CN110846721A - Monocrystalline silicon texturing additive formula containing polyalcohol and PEG - Google Patents
Monocrystalline silicon texturing additive formula containing polyalcohol and PEG Download PDFInfo
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- CN110846721A CN110846721A CN201910965957.2A CN201910965957A CN110846721A CN 110846721 A CN110846721 A CN 110846721A CN 201910965957 A CN201910965957 A CN 201910965957A CN 110846721 A CN110846721 A CN 110846721A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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- C30B29/06—Silicon
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Abstract
The invention relates to an additive formula of monocrystalline silicon texturing solution containing polyalcohol and PEG, which comprises the following components: polyol, PEG, organic acid sodium salt, inorganic salt and deionized water. Wherein the polyhydric alcohol is one or a mixture of more of MPD, ethylene glycol, 1, 2-propylene glycol, glycerol and 1, 4-butanediol, and the weight ratio of the polyhydric alcohol to the water is 0.5-2.5: 100; the PEG comprises one or more of PEG200, PEG400, PEG600, PEG800 and PEG1000, and the weight ratio of the PEG to water is 1.0-3.0: 100; the organic sodium salt is one or a mixture of more of sodium succinate, sodium oxalate, sodium benzoate and sodium isophthalate, and the weight ratio of the organic sodium salt to water is 0.1-1.0: 100; the inorganic salt is NaCl, KCl, Na2SO4、K2SO4、Na2SiO3The weight ratio of one or more of the above components to water is 0.1-1.0: 100. The formula of the single crystal silicon surface texturing agent is as follows: adding heavy metal into 1L of deionized water20.0-40.0mL of NaOH solution with the weight percentage concentration of 30 percent, and 8.0-18.0mL of the additive.
Description
Technical Field
The invention belongs to the technical field of solar cell monocrystalline silicon wafers, and particularly relates to a method for influencing texture surface making of a monocrystalline silicon wafer by using the type and content of polyalcohol and polymer thereof.
Background
Renewable resources are those that can be utilized by humans for a long period of time, solar energy being one of the most important, the energy of which is permanent to the earth. It follows that if humans can obtain solar energy in large quantities, efficiently, and at low cost, depending on technology, the energy sources owned by humans are unlimited. At present, the human beings have many ways of utilizing solar energy, but the total amount is very little, wherein the most important way is to carry out photoelectric conversion, and the corresponding core technology is a single crystal silicon solar cell.
The single crystal silicon solar cell mainly absorbs visible light part with the wavelength of 400-700 nm. The main material adopts 3-5 mm of P-type monocrystalline silicon. When light waves irradiate the surface of the cell, photons pass through the antireflection film and enter silicon, and photo-generated electron-hole pairs are excited. Photogenerated carriers contribute to the emission voltage if they can cross the depletion region before recombination. When a load is connected to two ends of the photovoltaic cell, the photovoltaic cell flows from the P area to the N area through the load, and power is output in the load. And then transmitted to each device capable of converting the electric energy through a lead, and the electric energy is converted into other forms of energy. And thus is ultimately utilized by humans.
Texturing on the surface of monocrystalline silicon is an important means for improving the photoelectric conversion efficiency of the silicon solar cell. Texturing is to use the anisotropic etching property of silicon to etch a pyramid-like or honeycomb-like structure on the surface. The purpose is two points: firstly, the area of a PN junction is increased; and secondly, the reflectivity of the monocrystalline silicon solar cell to light is reduced.
Monocrystalline silicon wafers can be etched by a certain concentration of alkali and are anisotropic, i.e. the etch rates on different crystal planes are different, which provides us with texturing possibilities. By using the principle, the monocrystalline silicon piece with the specific crystal orientation is put into the alkaline solution for corrosion, and the texturing operation can be completed. The reaction equation of the silicon wafer surface is as follows:
Si + H2O + 2OH-= SiO3 2-+ 2H2
because factors such as the alkali corrosion rate, the infiltration of the silicon surface, the escape of hydrogen and the like have important influence on the effect of the texturing process, the addition of the additive into the texturing solution is important for the whole texturing system, and the additive can directly influence the photoelectric conversion efficiency of the solar cell. The property can be utilized to select proper additives, so that the texture-making quality is improved, and the product is more complete. For example, when a small amount of surfactant is added into the texturing agent, the surface tension of the texturing solution can be effectively reduced, so that the reaction can be smoothly carried out, and the phenomenon that hydrogen bubbles can not be separated from the surface of the monocrystalline silicon wafer can not occur. A certain amount of acid substances are added into the texturing solution to reduce the concentration of hydroxide ions in the system, so that the reaction of silicon and hydroxide is slowed down, the texturing reaction rate is inhibited, the prepared textured surface is more uniform, and white spots and the like cannot be generated. On the contrary, if the reaction does not proceed sufficiently for a certain period of time, it is optional to add an appropriate amount of alkali to the texturing solution to allow the reaction to proceed smoothly.
At present, the common wool making liquid in industrial production is prepared from NaOH and Na2SiO3Isopropanol, deionized water and the like. The texture-making effect of the texture-making liquid is not ideal, and the size of the obtained pyramid is larger, generally 10-15 μm; the corrosion amount of the silicon chip is relatively large; the texturing stability is poor; the silicon wafer surface after texturing has poor uniformity, and obvious problems of black spots, white spots and the like can be seen. Therefore, if the texturing additive is added into the texturing solution, the problem can be well solved, and the method has important significance.
The invention mainly researches the influence of the types and contents of the polyhydric alcohols and the polymer polyhydric alcohols and other additives on the texturing effect of the monocrystalline silicon surface. Polyhydric alcohols, i.e. alcohols containing two or more hydroxyl groups in the molecule and having the general formula CnH2n+2-x(OH)x(x≥3). The polyhydric alcohol is generally dissolved in water, and most of the polyhydric alcohol is viscous liquid or crystalline solid with the characteristics of high boiling point, strong dissolving capacity for polar substances, low toxicity and volatility and the like. The boiling point, viscosity, relative density, melting point, etc. increase with increasing molecular weight. The polyol can be used for producing industrial products such as alkyd resin, varnish, polyester resin, explosive and the like and used as important intermediates for synthesizing drying oil, adhesive, plasticizer and surfactant. Polyethylene glycol (PEG) is a main representative of polymer polyols, and has the advantages of no toxicity, no irritation, good water solubility, and good compatibility with many organic matter components. They have excellent lubricity, moisture retention and dispersibility, can be used as adhesives, antistatic agents, softeners and the like, and are widely applied to industries such as cosmetics, pharmacy, chemical fibers, rubber, plastics, papermaking, paint, electroplating, pesticides, metal processing, food processing and the like.
Disclosure of Invention
The invention provides an additive of a monocrystalline silicon piece texturing solution, which is characterized in that when the monocrystalline silicon piece for a solar cell is subjected to surface texturing, the additive is added into an alkaline texturing solution, so that an excellent texturing effect is achieved. The size of the suede pyramid is small after the texturing, the distribution is narrow, the reflection of light can be effectively reduced, and therefore the photoelectric conversion efficiency of the assembled solar cell can be improved.
The invention provides an additive formula for monocrystalline silicon piece texturing solution, which comprises the following components: polyol, polymer polyol (polyethylene glycol), organic acid sodium salt, inorganic salt and the balance of deionized water.
On the basis of the scheme, the polyhydric alcohol in the additive is one or a mixture of more of MPD (3-methyl-1, 5-pentanediol), ethylene glycol, 1, 2-propanediol, glycerol and 1, 4-butanediol, and the weight ratio of the polyhydric alcohol to water is 0.5-2.5: 100.
On the basis of the scheme, the polymer polyol in the additive is PEG, the polymer polyol mainly comprises one or a mixture of more of PEG200, PEG400, PEG600, PEG800 and PEG1000, and the weight ratio of the PEG to water is 1.0-3.0: 100.
On the basis of the scheme, the organic sodium salt in the additive is one or a mixture of more of sodium succinate, sodium oxalate, sodium benzoate, sodium phenylacetate and sodium isophthalate, and the weight ratio of the organic sodium salt to water is 0.1-1.0: 100.
On the basis of the scheme, the inorganic salt in the additive is NaCl, KCl and Na2SO4、K2SO4、Na2SiO3One or more of the above components, and the weight ratio of inorganic salt to water is 0.1-1.0: 100.
The invention also provides a formula of the monocrystalline silicon piece surface texture surface making agent, which comprises the following components in percentage by weight: 20.0-40.0mL of NaOH solution with the weight percentage concentration of 30% is added into 1L of deionized water, and 8.0-18.0mL of the additive is added to obtain the alkaline wool making solution.
The surface texturing process of the monocrystalline silicon wafer comprises the following steps: (1) cleaning the cut monocrystalline silicon wafer in a pre-cleaning solution, cleaning the monocrystalline silicon wafer with deionized water, and immersing the monocrystalline silicon wafer in an alkaline wool making solution for wool making, wherein the wool making temperature is 75-90 ℃, and the wool making time is 7-15 min; (2) soaking the textured monocrystalline silicon wafer obtained in the step (1) in deionized water at room temperature for cleaning, and then carrying out mixed acid cleaning; (3) and soaking the acid-washed monocrystalline silicon piece into deionized water, cleaning, soaking the monocrystalline silicon piece into deionized water at 85 ℃, slowly pulling the monocrystalline silicon piece out, and drying the monocrystalline silicon piece in a drying box to obtain the texture-making monocrystalline silicon piece product.
When the alkaline texturing solution prepared by the additive is used for texturing, the size of pyramids formed on the surface of a monocrystalline silicon wafer is smaller than 4 mu m on average, the color of the whole surface of the silicon wafer is uniform, the average reflectivity is lower than 10%, and the etched silicon wafer amount is smaller than 4.5%.
The invention has the advantages that: after the additive is adopted, the texturing time can be shortened, and the texturing effect is obviously improved. The size of the textured pyramid is smaller, the distribution is more uniform, and the reflectivity of the silicon wafer is obviously reduced. The method also has beneficial effects on the finally obtained battery piece, and the yield of the battery piece is improved. In addition, the additive of the invention has no toxicity, no corrosiveness, no irritation, no combustion and explosion hazard, and no harm to human body and environment.
Drawings
FIG. 1 is a scanning electron microscope image of a textured surface of a single crystal silicon wafer obtained by an optimal additive formulation.
FIG. 2 is a scanning electron micrograph of a side of a single crystal silicon wafer obtained with the best additive formulation.
FIG. 3 is a partial enlarged view of a scanning electron microscope of a textured surface of a single crystal silicon wafer obtained by an optimal additive formulation.
FIG. 4 is a partial magnified view of a single crystal silicon wafer side taken by a scanning electron microscope of the best additive formulation.
FIG. 5 is a reflection spectrum of a textured surface of a single crystal silicon wafer obtained by an optimal additive formulation.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative only and are not to be construed as limiting the invention.
Example 1
The method comprises the following steps of: 1) preparing an additive: taking 1L of deionized water as a solvent, adding 8.0g of MPD, 40015.0g of PEG, 1.0g of sodium phenylacetate and 3.0g of NaCl for full dissolution; 2) preparing a texturing solution: adding 35.0mL of NaOH solution with the weight percentage concentration of 30% into 1L of deionized water, and adding 14.0mL of additive to obtain alkaline wool making solution; 3) placing the cut monocrystalline silicon piece in a precleaning solution at 65 ℃ for 5min, cleaning the monocrystalline silicon piece with deionized water, and immersing the monocrystalline silicon piece in a texturing solution, wherein the texturing solution temperature is 78 ℃, and the texturing time is 15 min; 4) soaking the textured monocrystalline silicon wafer in deionized water for cleaning for 1.5 min, and then cleaning for 6min by using mixed acid; 5) soaking the monocrystalline silicon wafer after acid washing in deionized water for washing for 1.5 min, then soaking in deionized water at 85 ℃ for slowly pulling out, placing the finished product in a drying box at 65 ℃ for drying for 3h, and obtaining the textured monocrystalline silicon wafer with the pyramid size of 1-4 mu m, the whole surface of the silicon wafer is uniform in color, the minimum reflectivity is 8.5%, and the corrosion silicon amount is 4.3%.
Example 2
The method comprises the following steps of: 1) preparing an additive: taking 1L of deionized water as a solvent, adding 12.0g of 1, 2-propylene glycol, 20.0g of PEG600, 2.0g of sodium isophthalate and 2.0g of KCl, and fully dissolving; 2) preparing a texturing solution: adding 38.0mL of NaOH solution with the weight percentage concentration of 30% into 1L of deionized water, and adding 12.0mL of additive to obtain alkaline wool making solution; 3) placing the cut monocrystalline silicon piece in a precleaning solution at 65 ℃ for 5min, cleaning the monocrystalline silicon piece with deionized water, and immersing the monocrystalline silicon piece in a texturing solution, wherein the temperature of the texturing solution is 82 ℃, and the texturing time is 13 min; 4) soaking the textured monocrystalline silicon wafer in deionized water for cleaning for 1.5 min, and then cleaning for 8min by using mixed acid; 5) and soaking the monocrystalline silicon wafer after acid washing in deionized water, washing for 1.5 min, soaking in deionized water at 85 ℃, slowly pulling out, and drying the finished product in a drying box at 65 ℃ for 3h to obtain the textured monocrystalline silicon wafer.
Example 3
The method comprises the following steps of: 1) preparing an additive: 1L deionized water is taken as a solvent, and 15.0g of 1, 4-butanediol, 20.0g of PEG800, 3.0g of sodium benzoate and Na are added2SO42.0g are fully dissolved; 2) preparing a texturing solution: adding 40.0mL of NaOH solution with the weight percentage concentration of 30% into 1L of deionized water, and adding 16.0mL of additive to obtain alkaline wool making solution; 3) placing the cut monocrystalline silicon piece in a precleaning solution at 65 ℃ for 5min, cleaning the monocrystalline silicon piece with deionized water, and immersing the monocrystalline silicon piece in a texturing solution, wherein the temperature of the texturing solution is 85 ℃, and the texturing time is 14 min; 4) soaking the textured monocrystalline silicon wafer in deionized water for cleaning for 1.5 min, and then cleaning for 6min by using mixed acid; 5) and soaking the monocrystalline silicon wafer after acid washing in deionized water, washing for 1.5 min, soaking in deionized water at 85 ℃, slowly pulling out, and drying the finished product in a drying box at 65 ℃ for 3h to obtain the textured monocrystalline silicon wafer.
Claims (7)
1. An additive for a monocrystalline silicon piece texturing solution is characterized by comprising the following components: polyol, polymer polyol (polyethylene glycol), organic acid sodium salt, inorganic salt and deionized water.
2. The additive of claim 1, wherein the polyol is one or more of MPD, ethylene glycol, 1, 2-propylene glycol, trimethylene glycol and 1, 4-butanediol, and the weight ratio of the polyol to water is 0.5-2.5: 100.
3. The additive of claim 1, wherein the polymer polyol is PEG, and mainly comprises one or more of PEG200, PEG400, PEG600, PEG800 and PEG1000, and the weight ratio of PEG to water is 1.0-3.0: 100.
4. The additive of claim 1, wherein the organic sodium salt is one or a mixture of sodium succinate, sodium oxalate, sodium benzoate and sodium isophthalate, and the weight ratio of the organic sodium salt to water is 0.1-1.0: 100.
5. The additive of claim 1, wherein the inorganic salt is NaCl, KCl, Na2SO4、K2SO4、Na2SiO3One or more of the above components, and the weight ratio of inorganic salt to water is 0.1-1.0: 100.
6. A preparation method of a texturing solution for the surface of a monocrystalline silicon wafer is characterized in that 20.0-40.0mL of NaOH solution with the weight percentage concentration of 30% is added into 1L of deionized water, and 10.0-20.0mL of additive is added to obtain an alkaline texturing solution.
7. Based on the claims 1-6, the texture etching solution prepared by the additive has the advantages that the size of pyramids formed on the surface of a monocrystalline silicon wafer is averagely less than 4 μm, the color of the whole surface of the silicon wafer is relatively uniform, the average reflectivity is less than 10 percent, and the etched silicon wafer amount is less than 4 percent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111139531A (en) * | 2020-03-18 | 2020-05-12 | 常州时创能源股份有限公司 | Texturing additive for monocrystalline silicon wafer and application thereof |
| CN111593413A (en) * | 2020-06-30 | 2020-08-28 | 常州时创能源股份有限公司 | Additive for monocrystalline silicon wafer chain type machine texturing and application thereof |
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