CN115172157B - Texture surface preparation method of monocrystalline silicon piece and solar cell - Google Patents

Texture surface preparation method of monocrystalline silicon piece and solar cell Download PDF

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Publication number
CN115172157B
CN115172157B CN202210807902.0A CN202210807902A CN115172157B CN 115172157 B CN115172157 B CN 115172157B CN 202210807902 A CN202210807902 A CN 202210807902A CN 115172157 B CN115172157 B CN 115172157B
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monocrystalline silicon
barrier layer
silicon piece
reaction barrier
alkali solution
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CN115172157A (en
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龚道仁
张良
辛科
张景
赵泽
周锡伟
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Anhui Huasheng New Energy Technology Co ltd
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Anhui Huasheng New Energy Technology Co ltd
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    • H01L31/0236—Special surface textures
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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Abstract

The invention relates to the technical field of solar cells, and particularly provides a method for preparing a texture surface of a monocrystalline silicon wafer and a corresponding solar cell, wherein the method comprises the following steps: respectively providing a monocrystalline silicon piece and an alkali solution, wherein the alkali solution is suitable for corroding one side surface of the monocrystalline silicon piece; forming a reaction barrier layer on the surface of one side of the monocrystalline silicon piece to be corroded, wherein the reaction barrier layer is provided with a plurality of openings penetrating through the reaction barrier layer; placing the monocrystalline silicon wafer with the reaction barrier layer in an alkali solution, and simultaneously forming a mask protection film on the surface of one side of the reaction barrier layer, which is opposite to the monocrystalline silicon wafer, and the side wall of the opening, wherein the mask protection film is adsorbed on the surface of the reaction barrier layer under the action of the alkali solution; the alkali solution reacts with the monocrystalline silicon piece, and an inverted pyramid suede is formed in the area of the monocrystalline silicon piece corresponding to the opening. The texture surface preparation method of the monocrystalline silicon piece can obtain the optimal inverted pyramid morphology, and further greatly improves the photoelectric conversion efficiency of the solar cell.

Description

Texture surface preparation method of monocrystalline silicon piece and solar cell
Technical Field
The invention relates to the technical field of solar cells, in particular to a method for preparing a texture surface of a monocrystalline silicon wafer and a corresponding solar cell.
Background
In the current solar cell manufacturing process, the texturing of the silicon wafer is an indispensable primary step, and the good textured structure can greatly improve the absorption of the solar cells to sunlight and improve the conversion efficiency. The traditional monocrystalline silicon slice texturing method generally uses alkali solution, utilizes anisotropic reaction to form forward pyramid texture surface under the assistance of additives, the texture surface has poor absorptivity to light when illumination is not direct and ambient light is mostly scattered light, and the protruding texture surface is more easily damaged by scratches and the like in the subsequent film layer deposition process, so that PN junction is damaged, a silicon slice substrate is exposed, and the yield and efficiency of the battery slice are affected.
Compared with the forward pyramid suede, the inverted pyramid suede has better absorption capability in weak light, and has relatively low requirement on the angle of illumination, so that the inverted pyramid suede is more suitable for a battery assembly installed at a fixed angle, and the sunken suede is less prone to damage of subsequent processes. The key point of forming the inverted pyramid suede on the surface of the silicon wafer substrate is that a reaction blocking layer is needed to block the area which does not need to form the inverted pyramid. At present, the conventional blocking mode adopts silicon dioxide as a reaction blocking layer, however, the inventor discovers that if only silicon dioxide is adopted as the reaction blocking layer in long-term experimental tests, in the process of forming the inverted pyramid suede by utilizing the reaction of alkali solution and monocrystalline silicon piece, the alkali solution and the silicon dioxide serving as the reaction blocking layer can also react, so that the formed inverted pyramid appearance has defects.
At present, no method for stably obtaining the shape of the preferred inverted pyramid exists. Therefore, the texture preparation method of the monocrystalline silicon piece in the prior art needs to be improved.
Disclosure of Invention
Therefore, the invention aims to solve the technical problem that the optimal inverted pyramid morphology is difficult to obtain in the prior art.
In order to solve the technical problems, the invention provides a method for preparing a texture surface of a monocrystalline silicon wafer, which comprises the following steps: providing a monocrystalline silicon piece and an alkali solution respectively, wherein the alkali solution is suitable for corroding one side surface of the monocrystalline silicon piece; forming a reaction barrier layer on the surface of one side of the monocrystalline silicon piece to be corroded, wherein the reaction barrier layer is provided with a plurality of openings penetrating through the reaction barrier layer; placing the monocrystalline silicon piece with the reaction barrier layer in the alkali solution, and simultaneously forming a mask protection film on the surface of one side of the reaction barrier layer, which is opposite to the monocrystalline silicon piece, and the side wall of the opening, wherein the mask protection film is adsorbed on the surface of the reaction barrier layer under the action of the alkali solution; the alkali solution reacts with the monocrystalline silicon piece, and an inverted pyramid suede is formed in the area of the monocrystalline silicon piece corresponding to the opening.
Optionally, the mask protection film is formed by mask substances in the mask protection agent, and the concentration of the mask substances in the mask protection agent is 0.5% -1.5%.
Optionally, the masking material comprises a metal chelate, a metal complex or a positively charged organic compound.
Optionally, the positively charged organic material comprises a quaternary ammonium salt.
Optionally, the quaternary ammonium salt comprises 3-chloro-2-hydroxypropyl trimethyl ammonium chloride.
Optionally, the concentration of the alkali solution is 2.5% -3.5%, the reaction temperature is 78-82 ℃, and the reaction time is 400-1000 s.
Optionally, the alkali solution comprises a sodium hydroxide solution or a potassium hydroxide solution.
Optionally, the step of forming a reaction barrier layer on the monocrystalline silicon piece includes: forming an initial reaction barrier layer on the monocrystalline silicon piece; openings are formed in the initial reaction barrier layer such that the initial reaction barrier layer forms the reaction barrier layer.
Optionally, the process of forming the initial reaction barrier layer includes: plasma enhanced chemical vapor deposition.
Optionally, the process of forming the plurality of openings in the initial reaction barrier layer includes: picosecond laser process.
Optionally, the initial reaction barrier layer is formed at a temperature of 670 ℃ to 720 ℃ for a time of 30 ℃ to 50 ℃.
Optionally, before forming the initial reaction barrier layer on the monocrystalline silicon piece, the method further comprises: and carrying out surface cleaning treatment on the monocrystalline silicon piece.
Optionally, the monocrystalline silicon piece and the reaction barrier layer are placed before the alkaline solution, further comprising: the mask protectant is added to the alkaline solution.
Optionally, the distance between adjacent openings is 2 μm-5 μm, and the diameter of the openings is 1 μm-10 μm.
Optionally, the thickness of the reaction blocking layer is 1nm-1.5nm.
The invention also provides a solar cell, which is obtained by taking the monocrystalline silicon wafer prepared by the texture preparation method of the monocrystalline silicon wafer as a substrate.
The technical scheme of the invention has the following advantages:
According to the preparation method of the texture surface of the monocrystalline silicon piece, the monocrystalline silicon piece and the alkali solution are respectively provided, and the alkali solution is suitable for corroding one side surface of the monocrystalline silicon piece; forming a reaction barrier layer on the surface of one side of the monocrystalline silicon piece to be corroded, wherein the reaction barrier layer is provided with a plurality of openings penetrating through the reaction barrier layer; placing the monocrystalline silicon piece with the reaction barrier layer in the alkaline solution, and forming a mask protection film on the surface of one side of the reaction barrier layer, which is opposite to the monocrystalline silicon piece, and the side wall of the opening, wherein the mask protection film is adsorbed on the surface of the reaction barrier layer under the action of the alkaline solution, so that an alkaline solution can react with the monocrystalline silicon piece in the opening to form an inverted pyramid suede; meanwhile, the mask protective film protects the reaction barrier layer when the alkali solution reacts with the monocrystalline silicon piece in the opening, so that the reaction of the reaction barrier layer and the alkali solution can be effectively avoided; under the condition of longer reaction time or higher temperature, the reaction blocking layer blocks the alkali solution from penetrating through the reaction blocking layer to react with the monocrystalline silicon piece, so that the defect of the inverted pyramid morphology formed by the reaction blocking layer is avoided. Therefore, the texture surface preparation method of the monocrystalline silicon piece can obtain the optimal inverted pyramid morphology, and further greatly improves the photoelectric conversion efficiency of the solar cell.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing a textured surface of a monocrystalline silicon piece according to an embodiment of the invention;
FIGS. 2-5 are schematic views illustrating a texture preparation process of a monocrystalline silicon wafer according to an embodiment of the present invention;
FIG. 6 is a flow chart of a method for preparing a textured monocrystalline silicon wafer according to an embodiment of the present invention;
Fig. 7 is a schematic structural diagram of a solar cell according to an embodiment of the invention.
Reference numerals illustrate:
100-monocrystalline silicon piece; a 2-reaction barrier layer; 3-mask protective film; k-opening; t-inverted pyramidal pile face; 1-monocrystalline silicon piece; 101-intrinsic hydrogen-rich amorphous silicon thin film; 102-P type amorphous silicon film; 103-a transparent conductive oxide film; 104-intrinsic amorphous silicon film; 105-N type amorphous silicon film; 106-a transparent conductive oxide film; 107-a first electrode; 108-a second electrode.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention provides a method for preparing a texture surface of a monocrystalline silicon wafer, referring to fig. 1, the method comprises the following steps:
Step S1: providing a monocrystalline silicon piece and an alkali solution respectively, wherein the alkali solution is suitable for corroding one side surface of the monocrystalline silicon piece;
step S2: forming a reaction barrier layer on the surface of one side of the monocrystalline silicon piece to be corroded, wherein the reaction barrier layer is provided with a plurality of openings penetrating through the reaction barrier layer;
Step S3: placing the monocrystalline silicon piece with the reaction barrier layer in the alkali solution, and simultaneously forming a mask protection film on the surface of one side of the reaction barrier layer, which is opposite to the monocrystalline silicon piece, and the side wall of the opening, wherein the mask protection film is adsorbed on the surface of the reaction barrier layer under the action of the alkali solution;
Step S4: the alkali solution reacts with the monocrystalline silicon piece, and an inverted pyramid suede is formed in the area of the monocrystalline silicon piece corresponding to the opening.
According to the preparation method of the texture surface of the monocrystalline silicon piece, the mask protection film is adsorbed on the surface of the reaction barrier layer under the action of the alkaline solution, so that the alkaline solution can react with the monocrystalline silicon piece in the opening to form the inverted pyramid texture surface; meanwhile, the mask protective film protects the reaction barrier layer when the alkali solution reacts with the monocrystalline silicon piece in the opening, so that the reaction of the reaction barrier layer and the alkali solution can be effectively avoided; under the condition of longer reaction time or higher temperature, the reaction blocking layer blocks the alkali solution from penetrating through the reaction blocking layer to react with the monocrystalline silicon piece, so that the defect of the inverted pyramid morphology formed by the reaction blocking layer is avoided. Therefore, the texture surface preparation method of the monocrystalline silicon piece can obtain the optimal inverted pyramid morphology, and further greatly improves the photoelectric conversion efficiency of the solar cell.
According to the preparation method of the texture surface of the monocrystalline silicon piece, the preparation process of the solar cell with the texture surface light trapping requirement, such as the preparation process of a heterojunction cell, can be matched by controlling the reaction time and the reaction temperature to realize random adjustment of the inverted pyramid shape of the monocrystalline silicon piece.
According to the preparation method of the texture surface of the monocrystalline silicon piece, the inverted pyramid texture surface is formed on one side surface of the monocrystalline silicon piece, and in other embodiments, the inverted pyramid texture surface can be formed on two side surfaces of the monocrystalline silicon piece.
The following describes in detail the texturing process of the monocrystalline silicon piece with reference to fig. 2 to 5.
In step S1, referring specifically to fig. 2, a single crystal silicon wafer 100 is provided, the single crystal silicon wafer 100 including a P-type single crystal silicon wafer or an N-type single crystal silicon wafer.
In step S2, specifically, with continued reference to fig. 2, a reaction barrier layer 2 is formed on a surface of a side to be etched of the monocrystalline silicon piece 100, and a plurality of openings K penetrating the reaction barrier layer 2 are formed in the reaction barrier layer 2.
In one embodiment, the distance between adjacent openings K is 2 μm-5 μm, for example 3 μm; if the distance between the adjacent openings K is smaller than 2 mu m, the interval between the adjacent openings K is too small, so that monocrystalline silicon wafers under the adjacent openings are easy to corrode and penetrate, the suede of the inverted pyramid structure cannot be obtained, and secondary reflection is affected; if the distance between the adjacent openings K is larger than 5 μm, secondary reflection is also affected, so that the reflectivity of the monocrystalline silicon surface is higher.
In one embodiment, the diameter of the opening K is 1 μm-10 μm, for example 5 μm; if the diameter of the opening K is smaller than 2 mu m, the diameter of the opening K is too small, so that the etching rate of the monocrystalline silicon piece by the alkali solution is slow, bubbles generated in the etching process can be adsorbed at the opening under the action of surface tension to prevent the bubbles generated in the reaction from escaping and the transport of reactants, the reaction speed is further reduced, and the uneven suede is caused; if the diameter of the opening K is larger than 10 μm, the corrosion speed is easy to be too high if the aperture of the opening K is too large, the appearance of the obtained inverted pyramid-shaped suede is poor, and the secondary reflection of light is affected.
According to the embodiment, the corrosion rate is effectively controlled by controlling the spacing and the diameter of the openings, so that the inverted pyramid suede structure with reasonable density and better morphology can be formed on the surface of the monocrystalline silicon wafer, the reflection loss can be controlled to be minimum, the secondary reflection of light can be effectively improved, the reflectivity is reduced, the distance between adjacent openings K is 2-5 mu m, the diameter of each opening K is 1-10 mu m, the obtained inverted pyramid suede structure is optimal on the premise of ensuring the corrosion rate, and the reflectivity of the monocrystalline silicon wafer after wool making is minimum. For example, by controlling the etching rate so that the diameter of the opening is between 1.2 μm and 1.9 μm and the depth of the opening is between 0.9 μm and 1.5 μm, the reflectivity of the inverted pyramidal pile surface can be between 2% and 4%.
In one embodiment, the step of forming the reaction barrier layer 2 on the surface of the side to be etched of the single crystal silicon wafer 100 includes: an initial reaction barrier layer is formed on the single crystal silicon wafer 100, and a plurality of openings K are formed in the initial reaction barrier layer so that the initial reaction barrier layer forms the reaction barrier layer 2.
In one embodiment, the material of the reaction barrier layer 2 comprises silicon dioxide. The material of the reaction barrier layer 2 comprises silicon dioxide, so that the suede preparation method of the monocrystalline silicon wafer is completely compatible with the existing equipment and process.
In one embodiment, the process of forming openings in the initial reaction barrier layer includes: picosecond laser process; the cross-sectional shape of the opening formed using the picosecond laser process includes a circular shape.
In other embodiments, the process of forming the plurality of openings in the initial reaction barrier layer may further include an etching process, such as a dry etching process or a wet etching process, and the cross-sectional shape of the openings formed using the dry etching process or the wet etching process may further include other shapes, such as a rectangle.
In one embodiment, the initial reaction barrier layer is formed at a temperature of 670 ℃ to 720 ℃, such as 700 ℃; if the temperature at which the initial reaction barrier layer is formed is lower than 670 ℃, it may be disadvantageous to improve the preparation efficiency; if the temperature for forming the initial reaction barrier layer is higher than 720 ℃, the temperature is too high, so that the quality of the monocrystalline silicon wafer is easily reduced, and the minority carrier lifetime of the monocrystalline silicon wafer is reduced.
In one embodiment, the initial reaction barrier layer is formed for a period of 30min to 50min, for example 45min; if the initial reaction barrier layer is formed for less than 30 minutes, insufficient oxidation of the initial reaction barrier layer may be caused; if the time for forming the initial reaction barrier layer exceeds 50 minutes, the oxidation time of the initial reaction barrier layer may be too long, which is disadvantageous to improve the preparation efficiency.
In one embodiment, the reaction barrier layer has a thickness of 1nm to 1.5nm, for example 1.2nm; if the thickness of the reaction barrier layer is smaller than 1nm, the reaction barrier layer is too thin, so that the degree of the reaction barrier layer for preventing the alkali solution from penetrating through the reaction barrier layer to react with the monocrystalline silicon piece is weakened, and the surface morphology of the inverted pyramid-shaped suede of the monocrystalline silicon piece is influenced; if the thickness of the reaction barrier layer is greater than 1.5nm, the depth of the formed openings is deeper, so that the preparation efficiency is reduced, and bubbles generated in the reaction process escape from the openings, the escape path of the bubbles can be prolonged by the deeper openings, the dredging speed of reactants is reduced, and the corrosion speed is influenced. The thickness of the reaction barrier layer is controlled to be 1nm-1.5nm, so that the corrosion rate is ensured, and the surface morphology of the inverted pyramid suede of the monocrystalline silicon wafer can be ensured.
Because the alkali solution is reacted with the monocrystalline silicon piece 100 in the opening K and the mask protection film 3 protects the reaction barrier layer 2, the reaction of the reaction barrier layer 2 with the alkali solution can be effectively avoided, the reaction barrier layer 2 with a thinner thickness is adopted, and the reaction barrier layer with a larger thickness is not required to be obtained by using a longer process time and a higher process temperature, so that the suede preparation method of the monocrystalline silicon piece provided by the embodiment can improve the preparation efficiency and save the material.
In one embodiment, the process of forming the initial reaction barrier layer includes: plasma enhanced chemical vapor deposition.
In one embodiment, the method further comprises, before forming the initial reaction barrier layer on the monocrystalline silicon piece 100: the monocrystalline silicon wafer 100 is subjected to surface cleaning treatment, wherein the surface cleaning treatment is used for removing a damaged layer on the monocrystalline silicon wafer, and is favorable for obtaining an inverted pyramid-shaped suede with a good appearance, and specifically, the monocrystalline silicon wafer is subjected to surface cleaning treatment by adopting an alkali solution, wherein the concentration of the alkali solution is 5% -10%, such as 6%, the alkali solution comprises a sodium hydroxide solution or a potassium hydroxide solution, and the cleaning time is 30s-70s, such as 60s.
In one embodiment, after the surface cleaning treatment is performed on the monocrystalline silicon piece 1, before the initial reaction barrier layer is formed on the monocrystalline silicon piece 100, the method further comprises: and removing organic residues after the cleaning treatment by adopting a mixed solution of an alkali solution and hydrogen peroxide.
In step S3, specifically referring to fig. 3, the monocrystalline silicon wafer 100 on which the reaction barrier layer 2 is formed is placed in the alkaline solution, and at the same time, a mask protection film 3 is formed on a side surface of the reaction barrier layer 2 facing away from the monocrystalline silicon wafer 100 and on a side wall of the opening, wherein the mask protection film 3 is adsorbed on the surface of the reaction barrier layer 2 under the action of the alkaline solution, and the mask protection film is formed of a mask material in a mask protection agent, and the concentration of the mask material in the mask protection agent is 0.5% -1.5%, for example 1.2%; if the concentration of the mask material in the mask protective agent is less than 0.5%, and the concentration of the mask material in the mask protective agent is too small, the formed mask protective film is insufficient in protecting the reaction barrier layer, so that the effect of preventing the reaction barrier layer from reacting with the alkali solution is weakened, and the degree of obtaining the appearance of the better inverted pyramid suede structure is small; if the concentration of the mask material in the mask protecting agent is more than 1.5%, the concentration of the mask material in the mask protecting agent is too high, so that resource waste is caused.
In one embodiment, the masking material comprises a metal chelate, a metal complex, or a positively charged organic compound; in other embodiments, the masking material may also include other materials that are electronegative in alkaline environments.
In one embodiment, the positively charged organic material comprises a quaternary ammonium salt, such as 3-chloro-2-hydroxypropyl trimethylammonium chloride. Compared with metal complex and chelate, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is organic, does not introduce metal ion pollution, has low requirement on industrial wastewater discharge, and is suitable for industrial practical application.
In step S4, specifically, referring to fig. 4 and 5 in combination, the alkali solution reacts with the monocrystalline silicon piece 100, and an inverted pyramidal textured surface T is formed in a region of the monocrystalline silicon piece 100 corresponding to the opening, so that the monocrystalline silicon piece 100 forms a monocrystalline silicon piece 1 having the inverted pyramidal textured surface T.
In one embodiment, the alkaline solution is added simultaneously with the masking agent to the reaction vessel, for example, 3% sodium hydroxide solution and 0.7% 3-chloro-2-hydroxypropyl trimethylammonium chloride solution.
In the prior art, silicon dioxide is used as a reaction barrier layer, and the silicon dioxide is an acidic oxide, and the acidic oxide can react with an alkali solution to generate silicate, so that the silicon dioxide can be prevented from being corroded and penetrated by the alkali solution due to overlong reaction time only by increasing the thickness of the silicon dioxide. In view of the negative charge characteristic of silicon dioxide in an alkaline environment, in this embodiment, a mask protecting agent is added while the alkaline solution is added, the mask protecting agent comprises a metal chelate, a metal complex or a positively charged organic substance, the silicon dioxide and the mask protecting agent generate electrostatic action in the alkaline environment, the silicon dioxide selectively adsorbs the mask protecting agent in the alkaline environment, and a mask protecting film is formed on the surface of the silicon dioxide, and the mask protecting film can effectively prevent the reaction blocking layer from reacting with the alkaline solution, so that the thickness of the reaction blocking layer can be thinner in this embodiment, and the material is saved while the preparation efficiency is improved.
In one embodiment, the concentration of the alkaline solution is 2.5% -3.5%, such as 3.0%; if the concentration of the alkali solution is less than 2.5%, and the concentration of the alkali solution is too low, the reaction rate of the alkali solution with the monocrystalline silicon piece 1 in the opening K to form an inverted pyramid-shaped suede is slower, and the required time for preparing the suede of the monocrystalline silicon piece is too long; the concentration of the alkali solution is greater than 3.5%, and if the concentration of the alkali solution is too high, the reaction rate of the alkali solution with the monocrystalline silicon piece 1 in the opening K to form an inverted pyramid suede is too high, which is not beneficial to controlling the reaction rate between the alkali solution and the monocrystalline silicon piece 1 so as to obtain the optimal inverted pyramid morphology.
In one embodiment, the reaction temperature of the alkaline solution with the monocrystalline silicon piece 1 within the opening K is 78-82 ℃, for example 80 ℃; if the reaction temperature of the alkali solution in the opening K and the monocrystalline silicon piece 1 is lower than 78 ℃ and is too low, the reaction speed of the alkali solution in the opening K and the monocrystalline silicon piece 1 is slower, and the time for preparing the texture of the monocrystalline silicon piece is too long; if the reaction temperature of the alkali solution in the opening K and the monocrystalline silicon piece 1 is higher than 82 ℃, and if the reaction temperature is too high, the reaction rate of the alkali solution in the opening K and the monocrystalline silicon piece 1 is too high, which is unfavorable for controlling the reaction rate between the alkali solution and the monocrystalline silicon piece 1.
In one embodiment, the reaction time of the alkaline solution with the monocrystalline silicon piece 100 in the opening K is 400s-1000s, for example 500s; if the reaction time of the alkali solution in the opening K and the monocrystalline silicon piece 100 is less than 400s, the reaction time of the alkali solution in the opening K and the monocrystalline silicon piece 100 is too short, the obtained inverted pyramid suede has poor appearance, and secondary reflection of light can be affected after the solar cell is prepared; if the reaction time of the alkali solution with the monocrystalline silicon piece 100 in the opening K exceeds 1000s, the reaction time of the alkali solution with the monocrystalline silicon piece 100 in the opening K is too long, the obtained inverted pyramid-shaped suede has poor morphology, and secondary reflection of light can be affected after the solar cell is prepared.
In one embodiment, the alkaline solution comprises sodium hydroxide solution or potassium hydroxide solution, and in other embodiments, the alkaline solution may further comprise other alkaline solutions that may react with monocrystalline silicon wafers.
In one embodiment, after the reaction of the alkaline solution with the monocrystalline silicon piece 100 in the opening K to form the inverted pyramidal textured surface T, the method further comprises: and removing the reaction barrier layer and the mask protective film, specifically, placing the monocrystalline silicon wafer subjected to texturing in an HF solution with the concentration of 10% to etch and remove the reaction barrier layer and the mask protective film, cleaning with deionized water, and drying to obtain the monocrystalline silicon wafer with the inverted pyramid structure.
In a specific embodiment, referring to fig. 6, the method for preparing the textured surface of the monocrystalline silicon wafer includes the following steps:
Step D1: providing a monocrystalline silicon piece;
step D2: forming an initial reaction barrier layer on the monocrystalline silicon piece by adopting a plasma enhanced chemical vapor deposition method;
step D3: forming openings in the initial reaction barrier layer such that the initial reaction barrier layer forms a reaction barrier layer;
step D4: simultaneously adding an alkali solution and a mask protective agent, wherein the mask protective agent forms a mask protective film on the surface of one side of the reaction barrier layer, which is opposite to the monocrystalline silicon piece, the alkali solution reacts with the monocrystalline silicon piece, and an inverted pyramid suede is formed in the area of the monocrystalline silicon piece corresponding to the opening;
step D5: and removing the mask protecting agent and the reaction blocking layer.
In this embodiment, the specific steps are: providing a monocrystalline silicon wafer, carrying out surface cleaning treatment on the monocrystalline silicon wafer by adopting a sodium hydroxide solution with the concentration of 5% to remove a damaged layer on the monocrystalline silicon wafer, and then adopting a mixed solution of an alkali solution and hydrogen peroxide to remove organic residues after the cleaning treatment; then, forming an initial reaction barrier layer on the monocrystalline silicon piece by adopting a plasma enhanced chemical vapor deposition method, wherein the oxidation temperature of the initial reaction barrier layer is 670 ℃, the oxidation time is 30min, and then, forming a plurality of openings in the initial reaction barrier layer by adopting a picosecond laser process to enable the initial reaction barrier layer to form a reaction barrier layer, wherein the thickness of the reaction barrier layer is 1nm, the distance between adjacent openings is 2 mu m, and the diameter of each opening is 2 mu m; and simultaneously adding a sodium hydroxide solution with the concentration of 2.5% and a 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution with the concentration of 0.5%, forming a mask protection film on the surface of the reaction barrier layer, which is opposite to the monocrystalline silicon wafer, on one side of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, wherein the reaction temperature of the sodium hydroxide solution in the opening and the monocrystalline silicon wafer is 78 ℃, the reaction time is 400s, forming an inverted pyramid suede, reacting the sodium hydroxide solution in the opening and the monocrystalline silicon wafer to form the inverted pyramid suede, removing the reaction barrier layer and the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, specifically, placing the monocrystalline silicon wafer after the wool making in an HF solution with the concentration of 10%, corroding to remove the reaction barrier layer and the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, washing with deionized water, and drying to obtain the monocrystalline silicon wafer with the inverted pyramid structure.
The monocrystalline silicon wafer with the better inverted pyramid structure prepared by the texture surface preparation method of the monocrystalline silicon wafer is taken as a substrate, the type of the prepared solar cell is taken as a heterojunction cell as an example, and the photoelectric conversion efficiency is tested and compared. As shown in fig. 7, one side with an inverted pyramid structure is the front side of the heterojunction cell, the side facing away from the inverted pyramid structure is the back side of the heterojunction cell, and on the basis of the monocrystalline silicon piece 1 with the inverted pyramid structure, an intrinsic hydrogen-rich amorphous silicon film 101, a P-type amorphous silicon film 102 and a transparent conductive oxide film 103 (TCO for short) are sequentially prepared outwards on the front side; an intrinsic amorphous silicon film 104, an N-type amorphous silicon film 105, and a transparent conductive oxide film 106 are sequentially prepared outwardly on the back surface. Of course, according to actual needs, the heterojunction battery further comprises: a first electrode 107 on a surface of the transparent conductive oxide film 103 on a part of the front surface facing away from the side of the single crystal silicon wafer 1; the transparent conductive oxide film 106 on the partial back surface faces the second electrode 108 on the surface of the monocrystalline silicon piece 1.
In one embodiment, the reaction time of the alkali solution with the single crystal silicon wafer 100 in the opening K is 400 seconds, the reaction temperature of the alkali solution with the single crystal silicon wafer 1 in the opening K is 82 ℃, and a mixed solution of 3% potassium hydroxide solution and 1% 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution is added. The diameter of the opening of the inverted pyramid-shaped pile face formed was 1.2 μm, and the height of the opening was 0.9 μm. Through testing, the photoelectric conversion efficiency of the finally formed solar cell is 24.75%.
In one embodiment, the reaction time of the alkali solution with the single crystal silicon wafer 1 in the opening K is 600 seconds, the reaction temperature of the alkali solution with the single crystal silicon wafer 1 in the opening K is 82 ℃, and a mixed solution of 3% potassium hydroxide solution and 1% 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution is added. The diameter of the opening of the inverted pyramid-shaped pile face formed was 1.5 μm, and the height of the opening was 1.2 μm. Through testing, the photoelectric conversion efficiency of the finally formed solar cell is 25.15%.
In one embodiment, the reaction time of the alkali solution with the single crystal silicon wafer 1 in the opening K is 800s, the reaction temperature of the alkali solution with the single crystal silicon wafer 1 in the opening K is 82 ℃, and a mixed solution of 3% potassium hydroxide solution and 1% 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution is added. The diameter of the opening of the inverted pyramid-shaped pile face formed was 1.7 μm, and the height of the opening was 1.4 μm. Through testing, the photoelectric conversion efficiency of the finally formed solar cell is 25.50%.
In one embodiment, the reaction time of the alkali solution with the single crystal silicon wafer 1 in the opening K is 1000s, the reaction temperature of the alkali solution with the single crystal silicon wafer 1 in the opening K is 82 ℃, and a mixed solution of 3% potassium hydroxide solution and 1% 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution is added. The diameter of the opening of the inverted pyramid-shaped pile face formed was 1.9 μm, and the height of the opening was 1.5 μm. Through testing, the photoelectric conversion efficiency of the finally formed solar cell is 25.50%.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (16)

1. The preparation method of the suede of the monocrystalline silicon piece is characterized by comprising the following steps of:
providing a monocrystalline silicon piece and an alkali solution respectively, wherein the alkali solution is suitable for corroding one side surface of the monocrystalline silicon piece;
Forming a reaction barrier layer on the surface of one side of the monocrystalline silicon piece to be corroded, wherein the reaction barrier layer is provided with a plurality of openings penetrating through the reaction barrier layer;
placing the monocrystalline silicon piece with the reaction barrier layer in the alkali solution, and simultaneously forming a mask protection film on the surface of one side of the reaction barrier layer, which is opposite to the monocrystalline silicon piece, and the side wall of the opening, wherein the mask protection film is adsorbed on the surface of the reaction barrier layer under the action of the alkali solution;
The alkali solution reacts with the monocrystalline silicon piece, and an inverted pyramid suede is formed in the area of the monocrystalline silicon piece corresponding to the opening.
2. The method for producing a textured monocrystalline silicon piece according to claim 1, wherein the mask protection film is formed of a mask material in a mask protection agent, and the concentration of the mask material in the mask protection agent is 0.5% -1.5%.
3. The method for producing a textured surface of a monocrystalline silicon piece according to claim 2, wherein the mask material comprises a metal chelate, a metal complex or a positively charged organic substance.
4. A method of preparing a textured surface of a monocrystalline silicon piece according to claim 3, the positively charged organic material comprising quaternary ammonium salts.
5. The method for producing a textured surface of a silicon wafer according to claim 4, wherein the quaternary ammonium salt comprises 3-chloro-2-hydroxypropyl trimethylammonium chloride.
6. The method for preparing a textured monocrystalline silicon piece according to claim 1, wherein the concentration of the alkali solution is 2.5% -3.5%, the reaction temperature is 78-82 ℃ and the reaction time is 400-1000 s.
7. The method for preparing a textured surface of a monocrystalline silicon piece according to claim 6, wherein the alkaline solution comprises sodium hydroxide solution or potassium hydroxide solution.
8. The method of preparing a textured monocrystalline silicon piece according to claim 1, the step of forming a reaction barrier layer on the monocrystalline silicon piece comprising:
Forming an initial reaction barrier layer on the monocrystalline silicon piece;
Openings are formed in the initial reaction barrier layer such that the initial reaction barrier layer forms the reaction barrier layer.
9. The method for producing a textured surface of a silicon single crystal wafer according to claim 8, characterized in that,
The process of forming the initial reaction barrier layer includes: plasma enhanced chemical vapor deposition.
10. The method for producing a textured surface of a silicon single crystal wafer according to claim 8, characterized in that,
The process of forming openings in the initial reaction barrier layer includes: picosecond laser process.
11. The method of preparing a textured monocrystalline silicon piece according to claim 8, wherein the initial reaction barrier layer is formed at a temperature of 670-720 ℃ for a time of 30-50 ℃.
12. The method of preparing a textured monocrystalline silicon piece according to claim 8, further comprising, prior to forming the initial reaction barrier layer on the monocrystalline silicon piece: and carrying out surface cleaning treatment on the monocrystalline silicon piece.
13. The method of claim 2 to 5, wherein the step of placing the monocrystalline silicon piece and the reaction barrier layer in front of the alkaline solution further comprises: the mask protectant is added to the alkaline solution.
14. The method for producing a textured surface of a single crystal silicon wafer according to any one of claims 1 to 12, wherein the distance between adjacent openings is 2 μm to 5 μm, and the diameter of the openings is 1 μm to 10 μm.
15. The method for producing a textured surface of a silicon single crystal wafer according to any one of claims 1 to 12, characterized in that,
The thickness of the reaction barrier layer is 1nm-1.5nm.
16. A solar cell, characterized in that the monocrystalline silicon piece prepared by the texture preparation method of the monocrystalline silicon piece according to any one of claims 1-15 is used as a substrate.
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