CN116247123A - Preparation method of P-type back tunneling oxidation passivation contact solar cell - Google Patents
Preparation method of P-type back tunneling oxidation passivation contact solar cell Download PDFInfo
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- CN116247123A CN116247123A CN202211465660.8A CN202211465660A CN116247123A CN 116247123 A CN116247123 A CN 116247123A CN 202211465660 A CN202211465660 A CN 202211465660A CN 116247123 A CN116247123 A CN 116247123A
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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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
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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
- H01L31/06—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 characterised by potential barriers
- H01L31/068—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 characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0682—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 characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
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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
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Abstract
The invention provides a preparation method of a P-type back tunneling oxidation passivation contact solar cell, which comprises the steps of oxidizing the back of a P-type monocrystalline silicon wafer to form an ultrathin tunneling oxidation layer, preparing a boron-doped silicon thin layer, and forming a phosphorus-doped silicon thin layer and a first passivation anti-reflection layer on the boron-doped silicon thin layer; holes are formed in the silicon nitride passivation anti-reflection layer, and the phosphorus doped silicon film layer is exposed; and further preparing a nickel alloy layer on the phosphorus doped silicon film layer corresponding to the hole opening part; performing phosphorus diffusion on the front side of the monocrystalline silicon piece, and manufacturing a selective emitter; forming a second passivation antireflection layer on the front surface of the monocrystalline silicon wafer after phosphorus diffusion, and forming an N-type heavily doped polycrystalline silicon layer on the basis of the second passivation antireflection layer, so that the composite loss of a metal contact area is reduced, and the conversion efficiency of the battery is improved; and the nickel alloy layer is very compact, and can effectively block penetration of aluminum, thereby ensuring that the battery has good passivation performance.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a preparation method of a P-type back tunneling oxidation passivation contact solar cell.
Background
The recent rapid development of the photovoltaic market accelerates the demand for efficient battery pieces, and how to realize cost reduction and synergy is still the most concern of photovoltaic technicians. The conventional monocrystalline PERC battery is characterized in that an alumina/silicon nitride dielectric layer is introduced into the back surface for passivation, and local metal contact is adopted, so that the back surface electron recombination is effectively reduced, and the conversion efficiency of the battery is improved. However, since the PERC cell limits the contact range of the back surface to the open area, a high recombination rate at the open area still exists. In order to further reduce the back recombination rate to realize the back integral passivation and remove the back grooving process, the full contact passivation technology is becoming an industrial research hot spot in recent years.
The full-contact passivation technology is to prepare an ultrathin tunneling oxide layer and a high-doped polysilicon film layer on the back of the battery, and the tunneling oxide passivation contact structure is formed by the ultrathin tunneling oxide layer and the high-doped polysilicon film layer. The structure provides good surface passivation for the back surface of the silicon wafer, and the ultrathin oxide layer can enable multi-sub tunneling to enter the polycrystalline silicon layer and simultaneously block minority carrier recombination, so that electrons are transversely transmitted and collected by metal in the polycrystalline silicon layer, thereby greatly reducing metal contact recombination current and improving open-circuit voltage and short-circuit current of the battery. The tunneling oxidation passivation contact technology mentioned in the prior patent document relates to different oxide materials as tunneling layers and is matched with a polysilicon film to realize passivation effect. Part of the patent also mentions a method for manufacturing a cell using tunneling oxide passivation contact technology, which process route is highly similar to single crystal passivation emitter and back side cells. But the conversion rate of the battery is low and the passivation effect is general.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for manufacturing a P-type back tunneling oxide passivation contact solar cell, the method comprising the steps of:
s1, performing previous process treatment on the front surface and the back surface of a P-type monocrystalline silicon piece;
s2, oxidizing the back surface of the monocrystalline silicon piece treated by the previous procedure to form an ultrathin tunneling oxide layer;
s3, preparing a polycrystalline silicon film layer on the ultrathin tunneling oxide layer;
s4, performing boron doping treatment on the polycrystalline silicon film layer, and forming a boron doped silicon film layer on the back surface;
s5, forming a phosphorus doped silicon thin film layer and a first passivation anti-reflection layer on the boron doped silicon thin layer;
the first passivation anti-reflection layer is formed by depositing aluminum oxide and silicon nitride passivation anti-reflection layer on the boron-doped silicon thin layer by adopting a plasma enhanced chemical vapor deposition method;
holes are formed in the silicon nitride passivation anti-reflection layer, and the phosphorus doped silicon film layer is exposed; preparing a nickel alloy layer on the phosphorus doped silicon film layer corresponding to the hole opening part of the silicon nitride passivation anti-reflection layer by using an electroless plating method;
preparing an aluminum electrode layer on the nickel alloy layer by using a screen printing method, and sintering to prepare a back electrode;
s6, performing phosphorus diffusion on the front surface of the monocrystalline silicon piece, and manufacturing a selective emitter;
s7, forming a second passivation anti-reflection layer on the front surface of the monocrystalline silicon piece after phosphorus diffusion; the second passivation anti-reflection layer is a silicon oxide and silicon nitride film layer formed on the front surface of the monocrystalline silicon wafer after phosphorus diffusion; forming an N-type heavily doped polycrystalline silicon layer on the basis of the second passivation anti-reflection layer, so that the composite loss of a metal contact area is reduced, and the conversion efficiency of the battery is improved;
s8, printing metal electrodes on the surfaces of the first passivation antireflection layer on the back surface and the second passivation antireflection layer on the front surface of the monocrystalline silicon wafer, and forming good contact between the metal electrodes and the monocrystalline silicon wafer, namely finishing the P-type back tunneling oxidation passivation contact of the solar cell;
and an Ag gate finger electrode is arranged in the front silicon nitride film layer, and the Ag gate finger electrode corresponds to the N-type heavily doped polysilicon layer and forms ohmic contact.
As a further improvement of the embodiment of the invention, the previous process treatment in the step S1 comprises removing impurities and mechanical damage on the surface of the silicon wafer and forming pyramid velvet on the front surfaceA noodle; etching the back surface of the monocrystalline silicon wafer to remove P doped N on the back surface of the silicon wafer + Junction and polishing the back surface; cleaning the surface of the P-type back surface tunneling oxidation passivation contact by using an acid solution, and removing a surface oxide layer;
the acid solution is one or two mixtures of HF and HCl, and the surface of the P-type monocrystalline silicon wafer comprises the surface of the P-type silicon wafer, the P+ surface of the P-type silicon wafer after boron heavy doping and the P-type surface of the N-type silicon wafer after boron doping.
As a further improvement of the embodiment of the invention, the main component of the nickel alloy layer is selected from one or a combination of more of nickel, nickel-phosphorus alloy and nickel-boron alloy;
the nickel alloy layer is doped with one or more microelements of chromium, copper, tin, silver and sulfur, and the doping amount is 0.01-1%;
the thickness of the silicon oxide layer is 1-2 nm, the thickness of the boron doped polysilicon layer is 20-200 nm, the thickness of the phosphorus doped silicon film layer is 20-500 nm, the thickness of the nickel alloy layer is 20-10000 nm, and the thickness of the aluminum electrode layer is 100-20000 nm;
the phosphorus-doped silicon film layer is selected from phosphorus-doped polysilicon, phosphorus-doped amorphous silicon and phosphorus-doped microcrystalline silicon.
As a further improvement of the embodiment of the present invention, the preparation method specifically includes preparing an ultrathin tunneling oxide layer on the back polishing surface by oxidation treatment with concentrated nitric acid oxidation, ozone oxidation or thermal oxidation, and depositing a polysilicon thin film layer on the ultrathin tunneling oxide layer by chemical vapor deposition;
the thickness of the ultrathin tunneling oxide layer is not more than 2nm; the deposition thickness of the polysilicon film layer is 20nm-2um;
the chemical vapor deposition method comprises a plasma enhanced chemical vapor deposition method or a low pressure chemical vapor deposition method, and the gas source is high-purity SiH 4 。
As a further improvement of the embodiment of the present invention, the electroless plating method in S5 is to deposit a nickel alloy layer on the phosphorus doped amorphous silicon under the induction of an optical field, an electric field or a sensitizer;
the preparation method of the silicon oxide is selected from any one of the following technologies: wet chemical oxidation, high temperature oxidation, plasma assisted oxidation, ozone oxidation, and plasma assisted atomic layer deposition.
As a further improvement of the embodiment of the invention, the HNO3 method, the ozone method and the UV/O method can also be adopted for obtaining the silicon oxide film on the tunneling oxide layer 3 A process and a thermal oxidation process;
as a further improvement of the embodiment of the present invention, the silicon oxide film used for the tunnel oxide layer used in the present invention may be also selected from aluminum oxide, molybdenum oxide, tungsten oxide, or titanium oxide.
As a further improvement of the embodiment of the invention, the oxidation treatment specifically comprises oxidizing the surface of the silicon wafer by adopting concentrated nitric acid with the mass concentration of 65-75%, controlling the temperature to be 20-120 ℃ and the reaction time to be not more than 10min, thus finishing the oxidation of the concentrated nitric acid; oxidizing the surface of the silicon wafer by adopting ozone with the concentration of 10-500 ppm, controlling the temperature to be 20-100 ℃ and the reaction time to be not more than 10min, thus finishing ozone oxidation; heating the surface of the silicon wafer in an oxygen or nitrogen-oxygen mixed gas atmosphere, controlling the oxygen volume concentration to be 10% -100%, controlling the temperature to be 500-800 ℃ and the time to be not more than 30min, and completing thermal oxidation.
As a further improvement of the embodiment of the invention, the boron doping treatment in the S4 specifically comprises the step of passing BBr on the surface of the P-type monocrystalline silicon piece 3 Performing boron doping treatment on the polycrystalline silicon film layer by using liquid diffusion source heat to generate a boron doped silicon film layer with a field passivation effect;
the boron atom doping concentration of the boron doping treatment is 1 multiplied by 10 19 -1×10 22 cm -3 。
As a further improvement of the embodiment of the invention, the preparation method further comprises the steps of removing borosilicate glass on the surface of the polysilicon film layer and removing the ultrathin tunneling oxide layer and the polysilicon film layer which are wound and plated on the front surface after the boron doping treatment.
As a further improvement of the embodiment of the invention, the first passivation anti-reflection layer is formed by depositing aluminum oxide and silicon nitride passivation anti-reflection layer on the boron-doped silicon thin layer by adopting a plasma enhanced chemical vapor deposition method;
the second passivation anti-reflection layer is a silicon oxide and silicon nitride film layer formed on the front surface of the monocrystalline silicon wafer after phosphorus diffusion.
As a further improvement of the embodiment of the invention, the phosphorus diffusion in the S6 specifically comprises the step of removing the surface of the P-type monocrystalline silicon piece after the wrap-around plating by POCl 3 The liquid diffusion source heat performs phosphorus diffusion on the front surface to form an emitter PN junction.
As a further improvement of the embodiments of the present invention, the method further comprises removing the front-side phosphosilicate glass after phosphorus diffusion.
As a further improvement of the embodiment of the invention, the concrete mode of boron doping comprises that a boron-containing gas source is introduced while a silicon layer is deposited by a chemical vapor deposition method, so as to directly form an in-situ doped silicon layer, wherein the doped boron source is high-purity borane; or depositing undoped intrinsic silicon thin layer by chemical vapor deposition method, and then passing through subsequent BBr 3 Or BCl 3 And (5) performing diffusion doping and ion implantation boron doping to realize boron doping.
As a further improvement of the embodiment of the invention, the method also comprises the steps of oxidizing and annealing the silicon wafer on the boron-doped silicon thin layer, so as to further improve the microstructure and performance of the silicon layer; the temperature of the oxidation annealing is 600-1000 ℃, the time is 10-60 min, the annealing process is carried out in nitrogen-oxygen mixed gas, and the volume concentration of oxygen is 10-100%.
As a further improvement of the embodiment of the present invention, the thickness of the silicon nitride passivation anti-reflection layer is 50-200nm.
As a further improvement of the embodiment of the present invention, the printed metal electrode is manufactured by printing Ag or Ag/Al paste by a screen printing method, and sintering.
Compared with the prior art, the invention has the following beneficial effects,
1. the invention provides a complete and feasible manufacturing process route of the P-type tunneling oxidation passivation contact solar cell, a phosphorus doped silicon film layer is deposited on boron doped polysilicon in the back structure of the cell, a nickel alloy layer which can block aluminum and provide good contact is deposited on the surface of the phosphorus doped silicon film layer, the diffusion and deposition rate of nickel in crystalline silicon is smaller, and most of nickel can form larger particles to be deposited on the surface of the phosphorus doped silicon film, so that the cell performance is not influenced, the nickel alloy layer is very compact, the penetration of aluminum can be effectively blocked, and the cell is ensured to have good passivation performance;
2. the invention adopts the technological method of doping the polysilicon film with boron on the back and diffusing phosphorus on the front, thereby effectively avoiding the secondary diffusion of phosphorus and further generating the phenomenon of mismatching of sheet resistance; the method of boron doping and phosphorus diffusion can be matched with the process of manufacturing the selective emitter by laser doping;
3. the invention relates to a simple process for manufacturing P-type tunneling oxidation passivation contact solar energy, which has simple and easy operation steps and strong operability.
4. In the manufacturing process of the cell, the front surface can be plated with the aluminum oxide and silicon nitride films, the contact resistance can be good through process adjustment, the sintering window can be widened, and the conversion efficiency of the P-type tunneling oxidation passivation contact solar cell can be improved.
5. The boron doping is realized by adopting a diffusion machine after the back surface of the polysilicon film is plated, or the amorphous silicon film is firstly manufactured and is annealed at high temperature after in-situ doping, so that the conversion from the amorphous silicon film to the polysilicon film can be realized, and the boron doping can be realized at the same time; the boron doped polysilicon film can be realized by using diffusion equipment, and boron doping can also be realized by an ion implantation mode, so that the boron doped polysilicon film is compatible with various existing processes.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present invention, which is described by the following specific examples.
The embodiment of the invention specifically discloses a preparation method of a P-type back tunneling oxidation passivation contact solar cell, which specifically comprises the following steps:
s1, performing previous process treatment on the front surface and the back surface of a P-type monocrystalline silicon piece;
s2, oxidizing the back surface of the monocrystalline silicon piece treated by the previous procedure to form an ultrathin tunneling oxide layer;
s3, preparing a polycrystalline silicon film layer on the ultrathin tunneling oxide layer;
s4, performing boron doping treatment on the polycrystalline silicon film layer, and forming a boron doped silicon film layer on the back surface;
s5, forming a phosphorus doped silicon thin film layer and a first passivation anti-reflection layer on the boron doped silicon thin layer;
the first passivation anti-reflection layer is formed by depositing aluminum oxide and silicon nitride passivation anti-reflection layer on the boron-doped silicon thin layer by adopting a plasma enhanced chemical vapor deposition method;
holes are formed in the silicon nitride passivation anti-reflection layer, and the phosphorus doped silicon film layer is exposed; preparing a nickel alloy layer on the phosphorus doped silicon film layer corresponding to the hole opening part of the silicon nitride passivation anti-reflection layer by using an electroless plating method;
preparing an aluminum electrode layer on the nickel alloy layer by using a screen printing method, and sintering to prepare a back electrode;
s6, performing phosphorus diffusion on the front surface of the monocrystalline silicon piece, and manufacturing a selective emitter;
s7, forming a second passivation anti-reflection layer on the front surface of the monocrystalline silicon piece after phosphorus diffusion; the second passivation anti-reflection layer is a silicon oxide and silicon nitride film layer formed on the front surface of the monocrystalline silicon wafer after phosphorus diffusion; forming an N-type heavily doped polycrystalline silicon layer on the basis of the second passivation anti-reflection layer, so that the composite loss of a metal contact area is reduced, and the conversion efficiency of the battery is improved;
s8, printing metal electrodes on the surfaces of the first passivation antireflection layer on the back surface and the second passivation antireflection layer on the front surface of the monocrystalline silicon wafer, and forming good contact between the metal electrodes and the monocrystalline silicon wafer, namely finishing the P-type back tunneling oxidation passivation contact of the solar cell;
an Ag gate finger electrode is arranged in the front silicon nitride film layer, and the Ag gate finger electrode and the N-type heavily doped polysilicon layer correspond to each other and form ohmic contact.
In the embodiment of the invention, the main component of the nickel alloy layer is selected from one or a plurality of combinations of nickel, nickel-phosphorus alloy and nickel-boron alloy;
preferably, the nickel alloy layer is doped with one or more microelements of chromium, copper, tin, silver and sulfur, and the doping amount is 0.01-1%;
specifically, the thickness of the silicon oxide layer is 1-2 nm, the thickness of the boron doped polysilicon layer is 20-200 nm, the thickness of the phosphorus doped silicon film layer is 20-500 nm, the thickness of the nickel alloy layer is 20-10000 nm, and the thickness of the aluminum electrode layer is 100-20000 nm;
the phosphorus-doped silicon film layer is selected from phosphorus-doped polysilicon, phosphorus-doped amorphous silicon and phosphorus-doped microcrystalline silicon.
Wherein, the electroless plating method in S5 is to deposit a nickel alloy layer on the phosphorus doped amorphous silicon under the induction of an optical field, an electric field or a sensitizer;
in the embodiment of the invention, the preparation method of the silicon oxide is selected from any one of the following technologies: wet chemical oxidation, high temperature oxidation, plasma assisted oxidation, ozone oxidation, and plasma assisted atomic layer deposition.
Specifically, the previous process treatment in S1 comprises removing impurities and mechanical damage on the surface of a silicon wafer, and forming pyramid suede on the front surface; etching the back surface of the monocrystalline silicon piece to form a polished surface; the surface contacted by the P-type back surface tunneling oxidation passivation is cleaned by an acid solution, wherein the surface comprises a front surface and a back surface, so that the surface oxide layer is removed.
The acid solution is one or two mixtures of HF and HCl, and the surface of the P-type monocrystalline silicon wafer comprises the surface of the P-type silicon wafer, the P+ surface of the P-type silicon wafer after boron heavy doping and the P-type surface of the N-type silicon wafer after boron doping;
the P-type monocrystalline silicon wafer is a commercially available product.
Further, preparing the ultrathin tunneling oxide layer specifically comprises oxidizing the back polishing surface by adopting concentrated nitric acid oxidation, ozone oxidation or thermal oxidation; alternatively, the silicon oxide film can be obtained on the tunneling oxide layerAdopts HNO3 method, ozone method and UV/O method 3 A process and a thermal oxidation process.
In the embodiment of the invention, the oxidation treatment specifically comprises oxidizing the surface of a silicon wafer by adopting concentrated nitric acid with the mass concentration of 65-75%, controlling the temperature to be 20-120 ℃ and the reaction time to be not more than 10min, thus finishing the oxidation of the concentrated nitric acid; oxidizing the surface of the silicon wafer by adopting ozone with the concentration of 10-500 ppm, controlling the temperature to be 20-100 ℃ and the reaction time to be not more than 10min, thus finishing ozone oxidation; heating the surface of the silicon wafer in an oxygen or nitrogen-oxygen mixed gas atmosphere, controlling the oxygen volume concentration to be 10% -100%, controlling the temperature to be 500-800 ℃ and the time to be not more than 30min, and completing thermal oxidation.
Further, depositing a polysilicon film layer on the ultrathin tunneling oxide layer by using a chemical vapor deposition method;
in the embodiment of the invention, the thickness of the ultrathin tunneling oxide layer is not more than 2nm; the deposition thickness of the polysilicon film layer is 20nm-2um.
Wherein the chemical vapor deposition method comprises a plasma enhanced chemical vapor deposition method or a low pressure chemical vapor deposition method, and the gas source is preferably high-purity SiH 4 。
Preferably, the boron doping treatment in S4 specifically comprises passing BBr on the surface of the P-type monocrystalline silicon piece 3 Performing boron doping treatment on the polycrystalline silicon film layer by using liquid diffusion source heat to generate a boron doped silicon film layer with a field passivation effect; wherein the boron atom doping concentration of the boron doping treatment is 1×10 19 -1×10 22 cm -3 。
Further, after the boron doping treatment, the preparation method further comprises the steps of removing borosilicate glass on the surface of the polycrystalline silicon film layer and removing the ultrathin tunneling oxide layer and the polycrystalline silicon film layer which are plated around the front surface.
Specifically, the first passivation anti-reflection layer is formed by depositing aluminum oxide and silicon nitride passivation anti-reflection layer on the boron-doped silicon thin layer by adopting a plasma enhanced chemical vapor deposition method; the second passivation anti-reflection layer is a silicon oxide and silicon nitride film layer formed on the front surface of the monocrystalline silicon wafer after phosphorus diffusion. The silicon oxide film used for the tunnel oxide layer used in the present invention may also be selected from aluminum oxide, molybdenum oxide, tungsten oxide, or titanium oxide.
The phosphorus diffusion in S6 specifically comprises the step of passing POCl (point of care interface) on the surface of the P-type monocrystalline silicon piece after the removal of the coiling plating 3 The liquid diffusion source heat performs phosphorus diffusion on the front surface to form an emitter PN junction.
Further, after phosphorus diffusion, a selective emitter is manufactured on the front surface of the silicon wafer in a laser doping mode, heavy doping is formed at the grid line, and light doping is formed at the outer position of the grid line, so that open-circuit voltage, short-circuit current and filling factor are further improved.
After phosphorus diffusion, the front phosphosilicate glass is removed to remove dead layers and edge leakage and to reduce dead layers to reduce recombination centers.
In the embodiment of the invention, the specific mode of boron doping comprises the steps of depositing a silicon layer by utilizing a chemical vapor deposition method, and simultaneously introducing a boron-containing gas source to directly form an in-situ doped silicon layer, wherein the doped boron source is high-purity borane; or depositing undoped intrinsic silicon thin layer by chemical vapor deposition method, and then passing through subsequent BBr 3 Or BCl 3 And (5) performing diffusion doping and ion implantation boron doping to realize boron doping.
Further, the silicon wafer is subjected to oxidation annealing on the boron-doped silicon thin layer, so that the microstructure and performance of the silicon layer are further improved; the temperature of the oxidation annealing is 600-1000 ℃, the time is 10-60 min, the annealing process is carried out in nitrogen-oxygen mixed gas, and the volume concentration of oxygen is 10-100%.
In the embodiment of the invention, the thickness of the silicon nitride passivation anti-reflection layer is 50-200nm.
Preferably, the printed metal electrode is screen printed, ag or Ag/Al paste is printed, and the electrode is fabricated and sintered.
Compared with the prior art, the invention has the following beneficial effects,
1. the invention provides a complete and feasible manufacturing process route of the P-type tunneling oxidation passivation contact solar cell, and is matched with the existing solar energy production process of the back contact of the P-type passivation emitter;
2. according to the invention, a silicon dioxide layer is formed on the front surface of the silicon wafer by using Low Pressure Chemical Vapor Deposition (LPCVD) or Plasma Enhanced Chemical Vapor Deposition (PECVD), and then an N-type heavily doped polysilicon layer is formed on the silicon dioxide layer, so that the composite loss of a metal contact area is reduced; in addition, atomic Layer Deposition (ALD) is carried out on the back of the silicon wafer to form an aluminum oxide layer, and then Plasma Enhanced Chemical Vapor Deposition (PECVD) is carried out on the aluminum oxide layer to form a silicon nitride layer, so that a large amount of fixed charge field passivation effect is provided by the surface dangling bond of an atomic state hydrogen saturated substrate, and further higher short circuit current is kept, the open circuit voltage is increased, the filling factor is improved, and the conversion efficiency of the battery is improved;
3. the invention adopts the technological method of doping the polysilicon film with boron on the back and diffusing phosphorus on the front, thereby effectively avoiding the secondary diffusion of phosphorus and further generating the phenomenon of mismatching of sheet resistance; the method of boron doping and phosphorus diffusion can be matched with the process of manufacturing the selective emitter by laser doping;
4. the manufacturing simple process for manufacturing the P-type tunneling oxidation passivation contact solar energy has the advantages of simple and easy operation steps and strong operability;
5. in the manufacturing process of the battery, the front surface can be plated with the aluminum oxide and the silicon nitride films, the contact resistance can be good through process adjustment, and the sintering window can be widened, so that the conversion efficiency of the P-type tunneling oxidation passivation contact solar battery can be improved;
6. the boron doping is realized by adopting a diffusion machine after the back surface of the polysilicon film is plated, or the amorphous silicon film is firstly manufactured and is annealed at high temperature after in-situ doping, so that the conversion from the amorphous silicon film to the polysilicon film can be realized, and the boron doping can be realized at the same time; the boron doped polysilicon film can be realized by using diffusion equipment, and boron doping can also be realized by an ion implantation mode, so that the boron doped polysilicon film is compatible with various existing processes.
7. According to the back structure of the battery, the phosphorus doped silicon film layer is deposited on the boron doped polysilicon, the nickel alloy layer which can block aluminum and provide good contact is deposited on the surface of the phosphorus doped silicon film layer, the diffusion and deposition rate of nickel in crystalline silicon are small, most of nickel can form larger particles to be deposited on the surface of the phosphorus doped silicon film surface, the performance of the battery cannot be influenced, the nickel alloy layer is quite compact, penetration of aluminum can be effectively blocked, and therefore the battery is guaranteed to have good passivation performance.
Claims (10)
1. The preparation method of the P-type back tunneling oxidation passivation contact solar cell is characterized by comprising the following steps of:
s1, performing previous process treatment on the front surface and the back surface of a P-type monocrystalline silicon piece;
s2, oxidizing the back surface of the monocrystalline silicon piece treated by the previous procedure to form an ultrathin tunneling oxide layer;
s3, preparing a polycrystalline silicon film layer on the ultrathin tunneling oxide layer;
s4, performing boron doping treatment on the polycrystalline silicon film layer, and forming a boron doped silicon film layer on the back surface;
s5, forming a phosphorus doped silicon thin film layer and a first passivation anti-reflection layer on the boron doped silicon thin layer;
the first passivation anti-reflection layer is formed by depositing aluminum oxide and silicon nitride passivation anti-reflection layer on the boron-doped silicon thin layer by adopting a plasma enhanced chemical vapor deposition method;
s6, performing phosphorus diffusion on the front surface of the monocrystalline silicon piece, and manufacturing a selective emitter;
s7, forming a second passivation anti-reflection layer on the front surface of the monocrystalline silicon piece after phosphorus diffusion; the second passivation anti-reflection layer is a silicon oxide and silicon nitride film layer formed on the front surface of the monocrystalline silicon wafer after phosphorus diffusion; forming an N-type heavily doped polycrystalline silicon layer on the basis of the second passivation anti-reflection layer;
s8, printing metal electrodes on the surfaces of the first passivation antireflection layer on the back surface and the second passivation antireflection layer on the front surface of the monocrystalline silicon wafer, and forming good contact between the metal electrodes and the monocrystalline silicon wafer, namely finishing the P-type back tunneling oxidation passivation contact of the solar cell;
and an Ag gate finger electrode is arranged in the front silicon nitride film layer, and the Ag gate finger electrode corresponds to the N-type heavily doped polysilicon layer and forms ohmic contact.
2. The method for manufacturing a P-type back surface tunneling oxide passivation contact solar cell according to claim 1, wherein the previous process treatment in S1 comprises removing impurities and mechanical damages on the surface of a silicon wafer, and forming pyramid suede on the front surface; etching the back surface of the monocrystalline silicon wafer to remove P doped N on the back surface of the silicon wafer + Junction and polishing the back surface; cleaning the surface of the P-type back surface tunneling oxidation passivation contact by using an acid solution, and removing a surface oxide layer;
the acid solution is one or two mixtures of HF and HCl, and the surface of the P-type monocrystalline silicon wafer comprises the surface of the P-type silicon wafer, the P+ surface of the P-type silicon wafer after boron heavy doping and the P-type surface of the N-type silicon wafer after boron doping.
3. The method for manufacturing a P-type back surface tunneling oxidation passivation contact solar cell according to claim 1, wherein the main component of the nickel alloy layer is one or more selected from the group consisting of nickel, nickel-phosphorus alloy, nickel-boron alloy;
the nickel alloy layer is doped with one or more microelements of chromium, copper, tin, silver and sulfur, and the doping amount is 0.01-1%;
the thickness of the silicon oxide layer is 1-2 nm, the thickness of the boron doped polysilicon layer is 20-200 nm, the thickness of the phosphorus doped silicon film layer is 20-500 nm, the thickness of the nickel alloy layer is 20-10000 nm, and the thickness of the aluminum electrode layer is 100-20000 nm;
the phosphorus-doped silicon film layer is selected from phosphorus-doped polysilicon, phosphorus-doped amorphous silicon and phosphorus-doped microcrystalline silicon.
4. The method for preparing the P-type back surface tunneling oxide passivation contact solar cell according to claim 1, wherein the preparing method specifically comprises preparing an ultrathin tunneling oxide layer on the back surface polished surface by oxidizing with concentrated nitric acid, ozone or thermal oxidation and depositing a polysilicon thin film layer on the ultrathin tunneling oxide layer by using a chemical vapor deposition method;
the thickness of the ultrathin tunneling oxide layer is not more than 2nm; the deposition thickness of the polysilicon film layer is 20nm-2um;
the chemical vapor deposition method comprises a plasma enhanced chemical vapor deposition method or a low pressure chemical vapor deposition method, and the gas source is high-purity SiH 4 。
5. The method for preparing the P-type back tunneling oxidation passivation contact solar cell according to claim 4, wherein the oxidation treatment specifically comprises oxidizing the surface of a silicon wafer by using concentrated nitric acid with a mass concentration of 65% -75%, controlling the temperature to be 20-120 ℃ and the reaction time to be not more than 10min, and completing the oxidation of the concentrated nitric acid; oxidizing the surface of the silicon wafer by adopting ozone with the concentration of 10-500 ppm, controlling the temperature to be 20-100 ℃ and the reaction time to be not more than 10min, thus finishing ozone oxidation; heating the surface of the silicon wafer in an oxygen or nitrogen-oxygen mixed gas atmosphere, controlling the oxygen volume concentration to be 10% -100%, controlling the temperature to be 500-800 ℃ and the time to be not more than 30min, and completing thermal oxidation.
6. The method for preparing a P-type back surface tunneling oxidation passivation contact solar cell according to claim 1, wherein the boron doping treatment in S4 specifically comprises passing BBr on the surface of a P-type monocrystalline silicon wafer 3 Performing boron doping treatment on the polycrystalline silicon film layer by using liquid diffusion source heat to generate a boron doped silicon film layer with a field passivation effect;
the boron atom doping concentration of the boron doping treatment is 1 multiplied by 10 19 -1×10 22 cm -3 。
7. The method of claim 1, further comprising removing borosilicate glass from the surface of the polysilicon film layer and removing the ultra-thin tunneling oxide layer and polysilicon film layer that are wrapped around the front surface after the boron doping process.
8. The method for manufacturing a P-type back surface tunneling oxide passivation contact solar cell according to claim 1, wherein the electroless plating method in S5 is to deposit a nickel alloy layer on the phosphorus doped amorphous silicon under the induction of an optical field, an electric field or a sensitizer;
the preparation method of the silicon oxide is selected from any one of the following technologies: wet chemical oxidation, high temperature oxidation, plasma assisted oxidation, ozone oxidation, and plasma assisted atomic layer deposition.
9. The method for manufacturing a P-type back surface tunneling oxide passivation contact solar cell according to claim 1, wherein the phosphorus diffusion in S6 specifically comprises passing POCl over the surface of the P-type monocrystalline silicon wafer after removal of the wrap-around plating 3 The liquid diffusion source heat performs phosphorus diffusion on the front surface to form an emitter PN junction.
10. The method of claim 1, further comprising removing the phosphosilicate glass of the front side after phosphorus diffusion.
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| CN117199186A (en) * | 2023-09-27 | 2023-12-08 | 淮安捷泰新能源科技有限公司 | Manufacturing method of N-TOPCON battery |
| CN117457757A (en) * | 2023-10-18 | 2024-01-26 | 西安隆基乐叶光伏科技有限公司 | Solar cell and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117199186A (en) * | 2023-09-27 | 2023-12-08 | 淮安捷泰新能源科技有限公司 | Manufacturing method of N-TOPCON battery |
| CN117457757A (en) * | 2023-10-18 | 2024-01-26 | 西安隆基乐叶光伏科技有限公司 | Solar cell and manufacturing method thereof |
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