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CN110729379B - Method for preparing black silicon substrate with ultra-low reflectivity micro-nano composite structure - Google Patents

Method for preparing black silicon substrate with ultra-low reflectivity micro-nano composite structure Download PDF

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CN110729379B
CN110729379B CN201910982886.7A CN201910982886A CN110729379B CN 110729379 B CN110729379 B CN 110729379B CN 201910982886 A CN201910982886 A CN 201910982886A CN 110729379 B CN110729379 B CN 110729379B
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silicon substrate
micro
composite structure
nano composite
ultra
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CN110729379A (en
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张丹
甘阳
申健
陈远东
汪郑扬
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Harbin Institute of Technology Shenzhen
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/70—Surface textures, e.g. pyramid structures
    • H10F77/707—Surface textures, e.g. pyramid structures of the substrates or of layers on substrates, e.g. textured ITO layer on a glass substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

一种具有超低反射率微纳复合结构的黑硅衬底制备方法，本发明涉及低反射率黑硅衬底制备领域。本发明要解决现有硅衬底表面反射率高，导致太阳能电池效率低的问题。方法：利用Cu金属催化辅助的化学蚀刻法，采用CuNO3、HF和H2O2混合溶液对硅衬底进行蚀刻，生成微米级尺寸陷光结构；再放入AgNO3与HF混合溶液中进行银纳米粒子的自组装沉积；然后采用HF与H2O2混合溶液进行Ag金属催化辅助的化学蚀刻，完成制备。本发明制备具有微纳图形阵列的硅衬底实现了超低的表面反射率，高效地制备微纳图形阵列结构，重复性高，并通过优化蚀刻条件可调控其反射率。本发明制备的具有超低反射率微纳复合结构的黑硅衬底用于太阳能电池中。

Figure 201910982886

A method for preparing a black silicon substrate with an ultra-low reflectivity micro-nano composite structure relates to the field of preparation of a low reflectivity black silicon substrate. The present invention solves the problem that the surface reflectivity of the existing silicon substrate is high, resulting in low efficiency of the solar cell. Methods: The silicon substrate was etched with CuNO 3 , HF and H 2 O 2 mixed solution by chemical etching method assisted by Cu metal catalysis to form a micron-sized light trapping structure; then put into the mixed solution of AgNO 3 and HF to carry out Self-assembled deposition of silver nanoparticles; then Ag metal-assisted chemical etching using a mixed solution of HF and H 2 O 2 to complete the preparation. The preparation of the silicon substrate with the micro-nano pattern array realizes ultra-low surface reflectivity, the micro-nano pattern array structure is efficiently prepared, the repeatability is high, and the reflectivity can be regulated by optimizing the etching conditions. The black silicon substrate with ultra-low reflectivity micro-nano composite structure prepared by the invention is used in solar cells.

Figure 201910982886

Description

Preparation method of black silicon substrate with ultralow-reflectivity micro-nano composite structure
Technical Field
The invention relates to the field of preparation of low-reflectivity black silicon substrates.
Background
The monocrystalline silicon solar cell is widely applied to the fields of aerospace, agriculture, chemical industry, energy and the like as a commercial solar cell with highest conversion efficiency and optimal industrialization efficiency in the current photovoltaic market. However, at present, optical loss at the surface of the silicon substrate becomes a major factor limiting the improvement of the efficiency of the solar cell. In order to improve the cell efficiency of solar cells, the optical loss at the surface of the silicon substrate must be reduced. At present, methods for reducing the optical loss of the surface of the substrate mainly comprise surface plating of an antireflection coating, adoption of a gate electrode and surface roughening and texturing treatment, wherein the surface roughening and texturing treatment is the most frequently adopted and most effective method for reducing the reflectivity of the silicon substrate and is beneficial to realization of a high-performance monocrystalline silicon solar cell.
The surface of a common patterned silicon substrate structure in the silicon solar cell is a positive pyramid structure and an inverted pyramid structure which are etched by a wet method and a columnar structure and a table-shaped structure which are etched by a dry method. However. The reflectivity of the solar cell surface prepared using the patterned silicon substrate having the above-described conventional micro structure can be reduced to only 10%, and the light loss is still serious. Therefore, the pattern light trapping structure with ultralow reflectivity prepared on the surface of the silicon substrate has important significance for improving the efficiency of the solar cell.
Disclosure of Invention
The invention provides a preparation method of a black silicon substrate with an ultra-low reflectivity micro-nano composite structure, aiming at solving the problem that the existing silicon substrate surface has high reflectivity and causes low efficiency of a solar cell.
A preparation method of a black silicon substrate with an ultralow-reflectivity micro-nano composite structure comprises the following steps:
firstly, adopting CuNO with the temperature of 40-100 DEG C3HF and H2O2Etching the silicon substrate by using the mixed solution, and controlling the etching time to be 1-60 min to obtain the silicon substrate with the micron-sized light trapping structure on the surface;
secondly, placing the silicon substrate obtained in the step one into AgNO with the temperature of 20-100 DEG C3And HF mixed solution, depositing silver nano particles;
thirdly, placing the silicon substrate deposited in the second step into HF and H with the temperature of 20-100 DEG C2O2Etching for 10-60 min in the mixed solution to obtain a silicon substrate with a micro-nano composite structure on the surface;
fourthly, putting the silicon substrate obtained in the third step into HNO with the temperature of 20-100 DEG C3And keeping the solution for 5-100 min, then flushing with deionized water, and blow-drying with nitrogen to obtain the black silicon substrate with the ultra-low reflectivity micro-nano composite structure.
Furthermore, in the first step, a micron-sized light trapping structure is prepared by adopting Cu catalytic etching.
Further, HNO is adopted in the fourth step3The solution removes the metal particles.
The invention adopts a two-step method to prepare silver nano-particles and a silicon nano-pore array.
The first step, the second step, the third step and the fourth step of the invention are all carried out reaction in a polytetrafluoroethylene container.
The invention has the beneficial effects that:
the silicon substrate of the micro-nano graphic array prepared by the invention realizes ultralow surface reflectivity, and the micro-nano graphic array structure is prepared efficiently and has high repeatability.
The method adopts a Cu metal catalytic chemical etching method to prepare the micron-sized light trapping structure on the surface of the silicon substrate, and then utilizes a two-step Ag metal catalytic chemical etching method to prepare the black silicon substrate with the micro-nano composite structure on the surface of the substrate. Scanning Electron Microscope (SEM) shows that the obtained black silicon substrate is rough in surface and dense in nano-pore distribution, and the structure can reflect and absorb incident light for multiple times and has excellent light capture capacity. The reflectivity measurement result shows that the surface reflectivity of the obtained black silicon substrate is as low as 2%; the external quantum efficiency of the 300-ion 1000nm band solar cell can be remarkably improved, and the external quantum efficiency is as high as 95%.
In addition, the polytetrafluoroethylene container is used in the first step, the second step, the third step and the fourth step, so that the reaction between the container material and the solution can be prevented; by controlling the concentration of the HF solution in the first step, the size, the depth and the occupancy ratio of the obtained micron-sized light trapping structure and the surface reflectivity of the black silicon substrate can be effectively regulated and controlled; by controlling the etching time in the third step, the depth, the size and the density of the obtained nano-pore structure and the surface reflectivity of the finally obtained black silicon substrate can be effectively regulated and controlled; step four adopts HNO3The solution completely removes the metal particles on the surface of the substrate, and avoids the influence of the existence of the metal particles on the reflectivity result determination.
The black silicon substrate with the ultralow-reflectivity micro-nano composite structure, which is prepared by the invention, is used in a solar cell.
Drawings
FIG. 1 is a SEM plan view of a surface of a silicon substrate with micro-scale light trapping structures obtained in a first step of the embodiment;
FIG. 2 is an SEM plan view (low magnification) of the surface of a black silicon substrate with an ultralow-reflectivity micro-nano composite structure prepared in the first embodiment;
FIG. 3 is an SEM plan view (high magnification) of the surface of a black silicon substrate with an ultralow-reflectivity micro-nano composite structure prepared in the first embodiment;
FIG. 4 is an SEM plan view (low magnification) of a section of a black silicon substrate with an ultralow-reflectivity micro-nano composite structure prepared in the first embodiment;
FIG. 5 is an SEM plan view (high magnification) of a section of a black silicon substrate with an ultralow-reflectivity micro-nano composite structure prepared in the first embodiment;
fig. 6 is a graph comparing the reflectivity of the black silicon substrate with the ultra-low reflectivity micro-nano composite structure prepared in the first embodiment with that of the smooth silicon substrate, wherein a curve "1" is the black silicon substrate prepared in the first embodiment, and a curve "2" is the smooth silicon substrate.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the embodiment of the invention provides a preparation method of a black silicon substrate with an ultralow-reflectivity micro-nano composite structure, which comprises the following steps:
firstly, adopting CuNO with the temperature of 40-100 DEG C3HF and H2O2Etching the silicon substrate by using the mixed solution, and controlling the etching time to be 1-60 min to obtain the silicon substrate with the micron-sized light trapping structure on the surface;
secondly, placing the silicon substrate obtained in the step one into AgNO with the temperature of 20-100 DEG C3And HF mixed solution, depositing silver nano particles;
thirdly, placing the silicon substrate deposited in the second step into HF and H with the temperature of 20-100 DEG C2O2Etching for 10-60 min in the mixed solution to obtain a silicon substrate with a micro-nano composite structure on the surface;
fourthly, putting the silicon substrate obtained in the third step at the temperature ofHNO at 20-100 DEG C3And keeping the solution for 5-100 min, then flushing with deionized water, and blow-drying with nitrogen to obtain the black silicon substrate with the ultra-low reflectivity micro-nano composite structure.
The silicon substrate of the micro-nano graphic array prepared by the embodiment realizes ultralow surface reflectivity, and the micro-nano graphic array structure is prepared efficiently and has high repeatability.
According to the embodiment, a micron-sized light trapping structure is prepared on the surface of a silicon substrate by a Cu metal catalytic chemical etching method, and then a black silicon substrate with a micro-nano composite structure is prepared on the surface of the substrate by a two-step Ag metal catalytic chemical etching method. Scanning Electron Microscope (SEM) shows that the obtained black silicon substrate is rough in surface and dense in nano-pore distribution, and the structure can reflect and absorb incident light for multiple times and has excellent light capture capacity. The reflectivity measurement result shows that the surface reflectivity of the obtained black silicon substrate is as low as 2%; the performance of the solar cell can be obviously improved.
In addition, the depth, the size and the density of the obtained nano-pore structure and the surface reflectivity of the finally obtained black silicon substrate can be effectively regulated and controlled by controlling the etching time in the third step; step four adopts HNO3The solution completely removes the metal particles on the surface of the substrate, and avoids the influence of the existence of the metal particles on the reflectivity result determination.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: step one of the CuNO3HF and H2O2CuNO in mixed solution3The concentration of (A) is 0.01-5.00 mol/L, HF and the concentration of (B) is 1-10 mol/L, H2O2The concentration of (b) is 0.1-10 mol/L. The rest is the same as the first embodiment.
According to the embodiment, the size, the depth and the occupancy ratio of the obtained micron-sized light trapping structure and the surface reflectivity of the black silicon substrate can be effectively regulated and controlled by controlling the concentration of the HF solution in the first step.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, the silicon substrate is (100) plane monocrystalline silicon. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the first step, the micron-sized light trapping structure is an inverted micron-sized silicon pattern structure with the size of 1-100 mu m. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: step two AgNO3And AgNO in HF mixed solution3The concentration of (b) is 0.01-10 mol/L, HF, and the concentration is 0.1-10 mol/L. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and in the second step, the deposition time is controlled to be 1-300 s. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: step three said HF and H2O2The concentration of HF in the mixed solution is 1-10 mol/L, H2O2The concentration of (b) is 0.1 to 5.0 mol/L. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: step three said HF and H2O2The concentration of HF in the mixed solution was 2 mol/L. The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: step three said HF and H2O2The concentration of HF in the mixed solution was 3 mol/L. The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and step three, etching a nano-pore structure with the size of 10-500 nm on the surface of the silicon substrate with the micro-nano composite structure. The other is the same as one of the first to ninth embodiments.
The concrete implementation mode eleven: the present embodiment differs from one of the first to tenth embodiments in that: the etching time in step three was 20 min. The rest is the same as one of the first to tenth embodiments.
The specific implementation mode twelve: this embodiment is different from one of the first to eleventh embodiments in that: the etching time in step three was 30 min. The rest is the same as in one of the first to eleventh embodiments.
The specific implementation mode is thirteen: the present embodiment differs from the first to twelfth embodiments in that: the etching time in step three was 40 min. The rest is the same as the first to twelfth embodiments.
The specific implementation mode is fourteen: the present embodiment is different from one to thirteen embodiments in that: the etching time in step three was 50 min. The rest is the same as one of the first to the thirteenth embodiments.
The concrete implementation mode is fifteen: the present embodiment is different from the first to the fourteenth embodiment in that: step four of HNO3The mass concentration of the solution was 68%. The rest is the same as the first to the fourteenth embodiments.
The specific implementation mode is sixteen: the present embodiment differs from one of the first to fifteenth embodiments in that: and the first step, the second step, the third step and the fourth step are all carried out in a polytetrafluoroethylene container. The rest is the same as one of the first to fifteenth embodiments.
In the first, second, third and fourth steps of the present embodiment, a teflon container is used, which prevents the container material from reacting with the solution.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
the embodiment provides a preparation method of a black silicon substrate with an ultralow-reflectivity micro-nano composite structure, which comprises the following steps:
firstly, adopting CuNO with the temperature of 70 DEG C3HF and H2O2Etching the silicon substrate with the mixed solution, wherein the CuNO is3The concentration is 0.08mol/L, HF, and the concentration is 2.3mol/L, H2O2The concentration is 2.0mol/L, the etching time is controlled to be 3min, and the micron-sized surface with micron-sized surface is obtainedA silicon substrate of a light trapping structure; the silicon substrate is (100) surface monocrystalline silicon, and the micron-sized light trapping structure is an inverted micron-sized silicon graphic structure with the size of 1-2 mu m;
secondly, placing the silicon substrate obtained in the step one into AgNO with the temperature of 25 DEG C3And HF mixed solution, depositing silver nano particles; wherein AgNO3The concentration is 0.05mol/L, HF, the concentration is 2.4mol/L, and the deposition time is 15 s;
thirdly, placing the silicon substrate deposited in the second step into HF and H with the temperature of 25 DEG C2O2Etching for 30min in the mixed solution to obtain a silicon substrate with a micro-nano composite structure on the surface; wherein the concentration of HF in the mixed solution is 4.8mol/L, H2O2The concentration is 0.5 mol/L; the micro-nano composite structure is a nano-pore structure with the etching size of 10-40nm on the surface of a silicon substrate with the micro-nano composite structure;
fourthly, putting the silicon substrate obtained in the third step into HNO with the temperature of 25 ℃ and the mass concentration of 68 percent3And keeping the solution in the solution for 30min, then flushing the solution by using deionized water, and drying the solution by using nitrogen to prepare the black silicon substrate with the ultralow-reflectivity micro-nano composite structure.
Fig. 1 is a SEM plan view of the surface of the silicon substrate with the micron-scale light trapping structure obtained in the first step of this embodiment, and it can be seen from the drawing that the micron-scale light trapping structure is an inverted micron-scale silicon pattern structure with a size of 1-2 μm.
Fig. 2 is an SEM plan view (low magnification) of the black silicon substrate surface with the ultra-low reflectance micro-nano composite structure prepared in this example; fig. 3 is an SEM plan view (high magnification) of the black silicon substrate surface with the ultra-low reflectance micro-nano composite structure prepared in this example; as can be seen from the figure, after the silicon substrate is treated by the Cu and Ag metal catalytic chemical etching method, the surface of the silicon substrate has a composite structure of micron-sized inverted patterns and nano-holes which are uniformly distributed, the size of the micron-sized light trapping structure is 1-2 μm, and the size of the nano-holes is 10-40 nm.
Fig. 4 is an SEM plan view (low magnification) of a section of a black silicon substrate with an ultra-low reflectance micro-nano composite structure prepared in this example; fig. 5 is an SEM plan view (high magnification) of a section of a black silicon substrate with an ultra-low reflectance micro-nano composite structure prepared in this example; as can be seen from the figure, after the silicon substrate is subjected to a Cu and Ag metal catalytic chemical etching method, the depth of the micron-scale light trapping structure on the surface of the silicon substrate is about 1 μm, and the nano-pores have the depth of the nano-scale.
Fig. 6 is a comparison graph of the reflectivity of the surfaces of a black silicon substrate with an ultra-low reflectivity micro-nano composite structure and a smooth silicon substrate prepared in this embodiment, where a curve "1" is the black silicon substrate prepared in this embodiment, and a curve "2" is the smooth silicon substrate; as can be seen from the figure, the reflectivity of the polished surface of the single crystal flat silicon sheet is as high as 40%, while the silicon substrate prepared by the embodiment has a micro-nano composite structure, and the reflectivity of the surface of the silicon substrate is reduced to 2%.
In summary, in the embodiment, a micro-nano composite structure is prepared on the surface of the (100) silicon substrate by using a Cu and Ag metal catalytic chemical etching method, and the micro-nano composite structure can reduce the reflectivity of the surface of the silicon substrate from 40% to 2%. Therefore, the micro-nano composite structure obtained by the embodiment has excellent light capturing capability, and the performance of the solar cell can be remarkably improved.

Claims (8)

1.一种具有超低反射率微纳复合结构的黑硅衬底制备方法，其特征在于该方法按以下步骤进行：1. a black silicon substrate preparation method with ultra-low reflectivity micro-nano composite structure is characterized in that the method is carried out according to the following steps: 一、采用温度为40～100℃的CuNO3、HF和H2O2混合溶液刻蚀硅衬底，控制刻蚀时间为1～60min，获得表面具有微米级陷光结构的硅衬底；1. The silicon substrate is etched with a mixed solution of CuNO 3 , HF and H 2 O 2 at a temperature of 40-100°C, and the etching time is controlled to be 1-60 minutes to obtain a silicon substrate with a micron-scale light trapping structure on the surface; 二、将步骤一获得的硅衬底放入温度为20～100℃的AgNO3和HF混合溶液中，进行银纳米颗粒的沉积；2. Put the silicon substrate obtained in step 1 into a mixed solution of AgNO 3 and HF at a temperature of 20-100° C. to deposit silver nanoparticles; 三、将步骤二沉积后的硅衬底放入温度为20～100℃的HF和H2O2混合溶液中，蚀刻30min，获得表面具有微纳复合结构的硅衬底；3. Put the silicon substrate deposited in step 2 into a mixed solution of HF and H 2 O 2 at a temperature of 20-100° C., and etch for 30 minutes to obtain a silicon substrate with a micro-nano composite structure on the surface; 四、将步骤三获得的硅衬底放入温度为20～100℃的HNO3溶液中，保持5～100min，然后采用去离子水冲洗，氮气吹干，制得所述具有超低反射率微纳复合结构的黑硅衬底；4. Put the silicon substrate obtained in step 3 into an HNO 3 solution with a temperature of 20-100° C., keep it for 5-100 min, then rinse it with deionized water, and dry it with nitrogen to obtain the ultra-low reflectance microstructure. Black silicon substrate of nanocomposite structure; 步骤一所述CuNO3、HF和H2O2混合溶液中CuNO3的浓度为0.01～5.00mol/L、HF的浓度为1～10mol/L、H2O2的浓度为0.1～10mol/L；The concentration of CuNO 3 in the CuNO 3 , HF and H 2 O 2 mixed solution in step 1 is 0.01-5.00 mol/L, the concentration of HF is 1-10 mol/L, and the concentration of H 2 O 2 is 0.1-10 mol/L ; 步骤一中微米级陷光结构为尺寸为1～100μm的倒置微米级硅图形结构。In step 1, the micron-scale light trapping structure is an inverted micron-scale silicon pattern structure with a size of 1-100 μm. 2.根据权利要求1所述的一种具有超低反射率微纳复合结构的黑硅衬底制备方法，其特征在于步骤一中硅衬底为(100)面单晶硅。2 . The method for preparing a black silicon substrate with an ultra-low reflectivity micro-nano composite structure according to claim 1 , wherein the silicon substrate in step 1 is (100) plane monocrystalline silicon. 3 . 3.根据权利要求1所述的一种具有超低反射率微纳复合结构的黑硅衬底制备方法，其特征在于步骤二所述AgNO3和HF混合溶液中AgNO3的浓度为0.01～10mol/L、HF的浓度为0.1～10mol/L。3. The method for preparing a black silicon substrate with an ultra-low reflectivity micro-nano composite structure according to claim 1, wherein the AgNO in the step 2 and the HF mixed solution has a concentration of 0.01 to 10 mol of AgNO. /L, and the concentration of HF is 0.1 to 10 mol/L. 4.根据权利要求1所述的一种具有超低反射率微纳复合结构的黑硅衬底制备方法，其特征在于步骤二中控制沉积时间为1～300s。4 . The method for preparing a black silicon substrate with an ultra-low reflectivity micro-nano composite structure according to claim 1 , wherein the deposition time in step 2 is controlled to be 1-300 s. 5 . 5.根据权利要求1所述的一种具有超低反射率微纳复合结构的黑硅衬底制备方法，其特征在于步骤三所述HF和H2O2混合溶液中HF的浓度为1～10mol/L，H2O2的浓度为0.1～5.0mol/L。5 . The method for preparing a black silicon substrate with an ultra-low reflectivity micro-nano composite structure according to claim 1 , wherein the concentration of HF in the mixed solution of HF and H 2 O 2 in step 3 is 1 to 1 . 10mol/L, the concentration of H 2 O 2 is 0.1～5.0mol/L. 6.根据权利要求1所述的一种具有超低反射率微纳复合结构的黑硅衬底制备方法，其特征在于步骤三所述微纳复合结构为在具有微纳复合结构的硅衬底表面刻蚀尺寸为10～500nm的纳米孔结构。6. The method for preparing a black silicon substrate with an ultra-low reflectivity micro-nano composite structure according to claim 1, wherein the micro-nano composite structure in step 3 is a silicon substrate with a micro-nano composite structure. Nanopore structures with a size of 10 to 500 nm are etched on the surface. 7.根据权利要求1所述的一种具有超低反射率微纳复合结构的黑硅衬底制备方法，其特征在于步骤四中HNO3溶液的质量浓度为68％。7 . The method for preparing a black silicon substrate with an ultra-low reflectivity micro-nano composite structure according to claim 1 , wherein the mass concentration of the HNO 3 solution in step 4 is 68%. 8 . 8.根据权利要求1所述的一种具有超低反射率微纳复合结构的黑硅衬底制备方法，其特征在于步骤一、步骤二、步骤三和步骤四均在聚四氟乙烯容器中进行反应。8. The method for preparing a black silicon substrate with an ultra-low reflectivity micro-nano composite structure according to claim 1, wherein step 1, step 2, step 3 and step 4 are all in a polytetrafluoroethylene container to react.
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