CN114267582A - Nitrogen-free crystalline silicon solar cell polishing method and polishing solution thereof - Google Patents
Nitrogen-free crystalline silicon solar cell polishing method and polishing solution thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-free crystalline silicon solar cell polishing method and polishing solution thereof. The SE monocrystalline silicon piece after diffusion is placed in the polishing solution, etching is carried out for 30-240 s at the temperature of 8-40 ℃, etching and polishing are carried out on the suede of the SE monocrystalline silicon piece, so that the upper part of the pyramid-shaped appearance structure is removed, and the pyramid base is left.
Description
Technical Field
The invention belongs to the technical field of polishing of crystalline silicon solar cells, and particularly relates to a nitrogen-free crystalline silicon solar cell polishing method and a polishing solution thereof.
Background
Solar cells are developing towards high efficiency, low cost, and environmental protection. At present, the efficiency of the conventional aluminum back surface field (Al-BSF) solar cell has not been greatly improved. The passivation emitter and back surface cell (PERC) process only needs to add the steps of back passivation and laser grooving on the basis of the original process so as to play the roles of passivating the surface and improving long-wave response, thereby greatly improving the cell efficiency. Therefore, PERC cell technology is becoming the mainstream of high efficiency solar cell technology in the market today. Due to the increased back passivation, higher requirements are placed on the flatness of the polished structure on the back of the cell. The improvement of the flatness of the back surface can increase the secondary reflection of the sunlight long wave band, further increase the absorption of transmitted light and improve the short-circuit current of the cell; in addition, the flat surface structure has a lower specific surface area, reduces the recombination of current carriers, and improves the passivation effect. The whole process of the PERC battery comprises the following steps: 1. texturing-2, diffusing-3, laser SE-4, etching (back polishing) -5, back coating (aluminum oxide and silicon nitride) -6, front coating (silicon nitride) -7, laser grooving-8, screen printing-9 and sintering.
At present, two general etching polishing modes in the industry are acid polishing and alkali polishing. And the acid polishing adopts mixed acid liquid of hydrofluoric acid and nitric acid to polish and etch the back of the diffused silicon wafer. The reflectivity of the surface after acid polishing is 25-30%, the polishing effect is general, and the consumption cost of chemical liquid is high. In addition, the emission of nitrogen in nitric acid causes great pressure on environmental protection, and the treatment cost of acid waste liquid is high. In order to reduce nitrogen emission, an alkali polishing process is developed, but the alkali polishing process needs to add an alkali polishing groove type device on the basis of a chain type device. In addition, the alkali polishing process is incompatible with the current SE process, the SE area needs to be protected by additionally adding an oxidation process in the process of adding the SE, the risk of process pollution is increased, and the process is complex and unstable.
In summary, the prior art has the following drawbacks: 1. the acid polishing process has poor polishing effect and low final efficiency due to low reflectivity. The acid solution cost is high, the waste water containing nitrate nitrogen is not environment-friendly, and the waste water treatment cost is high; 2. the alkali back polishing process needs three sets of equipment (an oxidation furnace, chain type removal of the phosphorus silicon glass on the back surface and groove type alkali polishing), the equipment investment cost is high, the compatibility with the SE process is poor, the whole process is complex, the process pollution risk is increased, and the process is unstable. In addition, the alkali polishing needs to be matched with the purchase of additional alkali polishing additives for use.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a nitrogen-free crystalline silicon solar cell polishing method and a polishing solution thereof, which have the advantages of simple process, easiness in implementation, effective reduction of chemical solution cost and waste liquid treatment cost, and good polishing effect.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a nitrogen-free crystalline silicon solar cell polishing method comprises the following steps:
(1) preparing a monocrystalline silicon wafer after diffusion preparation, wherein the monocrystalline silicon wafer is provided with a suede surface which is fully distributed with a pyramid appearance structure, the bottom side of the pyramid appearance structure is 1-5 micrometers, and the height of the pyramid appearance structure is 0.7-3.5 micrometers; the diffused monocrystalline silicon pieces comprise P-type and N-type silicon pieces and are suitable for original monocrystalline silicon, polycrystalline silicon and ingot casting monocrystalline silicon pieces;
(2) preparing a polishing solution: mixing and stirring a fluoride ion source, a chloride ion source, an oxidant and deionized water uniformly in sequence to obtain a polishing solution; wherein the concentration of the fluoride ion source is 0.1-8 mol/L, the concentration of the chloride ion source is 0.01-13 mol/L, and the concentration of the oxidant is 0.01-3 mol/L;
(3) and placing the diffused SE monocrystalline silicon wafer into the polishing solution, and etching at the temperature of 8-40 ℃ for 30-240 s, preferably at the temperature of 25-35 ℃ for 40-90 s. And etching and polishing the suede of the SE monocrystalline silicon wafer to remove the upper part of the pyramid appearance structure and leave a pyramid base, wherein the outline of the pyramid base is quadrilateral, the side length is 1-5 micrometers, and the height is 0.1-1 micrometer. The integral flatness is higher, and is comparable to crystal face polishing of alkali polishing, so that the passivation effect and the reflectivity are improved, the open voltage of the battery is further improved, and the short-circuit current is increased.
As a preferred embodiment of the present invention, the fluoride ion source is selected from hydrofluoric acid.
In a preferred embodiment of the present invention, the chlorine-containing ion source is selected from hydrochloric acid, sodium hypochlorite, sodium chlorite, chlorine dioxide, chlorine gas, sodium chlorate or sodium perchlorate.
In a preferred embodiment of the present invention, the source of chlorine-containing ions is selected from one or more of chloride ions, hypochlorite ions, chlorite ions, chlorate ions, perchlorate ions, and acids or salts containing the same.
In a preferred embodiment of the present invention, the chloride ion is selected from one or more of hydrochloric acid, sodium chloride, potassium chloride, and calcium chloride. One or more of chloride ion-containing salts such as hypochlorous acid, sodium hypochlorite, potassium hypochlorite, chlorous acid, sodium chlorite, potassium chlorite, chlorine dioxide, chlorine gas, chloric acid, sodium chlorate, potassium chlorate, perchloric acid, sodium perchlorate, potassium perchlorate, hydrochloric acid, sodium chloride, potassium chloride, calcium chloride and the like; specifically, the hypochlorite ions are selected from one or more of hypochlorous acid, sodium hypochlorite and potassium hypochlorite. The chlorite ion is one or more selected from chlorous acid, sodium chlorite, chlorine dioxide and potassium chlorite; the chlorate ions are selected from one or more of chloric acid, sodium chlorate and potassium chlorate; the perchlorate ion is selected from one or more of perchloric acid, sodium perchlorate and potassium perchlorate.
In a preferred embodiment of the present invention, the oxidizing agent is selected from one or more of sodium persulfate, hydrogen peroxide, acetic acid, potassium permanganate, and concentrated sulfuric acid.
As a preferable scheme of the invention, an additive with the mass ratio of 100: 0.2-5 is further added into the polishing solution in the step (2). After the additive is added, the smooth modification process is more stable, and the smooth modification effect is improved.
In a preferred embodiment of the present invention, the additive is one or more of sodium dodecyl sulfate, sodium silicate, benzyltrimethylammonium chloride, sodium citrate, and guar gum.
As a preferable scheme of the invention, the additive comprises the following components in percentage by mass: 0.5-5 parts by mass of sodium dodecyl sulfate, 0.2-2 parts by mass of sodium silicate, 0.5-2 parts by mass of benzyltrimethylammonium chloride, 1-3 parts by mass of sodium citrate and 100 parts by mass of water.
A nitrogen-free crystalline silicon solar cell polishing solution used in a nitrogen-free crystalline silicon solar cell polishing method.
The invention has the beneficial effects that: compared with an alkali polishing process, the polishing method provided by the invention has the advantages of simple and stable process, good polishing effect, high reflectivity, compatibility with the existing production line etching process, no need of adding polishing equipment, simple process, good etching, polishing and smoothing modification effects, capability of smoothing the tops and bottoms of pyramids and passivating the square frustum plane, controllable reflectivity, easiness in subsequent deposition of a passivation film, improvement of reflectivity, guarantee of product quality and improvement of solar cell efficiency, reasonable formula of the adopted polishing solution, no nitrogen, low waste liquid treatment cost, small environmental protection pressure, low cost of raw material chemical liquid medicine, easiness in obtaining, reduction of production cost and reduction of pollution to the environment.
The invention is further illustrated below with reference to the figures and examples.
Drawings
FIG. 1 is a SEM surface structure diagram of an SE single crystal silicon wafer before polishing.
FIG. 2 is a view showing the structure of the SEM surface after polishing by the polishing method of the present invention.
FIG. 3 is a structural view of a SEM cross section after polishing by the polishing method of the invention.
Fig. 4 is a structure diagram of the SEM surface obtained by the conventional acid polishing.
Detailed Description
Example 1: the embodiment provides a nitrogen-free polishing method of a crystalline silicon solar cell and a polishing solution thereof. In this embodiment, sodium hypochlorite has the effect of an oxidant, and an additional oxidant may not be required, but in other embodiments, an oxidant may also be added. And mixing hydrofluoric acid, sodium hypochlorite and deionized water to obtain the polishing solution, wherein the concentration of the sodium hypochlorite is 0.05mol/L, and the concentration of the hydrofluoric acid is 1.2 mol/L. Adding an additive into the nitrogen-free crystalline silicon solar cell polishing solution, wherein the mass ratio of the additive to the nitrogen-free crystalline silicon solar cell polishing solution is 2: 100. wherein the additive comprises 3 parts by mass of sodium dodecyl sulfate, 0.5 part by mass of sodium silicate, 1 part by mass of benzyltrimethylammonium chloride, 2 parts by mass of sodium citrate and 100 parts by mass of water. In this embodiment, the SE single crystal silicon wafer after diffusion is taken as an example, and in other embodiments, the SE single crystal silicon wafer may be a P-type or N-type silicon wafer, and may be suitable for polishing of original single crystal silicon, polycrystalline silicon, and ingot single crystal silicon wafers.
And placing the diffused SE monocrystalline silicon wafer into the nitrogen-free crystalline silicon solar cell polishing solution, and etching for 60s at the reaction temperature of 35 ℃ to obtain a polished sample. The reflectance after polishing was measured to be 38%.
Example 2: the embodiment provides a nitrogen-free crystalline silicon solar cell polishing method and polishing solution thereof, which are basically the same as those in embodiment 1, and are different in that the polishing solution comprises hydrofluoric acid, hydrogen peroxide, hydrochloric acid and an additive.
Mixing hydrofluoric acid, hydrogen peroxide and hydrochloric acid to obtain polishing solution, wherein the concentration of the hydrofluoric acid is 0.2mol/L, the concentration of the hydrogen peroxide is 0.5mol/L, and the concentration of the hydrochloric acid is 10.8 mol/L; adding an additive into the polishing solution, wherein the mass ratio of the additive to the polishing solution is 1: 100. the additive is composed of 1 part by mass of sodium dodecyl sulfate, 1 part by mass of sodium silicate, 0.5 part by mass of benzyltrimethylammonium chloride, 1 part by mass of sodium citrate and 100 parts by mass of water.
And placing the diffused SE monocrystalline silicon wafer into the nitrogen-free crystalline silicon solar cell polishing solution, and etching for 60s at the reaction temperature of 35 ℃ to obtain a polished sample. Referring to fig. 2 and fig. 3, the tip of the gold sub-tower can be better flattened to obtain a flat surface, which is more beneficial to deposition of a passivation film. The reflectance after polishing was tested to be 35%.
Example 3: the embodiment provides a method for polishing a nitrogen-free crystalline silicon solar cell and a polishing solution thereof, which are basically the same as the polishing solution 1 in the embodiment, and are different from the polishing solution in that the components of the polishing solution comprise hydrofluoric acid, sodium persulfate and hydrochloric acid. Mixing hydrofluoric acid, sodium persulfate and hydrochloric acid to obtain nitrogen-free crystalline silicon solar cell polishing solution, wherein the concentration of the hydrofluoric acid is 0.2mol/L, the concentration of the sodium persulfate is 0.3mol/L, and the concentration of the hydrochloric acid is 8.8 mol/L; adding an additive into the nitrogen-free crystalline silicon solar cell polishing solution, wherein the mass ratio of the additive to the nitrogen-free crystalline silicon solar cell polishing solution is 0.5: 100. the additive is composed of 3 parts by mass of sodium dodecyl sulfate, 2 parts by mass of sodium silicate, 2 parts by mass of benzyltrimethylammonium chloride, 3 parts by mass of sodium citrate and 100 parts by mass of water.
And placing the diffused SE monocrystalline silicon wafer into the nitrogen-free crystalline silicon solar cell polishing solution, and etching for 60s at the reaction temperature of 30 ℃ to obtain a polished sample. The reflectance after polishing was tested to be 33%.
Example 4: the embodiment provides a nitrogen-free polishing method of a crystalline silicon solar cell and a polishing solution thereof, which are basically the same as those in embodiment 1, and are different in that the polishing solution comprises hydrofluoric acid, sodium hypochlorite and deionized water. Mixing hydrofluoric acid, sodium hypochlorite and deionized water to obtain nitrogen-free crystalline silicon solar cell polishing solution, wherein the concentration of the sodium hypochlorite is 0.3mol/L, the concentration of the hydrofluoric acid is 0.8mol/L, adding an additive into the nitrogen-free crystalline silicon solar cell polishing solution, and the mass ratio of the additive to the nitrogen-free crystalline silicon solar cell polishing solution is 5: 100. wherein the additive comprises 0.5 part by mass of sodium dodecyl sulfate, 0.5 part by mass of sodium silicate, 1 part by mass of benzyltrimethylammonium chloride, 1 part by mass of sodium citrate and 100 parts by mass of water.
And placing the diffused SE monocrystalline silicon wafer into the nitrogen-free crystalline silicon solar cell polishing solution, and etching for 60s at the reaction temperature of 25 ℃ to obtain a polished sample. The reflectance after polishing was tested to be 40%.
Example 5: the embodiment provides a method for polishing a nitrogen-free crystalline silicon solar cell and a polishing solution thereof, which are basically the same as the polishing solution in embodiment 1, and are different in that the polishing solution comprises hydrofluoric acid, sodium hypochlorite, hydrogen peroxide and deionized water. Mixing hydrofluoric acid, sodium hypochlorite, hydrogen peroxide and deionized water to obtain the nitrogen-free crystalline silicon solar cell polishing solution, wherein the concentration of the hydrofluoric acid is 2mol/L, the concentration of the sodium hypochlorite is 0.5mol/L, and the concentration of the hydrogen peroxide is 0.3 mol/L.
Adding an additive into the nitrogen-free crystalline silicon solar cell polishing solution, wherein the mass ratio of the additive to the nitrogen-free crystalline silicon solar cell polishing solution is 3: 100. the additive is composed of 2 parts by mass of sodium dodecyl sulfate, 1 part by mass of sodium silicate, 1 part by mass of benzyltrimethylammonium chloride, 2 parts by mass of sodium citrate and 100 parts by mass of water.
And placing the diffused SE monocrystalline silicon wafer into the nitrogen-free crystalline silicon solar cell polishing solution, and etching for 60s at the reaction temperature of 30 ℃ to obtain a polished sample. The reflectance after polishing was tested to be 37%.
Example 6: the embodiment provides a nitrogen-free polishing method of a crystalline silicon solar cell and a polishing solution thereof, which are basically the same as the polishing method 1 in the embodiment, and are different in that the polishing solution comprises hydrofluoric acid, sodium hypochlorite, sulfuric acid and deionized water. Mixing hydrofluoric acid, sodium hypochlorite, sulfuric acid and deionized water to obtain polishing solution, wherein the concentration of the hydrofluoric acid is 1 mol/L; the concentration of sodium hypochlorite is 0.1 mol/L; the sulfuric acid content was 0.1 mol/L.
Adding an additive into the polishing solution, wherein the mass ratio of the additive to the nitrogen-free crystalline silicon solar cell polishing solution is 4: 100. the additive is composed of 4 parts by mass of sodium dodecyl sulfate, 1 part by mass of sodium silicate, 2 parts by mass of benzyltrimethylammonium chloride, 3 parts by mass of sodium citrate and 100 parts by mass of water.
And placing the diffused SE monocrystalline silicon wafer into the nitrogen-free crystalline silicon solar cell polishing solution, and etching for 90s at the reaction temperature of 30 ℃ to obtain a polished sample. The reflectance after polishing was tested to be 41%.
Example 7: the embodiment provides a method for polishing a nitrogen-free crystalline silicon solar cell and a polishing solution thereof, which are basically the same as the polishing solution in embodiment 1, except that the polishing solution comprises hydrofluoric acid, sodium chlorite and deionized water.
In this embodiment, the sodium chlorite has the effect of the oxidant, and the additional oxidant does not need to be added, but in other embodiments, the additional oxidant may be added.
Mixing hydrofluoric acid, sodium chlorite and deionized water to obtain nitrogen-free crystalline silicon solar cell polishing solution, wherein the concentration of the hydrofluoric acid is 2mol/L, and the concentration of the sodium chlorite is 0.025 mol/L; adding an additive into the nitrogen-free crystalline silicon solar cell polishing solution, wherein the mass ratio of the additive to the nitrogen-free crystalline silicon solar cell polishing solution is 1: 100. the additive is composed of 2 parts by mass of sodium dodecyl sulfate, 1 part by mass of sodium silicate, 2 parts by mass of benzyltrimethylammonium chloride, 2 parts by mass of sodium citrate and 100 parts by mass of water. And placing the diffused SE monocrystalline silicon wafer into the nitrogen-free crystalline silicon solar cell polishing solution, and etching for 60s at the reaction temperature of 35 ℃ to obtain a polished sample. The reflectance after polishing was tested to be 35%.
Comparative example 1: and (3) placing the diffused SE monocrystalline silicon wafer in a conventional hydrofluoric acid and nitric acid mixed acid liquid for polishing and etching to obtain the silicon wafer with the pit structure. Wherein the concentration of hydrofluoric acid is 2.7 mol/L; the concentration of the nitric acid is as follows: 9.7 mol/L; the reaction temperature was 12 ℃ and the reaction time was 60 s. The SEM surface structure thereof is shown in fig. 4.
Solar cells were prepared according to the PERC process flow from examples 1 to 7 and comparative example 1 and were tested for comparative solar cell performance, with specific results in table 1:
TABLE 1
| Uoc(V) | Jsc(mA/cm2) | FF(％) | Eff(％) | |
| Example 1 | 0.6886 | 39.97 | 81.71 | 22.49 |
| Example 2 | 0.6868 | 39.95 | 81.66 | 22.41 |
| Example 3 | 0.6855 | 39.94 | 81.63 | 22.35 |
| Example 4 | 0.6894 | 39.98 | 81.73 | 22.53 |
| Example 5 | 0.6882 | 39.96 | 81.70 | 22.47 |
| Example 6 | 0.6901 | 39.99 | 81.69 | 22.54 |
| Example 7 | 0.6873 | 39.94 | 81.62 | 22.41 |
| Comparative example 1 | 0.6865 | 39.91 | 81.58 | 22.35 |
By comparison of table 1, the silicon wafer processed by the nitrogen-free crystalline silicon solar cell polishing method according to the invention is basically superior to the conventional process in various performances of the solar cell prepared by the PERC process flow. The polishing solution disclosed by the invention is reasonable in formula, does not contain nitrogen, effectively avoids the emission of nitrogen in the acid polishing waste liquid, is low in waste liquid treatment cost and low in environmental protection pressure, and reduces the production cost and the pollution to the environment.
The above examples are only preferred embodiments of the present invention, and the present invention is not limited to all embodiments, and any technical solution using one of the above examples or equivalent changes made according to the above examples is within the scope of the present invention.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. In addition, although specific terms are employed herein, they are used in a descriptive sense only and not for purposes of limitation, as other methods and polishing solutions utilizing the same or similar components are within the scope of the invention.
Claims (10)
1. A method for polishing a nitrogen-free crystalline silicon solar cell is characterized by comprising the following steps:
(1) preparing an SE monocrystalline silicon wafer after diffusion preparation, wherein the SE monocrystalline silicon wafer is provided with a suede full of pyramid appearance structures, the bottom sides of the pyramid appearance structures are 1-5 micrometers, and the height of the pyramid appearance structures is 0.7-3.5 micrometers;
(2) preparing a polishing solution: mixing and stirring a fluoride ion source, a chloride ion source, an oxidant and deionized water uniformly in sequence to obtain a polishing solution; wherein the concentration of the fluoride ion source is 0.1-8 mol/L, the concentration of the chloride ion source is 0.01-13 mol/L, and the concentration of the oxidant is 0.01-3 mol/L; an additive is added into the polishing solution, and the mass ratio of the polishing solution to the additive is 100: 0.2-5;
(3) and placing the diffused SE monocrystalline silicon piece into the polishing solution, etching for 30-240 s at the temperature of 8-40 ℃, and performing etching and polishing treatment on the suede of the SE monocrystalline silicon piece to remove the upper part of the pyramid appearance structure and leave a pyramid base, wherein the outline of the pyramid base is quadrilateral, the side length is 1-5 micrometers, and the height is 0.1-1 micrometer.
2. The nitrogen-free crystalline silicon solar cell polishing method according to claim 1, wherein the fluoride ion source is selected from hydrofluoric acid.
3. The nitrogen-free crystalline silicon solar cell polishing method as claimed in claim 1, wherein the chlorine-containing ion source comprises one or more of chloride ions, hypochlorite ions, chlorite ions, chlorate ions, perchlorate ions, and acid or salt containing the same.
4. The nitrogen-free crystalline silicon solar cell polishing method as claimed in claim 3, wherein the hypochlorite ions are selected from one or more of hypochlorous acid, sodium hypochlorite and potassium hypochlorite; the chlorite ion is one or more selected from chlorous acid, sodium chlorite, chlorine dioxide and potassium chlorite; the chlorate ions are selected from one or more of chloric acid, sodium chlorate and potassium chlorate; the perchlorate ion is selected from one or more of perchloric acid, sodium perchlorate and potassium perchlorate.
5. The nitrogen-free crystalline silicon solar cell polishing method according to claim 3, wherein the chloride ions comprise one or more of hydrochloric acid, sodium chloride, potassium chloride and calcium chloride.
6. The method for polishing the nitrogen-free crystalline silicon solar cell as claimed in claim 1, wherein the oxidant comprises one or more of sodium persulfate, hydrogen peroxide, acetic acid, potassium permanganate and concentrated sulfuric acid.
7. The method for polishing the nitrogen-free crystalline silicon solar cell as claimed in claim 1, wherein an additive is further added into the polishing solution in the step (2) in a mass ratio of 100: 0.2-5.
8. The method for polishing the nitrogen-free crystalline silicon solar cell as claimed in claim 7, wherein the additive is one or more of sodium dodecyl sulfate, sodium silicate, benzyltrimethylammonium chloride, sodium citrate and guar gum.
9. The nitrogen-free crystalline silicon solar cell polishing method according to claim 7, wherein the additive consists of the following components in percentage by mass: 0.5-5 parts by mass of sodium dodecyl sulfate, 0.2-2 parts by mass of sodium silicate, 0.5-2 parts by mass of benzyltrimethylammonium chloride, 1-3 parts by mass of sodium citrate and 100 parts by mass of water.
10. A nitrogen-free crystalline silicon solar cell polishing solution used in the nitrogen-free crystalline silicon solar cell polishing method according to any one of claims 1 to 9.
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| CN115377252A (en) * | 2022-10-24 | 2022-11-22 | 英利能源发展(天津)有限公司 | Method for inhibiting polycrystalline silicon surface explosion film growth by PECVD method |
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