CN113299776A - Micro-nano mixed structure for enhancing light absorption of solar cell and preparation method thereof - Google Patents
Micro-nano mixed structure for enhancing light absorption of solar cell and preparation method thereof Download PDFInfo
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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
- 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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- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
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Abstract
The invention provides a micro-nano mixed structure for enhancing light absorption of a solar cell and a preparation method thereof. The method is characterized in that: the method comprises the following steps of (a) preparing a micro-nano mixed structure, namely black silicon (b) for short, by a chemical corrosion method, pouring PDMS (polydimethylsiloxane) glue on a structural surface of the pyramid-structured silicon wafer by taking the black silicon (b) as a template to obtain a mixed structure (c) of the black silicon and the PDMS glue, and finally obtaining a PDMS film (d) with the surface micro-nano mixed structure by a demoulding process. The invention can be used for silicon thin-film solar cells or other glass packaged surface optoelectronic devices, is an efficient surface light trapping structure, can obviously reduce the light reflectivity of the surface of the glass device, and improves the photoelectric conversion efficiency of the device.
Description
(I) technical field
The invention relates to a micro-nano mixed structure for enhancing light absorption of a solar cell and a preparation method thereof, belongs to the field of photoelectric devices, and particularly relates to a surface light trapping technology and micro-nano processing.
(II) background of the invention
At present, most of solar cell surfaces are of a planar structure, when light irradiates the cell surfaces, a large part of incident light is reflected, and a large amount of light energy on the cell surfaces is lost. The surface light trapping structure can effectively reduce the reflection of the light energy on the surface of the cell, enhance the light absorption of the solar cell, reduce the escape of the light energy in the cell and prolong the optical path to a certain extent, thereby improving the conversion efficiency of the cell. The micro-nano mixed structure generally refers to a mixed structure formed by the surface of a micro-structure and the surface of a nano-structure or the interval distribution of the micro-structure and the nano-structure, and is an efficient surface light trapping structure. The prepared silicon material with the micro-nano mixed structure has high-efficiency light energy capture capacity, the surface of the silicon material is black, the silicon material is called as black silicon, and compared with a traditional pyramid light trapping structure on the silicon surface, the silicon material has lower surface reflectivity. Polydimethylsiloxane (PDMS) is used as a high polymer material with good light transmission and chemical stability, has low cost and simple use, has good adhesion with a silicon wafer, and is widely applied to the fields of photoelectric devices and the like. The micro-nano mixed structure PDMS film is introduced to the surface of the solar cell, so that the cell can not be damaged, the industrial large-area production and popularization can be realized under the condition of not changing the original cell preparation process, the cell surface reflection is reduced, and the photoelectric conversion efficiency of the cell is improved.
In order to solve the problem of preparing a micro-nano mixed structure, two preparation methods are generally adopted, one is a femtosecond laser scanning method, and the other is a chemical etching method. The femtosecond laser equipment is expensive, the preparation area is small, and the process is complex, so a chemical corrosion method is mostly adopted. The method for manufacturing the black silicon and the black silicon surface passivation layer (Chinese patent: 201710686567.2) disclosed in 2017 by Lihuagao et al prepares a micro-nano mixed structure by soaking a process sheet by using a mixed solution and heating in a water bath. Leluol et al, in 2018, discloses a honeycomb-shaped wet-process black silicon suede structure and a preparation method thereof (Chinese patent: 201711005958.X), wherein diamond wire polycrystalline silicon wafers are subjected to hole digging and hole expanding operation, and NH is added into alkaline washing liquid in an alkaline washing tank3.H2O and H2O2Adding H into the pickling solution in the pickling tank2O2And preparing the micro-nano mixed structure. Black silicon, a preparation process and a preparation method of a black silicon-based MEMS device (Chinese patent: 201710871041.1) disclosed in 2017 by Maohai Corp et al form a polymer on a substrate, and then the polymer is polymerized by using a product in the process of removing the polymerAnd forming a nano forest structure at the initial position of the compound, and depositing a silicon film material layer on the nano forest structure to obtain the micro-nano mixed structure. The prepared micro-nano mixed structure improves the conversion efficiency of the battery to different degrees, but the process is complex, and the micro-nano mixed structure can only be applied to silicon solar batteries, so that the application and popularization of the micro-nano mixed structure are limited.
The invention discloses a micro-nano mixed structure for enhancing light absorption of a solar cell and a preparation method thereof, which can be widely applied to the fields of photoelectric devices and the like. Compared with the prior art, the method comprises the steps of etching the nanowire array on the pyramid structure silicon wafer (a) through a chemical corrosion method to obtain a micro-nano mixed structure, namely black silicon (b), pouring PDMS (polydimethylsiloxane) glue on the black silicon (b) by taking the black silicon (b) as a template to obtain a mixed structure (c) of the black silicon and the PDMS glue, and finally obtaining the PDMS film (d) with the surface micro-nano mixed structure through a demoulding process. Compared with a traditional pyramid structure, the surface micro-nano mixed structure has the advantages of better light trapping effect, lower reflectivity and higher photoelectric conversion efficiency of the battery. The preparation method can realize the 'copying' of the black silicon structure, can be applied to silicon thin-film solar cells, can also be applied to glass packaging surface solar cells, and has wider application prospect. Compared with the traditional preparation of a micro-nano mixed structure, the preparation method has the advantages of low price, easy popularization and capability of realizing industrialized large-area preparation.
Disclosure of the invention
The invention aims to provide a micro-nano mixed structure for enhancing light absorption of a solar cell and a preparation method thereof.
The purpose of the invention is realized as follows:
the invention provides a micro-nano mixed structure for improving light absorption of a solar cell and a preparation method thereof. The method is characterized in that: the method comprises the following steps of (a) preparing a micro-nano mixed structure, namely black silicon (b) for short, by a chemical corrosion method, pouring PDMS (polydimethylsiloxane) glue on a structural surface of the pyramid-structured silicon wafer by taking the black silicon (b) as a template to obtain a mixed structure (c) of the black silicon and the PDMS glue, and finally obtaining a PDMS film (d) with the surface micro-nano mixed structure by a demoulding process. In the preparation method, a pyramid-structured silicon wafer (a) is cleaned and then fixed on a glass substrate, then a nanowire array is etched on the silicon wafer by using a chemical reagent, and black silicon (b) is prepared after cleaning and drying; pouring the prepared PDMS film on the pyramid structure surface of the black silicon by taking the black silicon as a template, and performing vacuum pumping treatment to obtain a mixed structure (c) of the black silicon and the PDMS; and finally, heating at constant temperature of 70 ℃ until the PDMS glue is completely cured, and separating the black silicon (b) from the PDMS glue film by adopting a die drawing process to prepare the PDMS glue film with the surface micro-nano mixed structure.
The specific preparation process of the black silicon comprises the following steps: firstly, a silicon wafer with a gold-shaped structure is prepared industrially by cleaning with acetone, alcohol and deionized water, dried and then placed on a glass substrate. Soaking the cleaned silicon wafer in hydrofluoric acid HF solution for about 2 minutes to remove silicon dioxide SiO on the surface2(ii) a Secondly, the silicon slice with the SiO2 removed on the silicon surface is put into silver nitrate AgNO3In the mixed solution of the solution and the HF solution, silver films (particles) were deposited, and after 2 minutes, the horizontal was taken out. Horizontally putting the silicon chip with the deposited silver film into hydrofluoric acid HF and hydrogen peroxide H2O2And etching the nanowire array in the mixed solution. Thirdly, the reacted silicon chip is put into nitric acid HNO rapidly3In the solution of (4), ultrasonic cleaning is performed to remove silver particles on the surface. And after the silver particles are completely removed, washing with a large amount of deionized water. And then removing the glass fixed substrate, and drying the silicon wafer in an oven to obtain the black silicon.
The preparation method of the PDMS film with the surface micro-nano mixed structure comprises the following specific steps: firstly, uniformly mixing PDMS (polydimethylsiloxane) main body glue with a solid agent, and vacuumizing to remove air in a mixed solution; secondly, pouring the mixed glue with air removed on the black silicon, and vacuumizing again to ensure that air in the glue body and the pit structure is completely discharged; thirdly, heating at constant temperature of 70 ℃ until the PDMS glue is completely solid; and finally carefully pulling out the PDMS rubber mold containing the surface micro-nano mixed structure.
(IV) description of the drawings
FIG. 1 is a flow chart of preparation of a PDMS film with a surface micro-nano mixed structure.
FIG. 2 is a cross-sectional view of a silicon thin film solar cell with a surface micro-nano mixed structure. In the figure, 1 is a silicon thin film solar cell; 2 is refractive index matching fluid, the refractive index is quite similar to that of air, and is about 1; and 3, a PDMS film with a micro-nano mixed structure on the surface.
FIG. 3 is an electron microscope (SEM) image of a surface micro-nano mixed structure magnified 2000 times
FIG. 4 is a comparison graph of reflection spectra of PDMS films with a flat plate structure, a pyramid structure and a surface micro-nano mixed structure.
Fig. 5 is a comparison graph of performances (current-voltage relationship curves) of a PDMS thin-film solar cell with a flat-plate structure, a pyramid structure and a surface micro-nano mixed structure.
(V) detailed description of the preferred embodiments
The invention is further illustrated below with reference to specific examples.
Fig. 2 shows an example of a PDMS film with a surface micro-nano mixed structure. The specific implementation steps are as follows: first, a pyramidal silicon wafer having a diameter of 3 inches, a crystal orientation (100), and a thickness of about 500 μm was placed on a glass substrate, and the silicon wafer was washed with acetone, alcohol, and deionized water. Soaking the silicon wafer in HF solution with the concentration of 2% by volume fraction for 2 minutes to remove SiO on the surface2(ii) a Secondly, the soaked silicon chip is put into 0.035mol/L AgNO3In a mixed solution of the solution and 15 vol% HF solution (30 degrees), silver film (particles) was deposited, and after 2 minutes, it was taken out horizontally. Placing the silicon wafer with the deposited silver film into 10 vol% HF and 0.6 vol% H horizontally2O2Keeping the temperature in the mixed solution at 35 ℃, reacting for 10-30 minutes, and etching the nanowire array; thirdly, the reacted silicon chip is quickly put into HNO with the concentration of 30vol percent3In the solution of (2), ultrasonic cleaning is performed to remove the Ag particles on the surface. And after the Ag particles are completely removed, washing with a large amount of deionized water. Then removing the glass fixed substrate, and drying the glass fixed substrate by using a 60-DEG silicon wafer oven for about two hours to obtain black silicon; fourthly, uniformly mixing the PDMS main body glue and the solid agent according to the mass ratio of 10:1, and vacuumizing to remove air in the mixed liquid; fifthly, pouring the mixed glue with air removed onto the black silicon, and vacuumizing again to ensure that air in the glue and in the black silicon structure is completely exhaustedAnd (4) discharging. Heating at constant temperature of 70 ℃ for more than 4 hours until the PDMS glue is completely solid; and finally, carefully pulling out the PDMS rubber mold containing the surface micro-nano mixed structure. The PDMS film thus obtained was observed under an electron microscope at 2000 times magnification, and the results are shown in FIG. 4.
Fig. 3 shows an embodiment of a silicon thin film solar cell with a surface micro-nano mixed structure. The specific implementation steps are as follows: preparing a PDMS film 3 with a surface micro-nano mixed structure according to the embodiment, directly covering the prepared PDMS film 3 on the surface of a silicon thin film solar cell 1, filling a refractive index matching fluid 2 in the middle, and adding ethanol C2H5OH, liquid paraffin and bromonaphthalene C10H7Br is configured according to the proportion of 1:1:1 and is used for eliminating the influence of an air layer between the surface micro-nano mixed structure PDMS film 3 and the silicon thin film solar cell 1, and then the surface micro-nano mixed structure silicon thin film solar cell can be obtained.
FIG. 4 shows a comparison graph of reflection spectra of PDMS films with a flat plate structure, a pyramid structure and a surface micro-nano mixed structure. The PDMS film with the flat structure has the highest reflectivity, and the reflectivity value is 7-10%. The reflectivity of the PDMS film with the pyramid structure is much lower than that of a flat plate structure, and the reflectivity of the PDMS film with the surface micro-nano mixed structure is lower than that of the PDMS with the pyramid structure. The PDMS with the micro-nano mixed structure is similar to black silicon, and has very excellent light trapping property, particularly in the visible light region (400-800nm), the reflectivity is as low as 4%. The micro-nano mixed structure on the surface of the PDMS is mainly benefited, and the multiple absorption of light is realized.
Fig. 5 shows a comparison graph of I-V curves of 3 types of amorphous silicon thin-film solar cells covering different structures, and it can be seen that the short-circuit current covering a flat PDMS cell is the lowest, the current covering a pyramid structure PDMS cell is the next highest, and the current covering a surface micro-nano mixed structure PDMS silicon thin-film solar cell is the highest. The result shows that the light trapping property of the surface micro-nano mixed structure is better than that of a pyramid structure and better than that of a plane structure, and the photoelectric conversion efficiency of the cell can be effectively improved.
The specific implementation of the invention is described in detail above, but it should be reiterated that the core content of the invention is to prepare black silicon, and then perform PDMS casting by using the black silicon as a template to obtain a surface micro-nano mixed structure PDMS film. The invention is not limited to the specific embodiments described above, and various modifications and improvements can be made by those skilled in the art within the scope of the claims without affecting the essence of the design of the invention.
Claims (3)
1. The invention provides a micro-nano mixed structure for enhancing light absorption of a solar cell and a preparation method thereof. The method is characterized in that: the method comprises the following steps of (a) preparing a micro-nano mixed structure, namely black silicon (b) for short, by a chemical corrosion method, pouring PDMS (polydimethylsiloxane) glue on a structural surface of the pyramid-structured silicon wafer by taking the black silicon (b) as a template to obtain a mixed structure (c) of the black silicon and the PDMS glue, and finally obtaining a PDMS film (d) with the surface micro-nano mixed structure by a demoulding process. In the preparation method, a pyramid-structured silicon wafer (a) is cleaned and then fixed on a glass substrate, then a nanowire array is etched on the silicon wafer by using a chemical reagent, and black silicon (b) is prepared after cleaning and drying; pouring the prepared PDMS film on the pyramid structure surface of the black silicon by taking the black silicon as a template, and performing vacuum pumping treatment to obtain a mixed structure (c) of the black silicon and the PDMS; and finally, heating at constant temperature of 70 ℃ until the PDMS adhesive is completely cured, and separating the black silicon (b) from the PDMS adhesive film by adopting a die drawing process to obtain the PDMS adhesive film with the surface micro-nano mixed structure.
2. The surface micro-nano hybrid structure according to claim 1. The method is characterized in that: the surface micro-nano mixed structure is prepared by taking black silicon as a template, pouring PDMS (polydimethylsiloxane) glue on the surface of the black silicon structure, curing at a constant temperature and performing a die drawing process; the structure is a double anti-reflection structure consisting of a micron-scale pyramid structure and a nanometer-scale nanowire array structure.
3. The PDMS adhesive film of claim 1. The method is characterized in that: the period of the pyramid structure in the PDMS film is 10-20 μm, and the height of the nanowire array structure is 50-100 nm.
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| CN104362204A (en) * | 2014-11-14 | 2015-02-18 | 安徽工程大学 | Solar cell gain film, manufacturing method thereof and solar cell with the same |
| CN105758562A (en) * | 2016-03-29 | 2016-07-13 | 电子科技大学 | Flexible pressure sensor and preparation method thereof |
| CN106098963A (en) * | 2016-07-28 | 2016-11-09 | 上海大学 | There is optical thin film of random pyramid pattern matte and preparation method thereof |
| CN106750419A (en) * | 2016-12-02 | 2017-05-31 | 江南大学 | A kind of method that anti-stamping technique of use room temperature prepares thermoplastic polymer multilevel hierarchy |
| CN109103301A (en) * | 2018-08-30 | 2018-12-28 | 鲁东大学 | A kind of preparation method of polysilicon surface micro-nano compound structure |
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