CN112143590A - Silicon wafer cleaning additive, silicon wafer cleaning liquid and application thereof - Google Patents
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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Abstract
The invention discloses a silicon wafer cleaning additive, a silicon wafer cleaning solution and application, wherein the cleaning additive comprises the following components in parts by mass: 2-6 parts of chelating agent, 0.1-0.5 part of surfactant, 0.5-2 parts of penetrating agent, 2-5 parts of stabilizer and 80-90 parts of deionized water; the chelating agent is a metal chelating agent, the surfactant is a nonionic surfactant, the penetrating agent is polyethylene glycol, and the stabilizing agent is a cationic polymer; the silicon wafer cleaning solution contains an alkali solution or an acid solution and the silicon wafer cleaning additive. The method not only effectively removes the metal impurities on the surface of the silicon wafer, but also prevents the metal impurities from polluting the silicon wafer again; the cleanliness of the surface of the silicon chip is improved, the recombination caused by metal impurities is reduced, and the photoelectric conversion efficiency of the battery is improved; the silicon wafer cleaning additive is non-volatile, free of pungent smell, good in stability and free of damage to the silicon wafer.
Description
Technical Field
The invention relates to the field of silicon wafer cleaning, in particular to a silicon wafer cleaning additive capable of removing metal ions on the surface of a silicon wafer, a silicon wafer cleaning solution and application thereof.
Background
With the development of ultra-large scale integrated circuit technology and solar energy technology, the surface cleanliness of silicon wafers is more and more important. The silicon wafer cleaning is used as a basic process of the photovoltaic cell, and the cleaning degree can directly have great influence on the performance, reliability and yield of the cell.
In the cutting process of the solar-grade silicon wafer, a region close to 10um on the surface is in a damaged state, and is full of dangling bonds with high activity, so that external impurities are easily adsorbed, the silicon wafer is seriously contaminated, and generally, a physical or chemical method is adopted to clean pollutants on the surface of the silicon wafer so as to obtain a clean silicon wafer with a surface state meeting the standard. Moreover, each process of the solar cell piece in the production process is likely to be polluted, the pollution types comprise metal, organic matters, particles, natural oxide layers and the like, the metal, the organic matters, the particles, the natural oxide layers and the like exist on the surface of the silicon piece or in an oxide film through chemical or physical adsorption, an alkali solution prepared from hydrogen peroxide and alkali is usually selected, the organic matters and particle impurities are removed by utilizing strong oxidizability at a certain temperature, but the cleaning capacity of the pure alkali solution is limited, the pure alkali solution is required to be supplemented along with the decomposition of the hydrogen peroxide, and the process stability is poor; after alkaline washing, acid liquor mixed with hydrofluoric acid and hydrochloric acid is selected for cleaning, the natural oxide layer on the surface of the silicon wafer can be removed due to the corrosivity of the hydrofluoric acid, and metal ions on the surface of the silicon wafer are removed due to the complexation reaction of the hydrochloric acid and metal elements in the oxide layer. However, some metal ions remain on the surface of the actual silicon wafer, deep-level impurities and even multi-level impurities can be formed in the silicon wafer after the metal impurities are diffused at high temperature, and the capture cross section of the metal impurities on minority carriers in the silicon wafer is 2-3 orders of magnitude larger than that of normally doped elements (such as boron and phosphorus).
Therefore, it is very important to develop a silicon wafer cleaning agent capable of effectively removing metal ions on the surface of the silicon wafer.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a silicon wafer cleaning additive which can effectively remove metal ions on the surface of a silicon wafer, improve the photoelectric conversion efficiency of a solar cell and improve the yield of the solar cell.
Another object of the present invention is to provide a silicon wafer cleaning solution based on the above silicon wafer cleaning additive.
The third purpose of the invention is to provide the application of the silicon wafer cleaning solution.
The technical scheme is as follows: the technical scheme adopted by the invention is as follows:
the silicon wafer cleaning additive is composed of the following components in parts by mass: 2-6 parts of chelating agent, 0.1-0.5 part of surfactant, 0.5-2 parts of penetrating agent, 2-5 parts of stabilizer and 80-90 parts of deionized water; the chelating agent is a metal chelating agent, the surfactant is a nonionic surfactant, the penetrating agent is polyethylene glycol, and the stabilizing agent is a cationic polymer.
Further, the metal chelating agent is polyethyleneimine and serine.
Furthermore, the mass part of the polyethyleneimine is 1-3 parts, and the mass part of the serine is 1-3 parts.
Further, the nonionic surfactant is glycerol.
Further, the cationic polymer is a polyquaternium.
The invention also provides a silicon wafer cleaning solution which contains an alkali solution or an acid solution and the silicon wafer cleaning additive; the mass ratio of the silicon wafer cleaning additive to the alkali solution or the acid solution is 1-2%.
Further, the alkali solution is a mixed aqueous solution of hydrogen peroxide and inorganic alkali; the inorganic alkali is sodium hydroxide or potassium hydroxide;
furthermore, the alkali solution is a mixed aqueous solution of hydrogen peroxide with the mass percent of 4-10% and sodium hydroxide with the mass percent of 0.1-1%.
Further, the acid solution is a mixed aqueous solution of 5-20% by mass of hydrofluoric acid and 5-20% by mass of hydrochloric acid.
The invention also provides a silicon wafer cleaning method, which is used for cleaning the silicon wafer by using the silicon wafer cleaning solution.
Further, the silicon wafer cleaning method comprises the following steps:
(1) preparing a silicon wafer cleaning additive: adding 2-6 parts by mass of metal chelating agent, 0.1-0.5 part by mass of nonionic surfactant, 0.5-2 parts by mass of polyethylene glycol and 2-5 parts by mass of cationic polymer into 80-90 parts by mass of deionized water, and uniformly mixing to obtain a silicon wafer cleaning additive;
(2) preparing a silicon wafer cleaning solution: adding the silicon wafer cleaning additive prepared in the step (1) into an alkali solution according to the mass ratio of 1-2%, and uniformly mixing to prepare a silicon wafer cleaning solution; the aqueous alkali is a mixed aqueous solution of hydrogen peroxide with the mass percent of 4-10% and sodium hydroxide with the mass percent of 0.1-1%;
(3) cleaning a silicon wafer: and (3) putting the silicon wafer into the silicon wafer cleaning solution prepared in the step (2) for cleaning, and cleaning for 0.5-3 min at 40-80 ℃.
Wherein in the step (1), the metal chelating agent is 1-3 parts by mass of polyethyleneimine and 1-3 parts by mass of serine; the nonionic surfactant is glycerol; the cationic polymer is polyquaternium.
Further, the step (2) and the step (3) of the silicon wafer cleaning method can also be:
(2) preparing a silicon wafer cleaning solution: adding the silicon wafer cleaning additive prepared in the step (1) into an acid solution according to the mass ratio of 1-2%, and uniformly mixing to prepare a silicon wafer cleaning solution; the acid solution is a mixed aqueous solution of 5-20% by mass of hydrofluoric acid and 5-20% by mass of hydrochloric acid;
(3) cleaning a silicon wafer: and (3) putting the silicon wafer into the silicon wafer cleaning solution prepared in the step (2) for cleaning, and cleaning for 0.5-3 min at normal temperature.
The silicon wafer cleaning liquid prepared by the silicon wafer cleaning additive of the invention has the advantages that the polyethyleneimine and the serine are used as chelating agents, the chelating ligand of the chelating agents contains two or more than two ligands with lone pair electron atoms, the chelating ligand can simultaneously form two or more coordination bonds with central ions to generate coordination compounds with a ring structure, a metal chelate with higher stability than the complex is generated, all metals in almost periodic system can form the complex and the chelate, and the chelating effect is particularly excellent for heavy metals. Besides the chelating agent, the surfactant glycerol and the penetrant polyethylene glycol play a role in wetting and permeating on the surface of the silicon wafer, so that the cleaning effect on impurities such as organic matters, particles and metals is accelerated, and the stabilizer polyquaternium can prevent the impurities such as metal particles from being deposited on the surface of the silicon wafer again. The silicon wafer cleaning additive disclosed by the invention can be applied to alkaline solutions and acidic solutions, has good cleaning capability and stronger cleaning capability on metal impurities, is non-volatile, has good stability and does not damage silicon wafers.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the metal impurities on the surface of the silicon wafer are effectively removed, and the silicon wafer is prevented from being polluted again by the metal impurities;
(2) the recombination caused by surface metal impurities is reduced, and the photoelectric conversion efficiency of the solar cell is improved;
(3) the cleanliness of the surface of the silicon wafer is improved, and the yield of the solar cell is improved;
(4) the silicon wafer cleaning additive is non-volatile, free of pungent smell, good in stability and free of damage to the silicon wafer;
(5) the method is widely applied, is suitable for alkali solution or acid solution, and has the advantages of simple and easy cleaning method, high cleaning speed and easy popularization and use.
Drawings
FIG. 1 is a graph showing the comparison of the cleaning effects of example 1 of the present invention and comparative example 1;
FIG. 2 is a graph comparing the cleaning effects of example 3 of the present invention and comparative example 2;
FIG. 3 is a graph comparing the average efficiencies of silicon wafers fabricated into cells after cleaning according to example 1 and comparative example 1 of the present invention.
FIG. 4 is a graph comparing the average efficiencies of silicon wafers fabricated into cells after cleaning according to example 3 and comparative example 2 of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
The silicon wafer cleaning additive and the silicon wafer cleaning solution are suitable for procedures of cleaning with alkali liquor or acid liquor in the production process of solar cells, such as cleaning after texturing, cleaning after etching and the like.
Example 1
The method for cleaning the silicon wafer after texturing specifically comprises the following steps:
(1) preparing a silicon wafer cleaning additive: adding 3 parts by mass of polyethyleneimine, 1 part by mass of serine, 0.5 part by mass of glycerol, 2 parts by mass of polyethylene glycol and 2 parts by mass of polyquaternary ammonium salt into 90 parts by mass of deionized water, and uniformly mixing to obtain a silicon wafer cleaning additive;
(2) preparing a silicon wafer cleaning solution: adding the silicon wafer cleaning additive prepared in the step (1) into an alkali solution according to the mass ratio of 2% and uniformly mixing to prepare a silicon wafer cleaning solution; wherein the alkali solution is a mixed aqueous solution of hydrogen peroxide with the mass percent content of 4% and sodium hydroxide with the mass percent content of 1%;
(3) cleaning a silicon wafer: and (3) putting the silicon wafer into the silicon wafer cleaning solution prepared in the step (2) for cleaning, and cleaning for 2min at 40 ℃.
Example 2
The method for cleaning the etched silicon wafer specifically comprises the following steps:
(1) preparing a silicon wafer cleaning additive: adding 1 part by mass of polyethyleneimine, 3 parts by mass of serine, 0.1 part by mass of glycerol, 0.5 part by mass of polyethylene glycol and 5 parts by mass of polyquaternary ammonium salt into 80 parts by mass of deionized water, and uniformly mixing to obtain a silicon wafer cleaning additive;
(2) preparing a silicon wafer cleaning solution: adding the silicon wafer cleaning additive prepared in the step (1) into an alkali solution according to the mass ratio of 1% and uniformly mixing to prepare a silicon wafer cleaning solution; wherein the alkali solution is a mixed aqueous solution of hydrogen peroxide with the mass percent of 10% and sodium hydroxide with the mass percent of 0.1%;
(3) cleaning a silicon wafer: and (3) putting the silicon wafer into the silicon wafer cleaning solution prepared in the step (2) for cleaning, and cleaning for 0.5min at 80 ℃.
Example 3
The method for cleaning the silicon wafer after texturing specifically comprises the following steps:
(1) preparing a silicon wafer cleaning additive: adding 3 parts by mass of polyethyleneimine, 1 part by mass of serine, 0.5 part by mass of glycerol, 2 parts by mass of polyethylene glycol and 2 parts by mass of polyquaternary ammonium salt into 80 parts by mass of deionized water, and uniformly mixing to obtain a silicon wafer cleaning additive;
(2) preparing a silicon wafer cleaning solution: adding the silicon wafer cleaning additive prepared in the step (1) into an acid solution according to the mass ratio of 2%, and uniformly mixing to prepare a silicon wafer cleaning solution; wherein the acid solution is a mixed aqueous solution of hydrofluoric acid with the mass percent content of 20% and hydrochloric acid with the mass percent content of 5%;
(3) cleaning a silicon wafer: and (3) putting the silicon wafer into the silicon wafer cleaning solution prepared in the step (2) for cleaning, and cleaning for 0.5min at normal temperature.
Example 4
The method for cleaning the etched silicon wafer specifically comprises the following steps:
(1) preparing a silicon wafer cleaning additive: adding 1 part by mass of polyethyleneimine, 3 parts by mass of serine, 0.1 part by mass of glycerol, 0.5 part by mass of polyethylene glycol and 5 parts by mass of polyquaternary ammonium salt into 90 parts by mass of deionized water, and uniformly mixing to obtain a silicon wafer cleaning additive;
(2) preparing a silicon wafer cleaning solution: adding the silicon wafer cleaning additive prepared in the step (1) into an acid solution according to the mass ratio of 1%, and uniformly mixing to prepare a silicon wafer cleaning solution; wherein the acid solution is a mixed aqueous solution of hydrofluoric acid with the mass percent content of 5% and hydrochloric acid with the mass percent content of 20%;
(3) cleaning a silicon wafer: and (3) putting the silicon wafer into the silicon wafer cleaning solution prepared in the step (2) for cleaning, and cleaning for 3min at normal temperature.
Comparative example 1
The conventional cleaning of the silicon wafer is carried out by adopting the existing alkali solution, wherein the alkali solution is the aqueous solution of hydrogen peroxide and sodium hydroxide.
Comparative example 2
And conventionally cleaning the silicon wafer by using the conventional acid solution, wherein the acid solution is a mixed aqueous solution of hydrofluoric acid and hydrochloric acid.
The metal ion content of the silicon wafer surface after cleaning of example 1, example 3 and comparative examples 1-2 was measured by an ICP-MS measuring instrument, and a comparison of the graphs is shown in fig. 1 and fig. 2.
The silicon wafers after cleaning of example 1, example 3 and comparative examples 1-2 were fabricated into battery pieces using the same process conditions, and the average conversion efficiency of the fabricated battery pieces was tested, and a comparison graph thereof is shown in fig. 3 and 4.
As can be seen from FIGS. 1 and 2, the cleaning effect of example 1 is significantly better than that of comparative example 1, and the cleaning effect of example 3 is significantly better than that of comparative example 2, which shows that the silicon wafer cleaning additive of the present invention can greatly improve the cleanliness of the silicon wafer surface. As can be seen from fig. 3 and 4, the average conversion efficiency of the cell of example 1 was improved by about 0.12% over the average conversion efficiency of the cell of comparative example 1, and the average conversion efficiency of the cell of example 3 was improved by about 0.07% over the average conversion efficiency of the cell of comparative example 2, indicating that the silicon wafer cleaning additive of the present invention can improve the photoelectric conversion efficiency of the cell.
Claims (12)
1. A silicon wafer cleaning additive is characterized in that: the cleaning additive comprises the following components in parts by weight: 2-6 parts of chelating agent, 0.1-0.5 part of surfactant, 0.5-2 parts of penetrating agent, 2-5 parts of stabilizer and 80-90 parts of deionized water; the chelating agent is a metal chelating agent, the surfactant is a nonionic surfactant, the penetrating agent is polyethylene glycol, and the stabilizing agent is a cationic polymer.
2. The silicon wafer cleaning additive according to claim 1, wherein: the metal chelating agent is polyethyleneimine and serine.
3. The silicon wafer cleaning additive according to claim 2, wherein: the mass portion of the polyethyleneimine is 1-3 parts, and the mass portion of the serine is 1-3 parts.
4. The silicon wafer cleaning additive according to claim 1, wherein: the nonionic surfactant is glycerol.
5. The silicon wafer cleaning additive according to claim 1, wherein: the cationic polymer is polyquaternium.
6. A silicon wafer cleaning solution is characterized in that: containing an alkali solution or an acid solution, and the silicon wafer cleaning additive according to any one of claims 1 to 5; the mass ratio of the silicon wafer cleaning additive to the alkali solution or the acid solution is 1-2%.
7. The silicon wafer cleaning liquid as claimed in claim 6, wherein: the alkali solution is a mixed aqueous solution of hydrogen peroxide with the mass percent of 4-10% and sodium hydroxide with the mass percent of 0.1-1%.
8. The silicon wafer cleaning liquid as claimed in claim 6, wherein: the acid solution is a mixed aqueous solution of 5-20% by mass of hydrofluoric acid and 5-20% by mass of hydrochloric acid.
9. A silicon wafer cleaning method is characterized in that: cleaning the silicon wafer with the silicon wafer cleaning solution as set forth in any one of claims 6 to 8.
10. The method for cleaning silicon wafers according to claim 9, comprising the steps of:
(1) preparing a silicon wafer cleaning additive: adding 2-6 parts by mass of metal chelating agent, 0.1-0.5 part by mass of nonionic surfactant, 0.5-2 parts by mass of polyethylene glycol and 2-5 parts by mass of cationic polymer into 80-90 parts by mass of deionized water, and uniformly mixing to obtain a silicon wafer cleaning additive;
(2) preparing a silicon wafer cleaning solution: adding the silicon wafer cleaning additive prepared in the step (1) into an alkali solution according to the mass ratio of 1-2%, and uniformly mixing to prepare a silicon wafer cleaning solution; the aqueous alkali is a mixed aqueous solution of hydrogen peroxide with the mass percent of 4-10% and sodium hydroxide with the mass percent of 0.1-1%;
(3) cleaning a silicon wafer: and (3) putting the silicon wafer into the silicon wafer cleaning solution prepared in the step (2) for cleaning, and cleaning for 0.5-3 min at 40-80 ℃.
11. The silicon wafer cleaning method according to claim 10, wherein in the step (1), the metal chelating agent is 1 to 3 parts by mass of polyethyleneimine and 1 to 3 parts by mass of serine; the nonionic surfactant is glycerol; the cationic polymer is polyquaternium.
12. The silicon wafer cleaning method according to claim 10, wherein the steps (2) and (3) are further:
(2) preparing a silicon wafer cleaning solution: adding the silicon wafer cleaning additive prepared in the step (1) into an acid solution according to the mass ratio of 1-2%, and uniformly mixing to prepare a silicon wafer cleaning solution; the acid solution is a mixed aqueous solution of 5-20% by mass of hydrofluoric acid and 5-20% by mass of hydrochloric acid;
(3) cleaning a silicon wafer: and (3) putting the silicon wafer into the silicon wafer cleaning solution prepared in the step (2) for cleaning, and cleaning for 0.5-3 min at normal temperature.
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| CN115975738A (en) * | 2022-12-12 | 2023-04-18 | 嘉兴市小辰光伏科技有限公司 | Additive for reducing acid consumption in cleaning acid tank and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975738A (en) * | 2022-12-12 | 2023-04-18 | 嘉兴市小辰光伏科技有限公司 | Additive for reducing acid consumption in cleaning acid tank and application |
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