CN109273558B - Preparation method of chain wet black silicon battery piece with high conversion efficiency - Google Patents
Preparation method of chain wet black silicon battery piece with high conversion efficiency Download PDFInfo
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- CN109273558B CN109273558B CN201810984023.9A CN201810984023A CN109273558B CN 109273558 B CN109273558 B CN 109273558B CN 201810984023 A CN201810984023 A CN 201810984023A CN 109273558 B CN109273558 B CN 109273558B
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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 System
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
-
- 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
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the field of solar cells, and discloses a preparation method of a chain wet black silicon cell with high conversion efficiency, which comprises the following steps: 1) selecting a P-type polycrystalline diamond wire silicon wafer, sequentially cleaning the P-type polycrystalline diamond wire silicon wafer by using an organic alkali solution and water, and drying the P-type polycrystalline diamond wire silicon wafer; 2) and (3) coating SiON on the back and the periphery of the silicon wafer: h, film; 3) manufacturing a black silicon suede on the front side of the silicon wafer; 4) diffusing the front side of the silicon wafer to form a PN junction; 5) removing phosphorosilicate glass on the front side of the silicon wafer and etching SiON on the back side and the periphery of the silicon wafer by using an acid solution: h, washing and drying the membrane; 6) plating an antireflection film on the black silicon suede; 7) printing a positive electrode on the front side of the silicon wafer; 8) and printing a back electrode on the back of the silicon wafer, and sintering. The conversion efficiency of the black silicon battery piece prepared by the method is effectively improved, and the method is suitable for technical upgrading of subsequent polycrystalline battery pieces such as black silicon + PERC series batteries, black silicon + MWT series batteries and the like.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a preparation method of a chain wet black silicon cell with high conversion efficiency.
Background
Solar energy photo-electricity generation is one of clean and environment-friendly sustainable energy utilization forms at present, and is rapidly developed in recent years in the world. At present, crystalline silicon solar cells are the mainstream field of photovoltaic power generation, but the cost is too high, so that the traditional energy sources cannot be replaced temporarily, the cost is reduced, and the photoelectric conversion efficiency is increased, so that the problem of the greatest photovoltaic industry is solved. In the conventional production technology, a polycrystalline diamond wire silicon wafer is subjected to acid texturing to prepare a micron-sized worm-shaped structure, the polycrystalline reflectivity is higher by about 24-30%, so that a cell cannot effectively capture sunlight, and the conversion efficiency of the cell is lower. Among the methods for improving the conversion efficiency of the solar cell and realizing mass production, the method for reducing the surface reflectivity of the silicon wafer and enhancing the sunlight absorption is a very effective mode. The black silicon technology has a good light trapping effect, can greatly reduce the surface reflectivity of the silicon wafer and enhance the absorption of sunlight, thereby greatly improving the conversion efficiency of the polycrystalline silicon wafer, solving the problems that the diamond wire cut polycrystalline silicon wafer is difficult to generate fluff and the crystal lattice is obvious, and being popular with polycrystalline cell manufacturers.
The traditional polycrystalline chain type wet black silicon battery piece process route is as follows:
a) using chain type double-sided texturing equipment to manufacture a nano-grade textured surface, wherein the front side reflectivity is 19-23%, and the back side reflectivity is 21-25%;
b) using the front diffusion of a black silicon wafer to manufacture a PN junction, and controlling the sheet resistance to be 90-100R □;
c) using a chain type etching device, enabling the front surface and the diffusion surface of the texture to be upward, wherein the etching liquid medicine is a mixed aqueous solution of hydrofluoric acid and nitric acid, the concentration of the hydrofluoric acid liquid medicine is 5wt%, the concentration of the nitric acid liquid medicine is 30wt%, the etching temperature is 8-15 ℃, the etching speed is 2.2-3.0m/min, and the etching thinning amount is 0.10-0.15 g;
d, etching the silicon wafer, texturing, and plating an anti-reflection film on the diffusion surface;
e) printing positive and negative electrodes on the front and back surfaces of the silicon wafer, and then drying and sintering to form good ohmic contact;
f) the black silicon conversion efficiency was tested.
Finally, the two sides of the silicon wafer of the existing polycrystalline chain type wet black silicon equipment are both black silicon suede surfaces, and the low-reflectivity nanometer suede structures on the front and back surfaces can greatly improve the sunlight absorption rate. However, in the manufacturing process of the battery, the nano suede structure on the back side has no effect on the battery, and the recombination rate of the back side is increased, so that the conversion efficiency of the battery is influenced. Therefore, the black silicon texture surface on the back surface of the silicon wafer needs to be removed in the preparation of the battery. Therefore, the existing wet black silicon has difficulty in making a great breakthrough in the conversion efficiency of the battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides the preparation method of the chain wet black silicon battery piece with high conversion efficiency, the conversion efficiency of the black silicon battery piece prepared by the method is effectively improved, and the preparation method is suitable for technical upgrading of subsequent polycrystalline battery pieces such as black silicon + PERC series batteries, black silicon + MWT series batteries and the like.
The specific technical scheme of the invention is as follows: a preparation method of a chain wet black silicon battery piece with high conversion efficiency comprises the following steps:
1) and (3) selecting a P-type polycrystalline diamond wire silicon wafer, sequentially cleaning the P-type polycrystalline diamond wire silicon wafer by using an organic alkali solution and water, and drying the P-type polycrystalline diamond wire silicon wafer.
2) And (3) coating SiON on the back and the periphery of the silicon wafer: and (4) H film.
In step 2): and the back of the silicon wafer uses SiON: h film, which can be deposited at a rate as fast as one time compared with conventional silicon nitride films, and SiON: the H film also has the characteristic of excellent compactness, and can effectively resist the liquid medicine corrosion SiON: h film, thereby protecting the back of the silicon chip from being corroded by the liquid medicine. Further, SiON: the H film also has the characteristic of being rich in hydrogen ions, and the hydrogen ions can effectively passivate the back surface of the silicon wafer and in-vivo defects in the subsequent working procedures.
3) And manufacturing a black silicon suede on the front side of the silicon wafer.
In step 3): the silicon chip enters a chain type black silicon device, the front surface of the silicon chip is not plated with a film, and a nano-structure suede surface is manufactured by the corrosion of the liquid medicine. The back of the silicon wafer is provided with thick SiON: the H film is continuously thinned in the texturing process and the subsequent pickling process, and finally, thinner SiON: and (4) H film.
4) And diffusing the front surface of the silicon wafer to form a PN junction on the front surface.
In step 4): because the periphery and the back of the silicon chip have residual SiON: the H film can prevent a diffused phosphorus source from entering the periphery and the back of the silicon wafer in the high-temperature diffusion process, so that PN junctions are effectively formed only on the front of the silicon wafer, and PN junctions are not formed on the periphery and the back of the silicon wafer.
5) Acid washing with acid solution to remove phosphorosilicate glass on the front side of the silicon wafer and SiON on the back side and the periphery of the corroded silicon wafer: h, membrane H, then washing and drying.
6) And plating an antireflection film on the black silicon texture surface, and not plating the antireflection film on the back surface of the silicon wafer.
7) And printing a positive electrode on the front side of the silicon wafer.
8) And printing a back electrode on the back of the silicon wafer, and sintering to obtain a finished product.
The invention has the following technical effects:
1. the invention makes use of the compact SiON: the H film prevents the chemical liquid from corroding the back of the silicon wafer to manufacture the black silicon suede, thereby perfectly keeping the flatness, smoothness and high reflectivity of the back of the silicon wafer after being cleaned by the organic base and avoiding the double surfaces of the silicon wafer from being manufactured into the nano-grade black silicon suede in the texturing process. Compared with a suede structure, the back surface of the theoretical battery piece has good smoothness, the back surface has long minority carrier lifetime, low recombination rate and the probability of absorbing long-wave band light again, so that the electrical property can be effectively improved, and the conversion efficiency is improved.
2. The invention skillfully utilizes the SiON remained on the silicon chip after the black silicon texture surface is manufactured: the H film undergoes hydrogen passivation in a high temperature diffusion furnace. Residual SiON on the back of the silicon wafer: hydrogen ions in the H film diffuse through SiON in a long time high temperature diffusion furnace: the H film reaches the surface and the inside of the silicon wafer, so that the H film is combined with the surface and the inside defects of the silicon wafer to form a stable structure, the recombination rate of the back of the silicon wafer is reduced, and the conversion efficiency can be effectively improved.
3. The invention skillfully utilizes the SiON remained on the back and the periphery of the silicon wafer: the H film prevents phosphorus source from entering the silicon wafer in diffusion, and effectively prevents PN junctions from being formed around and on the back of the silicon wafer, so that the silicon wafer is cleaned by hydrofluoric acid to remove SiON on the periphery and on the back of the silicon wafer: the H film can achieve the purpose of conducting the positive electrode and the negative electrode. Compared with the existing chain wet method black silicon, the method uses a large amount of chemicals such as hydrofluoric acid, nitric acid, potassium hydroxide and the like, and achieves the purpose of saving the chemicals.
Preferably, in the step 1), the organic alkali solution is a tetramethylammonium hydroxide solution with the volume concentration of 5-20%, the cleaning temperature is normal temperature, the cleaning time is 150-300s, and the reflectivity of the front and back surfaces of the silicon wafer after cleaning is 45-60%.
Preferably, in the step 2), a low-pressure tubular PECVD device is used for coating, the silane flow rate is 500-2000sccm, the ammonia gas flow rate is 1000-5000sccm, the laughing gas flow rate is 2000-7000sccm, the deposition pressure is 1300-1800mTorr, and the total deposition time is 45-90 min; SiON: the film thickness of the H film is 100-150nm, and the refractive index is 1.85-2.2.
Preferably, in the step 3), a chain type black silicon device is adopted to manufacture a texture surface, the size of the texture surface after texture manufacturing is 500-900nm, and the reflectivity is 18-23%; SiON on the back of the silicon wafer after texturing: the thickness of the H film is 5-50 nm.
In the actual development process, the team of the invention also encounters the following technical problems: the team of the present invention found that in actual production, back SiON: the thickness of the H film is also very important, which if too thin would result in SiON: the H film is removed too early, and the back of the silicon wafer is corroded by the liquid medicine to form a black silicon suede structure, so that the efficiency is not obviously improved. In order to solve the technical problem, after a plurality of series of attempts, the team of the invention integrates various factors, namely SiON on the back surface of the silicon wafer: the thickness of the H film is increased to 100-150nm, and the thickness in the range can effectively resist the SiON corroded by the liquid medicine for manufacturing the groove body with the black silicon suede: and the H film protects the back surface of the silicon wafer from being corroded to form a black silicon nanometer suede structure, and meanwhile, the thickness of the H film is not too thick, so that other performances of the silicon wafer are influenced or the cost is increased.
Preferably, in step 4), the sheet resistance after diffusion is 90-100R □.
Preferably, in the step 5), a chain type phosphorosilicate glass removing device is adopted to remove phosphorosilicate glass, the acid solution is 10-15wt% of hydrofluoric acid solution, the acid washing time is 150-200s, the temperature is 60-90 ℃, and the reflectivity of the back surface of the silicon wafer after drying is 45-60%.
Preferably, in step 8), the paste composition used in back-printing the back electrode includes:
55-80wt% of aluminum powder,
0.5 to 3.0 weight percent of lead-free glass powder,
10-25wt% of organic carrier,
5-18wt% of solvent,
0.1 to 2.0 weight percent of auxiliary agent.
In the actual development process, the team of the invention finds that: the wet black silicon battery piece prepared by the method of the invention can meet the situation of unqualified back field tension. The reason for this is that the paste used when printing the electrodes on the back side is not suitable. The back suede of the original wet black silicon is of an uneven nano suede structure, which is beneficial to back aluminum sintering to form good contact, so that the tensile force meets the requirements of customers. The back surface of the black silicon battery piece is very smooth, so that the back aluminum is not favorably in good contact with the silicon piece, the adhesive force of the back aluminum is insufficient, the requirement cannot be completely met by adopting conventional slurry, and therefore the adhesive force of the back aluminum can be effectively improved by developing the slurry specially used for the silicon piece, and the technical problem is solved.
Preferably, the aluminum powder is spherical, the purity is more than 99.8%, the particle size is 0.5-2.0 μm, wherein the aluminum powder with the particle size of 0.5-1.0 μm accounts for 5-20% of the total weight, the aluminum powder with the particle size of 1.0-1.5 μm accounts for 20-60% of the total weight, and the aluminum powder with the particle size of 1.5-2.0 μm accounts for 20-40% of the total weight.
The diameter of the aluminum powder needs to be matched with different sizes. The aluminum powder has the advantages of small diameter, large surface area, full contact with silicon wafers and preferential melting at high temperature. The large particles have the advantage of excellent conductivity.
Preferably, the composition of the lead-free glass powder is as follows: 15-45wt% of bismuth oxide, 5-30wt% of boron oxide, 15-35wt% of silicon oxide, 5-25wt% of zinc oxide, 1-20wt% of calcium oxide and 1-15wt% of tin oxide; wherein the median particle size of the lead-free glass powder is less than 2 μm, the maximum particle size is less than 5 μm, and the softening temperature is 450-600 ℃.
The glass powder belongs to a relatively important component in the paste, and different component proportions of the glass powder have great influence on contact resistance between a printed silicon wafer and the silicon wafer, battery warping performance, paste tension and the like.
Preferably, the organic carrier is one of ethyl cellulose, acrylic resin and alkyd resin; the solvent is one of terpineol, butyl carbitol and butyl carbitol acetate; the auxiliary agent is phthalic acid ester.
Compared with the prior art, the invention has the beneficial effects that:
1. the product of the invention has better applicability, and is suitable for the subsequent technical upgrading of the polycrystalline cell, such as: black silicon + PERC series batteries, black silicon + MWT series batteries.
2. The invention has the advantages of simple process, good stability and the like.
3. The invention has the remarkable characteristic that the suede of the back of the battery is very smooth, which is beneficial to the reflection of long-wave band light to form secondary absorption.
4. The back of the battery has the characteristic of low recombination of majority carriers.
5. The back of the silicon wafer has a hydrogen ion passivation effect, and conversion efficiency is improved.
Drawings
FIG. 1 is a microscope photograph of a diamond wire silicon wafer (some characters in the drawing are not clear enough, but do not affect the understanding of the technical scheme of the invention);
FIG. 2 is a backside texture after wet black silicon etch of comparative example 1;
FIG. 3 is a backside texture image after the wet black silicon etch of example 1;
FIG. 4 is a schematic diagram of a surface structure of a conventional wet black silicon wafer made of a diamond wire silicon wafer;
FIG. 5 is a schematic diagram of the surface structure of a black silicon wafer prepared by a diamond wire silicon wafer by a wet process;
the reference signs are: 1-a silicon wafer is subjected to rough polishing by organic alkali and then is textured; 2-inside the silicon wafer; 3-black silicon wafer surface texture structure.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A preparation method of a chain wet black silicon battery piece with high conversion efficiency comprises the following steps:
1) selecting a P-type polycrystalline diamond wire silicon wafer, sequentially cleaning the P-type polycrystalline diamond wire silicon wafer by using an organic alkali solution and water, and drying the P-type polycrystalline diamond wire silicon wafer;
2) and (3) coating SiON on the back and the periphery of the silicon wafer: h, film;
3) manufacturing a black silicon suede on the front side of the silicon wafer;
4) diffusing the front surface of the silicon wafer to form a PN junction on the front surface;
5) acid washing with acid solution to remove phosphorosilicate glass on the front side of the silicon wafer and SiON on the back side and the periphery of the corroded silicon wafer: h, washing and drying the membrane;
6) plating an antireflection film on the black silicon suede, and not plating the antireflection film on the back of the silicon wafer;
7) printing a positive electrode on the front side of the silicon wafer;
8) and printing a back electrode on the back of the silicon wafer, and sintering to obtain a finished product.
Preferably, in the step 1), the organic alkali solution is a tetramethylammonium hydroxide solution with the volume concentration of 5-20%, the cleaning temperature is normal temperature, the cleaning time is 150-300s, and the reflectivity of the front and back surfaces of the silicon wafer after cleaning is 45-60%.
Preferably, in the step 2), a low-pressure tubular PECVD device is used for coating, the silane flow rate is 500-2000sccm, the ammonia gas flow rate is 1000-5000sccm, the laughing gas flow rate is 2000-7000sccm, the deposition pressure is 1300-1800mTorr, and the total deposition time is 45-90 min; SiON: the film thickness of the H film is 100-150nm, and the refractive index is 1.85-2.2.
Preferably, in the step 3), a chain type black silicon device is adopted to manufacture a texture surface, the size of the texture surface after texture manufacturing is 500-900nm, and the reflectivity is 18-23%; SiON on the back of the silicon wafer after texturing: the thickness of the H film is 5-50 nm.
Preferably, in step 4), the sheet resistance after diffusion is 90-100R □.
Preferably, in the step 5), a chain type phosphorosilicate glass removing device is adopted to remove phosphorosilicate glass, the acid solution is 10-15wt% of hydrofluoric acid solution, the acid washing time is 150-200s, the temperature is 60-90 ℃, and the reflectivity of the back surface of the silicon wafer after drying is 45-60%.
Preferably, in step 8), the paste composition used in back-printing the back electrode includes:
55-80wt% of aluminum powder,
0.5 to 3.0 weight percent of lead-free glass powder,
10-25wt% of organic carrier,
5-18wt% of solvent,
0.1 to 2.0 weight percent of auxiliary agent.
Preferably, the aluminum powder is spherical, the purity is more than 99.8%, the particle size is 0.5-2.0 μm, wherein the aluminum powder with the particle size of 0.5-1.0 μm accounts for 5-20% of the total weight, the aluminum powder with the particle size of 1.0-1.5 μm accounts for 20-60% of the total weight, and the aluminum powder with the particle size of 1.5-2.0 μm accounts for 20-40% of the total weight.
Preferably, the composition of the lead-free glass powder is as follows: 15-45wt% of bismuth oxide, 5-30wt% of boron oxide, 15-35wt% of silicon oxide, 5-25wt% of zinc oxide, 1-20wt% of calcium oxide and 1-15wt% of tin oxide; wherein the median particle size of the lead-free glass powder is less than 2 μm, the maximum particle size is less than 5 μm, and the softening temperature is 450-600 ℃.
Preferably, the organic carrier is one of ethyl cellulose, acrylic resin and alkyd resin; the solvent is one of terpineol, butyl carbitol and butyl carbitol acetate; the auxiliary agent is phthalic acid ester.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The preparation method is characterized in that 16000 pieces of P-type polycrystalline silicon wafers with the size of 156.75mm multiplied by 156.75mm are selected, the distribution type is uniformly divided into 4 groups, wherein 1-3 groups are examples 1-3, the preparation method is adopted, the 4 th group is a comparative example, the traditional wet black silicon preparation process is adopted, and four groups of wafers record each experimental data and efficiency and the like respectively in each process for comparison.
Example 1
1) The diamond wire polycrystalline silicon wafer uses a chain type organic alkali cleaning device, and the volume ratio of the used liquid medicine of tetramethyl ammonium hydroxide to pure water is 1: and 15, cleaning for 200s, and completing a pre-cleaning process through a subsequent water tank and a drying tank.
2) The silicon chip is inserted into the graphite boat carrier and adopts a tubular coating device, and the back of the silicon chip is coated with SiON: the H film had a film thickness of 100nm and a refractive index of 1.85. Depositing the SiON on the back surface of the silicon wafer by using the deposition pressure of 1500mTorr and the silane flow of 500sccm, the ammonia flow of 5000sccm and the laughing gas flow of 7000 sccm: the total time of the H membrane is 45 min.
3) And (3) SiON plating: h membrane silicon chip advances chain wet process black silicon equipment, and the black silicon matte face is makeed to silicon chip front, and the matte size is 700nm, and the reflectivity is 18%, and the reverse side is because of having SiON: the H film protection cannot be carried out on the texture, but the SiON: and (3) reacting the H film with hydrofluoric acid liquid medicine in wet black silicon equipment, and finally obtaining SiON on the back of the silicon wafer: the H film remained 10nm.
4) After the suede is manufactured, normal diffusion is carried out, and the sheet resistance is controlled to be 90R □.
5) After the diffusion is finished, the silicon wafer enters a chain type phosphorosilicate glass removing device, phosphorosilicate glass on the front side of the silicon wafer and SiON on the back side and the periphery of the silicon wafer are removed: and H, using hydrofluoric acid liquor with the concentration of 10%, pickling for 150s, reacting at the temperature of 60 ℃, and washing and drying the silicon wafer to obtain the silicon wafer with the back surface reflectivity of 45%.
6) And after the phosphorosilicate glass is removed, a low-pressure tubular PECVD device is adopted to plate the antireflection film on the black silicon suede surface, and the antireflection film is not plated on the back surface of the silicon wafer.
7) And plating an antireflection film silicon chip on the front surface, printing a positive electrode on the front surface by using conventional slurry and a screen printing method, and printing a back electrode on the back surface by using improved, enhanced and passivated slurry.
Wherein the reinforced passivation slurry comprises the following components: 68 wt% of aluminum powder, 2 wt% of lead-free glass powder, 17 wt% of organic carrier (ethyl cellulose), 12 wt% of solvent (terpineol) and 1.0 wt% of auxiliary agent (phthalic acid ester).
Wherein the aluminum powder is spherical, the purity is more than 99.8%, the particle size is 0.5-2.0 μm, wherein the aluminum powder with the particle size of 0.5-1.0 μm accounts for 17% of the total weight, the aluminum powder with the particle size of 1.0-1.5 μm accounts for 50% of the total weight, and the aluminum powder with the particle size of 1.5-2.0 μm accounts for 33% of the total weight.
Composition of the lead-free glass powder: 25wt% of bismuth oxide, 17 wt% of boron oxide, 25wt% of silicon oxide, 15wt% of zinc oxide, 10 wt% of calcium oxide and 8wt% of tin oxide; wherein the median particle size of the lead-free glass powder is less than 2 μm, the maximum particle size is less than 5 μm, and the softening temperature is 450-600 ℃.
8) And (4) forming a good ohmic contact by high-temperature sintering, and testing the conversion efficiency of the cell.
Example 2
1) The diamond wire polycrystalline silicon wafer uses a chain type organic alkali cleaning device, and the volume ratio of the used liquid medicine of tetramethyl ammonium hydroxide to pure water is 1: and 5, cleaning for 200s, and completing a pre-cleaning process through a subsequent water tank and a drying tank.
2) The silicon chip is inserted into the graphite boat carrier and adopts a tubular coating device, and the back of the silicon chip is coated with SiON: h film, 150nm thick, 2.0 refractive index. Depositing the SiON on the back surface of the silicon wafer by using the deposition pressure of 1500mTorr and the flow rate of silane of 700sccm, the flow rate of ammonia of 3000sccm and the flow rate of laughing gas of 4000 sccm: the total time of the H film is 50 min.
3) And (3) SiON plating: h membrane silicon chip advances chain wet process black silicon equipment, and the black silicon matte face is makeed to silicon chip front, and the matte size is 800nm, and the reflectivity is 19%, and the reverse side is because of having SiON: the H film protection cannot be carried out on the texture, but the SiON: and (3) reacting the H film with hydrofluoric acid liquid medicine in wet black silicon equipment, and finally obtaining SiON on the back of the silicon wafer: the H film remained 30 nm.
4) After the suede is manufactured, normal diffusion is carried out, and the sheet resistance is controlled to be 95R □.
5) After the diffusion is finished, the silicon wafer enters a chain type phosphorosilicate glass removing device, phosphorosilicate glass on the front side of the silicon wafer and SiON on the back side and the periphery of the silicon wafer are removed: and H, using hydrofluoric acid liquor with the concentration of 12%, pickling for 170s, reacting at the temperature of 80 ℃, and washing and drying the silicon wafer to obtain the silicon wafer with the back surface reflectivity of 55%.
6) And after the phosphorosilicate glass is removed, a low-pressure tubular PECVD device is adopted to plate the antireflection film on the black silicon suede surface, and the antireflection film is not plated on the back surface of the silicon wafer.
7) And plating an antireflection film silicon chip on the front surface, printing a positive electrode on the front surface by using conventional slurry and a screen printing method, and printing a back electrode on the back surface by using improved, enhanced and passivated slurry.
Wherein the reinforced passivation slurry comprises the following components: 62 wt% of aluminum powder, 3 wt% of lead-free glass powder, 15wt% of organic carrier (acrylic resin), 18wt% of solvent (butyl carbitol) and 2.0wt% of auxiliary agent (phthalate).
Wherein the aluminum powder is spherical, the purity is more than 99.8%, the particle size is 0.5-2.0 μm, wherein the aluminum powder with the particle size of 0.5-1.0 μm accounts for 10% of the total weight, the aluminum powder with the particle size of 1.0-1.5 μm accounts for 50% of the total weight, and the aluminum powder with the particle size of 1.5-2.0 μm accounts for 40% of the total weight.
Composition of the lead-free glass powder: 25wt% of bismuth oxide, 25wt% of boron oxide, 20wt% of silicon oxide, 20wt% of zinc oxide, 5wt% of calcium oxide and 5wt% of tin oxide; wherein the median particle size of the lead-free glass powder is less than 2 μm, the maximum particle size is less than 5 μm, and the softening temperature is 450-600 ℃.
8) And (4) forming a good ohmic contact by high-temperature sintering, and testing the conversion efficiency of the cell.
Example 3
1) The diamond wire polycrystalline silicon wafer uses a chain type organic alkali cleaning device, and the volume ratio of the used liquid medicine of tetramethyl ammonium hydroxide to pure water is 1: 5, the cleaning time is 300s, and the pre-cleaning process is completed through a subsequent water tank and a drying tank.
21) The silicon chip is inserted into the graphite boat carrier and adopts a tubular coating device, and the back of the silicon chip is coated with SiON: h film, 150nm thick, 2.08 refractive index. Depositing the SiON on the back of the silicon wafer by using the deposition pressure of 1500mTorr and the flow rate of silane of 900sccm, the flow rate of ammonia of 3000sccm and the flow rate of laughing gas of 3000 sccm: the total time of the H film is 50 min.
3) And (3) SiON plating: h membrane silicon chip advances chain wet process black silicon equipment, and the black silicon matte face is makeed to silicon chip front, and the matte size is 800nm, and the reflectivity is 19%, and the reverse side is because of having SiON: the H film protection cannot be carried out on the texture, but the SiON: and (3) reacting the H film with hydrofluoric acid liquid medicine in wet black silicon equipment, and finally obtaining SiON on the back of the silicon wafer: the H film was retained at 50 nm.
4) After the suede is manufactured, normal diffusion is carried out, and the sheet resistance is controlled to be 100R □.
5) After the diffusion is finished, the silicon wafer enters a chain type phosphorosilicate glass removing device, phosphorosilicate glass on the front side of the silicon wafer and SiON on the back side and the periphery of the silicon wafer are removed: and H, using hydrofluoric acid liquor with the concentration of 15%, pickling for 180s, reacting at the temperature of 90 ℃, and washing and drying the silicon wafer to obtain the silicon wafer with the back surface reflectivity of 60%.
6) And after the phosphorosilicate glass is removed, a low-pressure tubular PECVD device is adopted to plate the antireflection film on the black silicon suede surface, and the antireflection film is not plated on the back surface of the silicon wafer.
7) And plating an antireflection film silicon chip on the front surface, printing a positive electrode on the front surface by using conventional slurry and a screen printing method, and printing a back electrode on the back surface by using improved, enhanced and passivated slurry.
Wherein the reinforced passivation slurry comprises the following components: 69.4 wt% of aluminum powder, 0.5 wt% of lead-free glass powder, 25wt% of organic carrier (alkyd resin), 5wt% of solvent (butyl carbitol acetate) and 0.1 wt% of auxiliary agent (phthalic acid ester).
Wherein the aluminum powder is spherical, the purity is more than 99.8%, the particle size is 0.5-2.0 μm, wherein the aluminum powder with the particle size of 0.5-1.0 μm accounts for 15% of the total weight, the aluminum powder with the particle size of 1.0-1.5 μm accounts for 60% of the total weight, and the aluminum powder with the particle size of 1.5-2.0 μm accounts for 25% of the total weight.
Composition of the lead-free glass powder: 40 wt% of bismuth oxide, 10 wt% of boron oxide, 15wt% of silicon oxide, 20wt% of zinc oxide, 10 wt% of calcium oxide and 5wt% of tin oxide; wherein the median particle size of the lead-free glass powder is less than 2 μm, the maximum particle size is less than 5 μm, and the softening temperature is 450-600 ℃.
8) And (4) forming a good ohmic contact by high-temperature sintering, and testing the conversion efficiency of the cell.
Comparative example 1
The polycrystalline diamond wire silicon wafer is processed by adopting the conventional wet black silicon process in the background technology to manufacture the black silicon battery piece.
Comparative example 2 (SiON: H film thickness 20nm)
1) The diamond wire polycrystalline silicon wafer is cleaned by using chain type organic alkali cleaning equipment, the volume ratio of tetramethylammonium hydroxide to pure water is 1: 5, the cleaning time is 300s, and the pre-cleaning process is completed through a subsequent water tank and a drying tank.
2) The silicon chip is inserted into the graphite boat carrier and adopts a tubular coating device, and the back of the silicon chip is coated with SiON: the H film had a film thickness of 20nm and a refractive index of 2.08. Depositing the SiON on the back of the silicon wafer by using the deposition pressure of 1500mTorr and the flow rate of silane of 900sccm, the flow rate of ammonia of 3000sccm and the flow rate of laughing gas of 3000 sccm: the total time of the H film is 25 min.
3) And (3) SiON plating: and feeding the H-film silicon wafer into a chain type wet black silicon device, and corroding the front side and the back side of the silicon wafer by the liquid medicine at the same time. The front surface of the silicon chip reacts with the liquid medicine to manufacture a black silicon suede, the size of the suede is 800nm, and the reflectivity is 19%. SiON on the back of the silicon wafer: the H film also reacts with the chemical solution because the back SiON: the H film thickness is too thin of 20nm, resulting in SiON: the H film is removed too early, and the exposed silicon continues to react with the liquid medicine to generate a ditch-shaped suede with the size of 3um and the reflectivity of 23 percent.
4) After the suede is manufactured, normal diffusion is carried out, and the sheet resistance is controlled to be 100R □.
5) After the diffusion is finished, the silicon wafer enters a chain type phosphorosilicate glass removing device, phosphorosilicate glass on the front side of the silicon wafer and SiON on the back side and the periphery of the silicon wafer are removed: and H, using hydrofluoric acid liquor with the concentration of 15%, pickling for 180s, reacting at the temperature of 90 ℃, and washing and drying the silicon wafer to obtain the silicon wafer with the back surface reflectivity of 60%.
6) And after the phosphorosilicate glass is removed, a low-pressure tubular PECVD device is adopted to plate the antireflection film on the black silicon suede surface, and the antireflection film is not plated on the back surface of the silicon wafer.
7) And plating an antireflection film silicon chip on the front surface, printing a positive electrode on the front surface by using conventional slurry and a screen printing method, and printing a back electrode on the back surface by using improved, enhanced and passivated slurry.
Wherein the reinforced passivation slurry comprises the following components: 68 wt% of aluminum powder, 2 wt% of lead-free glass powder, 17 wt% of organic carrier (ethyl cellulose), 12 wt% of solvent (terpineol) and 1.0 wt% of auxiliary agent (phthalic acid ester).
Wherein the aluminum powder is spherical, the purity is more than 99.8%, the particle size is 0.5-2.0 μm, wherein the aluminum powder with the particle size of 0.5-1.0 μm accounts for 17% of the total weight, the aluminum powder with the particle size of 1.0-1.5 μm accounts for 50% of the total weight, and the aluminum powder with the particle size of 1.5-2.0 μm accounts for 33% of the total weight.
Composition of the lead-free glass powder: 25wt% of bismuth oxide, 17 wt% of boron oxide, 25wt% of silicon oxide, 15wt% of zinc oxide, 10 wt% of calcium oxide and 8wt% of tin oxide; wherein the median particle size of the lead-free glass powder is less than 2 μm, the maximum particle size is less than 5 μm, and the softening temperature is 450-600 ℃.
8) And (4) forming a good ohmic contact by high-temperature sintering, and testing the conversion efficiency of the cell.
The technical indexes are as follows:
respectively testing the electrical property data of the polycrystalline black silicon cell pieces in the examples 1-3 and the comparative examples 1-2; the electrical property test data is as follows:
| categories | Uoc(V) | Isc(A) | Rs(Ω) | Rsh(Ω) | FF（％) | Eta（％) | IRev2(A) | Count |
| Comparative example 1 | 0.638 | 9.221 | 0.00163 | 169 | 79.87 | 19.201 | 0.128 | 4000 |
| Comparative example 2 | 0.639 | 9.232 | 0.00163 | 650 | 80.05 | 19.291 | 0.103 | 4000 |
| Example 1 | 0.641 | 9.252 | 0.00154 | 784 | 80.11 | 19.415 | 0.08 | 4000 |
| Example 2 | 0.642 | 9.262 | 0.00149 | 687 | 80.23 | 19.495 | 0.09 | 4000 |
| Example 3 | 0.642 | 9.263 | 0.00151 | 652 | 80.21 | 19.492 | 0.09 | 4000 |
From the above table, it can be seen that when the method of the present invention is used to process a polycrystalline diamond wire silicon wafer into a black silicon cell, the conversion efficiency (Eta) is improved by 0.294% at most and 0.214% at least (Eta is generally difficult to improve, and the improvement of the above range is a significant advance in the art).
Wherein, the following is the comparison of the prior chain wet black silicon process flow with the chain wet black silicon process flow of the invention:
picture description:
FIG. 1 is a microscope picture of an original diamond wire, wherein the surface of a silicon wafer has a very shallow cutting damage layer.
Fig. 2 is a picture of the back side suede of the wet black silicon prepared in comparative example 1, wherein the original wet black silicon is prepared into a round hole-shaped black silicon suede on the back side of a silicon wafer based on a cutting damage layer on the original surface.
Fig. 3 is a black silicon back side suede image obtained in example 1, wherein the surface of the original silicon wafer has a very shallow cutting damage layer, and the suede is very flat after being cleaned by organic alkali, so that the flat suede structure can be well maintained in subsequent texturing and etching.
FIG. 4 is a simplified diagram of the surface structure of a conventional wet black silicon wafer made of a diamond wire silicon wafer: after the silicon wafer is roughly polished by organic alkali, the textured surface 1 forms black silicon wafer surface textured structures 3 on the front and back surfaces after texturing, and the interior 2 of the silicon wafer is unchanged.
FIG. 5 is a schematic diagram of the surface structure of a black silicon wafer prepared by a diamond wire silicon wafer by a high-efficiency wet method: after the silicon wafer is roughly polished by organic alkali, the textured surface 1 only forms a black silicon wafer surface textured structure 3 on the front surface after texturing, and the interior 2 of the silicon wafer is unchanged.
Compared with the black silicon suede of the comparative example 1, the black silicon suede of the embodiment 1 has the advantages that: 1. comparative example 1 a cell in which residues are easily retained and which is likely to react with a silicon wafer and a thin film on the surface of the silicon wafer in a subsequent process to cause poor appearance; 2. comparative example 1 is prone to residue retention, creating recombination centers, resulting in lower efficiency; 3. the back aluminum paste of the comparative example 1 is not easy to effectively fill the suede, so that cavities are formed, the series resistance is increased, and the efficiency is influenced; 4. the back of the invention is provided with a flat suede structure, and the back is printed with aluminum paste to form a mirror effect, so that light of long wave band which is about to penetrate through the silicon wafer is easily reflected back to the silicon wafer for absorption.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of a chain wet black silicon battery piece with high conversion efficiency is characterized by comprising the following steps:
1) selecting a P-type polycrystalline diamond wire silicon wafer, sequentially cleaning the P-type polycrystalline diamond wire silicon wafer by using an organic alkali solution and water, and drying the P-type polycrystalline diamond wire silicon wafer;
2) and (3) coating SiON on the back and the periphery of the silicon wafer: h, film formation: coating with low-pressure tubular PECVD equipment, wherein the silane flow is 500-2000sccm, the ammonia gas flow is 1000-5000sccm, the laughing gas flow is 2000-7000sccm, the deposition pressure is 1300-1800mTorr, and the total deposition time is 45-90 min; SiON: the thickness of the H film is 100-150nm, and the refractive index is 1.85-2.2;
3) manufacturing a black silicon suede on the front side of the silicon wafer; SiON on the back of the silicon wafer after texturing: the thickness of the H film is 5-50 nm;
4) diffusing the front surface of the silicon wafer to form a PN junction on the front surface;
5) acid washing with acid solution to remove phosphorosilicate glass on the front side of the silicon wafer and SiON on the back side and the periphery of the corroded silicon wafer: h, washing and drying the membrane;
6) plating an antireflection film on the black silicon suede, and not plating the antireflection film on the back of the silicon wafer;
7) printing a positive electrode on the front side of the silicon wafer;
8) and printing a back electrode on the back of the silicon wafer, and sintering to obtain a finished product.
2. The method as claimed in claim 1, wherein in step 1), the organic alkali solution is 5-20 vol% tetramethylammonium hydroxide solution, the cleaning temperature is room temperature, the cleaning time is 150-.
3. The method as claimed in claim 1, wherein in step 3), the chain-type wet black silicon device is used to fabricate a textured surface, the textured surface has a size of 500 nm and 900nm, and the reflectivity is 18-23%.
4. The method for preparing a chain wet black silicon battery plate with high conversion efficiency as claimed in claim 1, wherein the sheet resistance after diffusion in step 4) is 90-100 ohm/□.
5. The method as claimed in claim 1, wherein in step 5), the phosphorosilicate glass is removed by a chain-type phosphorosilicate glass removing device, the acid solution is 10-15wt% hydrofluoric acid solution, the acid washing time is 150-200s, the temperature is 60-90 ℃, and the reflectivity of the back surface of the silicon wafer after drying is 45-60%.
6. The method for preparing a chain wet black silicon battery plate with high conversion efficiency as claimed in claim 1, wherein in the step 8), when the back electrode is printed on the back side, the adopted slurry components comprise:
55-80wt% of aluminum powder,
0.5 to 3.0 weight percent of lead-free glass powder,
10-25wt% of organic carrier,
5-18wt% of solvent,
0.1 to 2.0 weight percent of auxiliary agent.
7. The method for preparing the chain type wet black silicon battery piece with high conversion efficiency according to claim 6, wherein the aluminum powder is spherical, the purity is greater than 99.8%, the particle size is 0.5-2.0 μm, wherein the aluminum powder with the particle size of 0.5-1.0 μm accounts for 5-20% of the total weight, the aluminum powder with the particle size of 1.0-1.5 μm accounts for 20-60% of the total weight, and the aluminum powder with the particle size of 1.5-2.0 μm accounts for 20-40% of the total weight.
8. The method for preparing the chain wet black silicon battery piece with high conversion efficiency as claimed in claim 6, wherein the composition of the lead-free glass powder is as follows: 15-45wt% of bismuth oxide, 5-30wt% of boron oxide, 15-35wt% of silicon oxide, 5-25wt% of zinc oxide, 1-20wt% of calcium oxide and 1-15wt% of tin oxide; wherein the median particle size of the lead-free glass powder is less than 2 mu m, the maximum particle size is less than 5 mu m, and the softening temperature is 450-600 ℃.
9. The method for preparing chain wet black silicon battery plate with high conversion efficiency as claimed in claim 6, wherein the organic vehicle is one of ethyl cellulose, acrylic resin and alkyd resin; the solvent is one of terpineol, butyl carbitol and butyl carbitol acetate; the auxiliary agent is phthalic acid ester.
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| CN107293606A (en) * | 2017-06-19 | 2017-10-24 | 浙江晶科能源有限公司 | P-type IBC battery structures and preparation method thereof |
| CN107268087A (en) * | 2017-06-23 | 2017-10-20 | 南京纳鑫新材料有限公司 | A kind of metal catalytic etching method for the polysilicon chip reflectivity for reducing Buddha's warrior attendant wire cutting |
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