake pipe is 2:2:1:1.
The flow ratio of the optimized air inlet pipe can enable the hydrogen halide gas to quickly fill the whole diffusion pipe, so that the surface of the silicon wafer is cleaned in an omnibearing manner without dead angles.
The method for doping the silicon slice with phosphorus or boron can be used in any process of silicon slice batteries needing phosphorus doping or boron doping, such as batteries with N-type TOPCon passivation contact structures, PERC batteries, PERT batteries and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a phosphorus doped gas pipeline provided by an embodiment of the present invention;
FIG. 2 is a schematic diagram of a boron doped gas pipeline provided by an embodiment of the present invention;
FIG. 3 is a PL test chart provided in example 1 of the present invention;
FIG. 4 is a PL test chart provided in comparative example 1 of the present invention;
1. the device comprises a first air inlet pipe, a second air inlet pipe, a third air inlet pipe, a fourth air inlet pipe, a 5, an oxygen air inlet pipe, a 6, a nitrogen air inlet pipe, a 7, a phosphorus source air inlet pipe, a 8 and a boron source air inlet pipe.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment of the invention provides a preparation method of a battery with an N-type TOPCon passivation contact structure, which comprises the following steps:
s1, removing a damaged layer of an N-type monocrystalline silicon wafer and performing alkali texturing treatment to form pyramid suede;
s2, performing boron diffusion on the front surface of the silicon wafer to form a front emitter, and performing boron diffusion by adopting a tubular diffusion furnace, wherein the specific process of boron diffusion is as follows:
sending the silicon wafer into a diffusion tube under the nitrogen atmosphere to finish boat feeding;
vacuumizing the diffusion tube to the vacuum degree of 150 mbar, and then introducing HI gas at 400 ℃ to clean the silicon wafer for 15min, wherein the HI gas flow rate is 2000sccm, the diffusion tube comprises a first air inlet pipe and a second air inlet pipe which are symmetrically distributed in the middle of the side wall and are used for introducing HI gas, a third air inlet pipe and a fourth air inlet pipe which are respectively used for introducing HI gas are respectively arranged in the lower part and the upper part of the side wall, the third air inlet pipe and the fourth air inlet pipe are symmetrically distributed in the center, and the air inlet flow rate ratio of the first air inlet pipe, the second air inlet pipe, the third air inlet pipe and the fourth air inlet pipe is 2.5:1.5:0.5:1.5; the pipeline arrangement of the diffusion pipe is shown in figure 2;
vacuumizing the diffusion tube until the vacuum degree is 80 mbar, and then conducting source connection, wherein the technological parameters in the source connection process are as follows: the flow rate of oxygen is 500sccm, the flow rate of boron tribromide is 500sccm, the temperature is 900 ℃ and the time is 15min; stopping introducing oxygen and boron tribromide after the source is completed, and pushing for 40min at 900 ℃ to realize boron doping;
after boron doping is finished, the diffusion tube is vacuumized to a vacuum degree of 110 mbar and then N is used for 2 Cooling in the atmosphere, and taking out the boat;
s3, removing borosilicate glass on the surface of the silicon wafer by using an acid solution system and polishing the back surface;
s4, sequentially depositing a tunneling oxide layer with the thickness of 1.5nm and a polysilicon layer with the thickness of 150nm on the back surface of the silicon wafer;
s5, performing phosphorus diffusion on the back surface of the silicon wafer to form a phosphorus doped polysilicon layer, and performing phosphorus diffusion by adopting a tubular diffusion furnace, wherein the specific process of phosphorus diffusion is as follows:
sending the silicon wafer into a diffusion tube in nitrogen atmosphere to finish boat feeding;
vacuumizing the diffusion tube until the vacuum degree is 100 mbar, then introducing HI gas at 400 ℃ to clean the silicon wafer for 10min, wherein the HI gas flow is 1000sccm, the diffusion tube comprises a first air inlet pipe and a second air inlet pipe which are symmetrically distributed in the middle of the side wall and are used for introducing the HI gas, a third air inlet pipe and a fourth air inlet pipe which are respectively used for introducing the HI gas are respectively arranged in the lower part and the upper part of the side wall, the third air inlet pipe and the fourth air inlet pipe are symmetrically distributed in the center, and the air inlet flow ratio of the first air inlet pipe, the second air inlet pipe, the third air inlet pipe and the fourth air inlet pipe is 2:2:1:1; the pipeline arrangement of the diffusion pipe is shown in figure 1;
vacuumizing the diffusion tube until the vacuum degree is 120 mbar, and then conducting source connection, wherein the technological parameters in the source connection process are as follows: the flow of oxygen is 300sccm, the flow of phosphorus oxychloride is 800sccm, the temperature is 850 ℃, and the time is 20min; stopping introducing oxygen and phosphorus oxychloride after the source is completed, and pushing for 20min at 850 ℃ to realize phosphorus doping;
after the phosphorus doping is finished, the diffusion tube is vacuumized to a vacuum degree of 110 mbar and then is subjected to N 2 Under the atmosphereCooling and taking out the boat;
s6, after the phosphosilicate glass is removed, sequentially depositing an aluminum oxide layer with the thickness of 5nm and a silicon nitride layer with the thickness of 80nm on the front surface of the silicon wafer; depositing a silicon nitride layer with the thickness of 65nm on the back surface of the silicon wafer;
and S7, respectively printing metal paste on the front and back surfaces of the silicon wafer, and forming a metal electrode through high-temperature sintering to obtain the N-type TOPCon passivation contact structure battery.
Example 2
The embodiment of the invention provides a preparation method of a battery with an N-type TOPCon passivation contact structure, which comprises the following steps:
s1, removing a damaged layer of an N-type monocrystalline silicon wafer and performing alkali texturing treatment to form pyramid suede;
s2, performing boron diffusion on the front surface of the silicon wafer to form a front emitter, and performing boron diffusion by adopting a tubular diffusion furnace, wherein the specific process of boron diffusion is as follows:
sending the silicon wafer into a diffusion tube in nitrogen atmosphere to finish boat feeding;
vacuumizing the diffusion tube to a vacuum degree of 110 mbar, and then introducing HBr gas at 600 ℃ to clean the silicon wafer for 8min, wherein the flow rate of the HBr gas is 800sccm, the diffusion tube comprises a first air inlet tube and a second air inlet tube which are symmetrically distributed in the middle of the side wall and are used for introducing the HBr gas, a third air inlet tube and a fourth air inlet tube which are respectively used for introducing the HBr gas are respectively arranged in the lower part and the upper part of the side wall, the third air inlet tube and the fourth air inlet tube are symmetrically distributed in the center, and the air inlet flow rate ratio of the first air inlet tube, the second air inlet tube, the third air inlet tube and the fourth air inlet tube is 2:1.5:1:1.5; the pipeline arrangement of the diffusion pipe is shown in figure 2;
vacuumizing the diffusion tube until the vacuum degree is 100 mbar, and then conducting source connection, wherein the technological parameters in the source connection process are as follows: the flow rate of oxygen is 800sccm, the flow rate of boron tribromide is 300sccm, the temperature is 1050 ℃, and the time is 20min; stopping introducing oxygen and boron tribromide after the source is completed, and pushing for 35min at 1050 ℃ to realize boron doping;
after boron doping is finished, the methodVacuumizing the diffusion tube to a vacuum degree of 110 mbar, and then carrying out vacuum treatment on the diffusion tube in N 2 Cooling in the atmosphere, and taking out the boat;
s3, removing borosilicate glass on the surface of the silicon wafer by using an acid solution system and polishing the back surface;
s4, sequentially depositing a tunneling oxide layer with the thickness of 1.5nm and a polysilicon layer with the thickness of 150nm on the back surface of the silicon wafer;
s5, performing phosphorus diffusion on the back surface of the silicon wafer to form a phosphorus doped polysilicon layer, and performing phosphorus diffusion by adopting a tubular diffusion furnace, wherein the specific process of phosphorus diffusion is as follows:
sending the silicon wafer into a diffusion tube in nitrogen atmosphere to finish boat feeding;
vacuumizing the diffusion tube to a vacuum degree of 80 mbar, and then introducing HBr gas to clean the silicon wafer for 5 minutes at 700 ℃, wherein the flow rate of the HBr gas is 500sccm, the diffusion tube comprises a first air inlet tube and a second air inlet tube which are symmetrically distributed in the middle of the side wall and are used for introducing the HBr gas, a third air inlet tube and a fourth air inlet tube which are symmetrically distributed in the center are respectively arranged at the lower part and the upper part of the side wall, and the air inlet flow rate ratio of the first air inlet tube, the second air inlet tube, the third air inlet tube and the fourth air inlet tube is 1.5:2.5:1.5:0.5; the pipeline arrangement of the diffusion pipe is shown in figure 1;
vacuumizing the diffusion tube until the vacuum degree is 150 mbar, and then conducting source connection, wherein the technological parameters in the source connection process are as follows: the flow rate of oxygen is 500sccm, the flow rate of phosphorus oxychloride is 500sccm, the temperature is 900 ℃ and the time is 15min; stopping introducing oxygen and phosphorus oxychloride after the source is completed, and pushing for 15min at 900 ℃ to realize phosphorus doping;
after the phosphorus doping is finished, the diffusion tube is vacuumized to a vacuum degree of 80 mbar and then is subjected to N 2 Cooling in the atmosphere, and taking out the boat;
s6, after the phosphosilicate glass is removed, sequentially depositing an aluminum oxide layer with the thickness of 5nm and a silicon nitride layer with the thickness of 80nm on the front surface of the silicon wafer; depositing a silicon nitride layer with the thickness of 65nm on the back surface of the silicon wafer;
and S7, respectively printing metal paste on the front and back surfaces of the silicon wafer, and forming a metal electrode through high-temperature sintering to obtain the N-type TOPCon passivation contact structure battery.
In order to better illustrate the technical solutions of the present invention, the following is further compared with examples of the present invention.
Comparative example 1
The comparative example provides a method for preparing a battery with an N-type TOPCon passivation contact structure, wherein the temperature of HI gas in boron doping in the step S2 is replaced by 800 ℃, the temperature of HI gas in phosphorus diffusion in the step S5 is replaced by 800 ℃, and the rest steps are consistent with those in the embodiment 1, and are not repeated.
Comparative example 2
The comparative example provides a method for manufacturing a battery with an N-type TOPCon passivation contact structure, wherein HI gas in boron doping in the step S2 is replaced by HCl gas, HI gas in phosphorus diffusion in the step S5 is replaced by HCl gas, and the rest of the steps are consistent with those in the embodiment 1, and are not repeated.
In order to better illustrate the characteristics of the phosphorus doped/boron doped silicon wafer provided in the embodiment of the present invention, the performance of the N-type TOPCon passivation contact structure cells prepared in the examples 1 to 2 and the comparative examples 1 to 2 was tested as follows.
Test example 1
The battery performance of the N-type TOPCon passivation contact structure batteries prepared in examples 1 to 2 and comparative examples 1 to 2 was tested, and the test results are shown in table 1 below.
TABLE 1
As can be seen from Table 1, by adopting the preparation method provided by the application, impurities in the air polluted by the silicon wafer can be thoroughly cleaned before the boron diffusion and phosphorus diffusion processes, and the conversion efficiency of the battery can be improved.
Test example 2
The PL test was performed on the batteries prepared in example 1 and comparative example 1, respectively, and the results thereof are shown in fig. 3 and 4.
As can be seen from fig. 3 to 4, under the same test scale, the PL test picture of comparative example 1 is darkened as a whole, while the PL test picture of example 1 is shiny as a whole, thus indicating that the preparation method provided in comparative example 1 is adopted to make the silicon wafer prepared have more defects and impurities therein, whereas the battery prepared by the method provided in the present invention has substantially no impurities, so that fig. 3 is shiny as a whole.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (8)
1. A method for doping silicon slice with phosphor or boron is characterized in that: the method comprises the following steps:
step one, sending a silicon wafer into a diffusion tube under the nitrogen atmosphere to finish boat feeding;
step two, vacuumizing the diffusion tube, and introducing hydrogen halide gas at the temperature of 300-700 ℃ to clean the silicon wafer, wherein the hydrogen halide is HBr or HI;
step three, vacuumizing the diffusion tube, and introducing oxygen and a doping source to perform phosphorus doping or boron doping;
step four, vacuumizing the diffusion tube, and then carrying out vacuum pumping on the diffusion tube in N 2 Cooling in the atmosphere, and taking out of the boat to obtain a phosphorus doped or boron doped silicon wafer;
the middle part of the side wall of the diffusion pipe is symmetrically provided with a first air inlet pipe and a second air inlet pipe for introducing hydrogen halide gas, the lower part and the upper part of the side wall are respectively provided with a third air inlet pipe and a fourth air inlet pipe for introducing the hydrogen halide gas, and the third air inlet pipe and the fourth air inlet pipe are in central symmetrical distribution.
2. The method of phosphorus or boron doping of a silicon wafer according to claim 1, wherein: the flow rate of the hydrogen halide gas is 500sccm to 2000sccm.
3. The method of phosphorus or boron doping of a silicon wafer according to claim 1, wherein: the cleaning time is 5-15 min.
4. The method of phosphorus or boron doping of a silicon wafer according to claim 1, wherein: the vacuum degree formed by vacuumizing is 80-150 mbar.
5. The method of phosphorus or boron doping of a silicon wafer according to claim 1, wherein: the process conditions of the phosphorus doping are as follows: the oxygen flow is 100 sccm-500 sccm, the phosphorus source flow is 200 sccm-1000 sccm, the temperature is 750 ℃ to 900 ℃, the power-on time is 15 min-25 min, and the propulsion time is 15 min-30 min.
6. The method of phosphorus or boron doping of a silicon wafer according to claim 1, wherein: the process conditions of the boron doping are as follows: the oxygen flow is 300 sccm-800 sccm, the boron source flow is 100 sccm-500 sccm, the temperature is 900-1050 ℃, the power-on time is 8-20 min, and the propulsion time is 30-100 min.
7. The method of phosphorus or boron doping of a silicon wafer according to claim 6, wherein: the ratio of the inlet flow rates of the first inlet pipe, the second inlet pipe, the third inlet pipe and the fourth inlet pipe is 1.5-2.5:1.5-2.5:0.5-1.5:0.5-1.5.
8. The method of phosphorus or boron doping of a silicon wafer according to claim 7, wherein: the air inlet flow ratio of the first air inlet pipe, the second air inlet pipe, the third air inlet pipe and the fourth air inlet pipe is 2:2:1:1.
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