CN110729379A - Preparation method of black silicon substrate with ultralow-reflectivity micro-nano composite structure - Google Patents
Preparation method of black silicon substrate with ultralow-reflectivity micro-nano composite structure Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 112
- 238000002310 reflectometry Methods 0.000 title claims abstract description 54
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 48
- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 67
- 239000010703 silicon Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000005530 etching Methods 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical group [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 101710134784 Agnoprotein Proteins 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000861 blow drying Methods 0.000 claims description 3
- 238000003486 chemical etching Methods 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- 238000001338 self-assembly Methods 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000012611 container material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000126 substance 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
- H01L31/18—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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- H—ELECTRICITY
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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
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
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- 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
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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
- Y02E10/547—Monocrystalline silicon PV cells
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- 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
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Abstract
The invention discloses a preparation method of a black silicon substrate with an ultralow-reflectivity micro-nano composite structure, and relates to the field of preparation of low-reflectivity black silicon substrates. The invention aims to solve the problem of low efficiency of a solar cell caused by high reflectivity of the surface of the existing silicon substrate. The method comprises the following steps: by Cu metal catalysis-assisted chemical etching method, CuNO is adopted3HF and H2O2Etching the silicon substrate by the mixed solution to generate a micron-sized light trapping structure; then placing in AgNO3Self-assembly deposition of silver nanoparticles is carried out in HF mixed solution; then HF and H are used2O2And carrying out chemical etching assisted by Ag metal catalysis on the mixed solution to finish the preparation. The silicon substrate with the micro-nano graphic array prepared by the invention realizes ultralow surface reflectivity, the micro-nano graphic array structure is efficiently prepared, the repeatability is high, and the reflectivity can be regulated and controlled by optimizing the etching condition. The prepared product has ultralow reflectivityThe black silicon substrate with the refractive index micro-nano composite structure is used in a solar cell.
Description
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 C3Mixing with HFIn the solution, depositing silver nanoparticles;
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 HF solution in step one, it is possible to effectively controlThe size, the depth and the occupancy ratio of the obtained micron-sized light trapping structure and the surface reflectivity of the black silicon substrate are 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 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.
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 andH2O2CuNO 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.
Detailed description of the inventionThe formula is 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, H2O2Controlling the etching time to be 3min, and obtaining a silicon substrate with a micron-sized light trapping structure on the surface, wherein the concentration of the silicon substrate is 2.0 mol/L; 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 (10)
1. A preparation method of a black silicon substrate with an ultralow-reflectivity micro-nano composite structure is characterized by comprising the following steps:
firstly, adopting CuNO with the temperature of 40-100 DEG C3HF and H2O2Etching the silicon substrate by the mixed solution for 1-60 min to obtain the silicon substrate with micron-sized surfaceA silicon substrate of a light trapping structure;
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.
2. The method for preparing the black silicon substrate with the ultra-low reflectivity micro-nano composite structure according to claim 1, wherein the CuNO is obtained in step one3HF 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.
3. The method for preparing the black silicon substrate with the ultra-low reflectivity micro-nano composite structure according to claim 1, wherein the silicon substrate in the first step is (100) plane monocrystalline silicon.
4. The method for preparing the black silicon substrate with the ultra-low reflectivity micro-nano composite structure according to claim 1, wherein the micron-sized light trapping structure in the first step is an inverted micron-sized silicon pattern structure with the size of 1-100 μm.
5. The method for preparing the black silicon substrate with the ultra-low reflectivity micro-nano composite structure according to claim 1, wherein AgNO is obtained in the second step3And AgNO in HF mixed solution3The concentration of (b) is 0.01-10 mol/L, HF, and the concentration is 0.1-10 mol/L.
6. The method for preparing the black silicon substrate with the ultra-low reflectivity micro-nano composite structure according to claim 1, wherein the deposition time is controlled to be 1-300 s in the second step.
7. The method for preparing the black silicon substrate with the ultra-low reflectivity micro-nano composite structure according to claim 1, wherein the HF and the H are obtained in step three2O2The concentration of HF in the mixed solution is 1-10 mol/L, H2O2The concentration of (b) is 0.1 to 5.0 mol/L.
8. The method for preparing the black silicon substrate with the ultra-low reflectivity micro-nano composite structure according to claim 1, wherein the micro-nano composite structure in the step three is a nano-pore structure with the etching size of 10-500 nm on the surface of the silicon substrate with the micro-nano composite structure.
9. The method for preparing the black silicon substrate with the ultra-low reflectivity micro-nano composite structure according to claim 1, characterized in that HNO is generated in the fourth step3The mass concentration of the solution was 68%.
10. The method for preparing the black silicon substrate with the ultra-low reflectivity micro-nano composite structure according to claim 1, wherein the first step, the second step, the third step and the fourth step are all carried out in a polytetrafluoroethylene container.
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