CN114388658A - Solar cell preparation method and solar cell - Google Patents
Solar cell preparation method and solar cell Download PDFInfo
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- CN114388658A CN114388658A CN202111680754.2A CN202111680754A CN114388658A CN 114388658 A CN114388658 A CN 114388658A CN 202111680754 A CN202111680754 A CN 202111680754A CN 114388658 A CN114388658 A CN 114388658A
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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
- H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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- Sustainable Energy (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a solar cell and a preparation method thereof, and relates to the technical field of solar photovoltaics. After the silicon substrate is provided, depositing a borosilicate glass layer on the front surface of the silicon substrate, coating etching slurry in a preset pattern area on the front surface of the silicon substrate to etch the borosilicate glass layer in the pattern area, and then carrying out boron doping on the front surface of the etched silicon substrate at a diffusion temperature for a first process time to form a first boron doping concentration in the pattern area and a second boron doping concentration outside the pattern area on the silicon substrate. According to the method, the borosilicate glass layer is prepared on the front side of the silicon substrate through deposition, the selective emitter structure with the first boron doping concentration in the pattern area and the second boron doping concentration outside the pattern area can be prepared through one-step boron diffusion, the time of the silicon substrate in a high-temperature environment is shortened, the minority carrier lifetime is prolonged, the bending deformation under the action of high-temperature stress is avoided, the borosilicate glass layer is removed through laser, the damage to the silicon substrate is avoided, and the battery efficiency is improved.
Description
Technical Field
The invention relates to the technical field of solar photovoltaics, in particular to a solar cell and a preparation method thereof.
Background
The TOPCon (Tunnel Oxide Passivated Contact) battery is a high-efficiency battery based on a selective carrier principle, wherein a layer of ultrathin silicon Oxide layer is prepared on the back surface of the TOPCon battery, and a layer of silicon doped layer is deposited to form a Passivated Contact structure on the back surface, so that the surface recombination and the metal Contact recombination are effectively reduced, and the battery efficiency is improved.
The TOPCon battery can improve efficiency by superposing a boron SE (Selective Emitter) structure on the front surface, and under the boron SE structure on the front surface, the area contacted by the thin grid lines on the front surface has low sheet resistance, high doping concentration and small contact resistance, so that the filling factor can be further improved; the sheet resistance of other areas is high, the doping concentration is low, the surface recombination can be reduced, and the optical response is improved, so that the open-circuit voltage and the short-circuit are improved, and the efficiency of the battery is improved. At present, a laser SE process is often adopted to prepare an SE structure.
However, the laser SE process damages the silicon substrate, affects minority carrier lifetime, and has complex process, high cost and great difficulty; moreover, the laser SE process requires two boron diffusions, each at a high temperature of about 1000 ℃, which affects the bulk life of the silicon substrate and thus the cell efficiency.
Disclosure of Invention
The invention provides a solar cell preparation method and a solar cell, and aims to reduce damage to a silicon substrate in a preparation process of a selective emitter structure, prolong minority carrier lifetime, simplify process flow, reduce cost, prolong the service life of the silicon substrate and improve cell efficiency.
In a first aspect of the embodiments of the present invention, an embodiment of the present invention provides a method for manufacturing a solar cell, where the method may include:
providing a silicon substrate;
depositing a borosilicate glass layer on the front side of the silicon substrate;
coating etching slurry in a preset pattern area on the front surface of the silicon substrate, and etching off the borosilicate glass layer in the pattern area;
and carrying out boron doping on the front surface of the etched silicon substrate for a first process time at a diffusion temperature, and forming a first boron doping concentration in the pattern area and a second boron doping concentration outside the pattern area on the silicon substrate.
Optionally, the depositing a borosilicate glass layer on the front side of the silicon substrate includes:
and depositing a borosilicate glass layer on the front surface of the silicon substrate by adopting normal-pressure chemical vapor deposition equipment based on a deposition source.
Optionally, the atmospheric pressure chemical vapor deposition apparatus includes a preheating chamber, a reaction chamber, and a cooling chamber, and the depositing a borosilicate glass layer on the front surface of the silicon substrate by using the atmospheric pressure chemical vapor deposition apparatus based on a deposition source includes:
conveying the silicon substrate into the preheating cavity, and preheating the silicon substrate at the temperature of 390-410 ℃;
conveying the silicon substrate into the reaction chamber, and depositing a borosilicate glass layer on the front side of the silicon substrate based on the deposition source at a temperature of 590-610 ℃ for a second process time;
and conveying the silicon substrate into the cooling cavity, and cooling the silicon substrate.
Optionally, the deposition source comprises diborane, silane, oxygen, nitrogen.
Optionally, the deposition source comprises diborane: silane: oxygen: the volume ratio of nitrogen gas is 8:12:12: 15.
Optionally, the thickness of the borosilicate glass layer is 90nm to 100 nm.
Optionally, the sheet resistance of the borosilicate glass layer ranges from 800 Ω/□ to 1200 Ω/□.
Optionally, the diffusion temperature is 950 ℃ to 1050 ℃.
Optionally, the first process time is 170min to 190 min.
Optionally, the second process time is 7min to 9 min.
Optionally, after performing boron doping on the front surface of the etched silicon substrate at the diffusion temperature for a first process time and forming a first boron doping concentration in the pattern region and a second boron doping concentration outside the pattern region on the silicon substrate, the method further includes:
sequentially preparing a tunneling oxide layer and a phosphorus-doped polycrystalline silicon layer on the back of the silicon substrate to form a passivation contact structure;
preparing an aluminum oxide layer on the front side of the silicon substrate;
preparing silicon nitride layers on the front side of the silicon substrate and the back side of the silicon substrate;
and preparing electrodes on the front side of the silicon substrate and the back side of the silicon substrate.
In a second aspect of the present invention, there is also provided a solar cell prepared by the method for preparing a solar cell according to the first aspect.
In the implementation of the invention, after a silicon substrate is provided, a borosilicate glass layer is deposited on the front surface of the silicon substrate, etching slurry is coated in a preset pattern area on the front surface of the silicon substrate to etch the borosilicate glass layer in the pattern area, and then boron doping is carried out on the front surface of the etched silicon substrate at a diffusion temperature for a first process time to form a first boron doping concentration in the pattern area and a second boron doping concentration outside the pattern area on the silicon substrate. In the implementation of the invention, the borosilicate glass layer is prepared on the front side of the silicon substrate through deposition, the selective emitter structure with the first boron doping concentration in the graphic area and the second boron doping concentration outside the graphic area can be prepared only by one-step boron diffusion after etching, the time of exposing the silicon substrate at high temperature in the process flow is reduced, the minority carrier lifetime is prolonged, the probability of bending deformation of the silicon substrate due to high-temperature stress change is reduced, the influence on the service life of the silicon wafer body is reduced, meanwhile, the laser SE process is not adopted, but the slurry etching is adopted, the damage to the silicon substrate in the process of removing the borosilicate glass layer by laser is avoided, the open-circuit voltage of the battery is improved, and the process complexity and the process cost are reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments of the present invention will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without inventive labor.
Fig. 1 is a flow chart illustrating steps of a method for manufacturing a solar cell according to an embodiment of the present invention;
FIG. 2 is a flow chart illustrating steps of another method for fabricating a solar cell according to an embodiment of the present invention;
fig. 3 shows a schematic structural diagram of a solar cell according to an embodiment of the present invention.
Description of reference numerals:
30-a solar cell; 301-N type silicon substrate; 302-passivating the contact structure; 303-a silicon nitride layer; 304-a back electrode; 305-a selective emitter structure; 306-an aluminum oxide/silicon nitride layer; 307-front electrode; 3051-a first boron doping concentration region; 3052-second boron doping concentration region.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, fig. 1 is a flowchart illustrating steps of a method for manufacturing a solar cell according to an embodiment of the present invention, where the method may include:
In the embodiment of the invention, an N-type silicon wafer can be processed according to process requirements to provide a silicon substrate, and optionally, the N-type silicon wafer can be cleaned, napped and the like, wherein the cleaning can remove organic impurities or inorganic impurities existing on the surface of the N-type silicon wafer in the forms of atoms, ions, particles, films and the like, chemical cleaning such as acid cleaning, solvent extraction cleaning, plasma cleaning and the like can be selected, and physical cleaning can be high-pressure cleaning, ultrasonic cleaning and the like; the texturing may be acid texturing, alkali texturing, electrochemical texturing, laser texturing, and the like, and the method for providing the silicon substrate is not particularly limited in the embodiments of the present invention.
102, depositing a borosilicate glass layer on the front side of the silicon substrate
In the embodiment of the present invention, a deposition method may be adopted to deposit a borosilicate glass layer on the front surface of the silicon substrate, that is, a chemical reaction is performed on the front surface of the silicon substrate based on a gaseous boron source to generate the borosilicate glass layer, optionally, a chemical vapor deposition method may be adopted to deposit the borosilicate glass layer, for example, a normal pressure chemical vapor deposition, a plasma enhanced chemical vapor deposition, and the like are adopted to prepare the borosilicate glass layer, and a boron diffusion light doping process is not required to be performed at a high temperature of about 1000 ℃ to form the borosilicate glass layer on the front surface of the silicon substrate, so that damage to the silicon substrate under the high temperature condition is avoided.
103, coating etching slurry in a preset pattern area on the front surface of the silicon substrate, and etching off the borosilicate glass layer in the pattern area.
In the embodiment of the invention, the borosilicate glass layer can be etched by using etching slurry, the borosilicate glass layer is coated in the preset pattern area on the front surface of the silicon substrate by using the etching slurry, so that the borosilicate glass layer in the preset pattern area on the front surface of the silicon substrate is removed, the silicon substrate in the pattern area is exposed, different doping concentrations can be formed in the pattern area of the silicon substrate and outside the pattern area in the subsequent boron diffusion process, a selective emitter structure is realized, and optionally, the etching slurry can be coated in the preset pattern area on the front surface of the silicon substrate by using a screen printing mode. The pattern area can be arranged according to the front side secondary grid pattern of the solar cell so as to realize high-concentration doping in the contact area on the front side of the metal grid line and the silicon substrate, so that the sheet resistance is low, the contact resistance is small, and the filling factor is improved; the low-concentration doping is realized in the region outside the contact region on the front surfaces of the metal grid line and the silicon substrate, so that the open-circuit voltage, the short-circuit current and the like are improved, the conversion efficiency of the solar cell is effectively improved, and the damage to the silicon substrate in the process of removing part of the borosilicate glass layer by laser burning in the laser etching SE process is avoided.
And 104, carrying out boron doping on the front surface of the etched silicon substrate at the diffusion temperature for a first process time, and forming a first boron doping concentration in the pattern area and a second boron doping concentration outside the pattern area on the silicon substrate.
In the embodiment of the invention, after removing the borosilicate glass layer in the preset pattern area on the front surface of the silicon substrate by etching, boron doping can be carried out on the silicon substrate at the diffusion temperature, optionally, the diffusion temperature and the first process time can be specifically set according to the doping concentration and the doping depth required by the boron doping, and the like, and as the borosilicate glass layer in the pattern area is removed by etching in the step 103, under the local blocking effect of the borosilicate glass layer, the first boron doping concentration is formed in the pattern area, and the second boron doping concentration is formed outside the pattern area, so that the selective emitter structure is realized, wherein the pattern area is the front surface of the silicon substrate except other areas in the pattern area.
In the embodiment of the present invention, a passivation contact structure or other functional layers such as a passivation layer, an anti-reflection layer, and a metal electrode may be further formed on the back surface of the silicon substrate to manufacture the solar cell.
In the implementation of the invention, after a silicon substrate is provided, a borosilicate glass layer is deposited on the front surface of the silicon substrate, etching slurry is coated in a preset pattern area on the front surface of the silicon substrate to etch the borosilicate glass layer in the pattern area, and then boron doping is carried out on the front surface of the etched silicon substrate at a diffusion temperature for a first process time to form a first boron doping concentration in the pattern area and a second boron doping concentration outside the pattern area on the silicon substrate. In the implementation of the invention, the borosilicate glass layer is prepared on the front side of the silicon substrate through deposition, the selective emitter structure with the first boron doping concentration in the graphic area and the second boron doping concentration outside the graphic area can be prepared only by one-step boron diffusion after etching, the time of exposing the silicon substrate at high temperature in the process flow is reduced, the minority carrier lifetime is prolonged, the probability of bending deformation of the silicon substrate due to high-temperature stress change is reduced, the influence on the service life of the silicon wafer body is reduced, meanwhile, the laser SE process is not adopted, but the slurry etching is adopted, the damage to the silicon substrate in the process of removing the borosilicate glass layer by laser is avoided, the open-circuit voltage of the battery is improved, and the process complexity and the process cost are reduced.
Referring to fig. 2, fig. 2 is a flow chart illustrating steps of another method for manufacturing a solar cell according to an embodiment of the present invention, where the method may include:
In the embodiment of the present invention, step 201 may refer to the related description of step 101, and is not described herein again to avoid repetition.
In the embodiment of the present invention, an alkali texturing process may be adopted to perform texturing on an N-type silicon wafer to provide a silicon substrate, and optionally, a mixed solution of potassium hydroxide and a texturing additive may be adopted, where the volume fraction of the potassium hydroxide is about 1%, and the N-type silicon wafer is corroded at a temperature of 77 ℃ to 83 ℃ for 495 seconds to 505 seconds to perform texturing, where the volume ratio of the mixed solution may be water: potassium hydroxide: texturing additive 354:5.5:2, the volume fraction of the potassium hydroxide is 1.5 percent under the mixture ratio, the etching amount of an alkali texturing process to the N-type silicon wafer can be 0.55 to 0.65 g, the reflectivity of the textured N-type silicon wafer can be 8.7 to 9.3 percent, and texturing additives can comprise a surfactant, a nucleating agent, a dispersing agent, a catalyst, a defoaming agent and the like.
In the embodiment of the invention, the atmospheric pressure chemical vapor deposition equipment is equipment for realizing the atmospheric pressure chemical vapor deposition process, can perform deposition under the condition that the reaction environment pressure is similar to the atmospheric pressure, adopts a deposition source to deposit the borosilicate glass layer on the front surface of the silicon substrate under the atmospheric pressure condition through the atmospheric pressure chemical vapor deposition equipment, and has controllable deposition process parameters, high deposition uniformity and high quality of the prepared film layer.
Optionally, the deposition source comprises diborane, silane, oxygen, nitrogen.
In the embodiment of the present invention, the deposition source may include gases such as diborane, silane, oxygen, and nitrogen, and different gases are introduced into the atmospheric pressure chemical vapor deposition apparatus as needed to be mixed, and react on the front side of the silicon substrate to generate the borosilicate glass layer.
Optionally, the deposition source comprises diborane: silane: oxygen: the volume ratio of nitrogen gas is 8:12:12: 15.
In the embodiment of the invention, the volume ratio of diborane, silane, oxygen and nitrogen in the deposition source can be 8:12:12:15, and on the basis, 8 equivalents of diborane, 12 equivalents of silane, 12 equivalents of oxygen and 15 equivalents of nitrogen can be introduced into the reaction chamber as the deposition source to prepare the borosilicate glass layer on the front surface of the silicon substrate.
Optionally, the atmospheric pressure chemical vapor deposition apparatus includes a preheating chamber, a reaction chamber, and a cooling chamber.
In the embodiment of the invention, the atmospheric pressure chemical vapor deposition equipment can comprise a preheating cavity, a reaction cavity and a cooling cavity, and a silicon substrate to be processed can be conveyed among different cavities through a conveying belt so as to realize the processes of preheating, deposition, cooling and the like of the silicon substrate, thereby depositing the borosilicate glass layer.
Optionally, the step 202 includes:
and step S11, transferring the silicon substrate into the preheating cavity, and preheating the silicon substrate at the temperature of 390-410 ℃.
In the embodiment of the invention, the silicon substrate can be firstly transferred into the preheating cavity, the preheating cavity can preheat the silicon substrate at the temperature of 390-410 ℃, and optionally, the temperature of the preheating cavity can be any temperature within the range of 390-410 ℃, such as 390 ℃, 391 ℃, 392 ℃, 393 ℃, 394 ℃, 395 ℃, 400 ℃, 405 ℃, 410 ℃ and the like.
And S12, conveying the silicon substrate into the reaction cavity, and depositing a borosilicate glass layer on the front surface of the silicon substrate at a temperature of 590-610 ℃ for a second process time based on the deposition source, wherein the deposition source comprises diborane, silane, oxygen and nitrogen.
In the embodiment of the present invention, after the silicon substrate is preheated, the silicon substrate may be transferred to a reaction chamber, and a deposition source may be used to react on the front surface of the silicon substrate in the reaction chamber to generate a deposition film layer, where the deposition source such as diborane, silane, oxygen, and nitrogen may be used to react on the front surface of the silicon substrate at a temperature of 590 ℃ to 610 ℃ for a second process time to prepare the borosilicate glass layer, and the temperature of the reaction chamber may be any temperature within 590 ℃ to 610 ℃, such as 590 ℃, 591 ℃, 592 ℃, 593 ℃, 594 ℃, 595 ℃, 600 ℃, 605 ℃, 610 ℃, and the like.
In the embodiment of the invention, diborane, silane, oxygen and nitrogen are used as a deposition source to deposit the borosilicate glass layer on the front surface of the silicon substrate in a reaction way, and the reaction equations (1) and (2) are as follows:
SiH4+O2→SiO2+2H2·························(1)
2B2H6+3O2→2B2O3+6H2·······················(2)
wherein silane and diborane react with oxygen respectively to form a borosilicate glass layer on the front surface of the silicon substrate.
Optionally, the thickness of the borosilicate glass layer is 90nm to 100 nm.
In the embodiment of the present invention, the thickness of the borosilicate glass layer may be any thickness between 90nm and 100nm, such as 90nm, 91nm, 92nm, 93nm, 94nm, 95nm, 96nm, 97nm, 98nm, 99nm, 100nm, and the like.
Optionally, the sheet resistance of the borosilicate glass layer ranges from 800 Ω/□ to 1200 Ω/□.
In the embodiment of the invention, the sheet resistance range of the borosilicate glass layer can be any sheet resistance between 800 Ω/□ -1200 Ω/□, such as 800 Ω/□, 810 Ω/□, 820 Ω/□, 830 Ω/□, 840 Ω/□, 850 Ω/□, 900 Ω/□, 950 Ω/□, 1000 Ω/□, 1050 Ω/□, 1100 Ω/□, 1150 Ω/□, 1200 Ω/□ and the like.
Optionally, the second process time is 7min to 9 min.
In the embodiment of the present invention, the second process time may be any time between 7min and 9min, such as 7.1min, 7.2min, 7.3min, 7.4min, 7.5min, 8min, 8.5min, 9min, and the like.
And step S13, transferring the silicon substrate into the cooling cavity, and cooling the silicon substrate.
In the embodiment of the invention, after the borosilicate glass layer is deposited on the front surface of the silicon substrate in the reaction cavity, the silicon substrate can be transported into the cooling cavity to be cooled, wherein the silicon substrate can be taken out from the normal-pressure chemical vapor deposition equipment after being cooled to the room temperature, and the silicon substrate with the borosilicate glass layer prepared on the front surface is obtained.
In the embodiment of the present invention, an etching slurry is coated in a preset image area on a front-side borosilicate glass layer of a silicon substrate, wherein the image area may be an area of a front-side secondary gate image on the front side of the silicon substrate to remove the borosilicate glass layer in the image area on the silicon substrate by etching, and a first boron doping concentration in the image area and a second boron doping concentration outside the image area are formed on the front side of the silicon substrate in a subsequent boron diffusion process based on a blocking effect of the remaining borosilicate glass layer. The etching slurry can be coated in a preset pattern area by adopting screen printing, and the etching slurry can be kept stand for 15-25 min after the screen printing so as to be fully reacted with the borosilicate glass layer, and the borosilicate glass layer in the pattern area can be fully removed, so that the silicon substrate in the pattern area is exposed.
And 204, carrying out boron doping on the front surface of the etched silicon substrate at the diffusion temperature for a first process time, and forming a first boron doping concentration in the pattern area and a second boron doping concentration outside the pattern area on the silicon substrate.
In the embodiment of the present invention, step 204 may correspond to the related description of step 104, and is not repeated herein to avoid repetition.
Optionally, the diffusion temperature is 950 ℃ to 1050 ℃.
In the embodiment of the present invention, the diffusion temperature may be any temperature in the range of 950 ℃ to 1050 ℃, such as 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, 1000 ℃, 1050 ℃, and the like.
Optionally, the first process time is 170min to 190 min.
In the embodiment of the present invention, the first process time may be any time within a range of 170min to 190min, such as 170min, 171min, 172min, 173min, 174min, 175min, 180min, 185min, 190min, and the like.
And 205, sequentially preparing a tunneling oxide layer and a phosphorus-doped polycrystalline silicon layer on the back surface of the silicon substrate to form a passivation contact structure.
In the embodiment of the invention, a silicon oxide layer can be prepared on the back of a silicon wafer to serve as a tunneling oxide layer, the silicon oxide layer can reduce the interface state density through chemical passivation, so that most current carriers are transported through tunneling, and a tunneling effect is realized, and minority current carriers are difficult to tunnel through the silicon oxide layer due to potential barriers, field effects and the like, so that the electron hole recombination probability can be reduced, selective contact of the most current carriers is realized, and the efficiency of the battery is effectively improved.
In the embodiment of the present invention, a phosphorus-doped polysilicon layer may be further prepared on the tunnel oxide layer, and optionally, a polysilicon layer may be deposited first by LPCVD (Low Pressure Chemical Vapor Deposition), and then phosphorus diffusion or ion implantation may be performed on the polysilicon layer to form a phosphorus-doped polysilicon layer, or a phosphorus-doped amorphous silicon or microcrystalline silicon layer may be deposited by PECVD (Plasma Enhanced Chemical Vapor Deposition), and then an annealing process is performed to obtain a phosphorus-doped polysilicon layer, so as to form a passivation contact structure with the bottom back surface of the silicon substrate of the tunnel oxide layer. The polysilicon layer coated around the front surface of the silicon substrate can be removed, so that the influence on the subsequent process, the battery efficiency and the like can be avoided.
And step 206, preparing an aluminum oxide layer on the front side of the silicon substrate.
In the embodiment of the invention, the aluminum oxide layer has a good field effect passivation effect, the surface of the boron doped layer is passivated, the carrier recombination is reduced, and the minority carrier lifetime is prolonged, so that the photoelectric conversion efficiency of the battery is improved.
In the embodiment of the present invention, a silicon nitride layer may be further prepared on the aluminum oxide layer and the phosphorus-doped polysilicon layer, that is, the front surface and the back surface of the silicon substrate, where the silicon nitride layer has good hydrogen passivation and antireflection effects, and can achieve a good bulk passivation effect, optionally, a stacked silicon nitride layer may be prepared on the aluminum oxide layer to achieve front surface passivation and antireflection effects of the battery, and a silicon nitride layer with a lower refractive index may be prepared on the phosphorus-doped polysilicon layer, so as to reduce light loss and improve light utilization rate.
And 208, preparing electrodes on the front side of the silicon substrate and the back side of the silicon substrate.
In the embodiment of the present invention, after each film layer is prepared, electrodes may be prepared on the front surface and the back surface of the silicon substrate to obtain a solar cell, optionally, the electrodes may be prepared by screen printing of metal paste and sintering, or by photolithography and electroplating, or by vacuum evaporation, and optionally, the electrodes may be silver electrodes, copper electrodes, aluminum electrodes, and the like, which is not particularly limited in this embodiment of the present invention.
In the implementation of the invention, after a silicon substrate is provided, a borosilicate glass layer is deposited on the front surface of the silicon substrate, etching slurry is coated in a preset pattern area on the front surface of the silicon substrate to etch the borosilicate glass layer in the pattern area, and then boron doping is carried out on the front surface of the etched silicon substrate at a diffusion temperature for a first process time to form a first boron doping concentration in the pattern area and a second boron doping concentration outside the pattern area on the silicon substrate. In the implementation of the invention, the borosilicate glass layer is prepared on the front side of the silicon substrate through deposition, the selective emitter structure with the first boron doping concentration in the graphic area and the second boron doping concentration outside the graphic area can be prepared only by one-step boron diffusion after etching, the time of exposing the silicon substrate at high temperature in the process flow is reduced, the minority carrier lifetime is prolonged, the probability of bending deformation of the silicon substrate due to high-temperature stress change is reduced, the influence on the service life of the silicon wafer body is reduced, meanwhile, the laser SE process is not adopted, but the slurry etching is adopted, the damage to the silicon substrate in the process of removing the borosilicate glass layer by laser is avoided, the open-circuit voltage of the battery is improved, and the process complexity and the process cost are reduced.
Fig. 3 is a schematic structural diagram of a solar cell 30 according to an embodiment of the present invention, as shown in fig. 3, the solar cell 30 includes an N-type silicon substrate 301, and a passivation contact structure 302, a silicon nitride layer 303, and a back electrode 304 on the back surface of the N-type silicon substrate 301, and the solar cell 30 further includes a selective emitter structure 305 on the front surface of the N-type silicon substrate 301, an aluminum oxide/silicon nitride layer 306, and a front electrode 307, wherein a pattern region where the selective emitter structure 305 contacts a metal gate line is a first boron doping concentration region 3051, and a region outside the other pattern region is a second boron doping concentration region 3052, and the first boron doping concentration is greater than the second boron doping concentration. In the implementation of the present invention, a sample cell and a comparative cell having the structures shown in fig. 3 are also provided, wherein the sample cell is prepared by the solar cell preparation method shown in any one of fig. 1 and 2, and the comparative cell is prepared by a conventional process, as follows:
preparation of sample cell
Step S21, carrying out alkali texturing process on the N-type silicon wafer through a groove type texturing cleaning machine to obtain a silicon substrate, wherein a mixed solution of potassium hydroxide and a texturing additive is used as an alkali liquor, and the volume ratio of the alkali liquor can be water: potassium hydroxide: the wool making additive is 354:5.5:2, wherein the wool making additive comprises a surfactant, a nucleating agent, a dispersing agent, a catalyst, a defoaming agent and the like; the process temperature of the texturing process can be 77-83 ℃, and the process time can be 495-505 seconds; the etching amount of the N-type silicon wafer by the texturing process is 0.55-0.65 g, and the reflectivity is 8.7-9.3%;
step S22, the silicon substrate is conveyed into a preheating cavity of the atmospheric pressure chemical vapor deposition equipment through a conveyor belt, and the silicon substrate is preheated at the temperature of 390-410 ℃; then, the silicon substrate is conveyed into a reaction cavity through a conveyor belt, and a borosilicate glass layer is deposited on the front surface of the silicon substrate through reaction of diborane, silane, oxygen and nitrogen in the reaction cavity, wherein the process temperature for depositing the borosilicate glass layer is 590-610 ℃, the process time is 7-9 min, and the thickness of the deposited borosilicate glass layer is 100 +/-10 nm; then the silicon substrate is transmitted to a cooling cavity for cooling, the silicon substrate is taken out after being cooled to room temperature, and the borosilicate glass layer is tested, wherein the square resistance range is 800-1200 omega/□;
step S23, coating etching slurry on the front side of the silicon substrate according to the front side secondary grid pattern of the solar cell in a screen printing machine, standing for 15-25 min after screen printing, washing in a groove type cleaning machine, drying and treating by a subsequent process, wherein the etching slurry mainly comprises fluoride;
s24, placing the dried silicon substrate in a boron diffusion furnace to perform heavy doping process at the process temperature of 950-1050 ℃, wherein the process time is 170-190 min, so that the square resistance of the front side of the silicon substrate is 55 omega/□ -65 omega/□;
step S25, performing alkali polishing on the back surface of the silicon substrate in a groove type cleaning machine, wherein alkali liquor is a mixed solution of potassium hydroxide and a polishing additive, the volume concentration of potassium hydroxide is 3.5% -4.5%, and water in the solution: potassium hydroxide: the volume ratio of the polishing additive is 340: 16: 4; wherein, the polishing additive can comprise a surfactant, sodium citrate, sodium benzoate and the like, the process temperature in the alkali polishing is 53-57 ℃, and the process time is 215-225 seconds; etching amount of the silicon substrate after alkali polishing is 0.18-0.22 g, and the back surface reflectivity of the silicon substrate is 41-43%;
step S26, depositing a tunneling oxide layer (SiO) on the back of the silicon substrate by LPCVD2) And a polysilicon (Poly) layer, wherein the tunneling oxide layer has a thickness of 1.2nm-1.8nm, and the polysilicon layer has a thickness of 100nm-140 nm;
step S27, injecting phosphorus on the polysilicon layer by a phosphorus diffusion furnace to form a passivation contact structure;
step S28, removing the polysilicon layer wound and plated on the front surface of the silicon substrate in a groove type cleaning machine, wherein the polysilicon layer is realized by adopting a mixed solution of potassium hydroxide and a polishing additive, the volume concentration of the potassium hydroxide is 3.5-4.5%, the process temperature is 63-69 ℃, and the process time is 190-210 seconds;
step S29, preparing an AlOx + SiNx (aluminum oxide + silicon nitride) passivation layer on the front side of the silicon substrate and preparing a SiNx passivation layer on the back side of the silicon substrate;
and S210, preparing electrodes on the front side and the back side of the silicon substrate through screen printing and sintering, and testing and sorting to obtain the sample cell.
Preparation of comparative cell
Step S31, carrying out alkali texturing process on the N-type silicon wafer through a groove type texturing cleaning machine to obtain a silicon substrate, wherein a mixed solution of potassium hydroxide and a texturing additive is used as an alkali liquor, and the volume ratio of the alkali liquor can be water: potassium hydroxide: the wool making additive is 354:5.5:2, wherein the wool making additive comprises a surfactant, a nucleating agent, a dispersing agent, a catalyst, a defoaming agent and the like; the process temperature of the texturing process can be 77-83 ℃, and the process time can be 495-505 seconds; the etching amount of the N-type silicon wafer by the texturing process is 0.55-0.65 g, and the reflectivity is 8.7-9.3%;
s32, putting the textured silicon substrate into a boron diffusion furnace to carry out a light doping process so that the front surface sheet resistance of the silicon substrate is 190 omega/□ -210 omega/□, wherein the process temperature of the light doping process is 950-1050 ℃, and the process time is 140-160 min;
step S33, in a laser, removing part of borosilicate glass layer on the front side of a silicon substrate by laser burning according to the front side grating pattern of the solar cell, and then carrying out alkali washing in a groove type cleaning machine to remove laser damage and then carrying out subsequent process treatment;
s34, placing the silicon substrate subjected to alkali washing in a boron diffusion furnace to perform heavy doping process at the process temperature of 950-1050 ℃, wherein the process time is 170-190 min, so that the square resistance of the front side of the silicon substrate is 55 omega/□ -65 omega/□;
step S35, performing alkali polishing on the back surface of the silicon substrate in a groove type cleaning machine, wherein alkali liquor is a mixed solution of potassium hydroxide and a polishing additive, the volume concentration of potassium hydroxide is 3.5% -4.5%, and water in the solution: potassium hydroxide: the volume ratio of the polishing additive is 340: 16: 4; wherein, the polishing additive can comprise a surfactant, sodium citrate, sodium benzoate and the like, the process temperature in the alkali polishing is 53-57 ℃, and the process time is 215-225 seconds; etching amount of the silicon substrate after alkali polishing is 0.18-0.22 g, and the back surface reflectivity of the silicon substrate is 41-43%;
step S36, depositing a tunneling oxide layer (SiO2) and a polycrystalline silicon (Poly) layer on the back surface of the silicon substrate by LPCVD, wherein the thickness of the tunneling oxide layer is 1.2nm-1.8nm, and the thickness of the polycrystalline silicon layer is 100nm-140 nm;
step S37, injecting phosphorus on the polysilicon layer by a phosphorus diffusion furnace to form a passivation contact structure;
step S38, removing the polysilicon layer wound and plated on the front surface of the silicon substrate in a groove type cleaning machine, wherein the polysilicon layer is realized by adopting a mixed solution of potassium hydroxide and a polishing additive, the volume concentration of the potassium hydroxide is 3.5-4.5%, the process temperature is 63-69 ℃, and the process time is 190-210 seconds;
step S39, preparing an AlOx + SiNx (aluminum oxide + silicon nitride) passivation layer on the front side of the silicon substrate and preparing a SiNx passivation layer on the back side of the silicon substrate;
and S310, preparing electrodes on the front side and the back side of the silicon substrate through screen printing and sintering, and testing and sorting to obtain the comparative cell.
In the practice of the present invention, performance tests were also performed on the sample cell and the comparative cell, including open circuit voltage (Voc), Fill Factor (FF), short circuit current (Isc), conversion efficiency (Eta), etc. of the solar cell, and the test results are shown in table 1 below:
TABLE 1
In the practice of the present invention, it can be seen from the test results set forth in table 1 that the open circuit voltage of the sample cell was increased by 5mV, the short circuit current by 20mA, the fill factor by 0.4% abs, and overall, the conversion efficiency by 0.3% abs compared to the control cell. The data show that compared with the comparative cell of the conventional process, the sample cell prepared by the method has the advantages that the open-circuit voltage, the short-circuit current, the filling factor, the conversion efficiency and the like are improved, and the damage of the high-temperature condition in the boron diffusion light doping process to the silicon substrate in the conventional process, including the bending deformation caused by high-temperature stress and the influence of the high-temperature condition on the service life of the silicon substrate body, are avoided by adopting the normal-pressure chemical vapor deposition equipment to deposit the borosilicate glass layer in the implementation of the method; furthermore, the borosilicate glass layer is etched by adopting screen printing, the damage of laser etching to the silicon substrate is also avoided, so that the conversion efficiency of the cell is improved, and the selective emitter structure is effectively prepared in the subsequent boron diffusion, wherein the front side contact area of the front side fine grid line and the silicon substrate is low in sheet resistance, high in boron doping concentration and small in contact resistance, so that the filling factor can be further improved, the sheet resistance of other areas is high, the boron doping concentration is low, the surface recombination is low, the optical response is effectively improved, and the performance parameters of the solar cell, such as open-circuit voltage, short-circuit current and the like, can be improved.
It should be noted that, for simplicity of description, the method embodiments are described as a series of acts or combination of acts, but those skilled in the art will recognize that the embodiments are not limited by the order of acts described, as some steps may occur in other orders or concurrently depending on the embodiments. Further, those skilled in the art will appreciate that the embodiments described in the specification are presently preferred and that no particular act is required to implement the embodiments of the application.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
Through the above description of the embodiments, those skilled in the art will clearly understand that the method of the above embodiments can be implemented by software plus a necessary general hardware platform, and certainly can also be implemented by hardware, but in many cases, the former is a better implementation manner. Based on such understanding, the technical solutions of the present invention may be embodied in the form of a software product, which is stored in a storage medium (such as ROM/RAM, magnetic disk, optical disk) and includes instructions for enabling a terminal (such as a mobile phone, a computer, a server, an air conditioner, or a network device) to execute the method according to the embodiments of the present invention.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method of fabricating a solar cell, the method comprising:
providing a silicon substrate;
depositing a borosilicate glass layer on the front side of the silicon substrate;
coating etching slurry in a preset pattern area on the front surface of the silicon substrate, and etching off the borosilicate glass layer in the pattern area;
and carrying out boron doping on the front surface of the etched silicon substrate for a first process time at a diffusion temperature, and forming a first boron doping concentration in the pattern area and a second boron doping concentration outside the pattern area on the silicon substrate.
2. The method of claim 1, wherein depositing a borosilicate glass layer on the front side of the silicon substrate comprises:
and depositing a borosilicate glass layer on the front surface of the silicon substrate by adopting normal-pressure chemical vapor deposition equipment based on a deposition source.
3. The method of claim 2, wherein the atmospheric pressure chemical vapor deposition apparatus comprises a preheating chamber, a reaction chamber, and a cooling chamber, and the depositing the borosilicate glass layer on the front side of the silicon substrate based on the deposition source using the atmospheric pressure chemical vapor deposition apparatus comprises:
conveying the silicon substrate into the preheating cavity, and preheating the silicon substrate at the temperature of 390-410 ℃;
conveying the silicon substrate into the reaction chamber, and depositing a borosilicate glass layer on the front side of the silicon substrate based on the deposition source at a temperature of 590-610 ℃ for a second process time;
and conveying the silicon substrate into the cooling cavity, and cooling the silicon substrate.
4. The method of claim 2, wherein the deposition source comprises diborane, silane, oxygen, nitrogen.
5. The method of claim 4, wherein the ratio of diborane: silane: oxygen: the volume ratio of nitrogen gas is 8:12:12: 15.
6. The method of claim 3, wherein the second process time is 7min to 9 min.
7. The method of claim 1, wherein the borosilicate glass layer has a thickness of 90nm to 100 nm; or the like, or, alternatively,
the sheet resistance range of the borosilicate glass layer is 800 omega/□ -1200 omega/□.
8. The method of claim 1, wherein the diffusion temperature is 950 ℃ -1050 ℃; or the like, or, alternatively,
the first process time is 170-190 min.
9. The method of claim 1, wherein the boron doping the front side of the etched silicon substrate at the diffusion temperature for a first process time after forming a first boron doping concentration within the pattern region and a second boron doping concentration outside the pattern region on the silicon substrate, further comprises:
sequentially preparing a tunneling oxide layer and a phosphorus-doped polycrystalline silicon layer on the back of the silicon substrate to form a passivation contact structure;
preparing an aluminum oxide layer on the front side of the silicon substrate;
preparing silicon nitride layers on the front side of the silicon substrate and the back side of the silicon substrate;
and preparing electrodes on the front side of the silicon substrate and the back side of the silicon substrate.
10. A solar cell, characterized in that it is produced by a solar cell production method according to any one of claims 1 to 9.
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