CN108615776B - Anti-reflection surface structure and corresponding production method - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- 239000010703 silicon Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 11
- 230000003667 anti-reflective effect Effects 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
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- 229910003460 diamond Inorganic materials 0.000 claims description 5
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- 238000005520 cutting process Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000002310 reflectometry Methods 0.000 abstract description 24
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- 238000002360 preparation method Methods 0.000 description 12
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- 239000000243 solution Substances 0.000 description 8
- 238000005530 etching Methods 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 238000000206 photolithography Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/547—Monocrystalline silicon PV cells
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Abstract
The invention provides an antireflection surface structure, which comprises a plurality of parallel inverted pyramid chains, wherein two inverted pyramid structure units adjacent to each other in each inverted pyramid chain are mutually overlapped. The four-time reflection ray path of the antireflection surface structure has a high proportion, and the reflectivity of the surface structure is greatly reduced.
Description
Technical Field
The invention belongs to the field of semiconductor photovoltaics, and particularly relates to an antireflection surface structure and a corresponding preparation method.
Background
A smooth silicon surface reflects about 30% of the solar energy back into the atmosphere, which severely limits the degree of solar utilization, so that the improvement in solar cell efficiency is limited. In order to improve the utilization degree of sunlight, two methods of surface preparation of a microstructure and plating of an antireflection film are widely applied to a silicon-based solar cell.
At present, the principle of anisotropic etching with alkali is utilized to prepare random positive pyramid structures on silicon surfaces, and the random positive pyramid structures are widely applied in industry. In addition, regular inverted pyramid structures fabricated using photolithography and the like are often used in the laboratory for the fabrication of high efficiency solar cells. However, the reflectivity of the two structures to light is still not ideal, the absorption of sunlight is reduced, and meanwhile, the fluctuation of the structure surface is large no matter the structure is a regular pyramid structure or an inverted pyramid structure, so that the preparation of a front metal grid line is not facilitated, the collection of current is reduced, and the further improvement of the performance of the solar cell is not facilitated.
Disclosure of Invention
It is therefore an object of the present invention to overcome the above-mentioned drawbacks of the prior art and to provide an anti-reflective surface structure comprising a plurality of parallel inverted pyramid chains, wherein two inverted pyramid structure elements adjacent to each other in each inverted pyramid chain overlap each other.
According to the antireflection surface structure of the present invention, preferably, the pitch between the inverted pyramid chains is zero.
According to the antireflection surface structure of the present invention, preferably, two inverted pyramid structural units adjacent to each other overlap in a diagonal direction of top surfaces of the inverted pyramid structural units.
According to the antireflection surface structure of the present invention, it is preferable that the ratio of the area of the overlapping region to the area of the top surface of the single inverted pyramid-shaped structural unit is 0.04 to 0.36.
According to the antireflection surface structure of the present invention, it is preferable that the ratio of the area of the overlapping region to the area of the top surface of the single inverted pyramid-shaped structural unit is 0.16.
According to the antireflection surface structure of the present invention, preferably, diagonals of top surfaces of two inverted pyramid-shaped structural units adjacent to each other overlap or are parallel to each other.
On the other hand, the invention also provides a preparation method of the antireflection surface structure, which comprises the following steps:
the method comprises the following steps: obtaining a silicon wafer by utilizing a diamond wire cutting technology;
step two: cleaning the silicon wafer; and
step three: and preparing a suede structure on the silicon wafer.
According to the method for producing an antireflection surface structure of the present invention, it is preferable to further include a step of washing the sample obtained in the step three.
According to the method for manufacturing an antireflection surface structure of the present invention, preferably, in the third step, the silicon wafer is placed in an acidic texturing solution to manufacture a textured structure.
In yet another aspect, the present invention also provides an anti-reflective surface structure, which is prepared using the preparation method according to the present invention.
In yet another aspect, the invention also provides a silicon wafer having an anti-reflective surface structure according to the invention.
Compared with the prior art, the four-time reflection ray path of the anti-reflection surface structure has higher proportion, so that the reflectivity of the surface structure can be greatly reduced, the electrical property of a cell prepared by a silicon wafer with the structure can be improved, and the efficiency of the solar cell can be improved.
Drawings
Embodiments of the invention are further described below with reference to the accompanying drawings, in which:
FIG. 1 illustrates four common ray paths;
FIG. 2 shows the reflectance versus wavelength for the four ray paths of FIG. 1;
FIG. 3 schematically illustrates a top view of two non-overlapping inverted pyramid structural units and a top view of two inverted pyramid structural units overlapping each other according to an embodiment of the invention;
FIG. 4 schematically illustrates a top view of an inverted pyramid chain in accordance with an embodiment of the invention;
FIG. 5 schematically illustrates a top view of a regular inverted pyramid structure, in accordance with an embodiment of the present invention;
FIG. 6 shows a perspective view of two inverted pyramid splices;
FIG. 7 shows a graph of reflectance versus wavelength for different surface structures; and
fig. 8 is a SEM image of a crystalline inverted pyramid structure prepared according to the first embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail by embodiments with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Sunlight may have different reflection characteristics on different surface structures. According to the reflection law of light, sunlight perpendicularly irradiates the surfaces of antireflection structures such as regular positive pyramids, regular inverted pyramids, random positive pyramids and the like, and all or part of four common ray paths such as A, B, C, D shown in fig. 1 can appear. The A ray path reflects twice on the surface, the B and C ray paths reflect three times on the surface, the third reflection angle of the B ray path is large, so that the reflectivity of the third reflection is high, and the D ray path reflects four times on the surface. Since each reflection increases the chance that the light will refract into the surface structure once, thereby reducing the reflectivity of the surface.
From the law of light reflection, it can be seen that the reflectivity of A, B, C, D in fig. 1 varies with wavelength, and it is evident that the fourth reflection ray path D has a very low reflectivity, while the second reflection ray path a has a higher reflectivity, and in addition, the third reflection ray path B has a higher reflectivity than the other third reflection ray path C, because the third reflection ray path B has a higher reflectivity than the third reflection ray path C. Based on this, the inventor thought to design a surface structure such that the ratio of C, D light paths, especially D light path, is high in the light path of sunlight on the surface structure, so that the reflectivity of the surface structure can be greatly reduced, thereby improving the efficiency of the solar cell.
The invention provides an antireflection surface structure, which comprises a regular inverted pyramid structure, wherein the regular inverted pyramid structure comprises a plurality of inverted pyramid chains parallel to each other, the inverted pyramid chains are structures formed by connecting a plurality of inverted pyramid structures, and in each inverted pyramid chain, adjacent inverted pyramid structure units are overlapped with each other along the diagonal direction of the square top surfaces of the inverted pyramid structure units. Referring to fig. 3-5, fig. 3 schematically illustrates a top schematic view of two non-overlapping inverted pyramid structural units and a top schematic view of two inverted pyramid structural units overlapping each other according to the present invention; FIG. 4 schematically illustrates a top view of an inverted pyramid chain in accordance with an embodiment of the present invention; FIG. 5 schematically illustrates a top view of a regular inverted pyramid structure, according to an embodiment of the invention. Specifically, the side length of the square top surface of a single inverted pyramid structural unit in the left drawing of fig. 3 is 2 μm, and the region where the square top surfaces of two inverted pyramid structural units in the right drawing of fig. 3 and two adjacent inverted pyramid structural units in fig. 4 and 5 overlap each other is a square having a side length of 0.8 μm, and therefore, the ratio of the area of the overlapping region to the area of the top surface of the single inverted pyramid structural unit is 0.16. The depth of each inverted pyramid structure was 1.414 μm. When the top surfaces overlap each other, the depth direction gradually starts to overlap with the increase of the overlapping area, and the non-overlapping areas exist independently of each other, which can also be understood as a structure in which two inverted pyramids are cut off at a corner and then the two inverted pyramids are spliced together, as shown in fig. 6, which is a schematic perspective view of splicing the two inverted pyramids.
In order to embody the effects of the present invention, the inventors calculated and compared the reflection and reflectance of several surface structures of the prior art with those of the present invention according to maxwell's equations, see table 1 below, and the anti-reflection surface structure of the present invention is referred to as a "crystal-like inverted pyramid structure" for simplicity.
TABLE 1
| A | B | C | D | R | |
| Regular pyramid structure | 88.89％ | 11.11％ | 0％ | 0％ | 13.926％ |
| Random positive pyramid structure | 68.33％ | 3.24％ | 22.34％ | 6.07％ | 11.362％ |
| Regular inverted pyramid structure | 59.26％ | 0.74％ | 40％ | 0％ | 10.727％ |
| Crystal-like inverted pyramid structure | 58.23％ | 0.71％ | 30.66％ | 10.4％ | 10.11％ |
A, B, C, D in Table 1 indicate the ratios of the four light paths A, B, C, D in FIG. 1, respectively, and R indicates the reflectance. The regular positive pyramid structure has 88.89% of path a, and thus the average reflectivity is 13.926%. The random regular pyramid structure reduces the proportion of the path A, improves the proportion of the paths C and D, and reduces the reflectivity to 11.362%. The proportion of the A path of the regular inverted pyramid structure is the lowest, although the D path is not provided, the proportion of the C path is 40%, and the reflectivity can reach 10.727%. Since the inverted pyramid structure is formed due to the difference in the etching speed of the (111) and (100) crystal planes during the etching process, the four planes of the inverted pyramid are the (111) crystal plane, the included angle between each plane of the structure is fixed, and thus the ratio of the secondary reflectance is difficult to be reduced. To further reduce the reflectivity, the area of the third reflection is converted into the area of the fourth reflection. The proportion of the path A of the crystal-shaped inverted pyramid structure is reduced to 58.23% and is lower than 59.26% of the regular inverted pyramid structure, and meanwhile, the proportion of the path D reaches 10.4%, so that the average reflectivity is reduced to 10.11%.
Fig. 7 shows a graph of reflectivity versus wavelength for different surface structures. It can be seen that the reflectivity of the crystalline inverted pyramid structure of the present invention is lower than the reflectivity of the three prior art structures.
The inventors have made further design and calculation, and as a result, found that the diagonals of two adjacent inverted pyramid structural units in the inverted pyramid chain of the antireflection surface structure of the present invention do not exactly overlap each other, as long as they are parallel to each other, and when the diagonals are offset and overlapped, it is also possible that the aspect ratio of the overlapped region is less than 1.5, and preferably, the aspect ratio of the overlapped region is 1. The size of each inverted pyramid structure is also not limited to the above as long as a certain overlap ratio is satisfied, and preferably, the ratio of the area of the overlap region to the area of the top surface of the single inverted pyramid structure unit is 0.04 to 0.36. In addition, the smaller the pitch between the inverted pyramid chains parallel to each other, the better, and the pitch of zero is the best.
To further verify the effectiveness of the design of the present invention, the present inventors prepared a crystalline inverted pyramid structure by way of specific examples.
First embodiment
The first embodiment provides a method for preparing a crystalline inverted pyramid structure, comprising the steps of:
the method comprises the following steps: cleaning a silicon wafer, specifically, putting the silicon wafer into an acidic solution of hydrofluoric acid or nitric acid to clean an original silicon wafer;
step two: and (3) preparing a textured structure on the cleaned silicon wafer, specifically, immersing the silicon wafer into an acidic texturing solution of copper nitrate, hydrofluoric acid and hydrogen peroxide, and etching for 15min at the temperature of 10 ℃ to obtain the textured structure. Wherein the concentration of copper ions in the acidic texturing solution is 0.01mmol/L, the concentration of hydrofluoric acid is 0.5mol/L, and the concentration of hydrogen peroxide is 0.1 mol/L.
Step three: and cleaning the silicon wafer with the textured structure in a nitric acid solution to remove metal particles.
A scanning electron SEM image of the crystal-like inverted pyramid structure prepared in this example is shown in fig. 8, and it can be seen that it includes a plurality of inverted pyramid chains, and the inverted pyramid structural units adjacent to each other in each inverted pyramid chain overlap each other. The inventors also tested the reflectivity of the surface structure prepared in this example, and the results showed that the reflectivity of the surface structure was 9.56%, which is substantially consistent with the results of the foregoing theoretical calculations. Compared with the random inverted pyramid anti-reflection silicon wafer in the prior art, the silicon wafer with the surface structure shown in fig. 8 has the reflectivity reduced by 1%, and in addition, because the opening of the structure is wider and the step height difference of the structure is smaller, the subsequent battery preparation is more facilitated, and therefore, the efficiency of the battery with the structure is also improved.
In the preparation method, the suede structure is directly prepared on the cleaned silicon wafer cut by the diamond wire. The diamond wire cutting leaves a parallel line cross on the surface of the silicon wafer, and people always think that the line cross needs to be removed, otherwise the subsequent preparation is influenced, therefore, the microstructure preparation in the prior art has the step of removing the line cross, and the inventor finds that the line cross is available, inverted pyramid structures which are overlapped with each other can be prepared by relying on the line cross, the inverted pyramid structures which are overlapped with each other can reduce the reflectivity of the surface, and the subsequent preparation of the suede structure can adopt any preparation method known in the art.
Second embodiment
This embodiment provides another method for preparing a crystalline inverted pyramid structure comprising the steps of:
the method comprises the following steps: cleaning a silicon wafer, specifically, putting the silicon wafer into an acidic solution of hydrofluoric acid or/and hydrogen peroxide to clean an original silicon wafer;
step two: and (3) preparing a textured structure on the cleaned silicon wafer, specifically, immersing the silicon wafer into an acidic texturing solution of cupric nitrate, hydrofluoric acid and hydrogen peroxide, and etching for 30s at the temperature of 80 ℃ to obtain the textured structure. Wherein the concentration of copper ions in the acidic texturing solution is 50mmol/L, the concentration of hydrofluoric acid is 10mol/L, and the concentration of hydrogen peroxide is 5 mol/L.
Step three: and cleaning the silicon wafer with the textured structure in ammonia water and hydrogen peroxide solution to remove metal particles.
The surface reflectivity of the crystal-like inverted pyramid structure prepared in this second example was found to be 9.83% by testing, which is also substantially consistent with the results of the foregoing theoretical calculations.
According to other embodiments of the present invention, in the foregoing preparation method, any acidic solution or alkaline solution known in the art may be used as the cleaning solution.
Any method of making a textured structure known in the art may be used in accordance with other embodiments of the present invention.
Although the present invention has been described by way of preferred embodiments, the present invention is not limited to the embodiments described herein, and various changes and modifications may be made without departing from the scope of the present invention.
Claims (6)
1. An antireflection surface structure comprising a plurality of parallel inverted pyramid chains, wherein two inverted pyramid structural elements adjacent to each other in each inverted pyramid chain overlap each other along a diagonal direction of a top surface of the inverted pyramid structural elements, wherein
The ratio of the area of the overlap region to the area of the top surface of the individual inverted pyramid structural elements was 0.16.
2. The anti-reflective surface structure of claim 1, wherein the spacing between the inverted pyramid chains is zero.
3. The antireflection surface structure of claim 1, wherein diagonals of top surfaces of two inverted pyramid-shaped structural units adjacent to each other overlap or are parallel to each other.
4. A method of making an anti-reflective surface structure, comprising the steps of:
the method comprises the following steps: obtaining a silicon wafer by utilizing a diamond wire cutting technology;
step two: cleaning the silicon wafer; and
step three: preparing a textured structure comprising a plurality of parallel inverted pyramid chains on the silicon wafer by means of the diamond wire cutting technique with the wires left on the surface of the silicon wafer crossing the silicon wafer
Two inverted pyramid structure units adjacent to each other in each inverted pyramid chain overlap each other along a diagonal direction of a top surface of the inverted pyramid structure units, wherein
The ratio of the area of the overlap region to the area of the top surface of the individual inverted pyramid structural elements was 0.16.
5. The method for producing an anti-reflective surface structure according to claim 4, further comprising a step of washing the sample obtained in the third step.
6. The method for preparing an anti-reflective surface structure according to claim 4, wherein in the third step, the silicon wafer is placed in an acidic texturing solution to prepare a textured structure.
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