CN113913188A - Monocrystalline silicon texturing agent and preparation method of textured monocrystalline silicon - Google Patents
Monocrystalline silicon texturing agent and preparation method of textured monocrystalline silicon Download PDFInfo
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Abstract
The invention discloses a monocrystalline silicon texturing agent and a preparation method of textured monocrystalline silicon; belongs to the technical field of monocrystalline silicon texturing; the monocrystalline silicon texturing agent comprises alkali liquor and a texturing additive; the flock additive includes modified polyvinyl alcohol; the modified polyvinyl alcohol is prepared by modifying polyvinyl alcohol with methyl carnosic acid. The preparation method comprises the following steps: s1: pretreating a monocrystalline silicon wafer; s2: placing the pretreated monocrystalline silicon wafer into a monocrystalline silicon texture surface making agent for texture surface making; s3: and cleaning and drying the textured monocrystalline silicon wafer to obtain textured monocrystalline silicon. The prepared monocrystalline silicon texturing agent has excellent stability and can reduce the foam performance, and when the agent is used for monocrystalline silicon treatment, the obtained textured monocrystalline silicon has a morphology structure with uniform texture and small size and has lower reflectivity.
Description
Technical Field
The invention belongs to the technical field of monocrystalline silicon texturing, and particularly relates to a monocrystalline silicon texturing agent and a preparation method of textured monocrystalline silicon.
Background
In the silicon crystal, the monocrystalline silicon solar cell has the advantages of high photoelectric conversion efficiency, long service life and gradually reduced cost, and the market share is gradually improved. Nowadays, many researchers at home and abroad are dedicated to improving the photoelectric conversion efficiency of solar cells, and the most common method at present is to etch the surface of a silicon wafer used for the solar cells and manufacture a textured structure on the surface. People use various processes to make the texture structure uniform, for example, various additives are added into the texture-making agent, so that the production cost is reduced, the reflection of the surface of the silicon wafer to sunlight can be reduced, and the photoelectric conversion efficiency of the solar cell is improved. At present, the diamond wire saw cutting technology is widely applied to the slicing process of silicon crystals, and the processed silicon wafers have the advantages of high processing efficiency, low production cost, small environmental pollution, good surface quality of the silicon wafers and the like. But the scratches after cutting are more and more diversified, and the requirements of the texturing solution required when the surface of the silicon wafer is textured are gradually improved.
In the prior art, for example, publication No. CN111485290A discloses a monocrystalline silicon texturing agent and a preparation method of textured monocrystalline silicon; the monocrystalline silicon texturing agent comprises an alkaline compound and an etchant; the etchant contains the following components: 5wt% -20 wt% of urea; 1-10 wt% of sodium lactate; the balance being water. And placing the monocrystalline silicon in a texturing agent, and heating to obtain textured monocrystalline silicon. The prepared texture-making agent can effectively reduce the probability of bright blocks, white spots and raindrops on the surface of a silicon wafer, so that the pyramid texture is small and uniform, and the qualification rate of textured monocrystalline silicon is obviously improved.
Disclosure of Invention
The invention aims to provide a monocrystalline silicon texturing agent with excellent stability and capability of reducing foam performance, which is used for monocrystalline silicon treatment to obtain textured monocrystalline silicon with a morphology structure with uniform textured surface and small size and lower reflectivity.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a monocrystalline silicon texturing agent comprises an alkali liquor and a texturing additive;
the texturing additive comprises modified polyvinyl alcohol;
the modified polyvinyl alcohol is prepared by modifying polyvinyl alcohol with methyl carnosic acid.
The invention adopts the modified polyvinyl alcohol as the component of the monocrystalline silicon texturing agent, which can possibly reduce the surface tension of the texturing agent, is beneficial to removing bubbles and ensures that the monocrystalline silicon texturing agent has excellent stability; on the other hand, the modified polyvinyl alcohol may have a better reticular structure, and when monocrystalline silicon is processed, the modified polyvinyl alcohol can be evenly and flatly paved on the surface of the monocrystalline silicon to obtain monocrystalline silicon with even texture, and further obtain textured monocrystalline silicon with excellent performance.
Further, in some embodiments of the present invention, the texturing additive further comprises tartaric acid, boric acid, sodium dodecyl sulfate, sodium benzoate, and water.
Further, in some embodiments of the present invention, the texturing additive comprises the following components in parts by weight: 5-25 parts of modified polyvinyl alcohol, 1-3 parts of tartaric acid, 0.5-1.5 parts of boric acid, 0.5-2.5 parts of sodium dodecyl sulfate, 0.25-1.75 parts of sodium benzoate and 50-85 parts of water.
Further, in some embodiments of the present invention, the alkali solution is one of an aqueous solution of sodium hydroxide and an aqueous solution of potassium hydroxide; the concentration of the alkali liquor is 2.5-5.5 wt%.
Further, in some embodiments of the present invention, the modified polyvinyl alcohol is prepared by: dissolving polyvinyl alcohol in water, adding the clary carnosic acid A and a catalyst, reacting under a heating condition, drying, washing and drying to obtain the modified polyvinyl alcohol.
Further, in some embodiments of the present invention, the polyvinyl alcohol is 10 to 20 parts by weight, the water is 70 to 120 parts by weight, the carnosic acid is 1 to 5 parts by weight, and the catalyst is 0.35 to 0.75 part by weight.
Further, in some embodiments of the present invention, the heating temperature is 75 to 90 ℃ for 2 to 4 hours.
Further, in some embodiments of the invention, the mass ratio of the alkali liquor to the wool making additive is 5-10: 1.
The invention also discloses a preparation method of the monocrystalline silicon texturing agent, which comprises the following steps: and uniformly mixing the alkali liquor, the texturing additive and water to prepare the monocrystalline silicon texturing agent.
The invention also discloses an application of the monocrystalline silicon texturing agent in preparation of textured monocrystalline silicon.
The invention also discloses a preparation method of the textured monocrystalline silicon, which comprises the following steps:
s1: pretreating a monocrystalline silicon wafer;
s2: placing the pretreated monocrystalline silicon wafer into a monocrystalline silicon texture surface making agent for texture surface making;
s3: and cleaning and drying the textured monocrystalline silicon wafer to obtain textured monocrystalline silicon.
According to the invention, the monocrystalline silicon piece is placed in the texturing agent containing modified polyvinyl alcohol for treatment, and all components interact with each other, so that the surface of the silicon can be uniformly corroded by alkali liquor, a textured structure with uniform texture and small size is obtained, and the textured monocrystalline silicon with low reflectivity is further obtained, and the textured monocrystalline silicon has wide application in the field of silicon solar cells.
Further, in some embodiments of the present invention, in step S1, the pretreatment step of the single crystal silicon wafer is: and (3) sequentially carrying out ultrasonic cleaning, water washing and absolute ethyl alcohol washing on the monocrystalline silicon wafer.
Further, in some embodiments of the present invention, in step S2, the texturing temperature is 65-85 ℃ and the texturing time is 10-20 min.
The invention has the following beneficial effects:
(1) the invention adopts the modified polyvinyl alcohol as the component of the monocrystalline silicon texturing agent, which can possibly reduce the surface tension of the texturing agent, is beneficial to removing bubbles and ensures that the monocrystalline silicon texturing agent has excellent stability; on the other hand, the modified polyvinyl alcohol may have a better reticular structure, and when monocrystalline silicon is processed, the modified polyvinyl alcohol can be evenly and flatly paved on the surface of the monocrystalline silicon to obtain monocrystalline silicon with even texture, and further obtain textured monocrystalline silicon with excellent performance.
(2) According to the invention, the monocrystalline silicon piece is placed in the texturing agent containing modified polyvinyl alcohol for treatment, and all components interact with each other, so that the surface of the silicon can be uniformly corroded by alkali liquor, a textured structure with uniform texture and small size is obtained, and the textured monocrystalline silicon with low reflectivity is further obtained, and the textured monocrystalline silicon has wide application in the field of silicon solar cells.
Therefore, the monocrystalline silicon texturing agent has excellent stability and can reduce the foam performance, and when the monocrystalline silicon texturing agent is used for monocrystalline silicon treatment, the obtained textured monocrystalline silicon has a morphology structure with uniform texture and small size and has lower reflectivity.
Drawings
FIG. 1 is a chart of the infrared spectra before and after modification of polyvinyl alcohol in example 1;
FIG. 2 is a foam volume of a single crystal texturing agent;
FIG. 3 is an SEM photograph of textured single crystal silicon in example 9.
Detailed Description
The following examples are provided to further illustrate the essence of the present invention. It should be noted that these examples are only intended to specifically describe the present invention and should not be construed as limiting the present invention. The reagents used in this example were all commercially available unless otherwise specified.
It should be noted that, in some embodiments of the present invention, the preparation method of the modified polyvinyl alcohol is: according to parts by weight, 10-20 parts of polyvinyl alcohol is dissolved in 70-120 parts of water, the polyvinyl alcohol is dissolved for 1-3 hours at the temperature of 70-80 ℃ and the stirring speed of 400-600 r/min, then 1-5 parts of methyl carnosic acid and 0.35-0.75 part of concentrated sulfuric acid with the mass concentration of 5% are added, the reaction is carried out for 2-4 hours at the temperature of 75-90 ℃, the mixture is dried for 20-30 minutes at the temperature of 50-75 ℃, washed for 3-5 times by deionized water, and dried for 40-60 minutes at the temperature of 50-75 ℃, and the modified polyvinyl alcohol is obtained.
It should be noted that, in some embodiments of the present invention, a method for preparing a monocrystalline silicon texturing agent includes: adding alkali liquor and water into the texturing additive, mechanically stirring for 15-30 min at 500-800 r/min until the mixture is uniformly mixed, then placing the mixture in a constant-temperature water bath at 45-55 ℃ for heat preservation for 20-30 min, wherein the mass ratio of the alkali liquor to the texturing additive to the water is 5-10: 1: 40-60, and preparing the monocrystalline silicon texturing agent, wherein the texturing additive comprises the following components: 5-25 parts of modified polyvinyl alcohol, 1-3 parts of tartaric acid, 0.5-1.5 parts of boric acid, 0.5-2.5 parts of sodium dodecyl sulfate, 0.25-1.75 parts of sodium benzoate and 50-85 parts of water.
In order to optimize the texturing effect and the texturing uniformity of the single-crystal texturing agent, the preferable measures adopted comprise: the wool making additive is added with 0.5-2.5 parts of a mixture of isomalt and disodium 5 '-inosinate, wherein the weight ratio of the isomalt to the disodium 5' -inosinate is 1: 0.25-0.5. The addition of the mixture of isomaltitol and 5' -disodium inosinate interacts with other components of the texturing additive to further improve the stability and defoaming property of the texturing agent, and then the texturing agent and alkali liquor jointly act on the monocrystalline silicon wafer to obtain monocrystalline silicon with more uniform texture and lower reflectivity.
It should be noted that, in some embodiments of the present invention, in step S1, the specific steps of the pretreatment of the single crystal silicon wafer are: selecting a monocrystalline silicon wafer without mechanical damage, ultrasonically cleaning the monocrystalline silicon wafer at 55-65 ℃ for 3-5 min, then sequentially cleaning with water, respectively washing with absolute ethyl alcohol for 2-3 times, and drying to obtain the pretreated monocrystalline silicon.
In some embodiments of the present invention, in step S2, the pretreated monocrystalline silicon piece is completely immersed in the texturing agent, and is textured at 65-85 ℃ for 10-20 min, and after the texturing is completed, the monocrystalline silicon piece is quickly taken out to obtain a textured monocrystalline silicon piece.
In some embodiments of the present invention, in step S3, the textured monocrystalline silicon wafer is washed with water for 3 to 5 times and dried to obtain textured monocrystalline silicon.
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
the preparation method of the modified polyvinyl alcohol comprises the following steps: 13 parts by weight of polyvinyl alcohol (purchased from Hubeixin Rundji chemical Co., Ltd.) was dissolved in 115 parts by weight of water at 75 ℃ for 2 hours with a stirring rate of 500r/min, 4.5 parts by weight of carnosic acid methyl and 0.45 part by weight of concentrated sulfuric acid having a mass concentration of 5% were added to the solution, the reaction was carried out at 90 ℃ for 3 hours, the solution was dried at 60 ℃ for 25 minutes, washed 3 times with deionized water, and dried at 60 ℃ for 40 minutes to obtain modified polyvinyl alcohol.
Example 2:
a preparation method of a monocrystalline silicon texturing agent comprises the following steps: adding a sodium hydroxide solution with the concentration of 4.5wt% and water into the texturing additive, mechanically stirring for 20min at the speed of 600r/min until the mixture is uniformly mixed, and then placing the mixture in a constant-temperature water bath with the temperature of 45 ℃ for heat preservation for 30min, wherein the mass ratio of the alkali liquor to the texturing additive to the water is 5:1:50, and preparing the monocrystalline silicon texturing agent, wherein the texturing additive comprises the following components: in example 1, 13 parts of modified polyvinyl alcohol, 2 parts of tartaric acid, 1.5 parts of boric acid, 0.5 part of sodium dodecylsulfate, 1.55 parts of sodium benzoate and 75 parts of water were used.
Example 3:
a method for preparing a monocrystalline silicon texturing agent, which is different from the embodiment 2: adding 4.5wt% of sodium hydroxide solution and water into the texturing additive, mechanically stirring for 30min at 500r/min until the mixture is uniformly mixed, and then placing the mixture in a thermostatic water bath at 50 ℃ for heat preservation for 25min, wherein the mass ratio of the alkali liquor to the texturing additive to the water is 8:1:60, and preparing the monocrystalline silicon texturing agent, wherein the components of the texturing additive are the same as those in example 2.
Example 4:
a method for preparing a monocrystalline silicon texturing agent, which is different from the embodiment 2: the ingredients of the texturing additive are 20 parts of modified polyvinyl alcohol, 3 parts of tartaric acid, 1 part of boric acid, 1.5 parts of sodium dodecyl sulfate, 1.75 parts of sodium benzoate and 85 parts of water in example 1.
Example 5:
a method for preparing a monocrystalline silicon texturing agent, which is different from the embodiment 2: the texturing additive comprises the following components: the modified polyvinyl alcohol in example 1 was 13 parts, 1 part of a mixture of isomalt and disodium 5 '-inosinate, wherein the weight ratio of isomalt to disodium 5' -inosinate was 1:0.25, 2 parts of tartaric acid, 1.5 parts of boric acid, 0.5 part of sodium dodecylsulfate, 1.55 parts of sodium benzoate, and 75 parts of water.
Example 6:
a method for preparing a monocrystalline silicon texturing agent, which is different from the embodiment 5: the components of the texturing additive are added with 2 parts of isomalt and 5 '-disodium inosinate mixture, wherein the weight ratio of the isomalt to the 5' -disodium inosinate mixture is 1: 0.25.
Example 7:
a method for preparing a monocrystalline silicon texturing agent, which is different from the embodiment 5: the weight ratio of isomalt to disodium 5' -inosinate mixture was 1: 0.5.
Example 8:
a method for preparing a monocrystalline silicon texturing agent, which is different from the embodiment 5: the texturing additive comprises the following components: polyvinyl alcohol (purchased from Hubei Xinrunder chemical Co., Ltd.) 13 parts, 1 part of isomalt and 5 '-disodium inosinate mixture, wherein the weight ratio of the isomalt to the 5' -disodium inosinate mixture is 1:0.25, 2 parts of tartaric acid, 1.5 parts of boric acid, 0.5 part of sodium dodecyl sulfate, 1.55 parts of sodium benzoate and 75 parts of water.
Example 9:
a preparation method of textured monocrystalline silicon comprises the following steps:
s1: selecting a monocrystalline silicon wafer without mechanical damage, ultrasonically cleaning the monocrystalline silicon wafer at 60 ℃ for 3min, then sequentially cleaning the monocrystalline silicon wafer with water and washing the monocrystalline silicon wafer with absolute ethyl alcohol for 3 times respectively, and drying to obtain pretreated monocrystalline silicon;
s2: and (3) completely soaking the pretreated monocrystalline silicon wafer in the texturing agent in the embodiment 2, texturing for 15min at 70 ℃, and quickly taking out after texturing to obtain the textured monocrystalline silicon wafer. (ii) a
S3: and (3) cleaning the textured monocrystalline silicon piece with water for 3 times, and drying to obtain textured monocrystalline silicon.
Example 10:
a textured single crystal silicon preparation method, which is different from the embodiment 9: in step S2, the pretreated single crystal silicon wafer was completely immersed in the texturing agent of example 3, and textured at 70 ℃ for 15 min.
Example 11:
a textured single crystal silicon preparation method, which is different from the embodiment 9: in step S2, the pretreated single crystal silicon wafer was completely immersed in the texturing agent of example 4, and textured at 70 ℃ for 15 min.
Example 12:
a textured single crystal silicon preparation method, which is different from the embodiment 9: in step S2, the pretreated single crystal silicon wafer was completely immersed in the texturing agent of example 5, and textured at 70 ℃ for 15 min.
Example 13:
a textured single crystal silicon preparation method, which is different from the embodiment 9: in step S2, the pretreated single crystal silicon wafer was completely immersed in the texturing agent of example 6, and textured at 70 ℃ for 15 min.
Example 14:
a textured single crystal silicon preparation method, which is different from the embodiment 9: in step S2, the pretreated single crystal silicon wafer was completely immersed in the texturing agent of example 7, and textured at 70 ℃ for 15 min.
Example 15:
a textured single crystal silicon preparation method, which is different from the embodiment 9: in step S2, the pretreated single crystal silicon wafer was completely immersed in the texturing agent of example 8, and textured at 70 ℃ for 15 min.
Comparative example 1:
a method for preparing a monocrystalline silicon texturing agent, which is different from the embodiment 2: the texturing additive comprises the following components: 13 portions of polyvinyl alcohol (purchased from Hubei Xin Rundg chemical Co., Ltd.), 2 portions of tartaric acid, 1.5 portions of boric acid, 0.5 portion of sodium dodecyl sulfate, 1.55 portions of sodium benzoate and 75 portions of water.
Comparative example 2:
a textured single crystal silicon preparation method, which is different from the embodiment 9: in step S2, the pretreated single crystal silicon wafer was completely immersed in the texturing agent of comparative example 1, and textured at 70 ℃ for 15 min.
And (3) performance test characterization:
1. modified polyvinyl alcohol Infrared Spectroscopy
And testing the infrared spectrograms of the polyvinyl alcohol before and after modification by a Nicolet 6700 type Fourier transform infrared spectrometer.
FIG. 1 is an infrared spectrum before and after modification of polyvinyl alcohol in example 1. Curves a and b are respectively infrared spectrograms of polyvinyl alcohol and modified polyvinyl alcohol; as can be seen from FIG. 1, the modified polyvinyl alcohol was found to be 3052cm in length relative to the polyvinyl alcohol-1The characteristic absorption peak appearing nearby is the stretching vibration of a benzene ring; at 2847cm-1The characteristic absorption peak appearing nearby is the symmetric stretching vibration of C-H in alkyl; at 1721cm-1The characteristic absorption peak appearing nearby is the stretching vibration of the ester group; therefore, the modified polyvinyl alcohol is prepared by modifying polyvinyl alcohol with the methyl carnosic acid.
2. Monocrystalline silicon texturing agent stability test
And (3) placing the monocrystalline silicon texturing agent sample at the temperature of 23 +/-2 ℃, and observing whether the texturing agent is layered or not and obvious precipitates.
TABLE 1 stability test results for monocrystalline silicon texturing agent
| Group of | Example 2 | Example 5 | Example 8 | Comparative example 1 |
| Stability of | Delamination occurred after 45 days | Delamination occurred after 60 days | Delamination occurred after 40 days | Delamination occurred after 26 days |
As can be seen from table 1, the stability of comparative example 2 and comparative example 1 is better than that of comparative example 1, which shows that the modified polyvinyl alcohol prepared by modifying polyvinyl alcohol with carnosic acid methyl ester is used as a component of the texturing agent, and the stability of the texturing agent is improved; comparing example 2 with example 5, and example 8 with comparative example 1, the stability of example 5 is better than that of example 2, and the stability of example 8 is better than that of comparative example 1, which shows that the addition of the mixture of isomalt and disodium 5 '-inosinate in the texturing agent further improves the stability of the texturing agent, and the modified polyvinyl alcohol, isomalt and the mixture of disodium 5' -inosinate act together to significantly improve the stability of the texturing agent, so that the texturing agent can be stored for a long time.
3. Foam performance test of single crystal texturing agent
Testing the foam performance of the texturing agent by adopting an oscillation method; 15mL of the texturing agent in the example 2, the example 5, the example 8 and the comparative example 1 is placed in a stoppered measuring cylinder, the vibration is stopped after 40s, the stoppered measuring cylinder is placed on a laboratory table, the foam height is recorded and timing is started, and the foam high degree is recorded at the same time until the foam completely disappears.
FIG. 2 shows the foam volume of the single crystal texturing agent. D1, D2, D3, D4 are example 2, example 5, example 8 and comparative example 1, respectively; as can be seen from fig. 2, at 0s, the foam volume of example 2 is less than 18mL, the foam volume of comparative example 2 and comparative example 1 is less than that of comparative example 1, and the defoaming time of example 2 is higher than that of comparative example 1, which illustrates that the polyvinyl alcohol is modified with carnosic acid methyl to obtain modified polyvinyl alcohol, which is used as a component of the texturing agent, so that the texturing agent has lower surface tension, facilitating the removal of bubbles; comparing example 2 with example 5, and example 8 with comparative example 1, the foam volume of example 5 is lower than that of example 2, and the foam volume of example 8 is lower than that of comparative example 1, which shows that the addition of the mixture of isomalt and disodium 5' -inosinate in the texturing agent further reduces the foam property of the texturing agent, so that the texturing agent can be contacted with monocrystalline silicon more uniformly to obtain uniform textured monocrystalline silicon.
4. Texture surface single crystal silicon surface morphology test
And observing the morphology of the prepared textured monocrystalline silicon sample by using a TM 3000 type scanning electron microscope.
FIG. 3 is an SEM photograph of textured single crystal silicon in example 9. As can be seen from fig. 3, the pyramidal structure on the textured single crystal silicon surface in example 3 is uniformly distributed, and has a fine and dense size.
5. Textured single crystal silicon reflectivity test
And testing the reflectivity of the textured monocrystalline silicon before and after texturing by using a Cary 100 self-visible spectrophotometer, observing the texture appearance of the monocrystalline silicon and observing the morphology of the textured monocrystalline silicon by using a metallographic microscope.
TABLE 2 textured appearance and relative reflectance of textured single crystal silicon
| Group of | Suede appearance | Texture surface appearance | Relative reflectance (%) |
| Example 9 | Is darker than black | No streak, fine and dense pyramid | 49.5 |
| Example 10 | Is darker than black | No streak, fine and dense pyramid | 47.3 |
| Example 11 | Is darker than black | No streak, fine and dense pyramid | 48.2 |
| Example 12 | Black colour | No streak, fine and uniform pyramid | 41.6 |
| Example 13 | Black colour | No streak, fine and uniform pyramid | 38.4 |
| Example 14 | Black colour | No streak, fine and uniform pyramid | 40.8 |
| Example 15 | Slightly black | No streak, fine and uniform pyramid | 58.6 |
| Comparative example 2 | Has slight whitening on the surface | Streak, sparse pyramid, bigger | 67.2 |
As can be seen from table 2, in examples 9 to 11, the textured surface of the single crystal silicon is black in appearance, the textured surface has no streak, and the pyramids are fine and dense; and the relative reflectivity is lower than 50%, comparing example 9 with comparative example 2, and the relative reflectivity of the textured monocrystalline silicon in example 9 is lower than that in comparative example 2, which shows that the modified polyvinyl alcohol is prepared by modifying polyvinyl alcohol with carnosic acid methyl, the modified polyvinyl alcohol is used as a component of a texturing agent, and the monocrystalline silicon is treated to obtain textured monocrystalline silicon with good textured appearance and lower relative reflectivity; in examples 12 to 14, the textured surface of the single crystal silicon has black appearance, the textured surface has no streak, and the pyramid is fine and uniform; and the relative reflectivity is lower than 42%, the textured surface appearance of textured monocrystalline silicon in example 12 is better than that in example 9, the relative reflectivity is lower than that in example 12, the textured surface appearance of textured monocrystalline silicon in example 15 is better than that in comparative example 2, and the relative reflectivity is lower than that in comparative example 2, which indicates that the mixture of isomaltitol and disodium 5' -inosinate is added into the texturing agent, and the monocrystalline silicon is treated to obtain the textured monocrystalline silicon with more excellent textured appearance and lower relative reflectivity, so that the textured monocrystalline silicon has wide application in the field of silicon solar cells.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A monocrystalline silicon texturing agent is characterized by comprising alkali liquor and a texturing additive;
the texturing additive comprises modified polyvinyl alcohol;
the modified polyvinyl alcohol is prepared by modifying polyvinyl alcohol with methyl carnosic acid.
2. The monocrystalline silicon texturing agent of claim 1, wherein the texturing additive further comprises tartaric acid, boric acid, sodium dodecyl sulfate, sodium benzoate and water.
3. The monocrystalline silicon texturing agent according to claim 2, wherein the texturing additive comprises the following components in parts by weight: 5-25 parts of modified polyvinyl alcohol, 1-3 parts of tartaric acid, 0.5-1.5 parts of boric acid, 0.5-2.5 parts of sodium dodecyl sulfate, 0.25-1.75 parts of sodium benzoate and 50-85 parts of water.
4. The monocrystalline silicon texturing agent according to claim 1, wherein the alkali solution is one of a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution; the concentration of the alkali liquor is 2.5-5.5 wt%.
5. The monocrystalline silicon texturing agent according to claim 1, wherein the preparation method of the modified polyvinyl alcohol comprises the following steps: dissolving polyvinyl alcohol in water, adding the clary carnosic acid A and a catalyst, reacting under a heating condition, drying, washing and drying to obtain the modified polyvinyl alcohol.
6. The monocrystalline silicon texturing agent of claim 1, wherein the mass ratio of the alkali liquor to the texturing additive is 5-10: 1.
7. The method for preparing a monocrystalline silicon texturing agent according to claim 1, comprising: and uniformly mixing the alkali liquor and the texturing additive to prepare the monocrystalline silicon texturing agent.
8. Use of a monocrystalline silicon texturing agent according to claim 1, characterized in that the monocrystalline silicon texturing agent is used in the production of textured monocrystalline silicon.
9. A preparation method of textured monocrystalline silicon is characterized by comprising the following steps:
s1: pretreating a monocrystalline silicon wafer;
s2: placing the pretreated monocrystalline silicon wafer into the monocrystalline silicon texture etching agent of claim 1 for texture etching;
s3: and cleaning and drying the textured monocrystalline silicon wafer to obtain textured monocrystalline silicon.
10. The method for preparing textured monocrystalline silicon, according to claim 9, wherein in the step S2, the texturing temperature is 65-85 ℃, and the texturing time is 10-20 min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114823972A (en) * | 2022-04-01 | 2022-07-29 | 浙江爱旭太阳能科技有限公司 | Solar cell and texturing cleaning method thereof |
| CN114823972B (en) * | 2022-04-01 | 2024-05-31 | 广东爱旭科技有限公司 | Solar cell and texturing and cleaning method thereof |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4376057A (en) * | 1980-11-26 | 1983-03-08 | International Business Machines Corporation | Etchant composition and use thereof |
| CN101962811A (en) * | 2010-11-01 | 2011-02-02 | 浙江晶科能源有限公司 | Monocrystalline silicon piece texturizing liquid and texturizing method thereof |
| CN103132079A (en) * | 2013-02-07 | 2013-06-05 | 睿纳能源科技（上海）有限公司 | Additive for acid texturing of diamond-wire-cutting polycrystalline silicon slices and application method thereof |
| CN104120495A (en) * | 2014-07-10 | 2014-10-29 | 上海应用技术学院 | A texturing liquid used for monocrystalline silicon surface texturing and a preparing method thereof |
| TW201518476A (en) * | 2013-11-01 | 2015-05-16 | Japan Vam & Poval Co Ltd | Texture-etching liquid, liquid additive for texture-etching liquid, textured substrate, method for manufacturing textured substrate, and solar cell |
| CN106222756A (en) * | 2016-09-30 | 2016-12-14 | 杭州飞鹿新能源科技有限公司 | Additive and application process thereof for diamond wire cutting fine-hair maring using monocrystalline silicon slice |
| CN106674168A (en) * | 2016-12-30 | 2017-05-17 | 成都普思生物科技股份有限公司 | Method for preparing przewalskinic acid A by hydrolysis conversion of salvianolic acid B |
| CN108004597A (en) * | 2017-11-09 | 2018-05-08 | 润峰电力有限公司 | A kind of polysilicon flocking additive and its etching method |
| CN108130598A (en) * | 2017-12-03 | 2018-06-08 | 宁波道乐新材料科技有限公司 | The special alkali flocking additive of Buddha's warrior attendant wire cutting monocrystalline silicon piece and its application method |
| WO2018124666A1 (en) * | 2016-12-29 | 2018-07-05 | 코닝 인코포레이티드 | Glass etching composition, and method for manufacturing anti-glare glass |
| CN109267154A (en) * | 2018-09-28 | 2019-01-25 | 横店集团东磁股份有限公司 | Buddha's warrior attendant wire cutting monocrystalline silicon surface etching method |
| CN109295498A (en) * | 2018-10-29 | 2019-02-01 | 钟祥博谦信息科技有限公司 | A kind of etching method of monocrystalline silicon piece |
| CN109427930A (en) * | 2017-09-04 | 2019-03-05 | 苏州易益新能源科技有限公司 | A method of flannelette is selectively prepared on crystal silicon chip surface |
| CN109750353A (en) * | 2019-03-14 | 2019-05-14 | 常州时创能源科技有限公司 | Monocrystalline silicon piece inverted pyramid making herbs into wool adjuvant and its application |
| CN110219053A (en) * | 2019-07-11 | 2019-09-10 | 徐臣 | A kind of flocking additive, Woolen-making liquid and etching method |
| CN111394797A (en) * | 2020-05-25 | 2020-07-10 | 彭晓晨 | Preparation method of additive with positive pyramid structure for N-type monocrystalline silicon |
-
2021
- 2021-12-14 CN CN202111520915.1A patent/CN113913188B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4376057A (en) * | 1980-11-26 | 1983-03-08 | International Business Machines Corporation | Etchant composition and use thereof |
| CN101962811A (en) * | 2010-11-01 | 2011-02-02 | 浙江晶科能源有限公司 | Monocrystalline silicon piece texturizing liquid and texturizing method thereof |
| CN103132079A (en) * | 2013-02-07 | 2013-06-05 | 睿纳能源科技（上海）有限公司 | Additive for acid texturing of diamond-wire-cutting polycrystalline silicon slices and application method thereof |
| TW201518476A (en) * | 2013-11-01 | 2015-05-16 | Japan Vam & Poval Co Ltd | Texture-etching liquid, liquid additive for texture-etching liquid, textured substrate, method for manufacturing textured substrate, and solar cell |
| CN104120495A (en) * | 2014-07-10 | 2014-10-29 | 上海应用技术学院 | A texturing liquid used for monocrystalline silicon surface texturing and a preparing method thereof |
| CN106222756A (en) * | 2016-09-30 | 2016-12-14 | 杭州飞鹿新能源科技有限公司 | Additive and application process thereof for diamond wire cutting fine-hair maring using monocrystalline silicon slice |
| WO2018124666A1 (en) * | 2016-12-29 | 2018-07-05 | 코닝 인코포레이티드 | Glass etching composition, and method for manufacturing anti-glare glass |
| CN106674168A (en) * | 2016-12-30 | 2017-05-17 | 成都普思生物科技股份有限公司 | Method for preparing przewalskinic acid A by hydrolysis conversion of salvianolic acid B |
| CN109427930A (en) * | 2017-09-04 | 2019-03-05 | 苏州易益新能源科技有限公司 | A method of flannelette is selectively prepared on crystal silicon chip surface |
| CN108004597A (en) * | 2017-11-09 | 2018-05-08 | 润峰电力有限公司 | A kind of polysilicon flocking additive and its etching method |
| CN108130598A (en) * | 2017-12-03 | 2018-06-08 | 宁波道乐新材料科技有限公司 | The special alkali flocking additive of Buddha's warrior attendant wire cutting monocrystalline silicon piece and its application method |
| CN109267154A (en) * | 2018-09-28 | 2019-01-25 | 横店集团东磁股份有限公司 | Buddha's warrior attendant wire cutting monocrystalline silicon surface etching method |
| CN109295498A (en) * | 2018-10-29 | 2019-02-01 | 钟祥博谦信息科技有限公司 | A kind of etching method of monocrystalline silicon piece |
| CN109750353A (en) * | 2019-03-14 | 2019-05-14 | 常州时创能源科技有限公司 | Monocrystalline silicon piece inverted pyramid making herbs into wool adjuvant and its application |
| CN110219053A (en) * | 2019-07-11 | 2019-09-10 | 徐臣 | A kind of flocking additive, Woolen-making liquid and etching method |
| CN111394797A (en) * | 2020-05-25 | 2020-07-10 | 彭晓晨 | Preparation method of additive with positive pyramid structure for N-type monocrystalline silicon |
Non-Patent Citations (3)
| Title |
|---|
| 丁兆兵等: "新型无醇单晶硅制绒添加剂的研究", 《人工晶体学报》 * |
| 王晴晴: "单晶硅制绒剂的研究", 《中国优秀硕士学位论文全文数据库》 * |
| 黄小龙等: "硅基太阳电池表面织构的研究进展", 《太阳能》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114823972A (en) * | 2022-04-01 | 2022-07-29 | 浙江爱旭太阳能科技有限公司 | Solar cell and texturing cleaning method thereof |
| CN114823972B (en) * | 2022-04-01 | 2024-05-31 | 广东爱旭科技有限公司 | Solar cell and texturing and cleaning method thereof |
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