CN111668347A - Preparation method of surface pn crystal silicon-based solar cell - Google Patents
Preparation method of surface pn crystal silicon-based solar cell Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 142
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 49
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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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0352—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035272—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
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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
- H01L31/04—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 at least one potential-jump barrier or surface barrier
- 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 at least one potential-jump barrier or surface barrier 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
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- 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 System
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a preparation method of a surface pn crystal silicon solar cell, which comprises the steps of cleaning, texturing, oxidizing and photoetching an original silicon wafer, forming surface pn junctions on the surface of the silicon wafer by adopting a selective local diffusion method, removing the pn junctions on the edge and the back, forming corresponding passivation layers on the front surface and the back surface, and forming electrodes by adopting a screen printing and sintering method. The preparation method of the surface pn crystal silicon solar cell is to perform local diffusion on the light receiving surface of the cell so as to form a surface pn junction, and the surface pn junction avoids the existence of a 'dead layer' on the surface of the traditional silicon solar cell, so that incident ultraviolet photons are completely converted into electric energy to be output, the efficiency of the silicon solar cell is favorably improved, and the surface pn junction solar cell can be used for power generation and can also be used for ultraviolet detection or solar spectrum detection.
Description
Technical Field
The invention belongs to the technical field of solar photovoltaics, and particularly relates to a preparation method of a surface pn crystal silicon solar cell.
Background
At present, the crystalline silicon solar cell is the main force of photovoltaic power generation, and the basic structure of the crystalline silicon solar cell is that n with the thickness of 0.3-0.5um is arranged on a light receiving surface+Layer (n)+p cell) or p of 0.35-0.6um+Layer (p)+n cells). In order to improve the photoelectric conversion efficiency of the solar cell, the light receiving surface is generally made into a heavily doped layer, but the heavily doped layer has a short minority carrier lifetime and no electric field. The layer absorbs photons in the ultraviolet band to generate photogenerated carriers, which cannot be effectively output by diffusion, and is generally called a "dead layer". Therefore, the existing solar cell has low photoelectric conversion efficiency in the ultraviolet light band, and when the solar cell is used as a detector, the ultraviolet detection effect is poor.
In order to solve the problem of "dead layer", the pn junction is made as shallow as possible, and the doping concentration of the light receiving surface is made as low as possible, so that the near ultraviolet light can be absorbed. However, the cell cannot fully utilize ultraviolet light, and the low doping concentration directly results in the open circuit voltage (V) of the celloc) Low, which is not beneficial to improving the photoelectric conversion efficiency of the battery.
In view of the above-mentioned state of the art, people usually use a solar radiometer made of thermopiles when measuring the radiation of all sunlight. The thermopile is a passive device, and the working principle of the thermopile is that radiation energy is converted into heat energy firstly by using the thermal effect of radiation, and then the heat energy is converted into electric energy. The reaction is slow, the accuracy is low (5 percent), and the requirement of accurately and rapidly measuring solar radiation cannot be met.
Disclosure of Invention
The invention provides a preparation method of a surface pn crystal silicon-based solar cell. Compared with the traditional silicon solar cell, the novel silicon solar cell carries out local diffusion on the light receiving surface of the cell so as to form a surface pn junction, and the surface pn junction avoids the existence of a dead layer on the surface of the conventional solar cell, so that incident ultraviolet photons are completely converted into electric energy to be output, thereby not only improving the conversion efficiency of the solar cell, but also being used for the rapid and accurate detection of sunlight full-waveband radiation, particularly ultraviolet detection.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method based on a surface pn crystal silicon solar cell comprises the steps of performing texturing, oxidation and photoetching on a silicon wafer, forming a surface pn junction on the surface of the silicon wafer by adopting a selective local diffusion method, then removing the pn junctions on the edge and the back, depositing passivation layers on the front surface and the back surface, and forming a positive electrode and a negative electrode by silk screen printing and sintering to obtain the surface pn crystal silicon solar cell.
The invention is further improved in that the resistivity of the silicon wafer is 1-3 omega-cm, and the thickness is 100-450 um.
The invention has the further improvement that the specific process of making the wool is as follows: firstly, ultrasonic cleaning is carried out on the surface of a silicon wafer by using an electronic cleaning agent, then corrosion texturing is carried out in a sodium hydroxide solution with the mass concentration of 1-1.5% and the temperature of 80-82 ℃, the texturing time is 15-25min, and then spraying, acid washing, rinsing, pre-dewatering and drying are carried out on the silicon wafer.
The further improvement of the invention is that the specific process of oxidation is as follows: carrying out surface oxidation on the silicon wafer after the texturing is finished to form a silicon dioxide film, wherein the oxidation temperature is 850-1150 ℃, and the oxidation time is 10-40 min; the thickness of the silicon dioxide film is 0.1-0.5 um.
The invention is further improved in that the specific process of the photoetching is as follows: spin-coating a positive photoresist on the oxidized silicon wafer, pre-drying the silicon wafer coated with the photoresist, performing ultraviolet light exposure on the pre-dried silicon wafer according to the pattern of a mask, developing the exposed silicon wafer, post-drying the developed silicon wafer, putting the silicon wafer into a hydrofluoric acid solution, corroding a silicon dioxide film in a region without the photoresist, namely a region to be diffused, and then removing the photoresist, cleaning and drying.
The further improvement of the invention is that the rotation speed of the spin coating is 1500-3000rpm, and the spin coating time is 30-120 s; the pre-drying temperature is 80-100 ℃, and the time is 10-15 min; the exposure time is 50-150 s; the developing time is 60-80 s; the post-drying temperature is 100-130 ℃, and the time is 15-20 min; the mass concentration of the hydrofluoric acid solution is 3% -10%, the corrosion time is 2-4min, and then the photoresist is removed.
The further improvement of the invention is that when the selective local diffusion method is adopted, the silicon wafer is a p-type silicon wafer, the diffusion temperature is 800-; the silicon wafer is an n-type silicon wafer, the diffusion temperature is 750-850 ℃, the time is 50-80min, and the depth of the formed pn junction is 0.35-0.6 um;
removing pn junctions on the edge and the back by adopting a wet etching process, wherein etching solutions are mixed solution of nitric acid and hydrofluoric acid and hydrochloric acid solution in sequence; wherein, the mass concentration of the nitric acid solution is 10-30%, the mass concentration of the hydrofluoric acid solution is 3-20%, the volume ratio of the nitric acid to the hydrofluoric acid is 1:1.5-1:3, and the mass concentration of the hydrochloric acid solution is 15-20%.
The further improvement of the invention is that if the silicon wafer is a p-type silicon wafer, a silicon dioxide film and a silicon nitride film are sequentially deposited on one surface with a surface pn junction to form a double-layer passivation film, wherein the thickness of the silicon dioxide film is 100-200 angstroms, the thickness of the silicon nitride film is 75-85nm, and an aluminum oxide film and the silicon nitride film are sequentially deposited on the other surface to form the double-layer passivation film, wherein the thickness of the aluminum oxide film is 20-50 angstroms, and the thickness of the silicon nitride film is 75-85 nm;
if the silicon wafer is an n-type silicon wafer, a silicon dioxide film and a silicon nitride film are sequentially deposited on one surface with a surface pn junction to form a double-layer passivation film, wherein the thickness of the silicon dioxide film is 100-200 angstroms, and the thickness of the silicon nitride film is 75-85nm, and the other surface is sequentially deposited with the silicon dioxide film and the silicon nitride film to form the double-layer passivation film, wherein the thickness of the silicon dioxide film is 100-200 angstroms, and the thickness of the silicon nitride film is 75-85 nm.
The invention has the further improvement that if the silicon chip is a p-type silicon chip, a positive electrode and a negative electrode are prepared on one surface with a surface pn junction by adopting a screen printing method, or the positive electrode and the negative electrode are led out from two surfaces of the silicon chip after a double-layer passivation film is formed;
if the silicon chip is an n-type silicon chip, a positive electrode and a negative electrode are prepared on one surface with a surface pn junction by adopting a screen printing method, or the positive electrode and the negative electrode are led out from two surfaces of the silicon chip after a double-layer passivation film is formed.
The further improvement of the invention is that if the silicon wafer is a p-type silicon wafer, if the anode is led out from the back, the double-layer passivation film is firstly burnt through by laser, then the anode is prepared by adopting a silver paste screen printing method on the surface, the anode is dried, then the cathode is prepared by adopting a silver paste screen printing method on the front, and the cathode is dried and sintered to obtain the surface pn-based crystalline silicon solar cell;
if the silicon wafer is an n-type silicon wafer, if the negative electrode is led out from the back side, silver paste is printed on the surface through silk screen printing, drying is carried out, then silver paste is printed on the front side through silk screen printing to prepare a positive electrode, drying and sintering are carried out, and the surface pn-based crystalline silicon solar cell is obtained;
wherein the width of the screen-printed fine grid is 35-45um, the distance between the fine grids is 1.4-1.6mm, and the width of the main grid is 0.7-0.8 mm.
Compared with the prior art, the invention has the following beneficial effects: the invention prepares a pn junction on the light receiving surface of a solar cell, belonging to an active device. Because the pn junction extends to the surface of the device, a potential barrier region exists on the surface of the light receiving surface, and photogenerated holes and electrons generated by ultraviolet light can be quickly separated under the action of an electric field of the potential barrier region to reach the anode and the cathode of the battery, so that the full-wave-band radiation of sunlight can be converted into electric energy, the problem of 'neck' for quickly and accurately detecting the full-wave-band radiation of the sunlight is solved at one stroke, and the market demand is huge. Compared with the traditional silicon solar cell, the preparation method of the surface pn crystal silicon solar cell provided by the invention has the advantages that the local diffusion is carried out on the light receiving surface of the cell, so that the surface pn junction is formed, the existence of a dead layer on the surface of the traditional silicon solar cell is avoided by the surface pn junction, the incident ultraviolet photons are all converted into electric energy to be output, and the defect that the ultraviolet cell V is a purple light cell can be overcomeocLow disadvantage, increase of VocThe phenomenon of 'dead layers' on the surface of the cell can be reduced, the conversion efficiency of the solar cell is further improved, and meanwhile, the solar spectrum wave band absorbed by the solar cell is expanded towards ultraviolet, so that the solar cell can be used for an ultraviolet detector or solar spectrum detection. The preparation method of the surface pn crystal silicon solar cell firstly realizes the introduction of the pn junction to the surface of the silicon cell, and the method is suitable for any silicon solar cell.
Furthermore, in the process of preparing the surface pn crystal silicon solar cell, if the positive and negative electrodes are led out from a single surface of the screen printing electrode, the process is simple and convenient, but the electrodes are all dropped on the front surface at the moment, so that shading loss is caused, and the cell efficiency is influenced; if the positive and negative electrodes are drawn out from both sides, the loss due to light shielding of the electrodes can be reduced, but the process becomes complicated.
Drawings
Fig. 1(a) is a schematic diagram of a surface pn junction p-type silicon solar cell electrode in which positive and negative electrodes are led out from one surface.
Fig. 1(b) is a schematic diagram of a surface pn junction n-type silicon solar cell electrode in which positive and negative electrodes are led out from one surface.
Fig. 2(a) is a cross-sectional view of a p-type silicon solar cell of the present invention.
Fig. 2(b) is a cross-sectional view of an n-type silicon solar cell of the present invention.
FIG. 3 is a process flow diagram of the present invention.
FIG. 4(a) shows a surface n+A process flow chart for preparing a p-crystal silicon solar cell.
FIG. 4(b) shows the surface p+A flow chart of a preparation process of the n-crystal silicon solar cell.
In the figure, 1 is a main gate, 2 is a fine gate, 3 is a silicon nitride film, 4 is a silicon dioxide film, 5 is a positive electrode, and 6 is n+Region 7 is a p-type silicon wafer, 8 is an aluminum oxide film, 9 is a negative electrode, and 10 is p+And the region 11 is an n-type silicon wafer.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
The core of the invention is that local diffusion is carried out on the light receiving surface of the battery, so as to form a surface pn junction. The surface pn junction avoids the existence of a 'dead layer' on the surface of the conventional solar cell, so that incident ultraviolet photons are completely converted into electric energy to be output, and the surface pn junction solar cell can be used for power generation and can also be used for ultraviolet detection or solar spectrum detection. The preparation method of the surface pn crystal silicon solar cell firstly realizes the introduction of the pn junction to the surface of the silicon cell, and the method is suitable for any silicon solar cell.
Referring to fig. 3, fig. 4(a) and fig. 4(b), a method for preparing a surface pn crystal silicon-based solar cell of the present invention comprises: firstly, selecting an original silicon wafer with the resistivity of 1-3 omega-cm and the thickness of 100-450 mu m, carrying out ultrasonic cleaning on the surface of the original silicon wafer by using an electronic cleaning agent, then carrying out corrosion texturing in a sodium hydroxide solution with the mass percentage concentration of 1-1.5% and the temperature of 80-82 ℃, wherein the texturing time is 15-25min, and carrying out spraying, acid cleaning, rinsing, pre-dewatering and drying on the silicon wafer after the preparation is finished. Then, carrying out surface oxidation on the silicon wafer after the texturing is finished to form a silicon dioxide film, wherein the temperature is 850-1150 ℃, and the oxidation time is 10-40 min; the thickness of the silicon dioxide film is 0.1-0.5 um. Photoetching the oxidized silicon wafer: firstly, uniformly spin-coating a positive photoresist on a silicon wafer by using a spin-coating method, wherein the spin-coating rotation speed is 1500-3000rpm, the time is 30-120s, the silicon wafer coated with the photoresist is placed into an oven for pre-drying, the temperature is 80-110 ℃, the time is 10-15min, carrying out ultraviolet exposure on the pre-baked silicon wafer according to the pattern of the mask for 50-150s, placing the exposed silicon wafer into a developing solution for development for 60-80s, placing the developed silicon wafer into an oven for post-baking at the temperature of 100-130 ℃ for about 15-20min, placing the silicon wafer into a hydrofluoric acid solution after baking, etching off the silicon dioxide film in the photoresist-free area, namely the area to be diffused, then removing photoresist, cleaning and drying, wherein the mass concentration of hydrofluoric acid solution is 3% -10%, the etching time is 2-4min, and removing photoresist after the etching is finished. Diffusing on the surface of the silicon wafer with the silicon dioxide film corroded, wherein if the silicon wafer is a p-type silicon wafer, the diffusion temperature is 800-; if the silicon wafer is an n-type silicon wafer, the diffusion temperature is 750-850 ℃, the diffusion time is 50-80min, and the depth of the formed pn junction is 0.35-0.6 um. Forming pn junctions on the edge and the back of the silicon wafer in the diffusion process, and corroding the pn junctions on the edge and the back of the silicon wafer by adopting a wet corrosion process, wherein the wet corrosion process adopts mixed solution of nitric acid with the mass concentration of 10% -30% and hydrofluoric acid with the mass concentration of 3% -20% (the volume ratio of the nitric acid to the hydrofluoric acid is 1:1.5-1:3), and hydrochloric acid solution with the mass concentration of 15% -20% to sequentially corrode.
Then depositing a passivation layer on the front surface and the back surface, if the silicon wafer is a p-type silicon wafer, sequentially depositing a silicon dioxide film 4 and a silicon nitride film 3 on the front surface to form a double-layer passivation film, wherein the thickness of the silicon dioxide film 4 is 100-200 angstroms, the thickness of the silicon nitride film 3 is 75-85nm, and sequentially depositing an aluminum oxide film 8 and the silicon nitride film 3 on the back surface to form the double-layer passivation film, wherein the thickness of the aluminum oxide film 8 is 20-50 angstroms, and the thickness of the silicon nitride film 3 is 75-85 nm. If the silicon wafer is an n-type silicon wafer, a silicon dioxide film 4 and a silicon nitride film 3 are sequentially deposited on the front surface to form a double-layer passivation film, wherein the thickness of the silicon dioxide film 4 is 100-200 angstroms, the thickness of the silicon nitride film 3 is 75-85nm, the silicon dioxide film 4 and the silicon nitride film 3 are sequentially deposited on the back surface to form the double-layer passivation film, wherein the thickness of the silicon dioxide film 4 is 100-200 angstroms, and the thickness of the silicon nitride film 3 is 75-85 nm.
Finally, screen printing an electrode and sintering, if the silicon wafer is a p-type silicon wafer, preparing a positive electrode and a negative electrode on one surface with a surface pn junction by adopting a screen printing method, or leading out the positive electrode and the negative electrode from two surfaces of the silicon wafer after a double-layer passivation film is formed; if the positive electrode is led out from the back side, the double-layer passivation film is burned through by laser, the positive electrode is prepared on the surface by adopting a silver paste screen printing method, the positive electrode is dried, the negative electrode is prepared on the front side by adopting a silver paste screen printing method, and the negative electrode is dried and sintered; if the silicon wafer is an n-type silicon wafer, preparing positive and negative electrodes on one surface with a surface pn junction by adopting a screen printing method, or leading out the positive and negative electrodes from two surfaces of the silicon wafer after a double-layer passivation film is formed; and if the negative electrode is led out from the back, silver paste is printed on the surface through screen printing, the surface is dried, silver paste is printed on the front surface through screen printing to prepare a positive electrode, and the positive electrode is dried and sintered. Wherein the width of the screen-printed fine grid is 35-45um, the distance between the fine grids is 1.4-1.6mm, and the width of the main grid is 0.7-0.8 mm.
The following are specific examples.
Example 1
Referring to FIG. 4(a), a surface n+The preparation method of the p-crystal silicon solar cell comprises the following steps: firstly, selecting a p-type silicon wafer 7 with the resistivity of 2 omega cm and the thickness of 400um, carrying out ultrasonic cleaning on the surface of the p-type silicon wafer 7 by using an electronic cleaning agent, then corroding and texturing in a sodium hydroxide solution with the mass percentage concentration of 1.5% and the temperature of 82 ℃ for 20min, and carrying out spraying, acid washing, rinsing, pre-dewatering and drying on the silicon wafer after the preparation of the textured surface is finished.
And then, carrying out surface oxidation on the silicon wafer after texturing to form a silicon dioxide film, wherein the oxidation temperature is 850 ℃, the oxidation time is 30min, and the silicon dioxide film with the thickness of about 0.3um is formed.
And photoetching the oxidized silicon wafer, firstly, uniformly spin-coating a positive photoresist on the silicon wafer by using a spin-coating method, wherein the spin-coating speed is 2000rpm and the time is 50s, placing the silicon wafer coated with the photoresist in an oven for prebaking at the temperature of 80 ℃ for 15min, carrying out ultraviolet exposure on the prebaked silicon wafer according to the pattern of a mask for 100s, placing the exposed silicon wafer in a developing solution for developing for 80s, placing the developed silicon wafer in the oven for postbaking at the temperature of 120 ℃ for about 20min, placing the silicon wafer in a hydrofluoric acid solution with the mass concentration of 8% after baking to corrode a silicon dioxide film in a region without the photoresist, namely a region to be diffused, and then carrying out degumming, cleaning and drying for 4 min.
Phosphorus diffusion is carried out on the surface of the silicon wafer with the silicon dioxide film etched away to form n+And in the region 6, the diffusion temperature is 900 ℃, the diffusion time is 70min, and a pn junction with the junction depth of about 0.4um is formed.
Forming pn junctions at the edge and the back of the silicon wafer in the diffusion process, and corroding the pn junctions at the edge and the back of the silicon wafer by adopting a wet corrosion process, wherein the wet corrosion process adopts mixed solution of nitric acid with the mass concentration of 20% and hydrofluoric acid with the mass concentration of 15% (the volume ratio of the nitric acid to the hydrofluoric acid is 1:3), and hydrochloric acid solution with the mass concentration of 20% to sequentially corrode.
Then depositing a passivation layer on the front surface and the back surface, sequentially depositing a silicon dioxide film 4 and a silicon nitride film 3 on the front surface to form a double-layer passivation film, wherein the thickness of the silicon dioxide film is 150 angstroms, and the thickness of the silicon nitride film is 80nm, and sequentially depositing an aluminum oxide film 8 and the silicon nitride film 3 on the back surface to form the double-layer passivation film, wherein the thickness of the aluminum oxide film is 40 angstroms, and the thickness of the silicon nitride film is 80 nm. Finally, preparing a positive electrode 5 and a negative electrode 9 by using silver paste by adopting a screen printing method, forming fine grids 2 with the width of 40um on the front surface, forming main grids 1 with the spacing of 1.5mm and the width of 0.8mm, and sintering to finally obtain a p-type silicon solar cell piece with the size of 156.75mm multiplied by 156.75mm, and referring to fig. 2 (a); the electrode of the p-type silicon solar cell is shown in fig. 1 (a).
The electrical performance indexes of the solar cell prepared in the embodiment are as follows:
the battery specification is as follows: 156.75mm x 156.75mm monocrystalline silicon p-type solar cell;
photoelectric conversion efficiency: 22.64 percent;
maximum output power: 5.53W;
open circuit voltage: 0.69V;
short-circuit current: 9.920A;
the optimal working voltage is as follows: 0.59V;
the optimal working current is as follows: 9.371A;
filling factor: 80.77 percent;
series resistance: 2.05 m.OMEGA.
Example 2
Referring to FIG. 4(b), a surface p+The preparation method of the n-crystal silicon solar cell comprises the following steps: firstly, selecting an n-type silicon wafer 11 with the resistivity of 2 omega cm and the thickness of 400um, carrying out ultrasonic cleaning on the surface of the n-type silicon wafer 11 by using an electronic cleaning agent, then corroding and texturing in a sodium hydroxide solution with the mass percentage concentration of 1.5% and the temperature of 82 ℃ for 15min, and spraying, pickling, rinsing, pre-dehydrating and drying the silicon wafer after the preparation is finished.
And then, carrying out surface oxidation on the silicon wafer after texturing to form a silicon dioxide film, wherein the oxidation temperature is 850 ℃, the oxidation time is 40min, and the silicon dioxide film with the thickness of about 0.35um is formed.
And photoetching the oxidized silicon wafer, firstly, uniformly spin-coating a positive photoresist on the silicon wafer by using a spin-coating method, wherein the spin-coating speed is 2000rpm and the time is 50s, placing the silicon wafer coated with the photoresist in an oven for prebaking at the temperature of 80 ℃ for 15min, carrying out ultraviolet exposure on the prebaked silicon wafer according to the pattern of a mask for 100s, placing the exposed silicon wafer in a developing solution for developing for 80s, placing the developed silicon wafer in the oven for postbaking at the temperature of 120 ℃ for about 20min, placing the silicon wafer in a hydrofluoric acid solution with the mass concentration of 8% after baking to corrode a silicon dioxide film in a region without the photoresist, namely a region to be diffused, and then carrying out degumming, cleaning and drying for 4 min.
Performing boron diffusion on the surface of the silicon wafer with the silicon dioxide film etched away to form p+In the region 10, the diffusion temperature is 850 ℃ and the time is 70min, and a pn junction with the junction depth of about 0.5um is formed.
Forming pn junctions at the edge and the back of the silicon wafer in the diffusion process, and corroding the pn junctions at the edge and the back of the silicon wafer by adopting a wet corrosion process, wherein the wet corrosion process adopts mixed solution of nitric acid with the mass concentration of 15% and hydrofluoric acid with the mass concentration of 8% (the volume ratio of the nitric acid to the hydrofluoric acid is 1:3), and hydrochloric acid solution with the mass concentration of 20% to sequentially corrode.
And then depositing a passivation layer on the front surface and the back surface, sequentially depositing a silicon dioxide film and a silicon nitride film on the front surface to form a double-layer passivation film, wherein the silicon dioxide film is 150 angstroms thick, the silicon nitride film is 80nm thick, and sequentially depositing the silicon dioxide film and the silicon nitride film on the back surface to form the double-layer passivation film, wherein the silicon dioxide film is 150 angstroms thick, and the silicon nitride film is 80nm thick. Finally, preparing a positive electrode 5 and a negative electrode 9 by using silver paste by adopting a screen printing method, forming fine grids 2 with the width of 40um on the front surface, forming main grids 1 with the spacing of 1.5mm and the width of 0.8mm, and sintering to finally obtain an n-type silicon solar cell piece with the size of 156.75mm multiplied by 156.75mm, and referring to fig. 2 (b); the electrode of the n-type silicon solar cell is shown in fig. 1 (b).
The electrical performance indexes of the solar cell manufactured in the embodiment are as follows:
the battery specification is as follows: a monocrystalline silicon n-type solar cell of 156.75mm × 156.75 mm;
photoelectric conversion efficiency: 22.31 percent;
maximum output power: 5.45W;
open circuit voltage: 0.68V;
short-circuit current: 9.927A;
the optimal working voltage is as follows: 0.58V;
the optimal working current is as follows: 9.397A;
filling factor: 80.74 percent;
series resistance: 2.12m omega.
Example 3
Referring to FIG. 4(a), a surface n+The preparation method of the p-crystal silicon solar cell comprises the following steps: firstly, selecting a p-type original silicon wafer with the resistivity of 1 omega cm and the thickness of 100um, carrying out ultrasonic cleaning on the surface of the original silicon wafer by using an electronic cleaning agent, then carrying out corrosion texturing in a sodium hydroxide solution with the mass percentage concentration of 1% and the temperature of 80 ℃, wherein the texturing time is 15min, and after the preparation is finished, spraying, pickling, rinsing, pre-dehydrating and drying the silicon wafer.
And then, carrying out surface oxidation on the silicon wafer after texturing to form a silicon dioxide film, wherein the oxidation temperature is 1000 ℃, the oxidation time is 10min, and the silicon dioxide film with the thickness of about 0.2um is formed.
And photoetching the oxidized silicon wafer, firstly, uniformly spin-coating a positive photoresist on the silicon wafer by using a spin-coating method, wherein the spin-coating speed is 1500rpm and the time is 120s, placing the silicon wafer coated with the photoresist in an oven for prebaking at 90 ℃ for 10min, carrying out ultraviolet exposure on the prebaked silicon wafer according to the pattern of a mask for 80s, placing the exposed silicon wafer in a developing solution for developing for 70s, placing the developed silicon wafer in the oven for postbaking at 100 ℃ for 20min, placing the silicon wafer in a hydrofluoric acid solution with the mass concentration of 10% after baking to corrode the silicon dioxide film of a region without the photoresist, namely a region to be diffused, for 4min, and then carrying out photoresist removal, cleaning and drying.
Phosphorus diffusion is carried out on the surface of the silicon wafer with the silicon dioxide film etched away to form n+And in the region 6, the diffusion temperature is 800 ℃, the time is 80min, and a pn junction with the junction depth of about 0.3um is formed.
Forming pn junctions at the edge and the back of the silicon wafer in the diffusion process, and corroding the pn junctions at the edge and the back of the silicon wafer by adopting a wet corrosion process, wherein the wet corrosion process adopts a mixed solution of nitric acid with the mass concentration of 10% and hydrofluoric acid with the mass concentration of 20% (the volume ratio of the nitric acid to the hydrofluoric acid is 1:2), and hydrochloric acid solution with the mass concentration of 15% to sequentially corrode.
Then, a passivation layer is deposited on the front surface and the back surface, a silicon dioxide film 4 and a silicon nitride film 3 are sequentially deposited on the front surface to form a double-layer passivation film, wherein the thickness of the silicon dioxide film is 100 angstroms, the thickness of the silicon nitride film is 85nm, and an aluminum oxide film 8 and the silicon nitride film are sequentially deposited on the back surface to form the double-layer passivation film, wherein the thickness of the aluminum oxide film is 50 angstroms, and the thickness of the silicon nitride film is 75 nm. Finally, leading out a positive electrode from the back, burning through a double-layer passivation film by adopting laser, preparing the positive electrode on the surface by adopting a silver paste screen printing method, drying, preparing a negative electrode on the front surface by adopting a silver paste screen printing method, drying and sintering to obtain a surface pn crystal silicon solar cell; wherein the width of the screen-printed fine grid is 35-45um, the distance between the fine grids is 1.4-1.6mm, and the width of the main grid is 0.7-0.8 mm.
Example 4
Referring to FIG. 4(a), a surface n+The preparation method of the p-crystal silicon solar cell comprises the following steps: firstly, selecting a p-type original silicon wafer with the resistivity of 3 omega cm and the thickness of 450um, carrying out ultrasonic cleaning on the surface of the original silicon wafer by using an electronic cleaning agent, then corroding the original silicon wafer in a sodium hydroxide solution with the mass percentage concentration of 1.2% and the temperature of 82 ℃ for 15min, and spraying, pickling, rinsing, pre-dehydrating and drying the silicon wafer after the preparation is finished.
And then, carrying out surface oxidation on the silicon wafer after texturing to form a silicon dioxide film, wherein the oxidation temperature is 1150 ℃, the oxidation time is 20min, and the silicon dioxide film with the thickness of about 0.3um is formed.
And photoetching the oxidized silicon wafer, firstly, uniformly spin-coating a positive photoresist on the silicon wafer by using a spin-coating method, wherein the spin-coating speed is 3000rpm and the time is 30s, placing the silicon wafer coated with the photoresist in an oven for prebaking at 100 ℃ for 10min, carrying out ultraviolet exposure on the prebaked silicon wafer according to the pattern of a mask for 120s, placing the exposed silicon wafer in a developing solution for developing for 60s, placing the developed silicon wafer in the oven for postbaking at 130 ℃ for 15min, placing the silicon wafer in a hydrofluoric acid solution with the mass concentration of 3% after baking to corrode a silicon dioxide film in a region without the photoresist, namely a region to be diffused, and corroding for 4min, and then, removing the photoresist, cleaning and drying.
Phosphorus diffusion is carried out on the surface of the silicon wafer with the silicon dioxide film etched away to form n+Zone 6, diffusion temperature 850 ℃ for timeAfter 60min, a pn junction with the junction depth of about 0.5um is formed.
Forming pn junctions at the edge and the back of the silicon wafer in the diffusion process, corroding the pn junctions at the edge and the back of the silicon wafer by adopting a wet corrosion process, and sequentially corroding by adopting a mixed solution of nitric acid with the mass concentration of 30% and hydrofluoric acid with the mass concentration of 3% (the volume ratio of the nitric acid to the hydrofluoric acid is 1:1.5) and a hydrochloric acid solution with the mass concentration of 15%.
Then, a passivation layer is deposited on the front surface and the back surface, a silicon dioxide film 4 and a silicon nitride film 3 are sequentially deposited on the front surface to form a double-layer passivation film, wherein the thickness of the silicon dioxide film is 200 angstroms, the thickness of the silicon nitride film is 85nm, and an aluminum oxide film 8 and the silicon nitride film are sequentially deposited on the back surface to form the double-layer passivation film, wherein the thickness of the aluminum oxide film is 20 angstroms, and the thickness of the silicon nitride film is 75 nm. Finally, preparing a positive electrode 5 and a negative electrode 9 by using silver paste by adopting a screen printing method, forming fine grids 2 with the width of 40um on the front surface, forming main grids 1 with the spacing of 1.5mm and the width of 0.8mm, and sintering to finally obtain a p-type silicon solar cell piece with the size of 156.75mm multiplied by 156.75mm, and referring to fig. 2 (a); the electrode of the p-type silicon solar cell is shown in fig. 1 (a).
Example 5
Referring to FIG. 4(b), a surface p+The preparation method of the n-crystal silicon solar cell comprises the following steps: firstly, selecting an n-type original silicon wafer with the resistivity of 2 omega cm and the thickness of 200um, carrying out ultrasonic cleaning on the surface of the original silicon wafer by using an electronic cleaning agent, then corroding the original silicon wafer in a sodium hydroxide solution with the mass percentage concentration of 1% and the temperature of 80 ℃, wherein the texturing time is 20min, and after the preparation is finished, spraying, pickling, rinsing, pre-dehydrating and drying the silicon wafer.
And then, carrying out surface oxidation on the silicon wafer after texturing to form a silicon dioxide film, wherein the oxidation temperature is 900 ℃, the oxidation time is 30min, and the silicon dioxide film with the thickness of about 0.1um is formed.
And photoetching the oxidized silicon wafer, firstly, uniformly spin-coating a positive photoresist on the silicon wafer by using a spin-coating method, wherein the spin-coating speed is 2500rpm and the time is 70s, placing the silicon wafer coated with the photoresist in an oven for prebaking at 100 ℃ for 10min, carrying out ultraviolet exposure on the prebaked silicon wafer according to the pattern of a mask for 50s, placing the exposed silicon wafer in a developing solution for developing for 70s, placing the developed silicon wafer in the oven for postbaking at 120 ℃ for 20min, placing the silicon wafer in a hydrofluoric acid solution with the mass concentration of 7% after baking to corrode a silicon dioxide film in a region without the photoresist, namely a region to be diffused, and then carrying out photoresist removal, cleaning and drying for 3 min.
Performing boron diffusion on the surface of the silicon wafer with the silicon dioxide film etched away to form p+In the region 10, the diffusion temperature is 750 ℃, the time is 80min, and a pn junction with the junction depth of about 0.35um is formed.
Forming pn junctions at the edge and the back of the silicon wafer in the diffusion process, corroding the pn junctions at the edge and the back of the silicon wafer by adopting a wet corrosion process, and sequentially corroding by adopting a mixed solution of nitric acid with the mass concentration of 30% and hydrofluoric acid with the mass concentration of 7% (the volume ratio of the nitric acid to the hydrofluoric acid is 1:2.5) and a hydrochloric acid solution with the mass concentration of 17%.
And then depositing a passivation layer on the front surface and the back surface, sequentially depositing a silicon dioxide film and a silicon nitride film on the front surface to form a double-layer passivation film, wherein the thickness of the silicon dioxide film is 100 angstroms, the thickness of the silicon nitride film is 80nm, and sequentially depositing the silicon dioxide film and the silicon nitride film on the back surface to form the double-layer passivation film, wherein the thickness of the silicon dioxide film is 200 angstroms, and the thickness of the silicon nitride film is 75 nm. Finally, leading out a negative electrode from the back, screen-printing silver paste on the surface, drying, screen-printing silver paste on the front to prepare a positive electrode, drying and sintering to obtain the surface pn crystal silicon solar cell;
wherein the width of the screen-printed fine grid is 35-45um, the distance between the fine grids is 1.4-1.6mm, and the width of the main grid is 0.7-0.8 mm.
Example 6
Referring to FIG. 4(b), a surface p+The preparation method of the n-crystal silicon solar cell comprises the following steps: firstly, selecting an n-type original silicon wafer with the resistivity of 2 omega cm and the thickness of 300um, carrying out ultrasonic cleaning on the surface of the original silicon wafer by using an electronic cleaning agent, and then carrying out corrosion texturing in a sodium hydroxide solution with the mass percentage concentration of 1.5% and the temperature of 82 ℃ to prepare the woolThe velvet time is 25min, and after the preparation is finished, the silicon wafer is sprayed, pickled, rinsed, pre-dehydrated and dried.
And then, carrying out surface oxidation on the silicon wafer after the texturing to form a silicon dioxide film, wherein the oxidation temperature is 1050 ℃, the oxidation time is 10min, and the silicon dioxide film with the thickness of about 0.5um is formed.
And photoetching the oxidized silicon wafer, firstly, uniformly spin-coating a positive photoresist on the silicon wafer by using a spin-coating method, wherein the spin-coating speed is 2800rpm and the time is 60s, placing the silicon wafer coated with the photoresist into an oven for prebaking at 90 ℃ for 12min, carrying out ultraviolet exposure on the prebaked silicon wafer according to the pattern of a mask for 150s, placing the exposed silicon wafer into a developing solution for developing for 80s, placing the developed silicon wafer into the oven for postbaking at 115 ℃ for 20min, placing the silicon wafer into a hydrofluoric acid solution with the mass concentration of 4% after drying to corrode a silicon dioxide film in a region without the photoresist, namely a region to be diffused, and corroding for 4min, and then, removing the photoresist, cleaning and drying.
Performing boron diffusion on the surface of the silicon wafer with the silicon dioxide film etched away to form p+In the region 10, the diffusion temperature is 850 ℃ and the time is 50min, and a pn junction with the junction depth of about 0.6um is formed.
Forming pn junctions at the edge and the back of the silicon wafer in the diffusion process, and corroding the pn junctions at the edge and the back of the silicon wafer by adopting a wet corrosion process, wherein the wet corrosion process adopts mixed solution of nitric acid with the mass concentration of 15% and hydrofluoric acid with the mass concentration of 8% (the volume ratio of the nitric acid to the hydrofluoric acid is 1:3), and hydrochloric acid solution with the mass concentration of 20% to sequentially corrode.
And then depositing a passivation layer on the front surface and the back surface, sequentially depositing a silicon dioxide film and a silicon nitride film on the front surface to form a double-layer passivation film, wherein the silicon dioxide film is 200 angstroms thick, the silicon nitride film is 75nm thick, and sequentially depositing the silicon dioxide film and the silicon nitride film on the back surface to form the double-layer passivation film, wherein the silicon dioxide film is 100 angstroms thick, and the silicon nitride film is 75nm thick. And finally, preparing a positive electrode 5 and a negative electrode 9 by using silver paste by adopting a screen printing method, forming fine grids 2 with the width of 40um and main grids 1 with the spacing of 1.5mm and the width of 0.8mm on the front surface, and sintering to obtain the n-type silicon solar cell.
Claims (10)
1. A preparation method based on a surface pn crystal silicon solar cell is characterized by comprising the steps of performing texturing, oxidation and photoetching on a silicon wafer, forming a surface pn junction on the surface of the silicon wafer by adopting a selective local diffusion method, removing pn junctions on the edge and the back, depositing passivation layers on the front side and the back side, and forming a positive electrode and a negative electrode by silk screen printing and sintering to obtain the surface pn crystal silicon solar cell.
2. The method as claimed in claim 1, wherein the silicon wafer has a resistivity of 1-3 Ω -cm and a thickness of 100-450 μm.
3. The preparation method of the surface pn crystal silicon-based solar cell as claimed in claim 1, wherein the texturing process comprises: firstly, ultrasonic cleaning is carried out on the surface of a silicon wafer by using an electronic cleaning agent, then corrosion texturing is carried out in a sodium hydroxide solution with the mass concentration of 1-1.5% and the temperature of 80-82 ℃, the texturing time is 15-25min, and then spraying, acid washing, rinsing, pre-dewatering and drying are carried out on the silicon wafer.
4. The preparation method of the surface pn crystal silicon-based solar cell as claimed in claim 1, wherein the oxidation process comprises: carrying out surface oxidation on the silicon wafer after the texturing is finished to form a silicon dioxide film, wherein the oxidation temperature is 850-1150 ℃, and the oxidation time is 10-40 min; the thickness of the silicon dioxide film is 0.1-0.5 um.
5. The method for preparing the surface pn crystal silicon-based solar cell as claimed in claim 1, wherein the photolithography comprises the following steps: spin-coating a positive photoresist on the oxidized silicon wafer, pre-drying the silicon wafer coated with the photoresist, performing ultraviolet light exposure on the pre-dried silicon wafer according to the pattern of a mask, developing the exposed silicon wafer, post-drying the developed silicon wafer, putting the silicon wafer into a hydrofluoric acid solution, corroding a silicon dioxide film in a region without the photoresist, namely a region to be diffused, and then removing the photoresist, cleaning and drying.
6. The method as claimed in claim 5, wherein the spin coating speed is 1500-3000rpm, and the spin coating time is 30-120 s; the pre-drying temperature is 80-100 ℃, and the time is 10-15 min; the exposure time is 50-150 s; the developing time is 60-80 s; the post-drying temperature is 100-130 ℃, and the time is 15-20 min; the mass concentration of the hydrofluoric acid solution is 3% -10%, the corrosion time is 2-4min, and then the photoresist is removed.
7. The method for preparing a surface pn crystal silicon solar cell as claimed in claim 1, wherein the selective local diffusion is adopted, the silicon wafer is a p-type silicon wafer, the diffusion temperature is 800-; the silicon wafer is an n-type silicon wafer, the diffusion temperature is 750-850 ℃, the time is 50-80min, and the depth of the formed pn junction is 0.35-0.6 um;
removing pn junctions on the edge and the back by adopting a wet etching process, wherein etching solutions are mixed solution of nitric acid and hydrofluoric acid and hydrochloric acid solution in sequence; wherein, the mass concentration of the nitric acid solution is 10-30%, the mass concentration of the hydrofluoric acid solution is 3-20%, the volume ratio of the nitric acid to the hydrofluoric acid is 1:1.5-1:3, and the mass concentration of the hydrochloric acid solution is 15-20%.
8. The method as claimed in claim 1, wherein if the silicon wafer is a p-type silicon wafer, a silicon dioxide film and a silicon nitride film are sequentially deposited on the surface having the surface pn junction to form a double-layer passivation film, wherein the silicon dioxide film has a thickness of 100-200 angstroms and the silicon nitride film has a thickness of 75-85nm, and an aluminum oxide film and a silicon nitride film are sequentially deposited on the other surface to form a double-layer passivation film, wherein the aluminum oxide film has a thickness of 20-50 angstroms and the silicon nitride film has a thickness of 75-85 nm;
if the silicon wafer is an n-type silicon wafer, a silicon dioxide film and a silicon nitride film are sequentially deposited on one surface with a surface pn junction to form a double-layer passivation film, wherein the thickness of the silicon dioxide film is 100-200 angstroms, and the thickness of the silicon nitride film is 75-85nm, and the other surface is sequentially deposited with the silicon dioxide film and the silicon nitride film to form the double-layer passivation film, wherein the thickness of the silicon dioxide film is 100-200 angstroms, and the thickness of the silicon nitride film is 75-85 nm.
9. The method for preparing a solar cell based on surface pn crystals as claimed in claim 1, wherein if the silicon wafer is a p-type silicon wafer, the positive and negative electrodes are prepared on the surface with surface pn junctions by screen printing, or the positive and negative electrodes are led out from the two surfaces of the silicon wafer after the double-layer passivation film is formed;
if the silicon chip is an n-type silicon chip, a positive electrode and a negative electrode are prepared on one surface with a surface pn junction by adopting a screen printing method, or the positive electrode and the negative electrode are led out from two surfaces of the silicon chip after a double-layer passivation film is formed.
10. The preparation method of the surface pn crystal silicon solar cell according to claim 9, wherein if the silicon wafer is a p-type silicon wafer, if the positive electrode is led out from the back surface, the double-layer passivation film is burned through by laser, then the positive electrode is prepared by the method of silver paste screen printing on the surface, the positive electrode is dried, then the negative electrode is prepared by the method of silver paste screen printing on the front surface, and the negative electrode is dried and sintered to obtain the surface pn crystal silicon solar cell;
if the silicon wafer is an n-type silicon wafer, if the negative electrode is led out from the back side, silver paste is printed on the surface through silk screen printing, drying is carried out, then silver paste is printed on the front side through silk screen printing to prepare a positive electrode, drying and sintering are carried out, and the surface pn-based crystalline silicon solar cell is obtained;
wherein the width of the screen-printed fine grid is 35-45um, the distance between the fine grids is 1.4-1.6mm, and the width of the main grid is 0.7-0.8 mm.
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