CN115148830A - Solar cell and preparation method thereof - Google Patents
Solar cell and preparation method thereof Download PDFInfo
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- CN115148830A CN115148830A CN202210799290.5A CN202210799290A CN115148830A CN 115148830 A CN115148830 A CN 115148830A CN 202210799290 A CN202210799290 A CN 202210799290A CN 115148830 A CN115148830 A CN 115148830A
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- 238000002161 passivation Methods 0.000 claims abstract description 108
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- 239000000758 substrate Substances 0.000 claims abstract description 73
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- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 claims abstract description 37
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims description 24
- 239000011574 phosphorus Substances 0.000 claims description 24
- 230000005641 tunneling Effects 0.000 claims description 23
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 22
- 229910052796 boron Inorganic materials 0.000 claims description 22
- 238000009792 diffusion process Methods 0.000 claims description 22
- 238000007650 screen-printing Methods 0.000 claims description 18
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- 238000000034 method Methods 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
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- 230000000295 complement effect Effects 0.000 claims description 6
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- 238000001035 drying Methods 0.000 claims description 5
- 238000005468 ion implantation Methods 0.000 claims description 5
- 238000001659 ion-beam spectroscopy Methods 0.000 claims description 5
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 claims description 3
- 238000000231 atomic layer deposition Methods 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
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- 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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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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
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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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Abstract
The invention provides a solar cell and a preparation method thereof, wherein the solar cell comprises: an N-type single crystal silicon substrate; p is + The doping layer is arranged on the front surface of the N-type single crystal silicon substrate; a first HfOx1Ny passivation layer disposed on the P + On the doped layer; a tetracene capping layer disposed on the first HfOx1Ny passivation layer; and a first SiNx layer disposed on the tetracene capping layer. According to the solar cell, through the tetracene coating technology, the HfOx1Ny passivation mode, the tetracene singlet exciton fission characteristic and the HfOx1Ny passivation layer, one photon can be achieved to excite two electrons, and the excellent passivation performance can be achieved, so that the photoelectric conversion efficiency of a cell piece can be further greatly improved, and the cell with excellent performance is obtained.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a solar cell and a preparation method thereof.
Background
In a solar cell, photons excite material molecules to release electrons, generating an electric current. Usually, only one electron can be excited by one photon, and the remaining energy of the high-energy photon is dissipated as heat. This greatly limits the photoelectric conversion efficiency of the solar cell. Furthermore, in order to ensure the efficiency and durability of the battery, the silicon material must have a surface passivation layer. Electrons generated in the excited material must pass through the passivation layer to reach the silicon material. Current passivation layers are too thick relative to the electron transport capability.
An Interdigital Back Contact (IBC) solar cell is one of the industrialized solar cells with the highest conversion efficiency at present, the cell takes N-type monocrystalline silicon as a substrate, a p-N junction and a metal electrode are all arranged on the back of the cell in an interdigital shape, the front side is not shaded by the electrode, the absorption of the cell to light is improved by surface texturing and an antireflection layer is added, and very high short-circuit current and photoelectric conversion efficiency are obtained.
The technical scheme of the existing IBC battery is as follows: firstly cleaning and texturing a silicon wafer, then carrying out antireflection and passivation treatment on the front surface of a battery, secondly forming a P-type emitter and an N-type Back Surface Field (BSF) on the back surface of the battery respectively through a mask technology, finally screen-printing a positive electrode and a negative electrode on the back surface of the battery, and finally preparing the battery piece through high-temperature sintering. The passivation of the back of the battery is realized by SiNx or silicon dioxide, a Topcon passivation structure is not superposed, the passivation effect of the back of the battery is general, and dark saturation current is large.
On the P-type emitter electrode surface of the N-type crystalline silicon battery, an aluminum oxide layer capable of fixing negative charges is formed on silicon atoms on the surface, so that a good field passivation effect can be realized; meanwhile, the material has lower defect density and higher charge density. However, the use of an aluminum oxide layer to achieve the field passivation effect has the following disadvantages: first, TMA (trimethylaluminum) precursors are used in the deposition of aluminum oxide layers, which are hazardous, having a toxicity rating of 3, a flammability rating of 3, and an explosiveness rating of 3. Secondly, the deposition preparation of the aluminum oxide layer needs heat treatment, and a better passivation effect is realized through an annealing condition, wherein the annealing temperature is usually 500-600 ℃; for thin film batteries or low temperature batteries, the ambient temperature is generally required to be lower than 350 ℃, and if the battery is annealed at a temperature of 500-600 ℃, the battery performance is influenced. Thus, the search for other negative fixed charge passivating agents than alumina is a new task facing the field of photovoltaic cell technology.
Therefore, it is particularly desirable to provide a solar cell with high photoelectric conversion efficiency and good passivation effect.
Disclosure of Invention
In order to solve the problems existing in the prior art, the application provides a solar cell which is high in photoelectric conversion efficiency and good in passivation effect.
According to an aspect of the present application, there is provided a solar cell including: an N-type single crystal silicon substrate; p + The doping layer is arranged on the front surface of the N-type monocrystalline silicon substrate; a first HfOx1Ny passivation layer disposed on the P + On the doped layer; a tetracene capping layer disposed on the first HfOx1Ny passivation layer; and a first SiNx layer disposed on the tetracene capping layer; wherein, in the first HfOx1Ny passivation layer, x1 can be 1-6,y can be 0-8.
Optionally, the solar cell further comprises: a tunneling oxide layer arranged on the back surface of the N-type monocrystalline silicon substrate; a second HfOx1Ny passivation layer disposed on the tunneling oxide layer; the second SiNx layer is arranged on the second HfOx1Ny passivation layer; wherein at least one opening extending through the second HfOx1Ny passivation layer and the second SiNx layer is provided in the second HfOx1Ny passivation layer and the second SiNx layer, and in the second HfOx1Ny passivation, x1 may be 1-6,y may be 0-8.
Optionally, the solar cell further comprises: positive electrodes and negative electrodes which are arranged at intervals; the positive electrode is arranged on the second SiNx layer; the negative electrode is disposed on the tunneling oxide layer and in the at least one opening; and an N + layer is further disposed between the negative electrode and the tunneling oxide layer, the N + layer being disposed in the at least one opening.
Alternatively, the thickness of the N-type single crystal silicon substrate is 100 to 160 μm, for example, the thickness of the N-type single crystal silicon substrate may be 100, 110, 120, 130, 140, 150, 160 μm or any value therebetween. The N-type single crystal silicon substrate has a resistivity of 0.4-10 Ω/□, for example, the N-type single crystal silicon substrate can have a resistivity of 0.4, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 Ω -cm or any value therebetween; p + The doped layer is a boron-doped monocrystalline silicon layer, and the square resistance of the P + doped layer is 100-160 Ω/□, such as P + The sheet resistance of the doped layers can be 100, 110, 120, 130, 140, 150, 160 Ω/□ or any value in between; and a P-N junction is formed between the P + doped layer and the N-type single crystal silicon substrate, the junction depth is 0.1-1.3 μm, for example, the junction depth can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2 or 1.3 μm or any value therebetween; the thickness of each of the first and second HfOx1Ny passivation layers is in the range of 0.2 to 1.4nm, for example, the thickness of each of the first and second HfOx1Ny passivation layers may be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4nm or any value therebetween; and the thicknesses of the first HfOx1Ny passivation layer and the second HfOx1Ny passivation layer may be the same or different; the thickness of the tetracene coating is 50-200nm, for example, the thickness of the tetracene coating can be 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200nm or any value therebetween; the thicknesses of the first SiNx layer and the second SiNx layer are 40-80nm, for example, the thicknesses of the first SiNx layer and the second SiNx layer can be 40, 50, 60, 70 and 80nm or any value between the thicknesses; the refractive index of the first and second SiNx layers is 1.8-2.5, for example, the refractive index of the first and second SiNx layers may be 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5 or any value therebetween. The tunneling oxide layer comprises a silicon oxide layer and a boron-doped polysilicon layer, the thickness of the silicon oxide layer is 0.5-2nm, for example, the thickness of the silicon oxide layer may be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.41.5, 1.6, 1.7, 1.8, 1.9, 2nm or any value in between. The thickness of the boron-doped polysilicon layer is 50-200nm, for example, the thickness of the boron-doped polysilicon layer may be 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200nm or any value therebetween. The N + layer is a phosphorus-containing layer.
According to another aspect of the present application, there is also provided a method of manufacturing a solar cell according to the first aspect of the present application, comprising the steps of: a) Treating a front side of an N-type single crystal silicon substrate to form P on the N-type single crystal silicon substrate + Doping the layer; b) Depositing a silicon oxide layer and a boron-doped polycrystalline silicon layer on the back of the N-type monocrystalline silicon substrate in sequence to form a tunneling oxide layer; c) At the P + Depositing HfOx1Ny on the doped layer and the tunnel oxide layer respectively to form a layer on the P + A first HfOx1Ny passivation layer on the doped layer and a second HfOx1Ny passivation layer on the tunneling oxide layer; d) Depositing a tetrabenzene layer on the first HfOx1Ny passivation layer; e) And respectively depositing SiNx on the tetracene layer and the second HfOx1Ny passivation layer to respectively form a first SiNx layer on the tetracene layer and a second SiNx layer on the second HfOx1Ny passivation layer.
Optionally, the method for manufacturing a solar cell further comprises the following steps: f) Sequentially printing etching slurry, phosphorus slurry and aluminum slurry in a grid line preset area on the surface of the second SiNx layer in a screen printing mode to form a negative electrode; g) Printing silver paste on the region, complementary to the preset grid line region, on the surface of the second SiNx layer in a screen printing mode to form a positive electrode; h) Annealing the solar cell after forming the positive electrode and the negative electrode.
Optionally, the front side of the N-type single crystal silicon substrate is treated to form P on the N-type single crystal silicon substrate + The step of doping the layer further comprises: a1 Carrying out double-sided texturing treatment on the N-type single crystal silicon substrate; a2 Implanting boron into the front surface of the N-type single crystal silicon substrate using an ion implantation method using a low pressure high temperature diffusion furnace and performing boron diffusion to form the P + doped layer; wherein: diffusion temperatureThe temperature is 800-1100 ℃; the diffusion time is 10-50 minutes; and a P-N junction is formed between the P + doped layer and the N-type monocrystalline silicon substrate. For example, the diffusion temperature may be 800, 900, 1000, 1100 ℃, or any temperature value therebetween; the diffusion time may be 10, 20, 30, 40, 50 minutes or any value in between.
In the step, the light absorption effect of the prepared whole solar cell can be increased and the light reflection can be reduced through the double-sided texturing treatment.
Optionally, in the step B), depositing the silicon oxide layer and the boron-doped polysilicon layer using at least one of LPCVD (low pressure chemical vapor deposition), PECVD (plasma enhanced chemical vapor deposition), APCVD (atmospheric pressure chemical vapor deposition), and thermal nitric acid; in the step C), the first HfOx1Ny passivation layer and the second HfOx1Ny passivation layer are deposited using at least one of ion beam sputtering, ALD (atomic layer deposition), magnetron sputtering, and PECVD; in the step D) above, the layer of pyromellitic dianhydride is deposited using a CVD method or a wet chemical method; in the step E), the first and second SiNx layers are deposited using a PECVD method.
Optionally, in the step F), the etching paste is an HF paste, and after printing the HF paste, at least one opening extending through the second HfOx1Ny passivation layer and the second SiNx layer is etched in the second HfOx1Ny passivation layer and the second SiNx layer; after the etching slurry is printed and before the phosphorus slurry is printed, a cleaning step is carried out to remove the redundant HF slurry and the damaged second HfOx1Ny passivation layer and the second SiNx layer; drying by using an oven between each printing step of printing the etching slurry, the phosphorus slurry and the aluminum slurry in sequence; the line width of an etched area of the HF slurry is 10-80 mu m, and the mass concentration of HF in the HF slurry is 5-40%.
Alternatively, the etched area linewidth of the HF paste may be 10, 20, 30, 40, 50, 60, 70, 80 μm or any value therebetween; the mass concentration of HF in the HF slurry can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, or any value therebetween.
Optionally, in the step H), annealing the solar cell includes: and sintering the solar cell in a sintering furnace, wherein the sintering annealing temperature is 600-1000 ℃, for example, the sintering annealing temperature is 600, 700, 800, 900, 1000 ℃ or any value therebetween.
The "phosphorous paste", "aluminum paste" and "silver paste" herein are commonly used pastes for forming batteries, which are well known to those of ordinary skill in the art and will not be described in detail herein. In addition, as used herein, an "HF paste" is a paste having HF as a main component and water as a solvent, and it will be understood by those skilled in the art that other auxiliary components similar to those in "phosphorous paste", "aluminum paste" and "silver paste" may be included in the "HF paste".
In addition, screen printing etching slurry, namely coating HF slurry (which has corrosiveness and can be used as an etchant) on a preset grid line area on the surface of the N-type monocrystalline silicon substrate in a screen printing mode; the screen printing plate design is complementary with the electrode printing screen printing plate, and the grid line part is hollowed out, so that an etching slurry layer with a corresponding pattern is formed on the surface of the N-type monocrystalline silicon substrate.
The technical scheme adopted by the invention can achieve the following beneficial effects:
1) According to the solar cell, through the tetracene coating technology, the HfOx1Ny passivation mode, the tetracene singlet exciton fission characteristic and the HfOx1Ny passivation layer, one photon can be achieved to excite two electrons, and the excellent passivation performance can be achieved, so that the photoelectric conversion efficiency of a cell piece can be further greatly improved, and the cell with excellent performance is obtained.
2) According to the solar cell, the HfOx1Ny passivation layer is adopted to replace a traditional aluminum oxide passivation layer, so that potential safety hazards caused by the use of a trimethylaluminum precursor are avoided, and the preparation process is high in safety.
3) The HfOx1Ny passivation layer prepared in the present application has a thickness in the range of 0.2-1.4nm, which is thinner than conventional passivation layers, facilitating electrons generated in tetracene to pass through the passivation layer.
4) The method has the advantages that the HF slurry is adopted for etching to replace a back laser grooving technology, the cost is low, the safety is good, and the etching depth can be accurately controlled by adjusting the concentration and the using amount of the HF slurry.
5) The application provides an IBC battery suitable for TOPCon and HfOx1Ny structures, and the IBC battery is high in photoelectric conversion efficiency and good in passivation performance.
Drawings
Fig. 1 is a schematic structural view of a solar cell according to an embodiment of the present invention.
Fig. 2 is a flowchart of a method of fabricating a solar cell according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the 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.
Example 1
As shown in the flow chart of fig. 2, an Interdigitated Back Contact (IBC) solar cell is prepared by the following steps:
step 1, carrying out double-sided texturing on an N-type monocrystalline silicon substrate: selecting an N-type monocrystalline silicon wafer as a substrate (namely, an N-type monocrystalline silicon substrate), and performing double-sided texturing treatment, wherein the thickness of the N-type monocrystalline silicon wafer is 130 mu m, and the resistivity is 0.4-1.2 omega cm;
step 2, implanting boron into the front surface of the N-type single crystal silicon substrate and performing boron diffusion to form P + Doping layer: injecting boron into the front surface of the N-type single crystal silicon substrate by using a low-pressure high-temperature diffusion furnace and an ion implantation method, and performing boron diffusion at the diffusion temperature of 1000 ℃ for 50 minutes to form a boron-doped single crystal silicon layer which is P + Doped layer of P + The square resistance of the doped layer is 130 omega/□, P + Doping layer and N-typeP-n junctions are formed among the monocrystalline silicon substrates, and the junction depth is 1 mu m;
step 3, depositing an oxide layer and a boron-doped polysilicon layer on the back of the N-type monocrystalline silicon substrate in sequence: depositing a silicon oxide layer and a boron-doped polycrystalline silicon layer on the back of the N-type monocrystalline silicon substrate in sequence by using LPCVD equipment to form a tunneling oxide layer; in the step, a boron-doped polysilicon layer can be formed by depositing a polysilicon layer firstly and then implanting boron into ions of the polysilicon layer, wherein the thickness of the formed silicon oxide layer is 1.6nm, and the thickness of the formed boron-doped polysilicon layer is 100nm;
and 4, respectively depositing HfOx1Ny passivation layers on the front surface and the back surface of the N-type single crystal silicon substrate: at P + Depositing HfOxNy on the doped layer and the tunneling oxide layer by ion beam sputtering to form a P-type metal layer + The first HfOx1Ny passivation layer and the second HfOx1Ny passivation layer are positioned on the tunneling oxide layer, and the film thickness of the first HfOx1Ny passivation layer and the film thickness of the second HfOx1Ny passivation layer which are deposited in the step are both 0.2nm;
and 5, depositing a tetracene film on the front surface of the N-type monocrystalline silicon substrate: depositing a tetracene thin film on the first HfOx1Ny passivation layer formed in the step 4 by using a CVD (chemical vapor deposition) device, wherein the film thickness of the formed tetracene thin film is 50nm;
step 6, depositing SiNx films on the front surface and the back surface of the N-type monocrystalline silicon substrate respectively: respectively depositing SiNx on the tetracene layer and the second HfOx1Ny passivation layer by using PECVD equipment to respectively form a first SiNx layer on the tetracene layer and a second SiNx layer on the second HfOx1Ny passivation layer, wherein the film thickness of the first SiNx layer and the film thickness of the second SiNx layer are 80nm, and the refractive index of the first SiNx layer and the second SiNx layer is 2.0;
and 7, sequentially printing HF etching slurry, phosphorus slurry and aluminum slurry on the back of the N-type single crystal silicon substrate to form a negative electrode: sequentially printing etching slurry, phosphorus slurry and aluminum slurry in a grid line region preset on the surface of the second SiNx layer in a screen printing mode to form a negative electrode; at least one opening extending through the second HfOx1Ny passivation layer and the second SiNx layer may be etched by printing (i.e., coating) using a corrosive HF paste as an etching paste in this step; by printing phosphor paste, N is formed + A layer;
after the etching slurry is printed and before the phosphorus slurry is printed, a cleaning step is needed to remove the redundant HF slurry and the damaged second HfOx1Ny passivation layer and the second SiNx layer; drying by using an oven between each printing step of printing the etching slurry, the phosphorus slurry and the aluminum slurry in sequence;
the line width of an etched area of the HF slurry is controlled to be 40 mu m, and the mass concentration of HF in the HF slurry is 20%;
step 8, screen printing silver paste on the back of the N-type monocrystal silicon substrate to form a positive electrode: printing silver paste on a region, complementary to the preset grid line region, on the surface of the second SiNx layer in a screen printing mode to form a positive electrode;
and 9, putting the solar cell into a sintering furnace for annealing to activate boron and phosphorus and sintering, wherein the sintering annealing temperature is 800 ℃, and the IBC solar cell is prepared. The resulting structure is shown in fig. 1, in which an opening extending through the second HfOx1Ny passivation layer and the second SiNx layer is etched by HF etching paste and N is formed in the opening by printing phosphor paste + None of the layers are shown in fig. 1.
Example 2
As shown in the flow chart of fig. 2, an Interdigitated Back Contact (IBC) solar cell is prepared by the following steps:
step 1, carrying out double-sided texturing on an N-type monocrystalline silicon substrate: selecting an N-type monocrystalline silicon wafer as a substrate (namely an N-type monocrystalline silicon substrate), and performing double-sided texturing treatment, wherein the thickness of the N-type monocrystalline silicon wafer is 130 mu m, and the resistivity is 0.4-1.2 omega cm;
step 2, implanting boron into the front surface of the N-type single crystal silicon substrate and performing boron diffusion to form P + Doping layer: injecting boron into the front surface of the N-type single crystal silicon substrate by using a low-pressure high-temperature diffusion furnace and an ion implantation method, and performing boron diffusion at the diffusion temperature of 1000 ℃ for 50 minutes to form a boron-doped single crystal silicon layer which is P + Doping layer, P + The square resistance of the doped layer is 130 omega/□, P + A p-N junction is formed between the doping layer and the N-type monocrystalline silicon substrate, and the junction depth is 1 mu m;
and 3, sequentially depositing an oxide layer and a boron-doped polycrystalline silicon layer on the back of the N-type monocrystalline silicon substrate: depositing a silicon oxide layer and a boron-doped polycrystalline silicon layer on the back of the N-type monocrystalline silicon substrate in sequence by using LPCVD equipment to form a tunneling oxide layer; in the step, a boron-doped polysilicon layer can be formed by depositing a polysilicon layer firstly and then implanting boron into ions of the polysilicon layer, wherein the thickness of the formed silicon oxide layer is 1.6nm, and the thickness of the formed boron-doped polysilicon layer is 100nm;
and 4, respectively depositing HfOx1Ny passivation layers on the front surface and the back surface of the N-type single crystal silicon substrate: at P + Depositing HfOxNy on the doped layer and the tunneling oxide layer by ion beam sputtering respectively to form a layer located on P + The first HfOx1Ny passivation layer and the second HfOx1Ny passivation layer are positioned on the tunneling oxide layer, and the film thickness of the first HfOx1Ny passivation layer and the film thickness of the second HfOx1Ny passivation layer which are deposited in the step are both 0.4nm;
and 5, depositing a tetracene film on the front surface of the N-type monocrystalline silicon substrate: depositing a tetracene thin film on the first HfOx1Ny passivation layer formed in the step 4 by using a CVD (chemical vapor deposition) device, wherein the film thickness of the formed tetracene thin film is 100nm;
step 6, depositing SiNx films on the front surface and the back surface of the N-type monocrystal silicon substrate respectively: respectively depositing SiNx on the tetracene layer and the second HfOx1Ny passivation layer by using PECVD equipment to respectively form a first SiNx layer on the tetracene layer and a second SiNx layer on the second HfOx1Ny passivation layer, wherein the film thickness of the first SiNx layer and the film thickness of the second SiNx layer are 80nm, and the refractive index of the first SiNx layer and the second SiNx layer is 2.0;
and 7, sequentially printing HF etching slurry, phosphorus slurry and aluminum slurry on the back of the N-type single crystal silicon substrate to form a negative electrode: sequentially printing etching slurry, phosphorus slurry and aluminum slurry in a grid line region preset on the surface of the second SiNx layer in a screen printing mode to form a negative electrode; at least one opening extending through the second HfOx1Ny passivation layer and the second SiNx layer may be etched by printing (i.e., coating) using a corrosive HF paste as an etching paste in this step; by printing phosphor paste, N is formed + A layer;
after the etching slurry is printed and before the phosphorus slurry is printed, a cleaning step is needed to remove the redundant HF slurry and the damaged second HfOx1Ny passivation layer and the second SiNx layer; drying by using an oven between each printing step of printing the etching slurry, the phosphorus slurry and the aluminum slurry in sequence;
the line width of an etched area of the HF slurry is controlled to be 40 mu m, and the mass concentration of HF in the HF slurry is 20 percent;
step 8, screen printing silver paste on the back of the N-type monocrystal silicon substrate to form a positive electrode: printing silver paste on a region, complementary to the preset grid line region, on the surface of the second SiNx layer in a screen printing mode to form a positive electrode;
and 9, putting the solar cell into a sintering furnace to anneal, activate boron and phosphorus and sinter, wherein the sintering annealing temperature is 800 ℃, and thus the IBC solar cell is manufactured. The resulting structure is shown in fig. 1, in which an opening extending through the second HfOx1Ny passivation layer and the second SiNx layer is etched by HF etching paste and N is formed in the opening by printing phosphor paste + None of the layers are shown in fig. 1.
Example 3
As shown in the flow chart of fig. 2, an Interdigitated Back Contact (IBC) solar cell was prepared as follows:
step 1, carrying out double-sided texturing on an N-type monocrystalline silicon substrate: selecting an N-type monocrystalline silicon wafer as a substrate (namely an N-type monocrystalline silicon substrate), and performing double-sided texturing treatment, wherein the thickness of the N-type monocrystalline silicon wafer is 130 mu m, and the resistivity is 0.4-1.2 omega cm;
step 2, implanting boron into the front surface of the N-type single crystal silicon substrate and performing boron diffusion to form P + Doping layer: injecting boron into the front surface of the N-type single crystal silicon substrate by using a low-pressure high-temperature diffusion furnace and an ion implantation method, and performing boron diffusion at the diffusion temperature of 1000 ℃ for 50 minutes to form a boron-doped single crystal silicon layer, namely P + Doping layer, P + The square resistance of the doped layer is 130 omega/□, P + A p-N junction is formed between the doping layer and the N-type monocrystalline silicon substrate, and the junction depth is 1 mu m;
and 3, sequentially depositing an oxide layer and a boron-doped polycrystalline silicon layer on the back of the N-type monocrystalline silicon substrate: depositing a silicon oxide layer and a boron-doped polycrystalline silicon layer on the back of the N-type monocrystalline silicon substrate in sequence by using LPCVD equipment to form a tunneling oxide layer; in the step, a boron-doped polycrystalline silicon layer can be formed by depositing a polycrystalline silicon layer and then implanting boron into ions of the polycrystalline silicon layer, wherein the thickness of the formed silicon oxide layer is 1.6nm, and the thickness of the formed boron-doped polycrystalline silicon layer is 100nm;
and 4, respectively depositing HfOx1Ny passivation layers on the front surface and the back surface of the N-type single crystal silicon substrate: at P + Depositing HfOxNy on the doped layer and the tunneling oxide layer by ion beam sputtering respectively to form a layer located on P + The first HfOx1Ny passivation layer and the second HfOx1Ny passivation layer are positioned on the tunneling oxide layer, and the film thickness of the first HfOx1Ny passivation layer and the film thickness of the second HfOx1Ny passivation layer which are deposited in the step are both 0.6nm;
and 5, depositing a tetracene film on the front surface of the N-type monocrystalline silicon substrate: depositing a tetracene thin film on the first HfOx1Ny passivation layer formed in the step 4 by using a CVD (chemical vapor deposition) device, wherein the film thickness of the formed tetracene thin film is 150nm;
step 6, depositing SiNx films on the front surface and the back surface of the N-type monocrystal silicon substrate respectively: respectively depositing SiNx on the tetracene layer and the second HfOx1Ny passivation layer by using PECVD equipment to respectively form a first SiNx layer on the tetracene layer and a second SiNx layer on the second HfOx1Ny passivation layer, wherein the film thickness of the first SiNx layer and the film thickness of the second SiNx layer are 80nm, and the refractive index of the first SiNx layer and the second SiNx layer is 2.0;
and 7, sequentially printing HF etching slurry, phosphorus slurry and aluminum slurry on the back of the N-type single crystal silicon substrate to form a negative electrode: sequentially printing etching slurry, phosphorus slurry and aluminum slurry in a grid line region preset on the surface of the second SiNx layer in a screen printing mode to form a negative electrode; at least one opening extending through the second HfOx1Ny passivation layer and the second SiNx layer may be etched by printing (i.e., coating) using a corrosive HF paste as an etching paste in this step; by printing phosphorus paste, N is formed + A layer;
after the etching slurry is printed and before the phosphorus slurry is printed, a cleaning step is needed to remove the redundant HF slurry and the damaged second HfOx1Ny passivation layer and the second SiNx layer; drying by using an oven between each printing step of printing the etching slurry, the phosphorus slurry and the aluminum slurry in sequence;
the line width of an etched area of the HF slurry is controlled to be 40 mu m, and the mass concentration of HF in the HF slurry is 20 percent;
step 8, performing screen printing silver paste on the back surface of the N-type monocrystalline silicon substrate to form a positive electrode: printing silver paste on a region, complementary to the preset grid line region, on the surface of the second SiNx layer in a screen printing mode to form a positive electrode;
and 9, putting the solar cell into a sintering furnace for annealing to activate boron and phosphorus and sintering, wherein the sintering annealing temperature is 800 ℃, and the IBC solar cell is prepared. The resulting structure is shown in fig. 1, in which an opening extending through the second HfOx1Ny passivation layer and the second SiNx layer is etched by HF etching paste and N is formed in the opening by printing phosphor paste + None of the layers are shown in fig. 1.
Comparative example 1
All steps are the same as in example 1, except that step 5 was not performed, that is, no tetracene thin film was formed.
Comparative example 2
All the steps are the same as those of embodiment 1, except that the first and second HfOxNy passivation layers formed in step 4 are replaced with first and second aluminum oxide layers, respectively.
And (3) performance testing:
the photoelectric conversion efficiency of the IBC solar cells prepared in examples 1 to 3 and comparative example 1 was measured using an I-V tester, respectively, and the measurement results are shown in table 1.
The passivation effect of the IBC solar cells prepared in examples 1-3 and comparative example 2 was tested using Sinton, respectively, and the test results are shown in table 2.
TABLE 1
| Group of | Eta(％) | Voc(mV) | Isc(A) | FF(％) | Rsh(Ω) | Rs(mΩ) | IRev2(A) |
| Example 1 | 24.87 | 0.7146 | 13.798 | 83.28 | 1701 | 0.001 | 0.038 |
| Example 2 | 24.73 | 0.7087 | 13.775 | 83.61 | 653 | 0.001 | 0.110 |
| Example 3 | 24.67 | 0.7082 | 13.825 | 83.19 | 4654 | 0.001 | 0.009 |
| Comparative example 1 | 24.48 | 0.7093 | 13.714 | 83.07 | 6787 | 0.001 | 0.007 |
TABLE 2
| Group of | Lifetime_(us) | Jo_(A/cm 2 ) | Implied_Voc_(V) | Implied_FF_(％) |
| Example 1 | 2638 | 2.09E-14 | 0.7268 | 88.48 |
| Example 2 | 2519 | 2.12E-14 | 0.7263 | 88.37 |
| Example 3 | 2089 | 2.20E-14 | 0.7245 | 87.66 |
| Comparative example 2 | 1672 | 2.49E-14 | 0.7213 | 87.13 |
As can be seen from table 1 above, the photoelectric conversion efficiency of the cell can be greatly improved by using the tetracene capping layer in the present application compared to comparative example 1, and the photoelectric conversion efficiency (Eta) is 0.39% higher than that of comparative example 1, and the advantages of the open-circuit voltage (Voc) and the short-circuit current (Isc) are mainly apparent.
As can be seen from table 2 above, compared with comparative example 2, by using HfOx1Ny as the passivation layer in the present application, the minority carrier Lifetime (Lifetime) and the hidden open circuit voltage (i-Voc) are significantly increased, the saturation current density (J0) is also reduced, and the passivation performance is better.
In summary, the solar cell provided by the application can not only realize that one photon excites two electrons, but also realize excellent passivation performance through the tetracene coating technology, the HfOx1Ny passivation mode, the tetracene singlet exciton fission characteristic and the HfOx1Ny passivation layer, so that the photoelectric conversion efficiency of the cell can be further greatly improved, and the cell with excellent performance can be obtained.
In the above embodiments of the present invention, the difference between the embodiments is mainly described, and different optimization features between the embodiments can be combined to form a better embodiment as long as they are not contradictory, and further description is omitted here in view of brevity of the text.
The above description is only an example of the present invention, and is not intended to limit the present invention. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. A solar cell, comprising:
an N-type single crystal silicon substrate;
P + the doping layer is arranged on the front surface of the N-type single crystal silicon substrate;
a first HfOx1Ny passivation layer disposed on the P + On the doped layer;
a tetracene capping layer disposed on the first HfOx1Ny passivation layer; and
a first SiNx layer disposed on the tetracene capping layer.
2. The solar cell of claim 1, further comprising:
a tunneling oxide layer arranged on the back surface of the N-type monocrystalline silicon substrate;
the second HfOx1Ny passivation layer is arranged on the tunneling oxide layer;
the second SiNx layer is arranged on the second HfOx1Ny passivation layer;
wherein at least one opening extending through the second HfOx1Ny passivation layer and the second SiNx layer is provided in the second HfOx1Ny passivation layer and the second SiNx layer.
3. The solar cell of claim 2, further comprising: positive electrodes and negative electrodes which are arranged at intervals;
the positive electrode is arranged on the second SiNx layer;
the negative electrode is disposed on the tunneling oxide layer and in the at least one opening;
and an N + layer is further disposed between the negative electrode and the tunneling oxide layer, the N + layer being disposed in the at least one opening.
4. The solar cell according to claim 3, wherein the N-type single-crystal silicon substrate has a thickness of 100 to 160 μm and a resistivity of 0.4 to 10 Ω -cm;
P + the doped layer is a boron-doped monocrystalline silicon layer, and the square resistance of the P + doped layer is 100-160 omega/□; and said P is + A p-N junction is formed between the doping layer and the N-type monocrystalline silicon substrate, and the junction depth is 0.1-1.3 mu m;
the thicknesses of the first HfOx1Ny passivation layer and the second HfOx1Ny passivation layer are both in the range of 0.2-1.4nm, and the thicknesses of the first HfOx1Ny passivation layer and the second HfOx1Ny passivation layer are the same or different;
the thickness of the tetracene covering layer is 50-200nm;
the thickness of the first SiNx layer and the second SiNx layer is 40-80nm, and the refractive index of the first SiNx layer and the second SiNx layer is 1.8-2.5;
the tunneling oxide layer comprises a silicon oxide layer and a boron-doped polycrystalline silicon layer, the thickness of the silicon oxide layer is 0.5-2nm, and the thickness of the boron-doped polycrystalline silicon layer is 50-200nm;
said N is + The layer is a phosphorus-containing layer.
5. The method for manufacturing a solar cell according to any one of claims 1 to 4, comprising the steps of:
a) Processing the front surface of an N-type single crystal silicon substrate to form a P + doped layer on the N-type single crystal silicon substrate;
b) Depositing a silicon oxide layer and a boron-doped polycrystalline silicon layer on the back of the N-type monocrystalline silicon substrate in sequence to form a tunneling oxide layer;
c) At the P + Depositing HfOx1Ny on the doped layer and the tunnel oxide layer respectively to form a layer on the P + A first HfOx1Ny passivation layer on the doped layer and a second HfOx1Ny passivation layer on the tunneling oxide layer;
d) Depositing a tetrabenzene layer on the first HfOx1Ny passivation layer;
e) And respectively depositing SiNx on the tetracene layer and the second HfOx1Ny passivation layer to respectively form a first SiNx layer on the tetracene layer and a second SiNx layer on the second HfOx1Ny passivation layer.
6. The method for manufacturing a solar cell according to claim 5, further comprising the steps of:
f) Sequentially printing etching slurry, phosphorus slurry and aluminum slurry in a grid line preset area on the surface of the second SiNx layer in a screen printing mode to form a negative electrode;
g) Printing silver paste on the region, complementary to the preset grid line region, on the surface of the second SiNx layer in a screen printing mode to form a positive electrode;
h) Annealing the solar cell after forming the positive electrode and the negative electrode.
7. The method for manufacturing a solar cell according to claim 5, wherein the front surface of the N-type single-crystal silicon substrate is treated to form P on the N-type single-crystal silicon substrate + The step of doping the layer further comprises:
a1 Carrying out double-sided texturing treatment on the N-type single crystal silicon substrate;
a2 Implanting boron into the front surface of the N-type single crystal silicon substrate using an ion implantation method using a low pressure high temperature diffusion furnace and performing boron diffusion to form the P + Doping the layer;
wherein: the diffusion temperature is 800-1100 ℃;
the diffusion time is 10-50 minutes;
the P is + And a p-N junction is formed between the doping layer and the N-type monocrystalline silicon substrate.
8. The method of claim 5, wherein in the step B), the silicon oxide layer and the boron-doped polysilicon layer are deposited by at least one of LPCVD, PECVD, APCVD and thermal nitric acid;
in the step C), the first HfOx1Ny passivation layer and the second HfOx1Ny passivation layer are deposited by at least one of ion beam sputtering, ALD, magnetron sputtering, and PECVD;
in the step D) above, the layer of pyromellitic dianhydride is deposited using a CVD method or a wet chemical method;
in the step E), the first and second SiNx layers are deposited using a PECVD method.
9. The method according to claim 6, wherein in step F) the etching paste is a HF paste, and after printing the HF paste, at least one opening is etched in the second HfOx1Ny passivation layer and the second SiNx layer extending through the second HfOx1Ny passivation layer and the second SiNx layer;
after the etching slurry is printed and before the phosphorus slurry is printed, a cleaning step is carried out to remove the redundant HF slurry and the damaged second HfOx1Ny passivation layer and the second SiNx layer;
drying by using an oven between each printing step of printing the etching slurry, the phosphorus slurry and the aluminum slurry in sequence;
the line width of an etched area of the HF slurry is 10-80 mu m, and the mass concentration of HF in the HF slurry is 5-40%.
10. The method for manufacturing a solar cell according to claim 6,
in the step H), the annealing the solar cell includes:
and sintering the solar cell in a sintering furnace at the sintering annealing temperature of 600-1000 ℃.
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Application publication date: 20221004 |
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| RJ01 | Rejection of invention patent application after publication |