CN111739794B - Boron diffusion method, solar cell and manufacturing method thereof - Google Patents
Boron diffusion method, solar cell and manufacturing method thereof Download PDFInfo
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 159
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 238000009792 diffusion process Methods 0.000 title claims abstract description 158
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000151 deposition Methods 0.000 claims abstract description 90
- 230000008021 deposition Effects 0.000 claims abstract description 87
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 43
- 239000010703 silicon Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 238000002161 passivation Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000001465 metallisation Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000007547 defect Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000005215 recombination Methods 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005468 ion implantation Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- -1 silver-aluminum Chemical compound 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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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
- H01L21/2252—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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- 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
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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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
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
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Abstract
The application provides a boron diffusion method of a solar cell, the solar cell and a manufacturing method thereof. The boron diffusion method comprises the following steps: placing the pretreated N-type silicon wafer in a diffusion furnace, and performing first boron diffusion deposition at a first temperature; after the first boron diffusion deposition, the temperature in the diffusion furnace is increased from the first temperature to the second temperature, and junction pushing is carried out; after junction pushing, the temperature in the diffusion furnace is reduced from the second temperature to a third temperature, and the second boron diffusion deposition is carried out at the third temperature. The invention adopts a two-step deposition method, wherein the first step deposition can be used for preparing a lightly doped region, and the second step deposition can provide enough boron diffusion source for subsequent laser doping, so that a proper heavily doped region is obtained, and the conversion efficiency of the battery is improved.
Description
Technical Field
The application relates to the technical field of solar cell preparation, in particular to a boron diffusion method, a solar cell and a manufacturing method thereof.
Background
Currently, photovoltaic power generation technology has been commercialized and commercialized as a mainstream technology for utilizing solar energy resources. In order to further promote the utilization and popularization of photovoltaic cell products, the battery efficiency needs to be gradually improved, and the electricity cost is reduced. In recent years, N-type solar cells have been receiving attention because of their excellent characteristics such as low light attenuation, good stability, and double-sided power generation, and the N-type solar cells have been becoming increasingly popular in the photovoltaic market. The front side of the N-type solar cell is generally manufactured into a P-type emitter by utilizing a boron diffusion process. The boron-diffused selective emitter (SE, selective Emitter) structure cell is formed by heavily doping (P) the boron-diffused metal gate line and the relief region (electrode contact portion) of the silicon wafer ++ ) While the non-metallic contact region between the metallic electrodes achieves light doping (P + ). The structure can effectively reduce the contact resistance and metal recombination of the metal region and improve the open circuit voltage. Meanwhile, auger recombination of a non-metal contact area, namely a lightly doped area is reduced, and short-wave quantum efficiency is effectively improved, so that short-circuit current of the semiconductor device is improved.
In the preparation process of the N-type crystalline silicon solar cell, front-side boron diffusion is a key step. However, the current boron diffusion process of the N-type battery has the defects that the service life of the N-type battery is reduced due to high temperature, and in addition, higher metal recombination is brought by the ablative property of silver-aluminum paste in metallization, so that the efficiency of the N-type battery is limited.
In the prior art, a plurality of methods for preparing the boron-expanded SE structure battery of the N-type solar battery comprise a screen printing boron paste method, an ion implantation method, a wet etching method and the like. The ion implantation localized doping method requires an expensive ion implanter, the boron (B) ion implantation technology is difficult, and meanwhile, the B ion implantation annealing temperature is high and B atom clusters are easy to form a composite center. The method for preparing the SE structure by adopting the screen printing boron paste method can cause pollution to a furnace tube, and meanwhile, the removal of the boron paste is also a problem. In addition, the current boron doping method mainly comprises a boric acid spin-coating method and a high-temperature diffusion method, wherein the boric acid spin-coating method is difficult to produce in a large scale, and the doped surface is difficult to clean; the uniformity of the diffusion sheet resistance obtained by the high-temperature diffusion method is poor, the service life of minority carriers can be reduced, the conversion efficiency of a battery is affected, and the high-temperature diffusion method is difficult to provide enough boron source for subsequent laser doping.
Disclosure of Invention
The purpose of the application is to provide a boron diffusion method, a solar cell and a manufacturing method thereof, wherein the process is simple, the temperature requirement on the boron diffusion process is low, the damage to a boron diffusion machine is reduced, and the open-circuit voltage and the short-circuit current of the cell can be improved.
In order to achieve the above purpose, the technical scheme adopted in the application is as follows:
according to one aspect of the present application, there is provided a boron diffusion method comprising the steps of:
placing the pretreated N-type silicon wafer in a diffusion furnace, and performing first boron diffusion deposition at a first temperature;
after the first boron diffusion deposition, the temperature in the diffusion furnace is increased from the first temperature to the second temperature, and junction pushing is carried out;
after junction pushing, the temperature in the diffusion furnace is reduced from the second temperature to a third temperature, and the second boron diffusion deposition is carried out at the third temperature.
The boron diffusion method adopts a two-step deposition mode, wherein the first-step deposition can be used for preparing a lightly doped region, and the second-step deposition can provide a sufficient boron diffusion source for subsequent laser doping, so that a proper heavily doped region is obtained. The process has more concise steps, reduces the high-temperature process, and is beneficial to controlling defects and a composite center introduced in the preparation process.
Specifically, in the boron diffusion method, the pretreated N-type silicon wafer is placed in a diffusion furnace, and the first boron diffusion deposition is carried out at a first temperature, so that P can be formed on the surface of the N-type silicon wafer + A layer; performing second boron diffusion deposition at a third temperature, and forming high-sheet-resistance lightly doped P on the surface of the N-type silicon wafer + The layers, i.e. the lightly doped regions, are formed. In addition, the method can reduce damage to the boron diffusion machine by regulating and controlling the temperature in the two boron diffusion deposition and junction pushing processes, and the third temperature of the second boron diffusion deposition is lower than the second temperature of the junction pushing process, so that the secondary junction pushing process caused by the second high-temperature deposition can be prevented, the original shallow doping region is reserved, the passivation performance is good, and meanwhile, sufficient boron doping sources can be provided for subsequent laser heavy doping, and a proper heavy doping region is further obtained.
In one possible implementation, the first temperature is 800-900 ℃, inclusive.
In one possible implementation, the third temperature is 800-900 ℃, inclusive.
In one possible implementation, the first temperature is 850-880 ℃, inclusive.
In one possible implementation, the third temperature is 850-880 ℃, inclusive.
In one possible implementation, the second temperature is higher than the first temperature and the third temperature, respectively, and the second temperature is <950 ℃.
In one possible implementation, the second temperature is less than or equal to 920 ℃.
In one possible implementation, the performing a first boron diffusion deposition includes:
introducing nitrogen, oxygen and a boron source into the diffusion furnace for first boron diffusion deposition, wherein the deposition time is 10-60min, the flow rate of the nitrogen is 10000-30000sccm, the flow rate of the oxygen is 30-200sccm, and the flow rate of the boron source is 100-600sccm; these numerical ranges are inclusive of the endpoints.
In one possible implementation, the boron source includes, but is not limited to, BBr 3 、BCl 3 Etc.
In one possible implementation, the performing the pushing includes:
introducing oxygen or mixed gas containing oxygen and nitrogen into the diffusion furnace for knot pushing, wherein the knot pushing time is 5-10min, and the flow of the oxygen or the mixed gas containing oxygen and nitrogen is 10000-30000sccm; these numerical ranges are inclusive of the endpoints.
In one possible implementation, the performing the second boron diffusion deposition includes:
introducing nitrogen, oxygen and a boron source into the diffusion furnace for secondary boron diffusion deposition, wherein the deposition time is 10-60min, the flow rate of the nitrogen is 10000-30000sccm, the flow rate of the oxygen is 30-300sccm, and the flow rate of the boron source is 100-900sccm; these numerical ranges are inclusive of the endpoints.
In a possible implementation manner, in the boron diffusion method, the heating rate may be 8-20 ℃/min, and the cooling rate may be 4-10 ℃/min; these numerical ranges are inclusive of the endpoints.
According to another aspect of the present application, there is provided a method for manufacturing a solar cell, including a boron diffusion step, a laser doping step, a passivation step, and a metallization step, wherein the boron diffusion step adopts the boron diffusion method as described above, a lightly doped region of boron is formed by using the boron diffusion step, and a heavily doped region of boron is formed by using the laser doping step.
In one possible implementation, the parameters of the laser doping step include: the laser power is 10-100W, and the scanning speed is 2500-10000mm/s.
According to another aspect of the present application, there is provided a solar cell fabricated using the method of fabricating a solar cell as described above.
Compared with the prior art, the technical scheme provided by the application can achieve the following beneficial effects:
the boron diffusion method provided by the application adopts a two-step deposition method, wherein the first-step deposition can be used for preparing a lightly doped region, and the second-step deposition can provide a sufficient boron diffusion source for subsequent laser doping, so that a proper heavily doped region is obtained. Particularly, the method regulates and controls the temperature in the two boron diffusion deposition and junction pushing processes, so that the second temperature of the junction pushing process is higher than the first temperature of the first deposition and the third temperature of the second deposition respectively, the first deposition and the second deposition are carried out at lower temperature, the damage to a boron diffusion machine can be reduced, the third temperature of the second boron diffusion deposition is lower than the second temperature of the junction pushing process, the secondary junction pushing process caused by the second high-temperature deposition can be prevented, the original shallow doping region is reserved, the passivation performance is better, and meanwhile, sufficient boron doping sources can be provided for subsequent laser heavy doping, so that a proper heavy doping region is obtained.
The process has more concise steps, reduces the high-temperature process, and is beneficial to controlling defects and a composite center introduced in the preparation process. The SE structure battery prepared by the method can effectively improve the open-circuit voltage and the short-circuit current of the battery, so that the battery efficiency is effectively improved by at least 0.2 percent.
The manufacturing method of the solar cell and the cell obtained by the manufacturing method, including the boron diffusion method, have all the characteristics and advantages of the boron diffusion method, and are not described herein.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, 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 flow chart of a boron diffusion method according to an exemplary embodiment of the present application;
fig. 2 is a schematic flow chart of a method for manufacturing a solar cell according to an exemplary embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone.
It should be understood that the terms "upper," "lower," and the like in the embodiments of the present application are described in terms of the drawings and are not to be construed as limiting the embodiments of the present application. In addition, it will be understood that when an element is referred to as being "on" or "under" another element, it can be directly on the other element or be indirectly on the other element through intervening elements. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
All technical features mentioned herein as well as preferred features may be combined with each other to form new solutions, unless specified otherwise. Unless defined or otherwise indicated, the terms of art and science used herein have the same meaning as those familiar to one of ordinary skill in the art.
In the present invention, unless otherwise indicated, the numerical range "a-b" represents an abbreviated representation of any combination of real numbers between a and b, including a and b, where a and b are both real numbers. For example, the numerical range "800-900" means that all real numbers between "800-900" have been listed throughout, and "800-900" is simply a shorthand representation of a combination of these values.
The "range" disclosed herein may take the form of a lower limit and an upper limit, which may be one or more lower limits and one or more upper limits, respectively.
In the process of preparing the N-type solar cell, the method of combining boron diffusion with laser doping has the advantages of simple process, easy realization and the like, and on the basis of increasing laser equipment, the SE structure can be realized by only debugging the boron diffusion process, and compared with other methods, the method has low cost and low risk. The method comprises the steps of preparing a lightly doped region on the whole surface of a silicon wafer by boron diffusion, and then forming a heavily doped region on a metal contact region by laser, wherein a proper boron diffusion process is a key of the method for preparing the SE structure. However, as those skilled in the art understand, as the background art indicates, the existing boron diffusion method of N-type silicon wafer has more or less certain drawbacks, for example, the existing high temperature diffusion method has difficulty in providing enough boron source for the subsequent laser doping, and the development of the Selective Emitter (SE) structure prepared by adopting the combination of boron diffusion and laser doping is limited, so that further improvement on the boron diffusion process is needed.
Therefore, in order to overcome the defect of the prior art, the technical scheme of the embodiment of the invention provides a boron diffusion method, a solar cell (N-type solar cell) and a manufacturing method thereof, so as to reduce the high-temperature process, facilitate the control of defects and a composite center introduced in the preparation process, provide enough boron source for the subsequent laser doping, and further improve the conversion efficiency of the cell.
The embodiment of the application provides a boron diffusion method for an N-type solar cell, which comprises the following steps of:
placing the pretreated N-type silicon wafer into a diffusion furnace, and performing first boron diffusion deposition at a first temperature to form P + A layer;
after the first boron diffusion deposition, the temperature in the diffusion furnace is increased from the first temperature to the second temperature, and junction pushing is carried out;
after junction pushing, the temperature in the diffusion furnace is reduced from the second temperature to the third temperature, and the second boron diffusion deposition is carried out at the third temperature, so that the P with high sheet resistance and light doping can be formed + The layers, i.e. the lightly doped regions, are formed.
The boron diffusion method for the N-type solar cell adopts a two-step deposition method, wherein the first-step deposition can be used for preparing a lightly doped region, and the second-step deposition can provide a sufficient boron diffusion source for subsequent laser doping, so that a proper heavily doped region is obtained. Specifically, in the boron diffusion method, the pretreated N-type silicon wafer is placed in a diffusion furnace, and the first boron diffusion deposition is carried out at a first temperature, so that P can be formed on the surface of the N-type silicon wafer + A layer; then the temperature is raised to a second temperature, and junction pushing is carried out at the second temperature, so that boron atoms can be doped into silicon; then the temperature is reduced to a third temperature, and the second boron diffusion deposition is carried out at the third temperature, so that the high-sheet-resistance lightly doped P can be formed on the surface of the N-type silicon wafer + The layers, i.e. the lightly doped regions, are formed.
According to the method, through regulating and controlling the temperature in the twice boron diffusion deposition and junction pushing process, the second temperature of the junction pushing process is higher than the first temperature of the first deposition and the third temperature of the second deposition respectively, the first deposition and the second deposition are carried out at lower temperatures, damage to a boron diffusion machine can be reduced, the third temperature of the second boron diffusion deposition is lower than the second temperature of the junction pushing process, the twice junction pushing process caused by the second high-temperature deposition can be prevented, an original shallow doping region is reserved, good passivation performance is achieved, and meanwhile, sufficient boron doping sources can be provided for subsequent laser heavy doping, so that a proper heavy doping region is obtained.
The boron diffusion process has low temperature requirement, simpler process steps, reduced damage to a boron diffusion machine, reduced high-temperature process, and contribution to control of defects and a composite center introduced in the preparation process. The SE structure battery prepared by the method can effectively improve the open-circuit voltage and the short-circuit current of the battery, so that the battery efficiency is effectively improved by at least 0.2 percent or more.
It can be understood that the "push junction" can also be a "push well" or a "push junction", which pushes the boron source diffused on the silicon surface deeper, so that the boron on the surface of the silicon wafer after the first deposition is more fully diffused into the interior, thereby reducing the surface concentration and preventing the surface doping concentration from being too high and compounding to form a dead layer seriously.
In the boron diffusion process of the N-type silicon wafer, a low-temperature diffusion deposition high-temperature pushing process is adopted, and the two diffusion deposition temperatures and the pushing junction temperature are regulated and optimized, so that the surface recombination rate of the solar cell and the lattice damage on the surface of the silicon wafer can be reduced, the boron diffusion quality is improved, the qualification rate of the silicon wafer after boron diffusion is improved, and the conversion efficiency of the cell is further improved. Specifically, in some embodiments, during the first boron diffusion deposition, the first temperature is 800-900 ℃, further may be 820-890 ℃, further may be 850-880 ℃; typically, but not by way of limitation, the first temperature may be, for example, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃ or any value in the range consisting of any two of these values.
Compared with the prior art that the deposition temperature is generally more than or equal to 900 ℃ or more than or equal to 920 ℃, the embodiment of the invention controls the first diffusion deposition temperature to be 800-900 ℃, especially 850-880 ℃, and reduces the deposition temperature, so that the deposition speed of the surface of the silicon wafer can be controlled by controlling the temperature during low-temperature deposition, which is beneficial to reducing internal lattice defects, further is beneficial to improving the boron diffusion quality, improving the qualification rate of the silicon wafer after boron diffusion, and further improving the conversion efficiency of a battery.
Specifically, in some embodiments, during the second boron diffusion deposition, the third temperature is 800-900 ℃, further may be 820-890 ℃, further may be 850-880 ℃; typically, but not by way of limitation, the third temperature may be, for example, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃ or any value within a range comprised of any two of these values.
In the two diffusion deposition processes, the first temperature and the third temperature may be the same or slightly different, and in practical application, the first temperature and the third temperature may be flexibly adjusted within the range of 800-900 ℃ respectively.
In the boron diffusion method, the two deposition temperatures are lower and are less than 920 ℃ and even less than or equal to 900 ℃, compared with the existing high-temperature diffusion method, the deposition temperature is reduced, so that the deposition speed of the surface of the silicon wafer can be controlled by controlling the temperature during low-temperature deposition, the internal lattice defects can be reduced, the boron diffusion quality can be improved, the qualification rate of the silicon wafer after boron diffusion can be improved, and the conversion efficiency of a battery can be further improved. Particularly, the temperature of the second diffusion deposition is reduced, the second junction pushing process caused by the second high-temperature deposition can be prevented, the original shallow doped region is reserved, the passivation performance is better, and meanwhile, a sufficient boron doped source can be provided for laser heavy doping, and the boron doped region is a metal contact region.
Specifically, in some embodiments, during the pushing the junction, the second temperature is higher than the first temperature, and the second temperature is higher than the third temperature, the second temperature is less than 950 ℃, further may be less than or equal to 920 ℃, further may be greater than 900 ℃ and less than or equal to 920 ℃; typically, but not by way of limitation, the second temperature may be, for example, 905 ℃, 910 ℃, 915 ℃, 920 ℃, 925 ℃, 930 ℃, 940 ℃, 945 ℃, 949 ℃ and any value in the range consisting of any two of these values.
The junction pushing step can enable boron on the surface of the silicon wafer after the first diffusion deposition to be more fully diffused into the inner part, so that the surface concentration is reduced, and the influence of a dead layer is reduced. And the advanced junction-making temperature after the first step of deposition is lower than 950 ℃ to ensure that the P with high sheet resistance and light doping is obtained + A layer. In addition, oxygen or a mixed gas containing oxygen is introduced in the junction pushing step after the first diffusion deposition to effectively reduce the surface concentration of the lightly doped region, thereby reducing the recombination rate.
By comprehensively considering the method, the embodiment of the invention limits the first temperature, the second temperature and the third temperature in the ranges, greatly reduces the recombination rate of the diffused silicon wafer surface and the lattice damage of the silicon wafer surface, improves the uniformity of the boron diffusion sheet resistance, has better passivation performance, can provide sufficient boron doping sources for the subsequent laser heavy doping, and is beneficial to improving the conversion efficiency of the battery. By adopting the two low-temperature diffusion deposition and one high-temperature propulsion processes with the conditions in the range, the prepared SE structure battery can effectively improve the open-circuit voltage and the short-circuit current of the battery, and the conversion efficiency of the battery can be effectively improved by at least 0.2 percent or more.
Specifically, according to an embodiment of the present invention, referring to fig. 1, the boron diffusion method for an N-type solar cell includes: the method comprises the steps of S201 first boron diffusion deposition, S202 junction pushing, S203 second boron diffusion deposition and S204 cooling out of the boat, and a boron diffusion method will be described in detail below. It should be noted that, in the boron diffusion method, the first temperature, the second temperature and the third temperature in the above operation ranges are not limited to specific implementations, and those skilled in the art may appropriately adjust the deposition time, the gas flow rate and the like according to practical situations. In order to ensure the manufacturing efficiency of the silicon wafer, the specific process conditions of the boron diffusion method for the N-type solar cell comprise:
s201, performing first boron diffusion deposition;
in the step, the N-type silicon wafer after texturing and cleaning is placed into a diffusion furnace, and the temperature is raised to a first temperature, wherein the first temperature can be 800-900 ℃, can be 820-890 ℃, and can be 850-880 ℃.
Alternatively, the heating rate may be 8-20 ℃/min, further 10-15 ℃/min, and typical but non-limiting examples may be 8 ℃/min, 9 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min, 18 ℃/min, 20 ℃/min, etc.
After the temperature in the diffusion furnace is increased to a preset temperature, namely, the first temperature, the isothermal stability can be realized for a few minutes, and then nitrogen, oxygen and a boron source are introduced into the diffusion furnace for carrying out first boron diffusion deposition; the deposition time is 10-60min, and typical but not limiting examples can be 10min, 20min, 30min, 40min, 60min, etc.; the flow rate of nitrogen is 10000-30000sccm, and typical but not limiting examples thereof include 10000sccm, 15000sccm, 20000sccm, 25000sccm, 30000sccm, etc.; the flow rate of oxygen is 30-200sccm, and typical but not limiting examples may be 30sccm, 40sccm, 50sccm, 60sccm, 80sccm, 100sccm, 150sccm, 200sccm, etc.; the flow rate of the boron source is 100-600sccm, and typical but non-limiting examples may be 100sccm, 200sccm, 300sccm, 400sccm, 500sccm, 600sccm, etc.
In the deposition time and flow range, the silicon wafer manufacturing efficiency is guaranteed, the waste of resources is reduced, and the boron diffusion silicon wafer with good internal uniformity is obtained.
Alternatively, the boron source includes, but is not limited to, boron tribromide (BBr 3 ) Boron trichloride (BCl) 3 ) Etc. It should be noted that the specific type of boron source is not limited in the embodiments of the present invention, and boron sources commonly used or well known in the art, such as BBr, may be used 3 、BCl 3 Etc., which has the advantage of relatively low cost and high purity.
S202, pushing knots;
in the step, the temperature is increased from the first temperature to the second temperature, oxygen or mixed gas containing oxygen and nitrogen is introduced into a diffusion furnace to push the junction, and a boron source is pushed into the N-type silicon wafer.
Wherein the second temperature is less than 950 ℃, and the second temperature is less than or equal to 920 ℃,so as to ensure that the high sheet resistance lightly doped P is obtained in the junction pushing step + A layer.
Alternatively, the temperature rate may be 8-20℃/min, further 10-15℃/min, and typical but non-limiting examples may be 8℃/min, 9℃/min, 10℃/min, 12℃/min, 15℃/min, 18℃/min, 20℃/min, etc.
The junction pushing process requires a certain amount of oxygen (O) 2 ) Alternatively, a mixed gas containing oxygen and nitrogen, i.e., N, may be introduced 2 /O 2 Mixing.
Wherein the time for pushing knot is 5-10min, and typical but non-limiting examples can be 5min, 6min, 7min, 8min, 10min, etc.; o (O) 2 Or N 2 /O 2 The flow rate of the mixed gas is 10000 to 30000sccm, and typical examples include, but not limited to, 10000sccm, 15000sccm, 20000sccm, 25000sccm, 30000sccm, and the like.
In the pushing time and flow range, the silicon wafer manufacturing efficiency is guaranteed, and the waste of resources is reduced.
S203, performing second boron diffusion deposition;
in this step, the temperature is reduced from the second temperature to a third temperature, which may be 800-900 ℃, further may be 820-890 ℃, further may be 850-880 ℃.
Alternatively, the cooling rate may be 4-10deg.C/min, further may be 5-9deg.C/min, and typically but not limited to, for example, 4deg.C/min, 5deg.C/min, 6deg.C/min, 7deg.C/min, 8deg.C/min, 9deg.C/min, 10deg.C/min, etc.
After the temperature in the diffusion furnace is reduced to a preset temperature, namely a third temperature, introducing nitrogen, oxygen and a boron source into the diffusion furnace for carrying out secondary boron diffusion deposition; the deposition time is 10-60min, and typical but not limiting examples can be 10min, 20min, 30min, 40min, 60min, etc.; the flow rate of nitrogen is 10000-30000sccm, and typical but not limiting examples thereof include 10000sccm, 15000sccm, 20000sccm, 25000sccm, 30000sccm, etc.; the flow rate of oxygen is 30-300sccm, and typical but not limiting examples may be 30sccm, 40sccm, 50sccm, 60sccm, 80sccm, 100sccm, 150sccm, 200sccm, 250sccm, 300sccm, etc.; the flow rate of the boron source is 100-900sccm, and typical but non-limiting examples may be 100sccm, 200sccm, 300sccm, 400sccm, 500sccm, 600sccm, 700sccm, 900sccm, etc.
In addition, in the operation process, other gases can be adopted for replacing the nitrogen, so long as the silicon wafer can be ensured not to be oxidized.
In the deposition time and flow range, the silicon wafer manufacturing efficiency is guaranteed, the waste of resources is reduced, and the subsequent treatment process is facilitated.
S204, cooling the boat, and completing the boron diffusion process.
The embodiment of the invention also provides a manufacturing method of the solar cell, which comprises a boron diffusion step, a laser doping step, a passivation step and a metallization step, wherein the boron diffusion step adopts the boron diffusion method, a lightly doped region of boron is formed by utilizing the boron diffusion step, and a heavily doped region of boron is formed by utilizing the laser doping step.
The embodiment of the invention adopts a mode of combining boron diffusion and laser doping to prepare the Selective Emitter (SE) structure, has simple process, reduces high-temperature process, is beneficial to controlling defects and composite centers introduced in the preparation process, and can provide sufficient boron doping sources for laser heavy doping. The SE battery prepared by the method can effectively improve the open-circuit voltage and the short-circuit current of the battery, so that the battery efficiency is effectively improved by 0.2% or more.
The embodiment of the invention is not limited to the specific implementation manner of the laser doping step, for example, the operation power and the like can be appropriately regulated and controlled by a person skilled in the art according to the actual situation. In order to ensure the manufacturing efficiency of the N-type solar cell, the embodiment of the invention can select the parameters of the laser doping step to include: the laser power is 10-100W, and may be, for example, typically but not limited to, 10W, 20W, 50W, 80W, 100W, etc.; the scanning rate is 2500-10000mm/s, and may be, for example, 2500mm/s, 3000mm/s, 4000mm/s, 5000mm/s, 6000mm/s, 8000mm/s, 10000mm/s, etc., typical but not limiting.
In the method for manufacturing an N-type solar cell, specific conditions of the passivation step and the metallization step are not particularly limited, and those skilled in the art can know that the method can be appropriately controlled according to actual conditions. In addition, the method may further include other post-treatment steps, and the specific process of post-treatment is not particularly limited, and may be performed in a manner well known in the art, and the present invention will not be described in detail herein.
Optionally, referring to fig. 2, the method for manufacturing a solar cell includes the following steps:
s100, cleaning and texturing the N-type silicon wafer;
s200, placing the N-type silicon wafer subjected to texturing into a diffusion furnace for performing a boron diffusion process to obtain high-sheet-resistance lightly doped P + The layer specifically comprises:
s201, raising the temperature of a diffusion furnace tube to a first temperature, for example, 850-880 ℃, and after the temperature is stable, introducing nitrogen, oxygen and a boron source into the diffusion furnace to perform first boron diffusion deposition;
s202, raising the temperature from the first temperature to a second temperature, if the temperature is raised to be less than 950 ℃, and introducing oxygen or mixed gas containing oxygen and nitrogen into a diffusion furnace to push a junction, so as to push a boron source into an N-type silicon wafer;
s203, reducing the temperature from the second temperature to a third temperature, such as 850-880 ℃, and introducing nitrogen, oxygen and boron sources into the diffusion furnace to perform second boron diffusion deposition;
s204, cooling and discharging the boron from the boat to finish the boron diffusion process. A lightly doped region is formed by this boron diffusion process.
S300, forming a heavy doping region in the metal doping region of the N-type silicon wafer after boron diffusion by using a laser method.
S400, performing subsequent N-type silicon wafer battery working procedure treatment.
After laser doping, a SE structure, i.e. a selective emitter structure, is formed, and then a passivation layer, which may be one or more layers, may be formed on the front and/or back side of the silicon wafer. The passivation layer may include, but is not limited to, silicon oxynitride, aluminum oxide, silicon nitride, and the like. A metallization step may then be performed, i.e. forming electrodes in the heavily doped regions. The electrode forms ohmic contact with the heavily doped region and can be used for collecting electric energy converted from solar energy. Alternatively, the electrodes may be formed by a screen printing process. For example, a screen printing technique may be used to print a conductive paste on the heavily doped region and dry it, and a gate electrode corresponding to the heavily doped region may be formed. The conductive paste can be conductive silver paste with penetrability, and can penetrate through the passivation layer after being sintered so as to form ohmic contact with the silicon chip through the conductive heavily doped region. In the preparation of the N-type solar cell, the operation steps or specific operation modes after laser doping are not limited, and can be controlled according to the actual situation by referring to the prior art or by a person skilled in the art, and will not be described in detail herein.
The embodiment of the application also provides a solar cell, namely an N-type solar cell, which is manufactured by adopting the manufacturing method of the solar cell.
It should be understood that the N-type solar cell of the present invention is based on the same inventive concept as the boron diffusion method for an N-type solar cell and the method for manufacturing an N-type solar cell described above, and thus has at least the same advantages as the boron diffusion method for an N-type solar cell and the method for manufacturing an N-type solar cell described above, and will not be described in detail herein.
The boron diffusion method, the solar cell, and the manufacturing method thereof are all common parameters and conventional operation modes that are easily understood by those skilled in the art, such as a cleaning and texturing process, a subsequent N-type silicon wafer cell processing process, etc., and may be controlled by those skilled in the art with reference to the prior art or according to the actual situation, so that the detailed description thereof may be omitted.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
It is noted that a portion of this patent document contains material which is subject to copyright protection. The copyright owner has reserved copyright rights, except for making copies of patent documents or recorded patent document content of the patent office.
Claims (6)
1. The manufacturing method of the solar cell comprises a boron diffusion step, a laser doping step, a passivation step and a metallization step, and is characterized in that a lightly doped region of boron is formed by utilizing the boron diffusion step, a heavily doped region of boron is formed by utilizing the laser doping step, and the boron diffusion step comprises the following steps:
placing the pretreated N-type silicon wafer in a diffusion furnace, and performing first boron diffusion deposition at a first temperature;
after the first boron diffusion deposition, the temperature in the diffusion furnace is increased from the first temperature to the second temperature, and junction pushing is carried out;
after junction pushing, the temperature in the diffusion furnace is reduced from the second temperature to a third temperature, and the second boron diffusion deposition is carried out at the third temperature;
the second temperature is higher than the first temperature and the third temperature respectively, the second temperature is higher than 900 ℃ and less than or equal to 920 ℃, the first temperature is 800-900 ℃, and the third temperature is 800-900 ℃.
2. The method of claim 1, wherein the first temperature is 850-880 ℃;
and/or, the third temperature is 850-880 ℃.
3. The method of any one of claims 1-2, wherein performing a first boron diffusion deposition comprises:
introducing nitrogen, oxygen and a boron source into the diffusion furnace for first boron diffusion deposition, wherein the deposition time is 10-60min, the flow rate of the nitrogen is 10000-30000sccm, the flow rate of the oxygen is 30-200sccm, and the flow rate of the boron source is 100-600sccm.
4. The method of any one of claims 1-2, wherein the performing a push junction comprises:
oxygen or mixed gas containing oxygen and nitrogen is introduced into the diffusion furnace for knot pushing, the knot pushing time is 5-10min, and the flow of the oxygen or the mixed gas containing oxygen and nitrogen is 10000-30000sccm.
5. The method of any one of claims 1-2, wherein performing a second boron diffusion deposition comprises:
introducing nitrogen, oxygen and a boron source into the diffusion furnace for secondary boron diffusion deposition, wherein the deposition time is 10-60min, the flow rate of the nitrogen is 10000-30000sccm, the flow rate of the oxygen is 30-300sccm, and the flow rate of the boron source is 100-900sccm.
6. A solar cell manufactured by the method of any one of claims 1 to 5.
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| CN114464701A (en) * | 2022-01-17 | 2022-05-10 | 常州时创能源股份有限公司 | Diffusion method of crystalline silicon solar cell and application thereof |
| CN115132880A (en) * | 2022-07-05 | 2022-09-30 | 正泰新能科技有限公司 | Diffusion method and preparation method for solar cell multi-deposition doping source |
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