CN110745777B - Regular pyramid as well as preparation method and application thereof - Google Patents
Regular pyramid as well as preparation method and application thereof Download PDFInfo
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- CN110745777B CN110745777B CN201911039401.7A CN201911039401A CN110745777B CN 110745777 B CN110745777 B CN 110745777B CN 201911039401 A CN201911039401 A CN 201911039401A CN 110745777 B CN110745777 B CN 110745777B
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Abstract
The invention discloses a regular pyramid and a preparation method and application thereof. The pyramid array substrate which is regularly arranged, uniformly distributed and adjustable in period size is prepared through a simple colloid sphere technology, an interface processing technology and a wet etching technology. The invention also prepares single or composite functional materials with strong stability, good repeatability, adjustable structure size and various appearances on the regular cone surface by a simple physical or chemical interface assembly technology, such as a metal nanometer bowl, a semiconductor hollow nanometer needle, a porous organic framework and the like, and finally forms the composite functional substrate. The prepared composite functional substrate has a large specific surface area and a regular micro-nano array, and can be applied to the fields of trace substance detection, energy sources and the like.
Description
Technical Field
The invention relates to a regular pyramid as well as a preparation method and application thereof, belonging to the technical field of nano materials and nanochemistry.
Background
In recent years, various periodic nanostructures have been fabricated, and these materials have been widely used in various fields due to their unique optical, electrical, mechanical, catalytic, and magnetic properties. The noble metal nano array structure has the characteristics of periodicity and a nano structure, and has wide application prospect due to the Surface Plasmon Resonance (SPR) characteristic of noble metal. The method is one of the most effective methods for preparing periodic nanostructures by using self-assembled monolayer PS beads as templates, and the method is used to successfully prepare nano bowl-shaped array structures, honeycomb structures, annular array structures and other nanostructures. Among the nano structures, the silver bowl array structure has a very wide application prospect in the aspects of nano particle selection, biomedicine, nano microfluidic devices, magnetic enhancement, electromagnetic field enhancement, electrochemical catalysis and the like, and is paid much attention to. The silver nanometer bowl array has a controllable periodic bowl-shaped structure and a good focusing electromagnetic field effect, so that the application of the silver nanometer bowl array in Surface Enhanced Raman Scattering (SERS) is greatly improved, and great interest of people in ordered porous metal materials is aroused. However, the simple 2D structure of the silver bowl array limits the effective absorption and utilization of light, and thus limits the application of the silver bowl array in SERS.
Compared with the two-dimensional plasma nanostructure widely applied at present, the 3D plasma (noble metal) nanostructure has stronger Surface Enhanced Raman Scattering (SERS) performance. Particularly, the 3D silicon pyramid array has stronger light trapping capability and has larger contribution to enhancing the slow signal. Therefore, to further improve SERS substrate performance and stability, a regular array of pyramidal silicon cones is required. In recent years, the construction of ordered pyramid silicon cone arrays generally employs a photolithographic mask method, a nanoimprint mask method, a vapor phase mask method, a reactive ion mask method, and the like. Although these methods can obtain strong, uniform, and highly repeatable signals, they are costly, complex, and time-consuming, limiting their widespread use.
Disclosure of Invention
In order to solve the technical problems, the bionic silicon cone array substrate with ordered period and uniform distribution is prepared by a simple colloid ball technology, a wet etching technology and an interface processing technology.
The first purpose of the invention is to provide a method for preparing a regular pyramid, which comprises the following steps:
(1) Assembling single-layer balls: self-assembling the colloid balls at a gas-liquid interface to obtain single-layer balls which are closely arranged;
(2) Hydrogen bond acting force is formed between the single-layer ball and the silicon chip substrate: will go to stepTransferring the monolayer ball obtained in the step (1) to the surface of a silicon chip by adopting a method containing O 2 Or containing O 2 The colloidal globule and the silicon chip are treated by the reactive ion gas or ultraviolet ozone, and then the colloidal globule and the silicon chip are washed by water, and hydrogen bond acting force is formed at the contact part of the colloidal globule and the silicon chip;
(3) Wet etching: and (3) placing the colloidal spheres and the silicon wafers treated in the step (2) in an alkaline solution for etching for 1-50 min to obtain the regular pyramid.
Further, in the step (1), the material of the colloidal beads is one of silicon dioxide, polystyrene, polymethyl methacrylate, polyacrylic acid, polylactic acid, chitosan, gelatin, albumin, starch or derivatives thereof.
Further, in the step (3), the alkaline solution is an inorganic base, an organic base or a mixture thereof.
Furthermore, the etching temperature is 20-99 ℃.
Further, the method further comprises the step of copying the regular pyramid prepared in the step (3), or coating the surface of the regular pyramid, or imprinting the regular pyramid to prepare a new regular pyramid.
The second purpose of the invention is to provide a regular cone prepared by the method.
The third purpose of the invention is to provide a composite substrate modified by a nanometer bowl-shaped material, wherein the composite substrate is formed by assembling the nanometer bowl-shaped material on the surface of the regular cone, the height of the regular cone is 0.1-100 mu m, the height of the nanometer bowl is 0.01-10 mu m, and the diameter of the bowl opening is 0.01-10 mu m.
Further, the material of the nanometer bowl is one or two of a semiconductor and a metal.
Furthermore, the semiconductor is one or more of silicon, metal oxide, metal sulfide, metal phosphide and conductive polymer.
Further, the metal is one or more of gold, silver, palladium, platinum, copper, lithium and sodium.
The fourth purpose of the invention is to provide a composite substrate modified by the hollow nano needle-shaped material, wherein the composite substrate is formed by assembling the hollow nano needle-shaped material on the surface of the regular cone, the height of the regular cone is 0.1-100 mu m, the length of the hollow nano needle is 0.1-10 mu m, the wall thickness is 5-100 nm, the diameter of an upper narrow opening is 5-1000 nm, and the diameter of a lower wide opening is 10-1100 nm.
Furthermore, the hollow nano needle is made of one or two of a semiconductor and a metal.
Furthermore, the semiconductor is one or more of silicon, metal oxide, metal sulfide, metal phosphide and conductive polymer.
Further, the metal is one or more of gold, silver, palladium, platinum, copper, lithium and sodium.
The fifth purpose of the invention is to provide a composite substrate modified by metal organic framework materials or covalent organic framework materials, wherein the composite substrate is formed by sequentially assembling semiconductors, metals and metal organic framework materials or semiconductors, metals and covalent organic framework materials on the surface of the regular cone from bottom to top to construct a metal organic mining machine/metal.
The invention has the beneficial effects that:
the invention discloses a regular pyramid as well as a preparation method and application thereof. The pyramid array substrate with regular arrangement, uniform distribution and adjustable period size is prepared by a simple colloid ball technology, an interface processing technology and a wet etching technology. The invention also prepares single or composite functional materials with strong stability, good repeatability, adjustable structure size and various appearances on the regular cone surface by a simple physical or chemical interface assembly technology, such as a metal nanometer bowl, a semiconductor hollow nanometer needle, a porous organic framework and the like, and finally forms the composite functional substrate. The prepared composite functional substrate has a large specific surface area and a regular micro-nano array, and can be applied to the fields of trace substance detection, energy sources and the like.
Drawings
FIG. 1 is an SEM image of a pyramidal silicon cone array;
FIG. 2 is an SEM image of a silicon cone composite substrate modified by silver nanometer bowls;
FIG. 3 is an ultraviolet absorption spectrum of a silver nanobowl modified silicon cone composite substrate;
FIG. 4 is a Raman spectrum of a silver nanobowl modified silicon cone composite substrate at different reaction times;
FIG. 5 is a Raman spectrum of a 3D silver bowl substrate and a 2D silver bowl substrate;
FIG. 6 is Raman spectra measured by randomly taking 10 points on a 3D silver bowl substrate;
FIG. 7 is a Raman spectrum of a 3D silver bowl substrate for detecting rhodamine 6G with different concentrations;
fig. 8 is a raman spectrum of a 3D silver bowl based detection mixture.
Detailed Description
The present invention is further described below with reference to specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
(1) Test of anti-reflection Property
And testing the ultraviolet-visible reflectance spectrum and the absorption spectrum of all samples by adopting a UV-3600plus ultraviolet-visible spectrophotometer of Shimadzu, japan, wherein the scanning speed is medium speed, and the testing range is 200 nm-1500 nm.
(2) Micro-topography testing
The microscopic morphology of the samples was observed using a scanning electron microscope, model S-4800, hitachi, japan, all without the need for gold spraying.
(3) Elemental composition test
And analyzing the element composition and content of the sample by adopting an X-ray electronic spectrometer in cooperation with a field emission electron microscope.
(4) X-ray diffractometer (XRD)
The crystal form of the sample was analyzed by XRD form D8 of bruker AXS ltd, germany. The test range is 20-80 deg.
(5) Raman testing
Limited trade in Renyshao EnglandThe company inVia micro confocal raman spectrometer performs raman performance detection on all samples. Firstly, rhodamine 6G is selected as a probe molecule, and the concentration is 10 -4 To 10 -13 And M. Then, 10. Mu.L of rhodamine 6G solution with different concentrations are added dropwise to 1X 1cm 2 The surface of a SERS substrate. Finally, the above samples were subjected to raman test.
The method prepares the ordered pyramid silicon cone array with controllable period by a colloid sphere technology, an interface processing technology and a wet etching technology, and then assembles one or more layers of materials on the surface of the silicon cone array by a chemical or physical assembly technology to form a composite substrate. The specific procedures were as in example 1, example 2, example 9, example column 10:
example 1: construction of regular pyramid silicon cone array
1. Assembly process of 1350nm Polystyrene (PS) sphere monolayer film
First, a small amount of sodium lauryl sulfate was added dropwise to a petri dish containing deionized water to reduce the surface tension. Then, the PS spheres with the particle size of 1350nm are dripped on the liquid surface in the culture dish, and the hexagonal close-packed PS colloidal sphere single-layer film is formed by self-assembly by utilizing the capillary force generated by the meniscus between the PS spheres at the gas-liquid interface. Finally, it is transferred to the surface of the silicon wafer.
2. Hydrogen bond acting force forming process between PS ball and silicon chip substrate
Firstly, carrying out plasma gas O on the PS monolayer spheres which are self-assembled and densely packed in a hexagonal shape on the surface of a silicon wafer 2 And (6) processing. And then, washing the surface of the sample by deionized water, so that abundant hydroxyl groups are generated on the surface of the PS sphere and the surface of the silicon wafer, and a strong hydrogen bond acting force is formed at the contact position.
3. Wet etching process
Because the PS balls and the silicon wafer form a strong hydrogen bond acting force, the PS balls stably act on the surface of the silicon wafer in a KOH solution, the silicon wafer is subjected to etching reaction by taking the PS balls as a template at the temperature of 80 ℃, the limitation that the colloidal ball template cannot induce the ordered etching of monocrystalline silicon in alkali liquor is overcome, the silicon wafer is etched to form a silicon cone after 510s reaction, the PS balls on the top of the silicon cone can fall off, and the pyramid silicon cone array which is regularly arranged is obtained.
Example 2: construction of silver nanometer bowl modified silicon cone composite substrate
1. Assembly process of 180nm Polystyrene (PS) sphere monolayer film
Firstly, dripping a small amount of lauryl sodium sulfate into a culture dish filled with deionized water to reduce the surface tension; then, 180nm PS spheres are dripped on the liquid level in a culture dish, and a hexagonal close-packed PS colloidal sphere single-layer film is formed by self-assembly by utilizing the capillary force generated by the meniscus between the PS spheres at the gas-liquid interface.
2. Assembly process of continuous Ag nanometer bowl on surface of regular pyramid silicon cone array
First, a silver nitrate solution and a sodium citrate solution were blended and stirred for 15min. Then, transferring the single-layer film of the PS colloidal spheres with the diameter of 180nm in the previous step into the mixed solution, and reacting for 40min under the heating condition of 90 ℃ to successfully obtain the PS microspheres with the metal Ag films attached to the lower surfaces. And then, transferring the PS pellets with the metal Ag film attached to the lower surface to the surface of the regular pyramid silicon cone array. And finally, removing the PS pellets by using ethanol to obtain a silver nanometer bowl silicon cone array, namely the 3D silver bowl substrate.
Example 3: microstructure of pyramid silicon cone array
Firstly, assembling a layer of PS sphere single-layer film on a cleaned silicon wafer, then carrying out surface treatment on the PS sphere single-layer film by using oxygen as etching gas, and then placing the treated sample substrate into a KOH solution with the temperature of 80 ℃ and the pH value of 14 for carrying out chemical wet etching. Since the atomic densities on Si (100) and Si (111) are different, the KOH etch rate of Si (111) is 30 times lower than that of Si (100). Thus, specific anisotropy angles are formed on the (100) and (111) planes. The PS ball sites on the surface of the silicon wafer provide a mask for etching, and disordered etching in the etching process is avoided. The PS sphere sites are used as vertexes, and conical arrays with smooth side walls of 54.7 degrees are uniformly distributed on the surface of the silicon wafer. When the etching time is 510s, a large-area uniform ordered silicon cone array with a stable morphology structure is formed, as shown in figure 1.
Example 4: microstructure of silver nanometer bowl modified silicon cone composite substrate
And constructing a silver bowl array by using the constructed pyramid silicon cone array as a template. Preparing a layer of silver film at the bottom of the single-layer 180nm PS ball on the water surface by a chemical reduction method, slightly fishing out the silver bowl by using a 3D ordered silicon cone substrate, and transferring the silver bowl array from the water surface to the surface of the silicon pyramid array to obtain the 3D ordered silver bowl array tightly attached to the silicon pyramid array, wherein the 3D ordered silver bowl array is shown in figure 2. As seen from SEM, the formed 3D ordered silver bowl array has complete periodic structure and no breakage. As seen from the cross section, the bottom of the silver bowl is tightly attached to the silicon cone.
Example 5: ultraviolet absorption performance of silver nanometer bowl modified silicon cone composite substrate
The 3D silver bowl substrate was characterized spectrally by an ultraviolet-visible absorption spectrometer, the results of which are shown in fig. 3. After the Ag bowl is compounded, the absorption is obviously enhanced because in a submicron structure, highly-reflected metal can show strong absorption in a visible light wave band due to the oscillation of resonance charges of plasmas thereof, and the plasmas on the local surface of the Ag nanometer bowl are strongly coupled with incident light, so that the absorption is obviously increased. And due to the periodic three-dimensional ordered structure, the structure has good control effect on incident light, and strong light absorption is caused. The plasma resonance absorption peak of the SERS substrate is observed to be about 536nm, a good resonance coupling effect is achieved, and the phenomenon is predicted to be beneficial to amplification of a Raman signal on the surface of the SERS substrate.
Example 6: raman performance of silver nanometer bowl modified silicon cone composite substrate
Using a concentration of 10 -4 And (3) taking rhodamine 6G of M as a probe molecule, and carrying out Raman test. First, peak assignment was performed on the raman spectra: 1656, 1603, 1574, 1515, 1368 and 1317cm in spectrogram -1 Is identified as a series of C = C double bond stretching vibrations associated with the benzene ring, 1186cm -1 C-H bending vibration, lower than 1186cm -1 In-plane and out-of-plane deformation vibrations of the benzene ring can be referred to. It is obvious from FIG. 4 that the signal intensity of Raman spectrum of rhodamine 6G increases with the reduction time of the silver bowl, and then decreases, and the Raman spectrum shows that the reaction time of the in-situ grown metal film is 40minThe raman signal is best. When the time is less than 40min, the reduction time is short, the thickness of the silver bowl is thin, the bowl mouth can deform when the silicon cone is fished up, and particularly the silicon cone joint is easy to collapse. When the reduction time is 40min, the thickness of the bowl can ensure that the silver bowl does not deform in the process of fishing up the silicon cone, and a uniform silver bowl array is formed. The silicon cone connection also maintains a good structure. When the reduction time is longer than 40min, the Ag film at the bottom of the bowl is thick, the fluctuation of the silver bowl array on the silicon cone is reduced, the appearance advantage of the 3D bionic silicon cone substrate is reduced, and the absorption of light is reduced, so that the Raman intensity is influenced.
In order to verify that the raman enhancement performance of the 3D silver bowl substrate under the optimal condition is better than that of the 2D silver bowl substrate, fig. 5 shows a comparison graph of raman spectra corresponding to the two substrates, and the raman intensity of the 3D silver bowl substrate is obviously higher than that of the 2D silver bowl substrate. Under the same reaction condition, the surface area of the 3D silver bowl substrate supported by the ordered silicon cones is much larger than that of a planar 2D silver bowl, and compared with the planar surface, due to the existence of periodic holes, the surface area of the array is increased, and the solid carrying capacity of rhodamine 6G can be effectively improved; and the fluctuant appearance of the silicon cone is more helpful to strengthen the local surface plasma resonance.
To verify the uniformity of the substrate, fig. 6 shows the raman spectra measured at 10 random points on the same 3D silver bowl substrate under the optimal conditions. The characteristic peak of rhodamine 6G can be obtained from Raman spectra of 10 points, the difference is small, each point has high SERS activity, and the selection is 1368cm -1 The relative standard deviation value of the characteristic peak of (1) is 4.3746% by statistical calculation. The substrate had good uniformity as calculated. Fig. 7 shows raman spectra of different concentrations of rhodamine 6G on a 3D silver bowl substrate. As can be seen from the figure, the lowest detection concentration can reach 10 -13 M, shows that the substrate has very high sensitivity and realizes single molecule detection.
Example 7: silver nanometer bowl modified silicon cone composite substrate for mixture Raman detection
A 3D silver bowl array under optimal conditions was used to detect more complex mixture solutions consisting of crystal violet, malachite green, methylene blue and rhodamine 6G. As shown in fig. 8, the raman of their mixture was collected, and their own spectra were also collected for comparison. Crystal violet, malachite green, methylene blue and rhodamine 6G in the mixture. The characteristic peaks of all molecules are easily identified. The results show that the substrates prepared by the invention have potential in the detection of complex mixture solutions.
Example 8: construction of gold nanometer bowl modified silicon cone composite substrate
1. Assembly process of 300nm Polystyrene (PS) ball monolayer film
Firstly, dripping a small amount of lauryl sodium sulfate into a culture dish filled with deionized water to reduce the surface tension; then, the PS spheres with the size of 300nm are dripped on the liquid level in the culture dish, and the hexagonal close-packed PS colloidal sphere single-layer film is formed by self-assembly by utilizing the capillary force generated by the meniscus between the PS spheres at the gas-liquid interface.
2. Assembling process of continuous gold nanometer bowl on surface of regular pyramid silicon cone array
First, a 5mM chloroauric acid solution was prepared, 100mL was added to a three-necked flask, and stirred for 15min, followed by 3mL of a sodium citrate solution. Meanwhile, the monolayer film of PS colloidal spheres with the diameter of 300nm in the previous step is transferred into the mixed solution and reacts for 15min under the heating condition of 95 ℃, and the spheres with partial metal Au films are successfully obtained. And finally, fishing the small balls with the metal Au films attached to the lower surfaces of the regular pyramid silicon cones obtained in the embodiment 1, and removing the PS small balls by using ethanol to obtain a gold nanometer bowl silicon cone array, namely a 3D gold bowl substrate.
Example 9: construction of silver/zinc ferrite hollow nano needle modified silicon cone composite substrate
Composite substrate modified by hollow nano needle-shaped material
1. Assembly process of 800nm Polystyrene (PS) sphere monolayer film
First, a small amount of sodium lauryl sulfate was added dropwise to a petri dish containing deionized water to reduce the surface tension. Then, 800nm PS spheres are dripped on the liquid level in a culture dish, and a hexagonal close-packed PS colloidal sphere single-layer film is formed by self-assembly by utilizing the capillary force generated by the meniscus between the PS spheres at the gas-liquid interface. Finally, it is transferred to the surface of the silicon wafer.
2. Hydrogen bond acting force forming process between PS ball and silicon chip substrate
Firstly, carrying out ultraviolet ozone treatment on the PS monolayer spheres which are self-assembled and hexagonal and closely packed on the surface of the silicon wafer. And then, washing the surface of the sample by deionized water, so that abundant hydroxyl groups are generated on the surface of the PS sphere and the surface of the silicon wafer, and a strong hydrogen bond acting force is formed at a contact position.
3. Wet etching process
Because the PS balls and the silicon wafer form a strong hydrogen bond acting force, the PS balls stably act on the surface of the silicon wafer in a KOH solution, the silicon wafer is subjected to etching reaction by taking the PS balls as a template at 75 ℃, the limitation that the colloidal ball template cannot induce ordered etching of monocrystalline silicon in alkali liquor is overcome, after 440s reaction, the silicon wafer is etched to form a silicon cone, and the PS balls at the top of the silicon cone can fall off, so that the pyramid silicon cone array in regular arrangement is obtained.
4. Construction process of Ag particle modified zinc ferrite hollow nanoneedle silicon cone array
Firstly, orderly placing a regular silicon cone array in a zinc acetate solution for hydrothermal reaction for 10 hours at 70 ℃ and then in FeCl 3 Reacting in the solution for 1h at 90 ℃ and reacting in ammonia water for 5min at normal temperature to form the zinc ferrite hollow nano needle. And then placing the zinc ferrite nanotube silicon cone array in a mixed solution of sodium citrate and silver nitrate to react for 60min to obtain the Ag particle modified zinc ferrite hollow nanoneedle silicon cone array.
Example 10: construction of ZIF-8 modified Ag/ZnO/silicon cone composite substrate
1. Assembly process of 1500nm Polystyrene (PS) sphere monolayer film
First, a small amount of sodium lauryl sulfate was added dropwise to a petri dish containing deionized water to reduce the surface tension. Then, 1500nm PS spheres are dripped on the liquid level in a culture dish, and a hexagonal close-packed PS colloidal sphere single-layer film is formed by self-assembly by utilizing the capillary force generated by the meniscus between the PS spheres at the gas-liquid interface. Finally, it is transferred to the surface of the silicon wafer.
2. Hydrogen bond acting force forming process between PS ball and silicon chip substrate
Firstly, carrying out ultraviolet ozone treatment on the PS monolayer spheres which are self-assembled and hexagonal and closely packed on the surface of the silicon wafer. And then, washing the surface of the sample by deionized water, so that abundant hydroxyl groups are generated on the surface of the PS sphere and the surface of the silicon wafer, and a strong hydrogen bond acting force is formed at a contact position.
3. Wet etching process
Because the PS balls and the silicon wafer form a strong hydrogen bond acting force, the PS balls stably act on the surface of the silicon wafer in a KOH solution, the silicon wafer is subjected to etching reaction by taking the PS balls as a template at 75 ℃, the limitation that the colloidal ball template cannot induce the ordered etching of monocrystalline silicon in alkali liquor is overcome, after the reaction for 600s, the silicon wafer is etched to form a silicon cone, the PS balls at the top of the silicon cone can fall off, and the pyramid silicon cone array which is regularly arranged is obtained.
4. Construction process of ZIF-8 modified Ag/ZnO/silicon cone composite substrate
Firstly, orderly placing a regular silicon cone array in a zinc acetate solution for hydrothermal reaction for 10 hours at 70 ℃, reacting in a mixed solution of sodium citrate and silver nitrate for 60min, and carrying out DMF/H reaction 2 And reacting in the solution of O2-methylimidazole for 6 hours to obtain the ZIF-8 modified Ag/ZnO/silicon cone array composite substrate.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (4)
1. The composite substrate modified by the nanometer bowl-shaped material is characterized in that the nanometer bowl-shaped material is assembled on the surface of a regular cone, the height of the regular cone is 0.1-100 mu m, the height of the nanometer bowl is 0.01-10 mu m, and the diameter of the bowl opening is 0.01-10 mu m;
the regular cone is prepared by the following steps:
(1) Assembling a single-layer ball: self-assembling the colloid balls at a gas-liquid interface to obtain single-layer balls which are closely arranged;
(2) Hydrogen bond acting force is formed between the monolayer ball and the silicon wafer substrate: transferring the monolayer balls obtained in the step (1) to the surface of a silicon wafer, and adopting a material containing O 2 Or containing O 2 The colloidal globule and the silicon chip are treated by the reactive ion gas or ultraviolet ozone, and then the colloidal globule and the silicon chip are washed by water, and hydrogen bond acting force is formed at the contact part of the colloidal globule and the silicon chip;
(3) Wet etching: placing the colloidal spheres and the silicon wafers processed in the step (2) in an alkaline solution for etching for 1-50 min to obtain a regular pyramid;
and (4) copying the regular pyramid prepared in the step (3), or coating the surface of the regular pyramid, or imprinting the regular pyramid to prepare the regular pyramid.
2. The nanocowl material modified composite substrate according to claim 1, wherein the nanocowl material is one or both of a semiconductor and a metal.
3. The composite substrate according to claim 1, wherein in step (1), the material of the colloidal beads is one of silica, polystyrene, polymethyl methacrylate, polyacrylic acid, polylactic acid, chitosan, gelatin, albumin, starch, or derivatives thereof.
4. The composite substrate of claim 1, wherein in step (3), the alkaline solution is an inorganic base, an organic base, or a mixture thereof; the etching temperature is 20-99 DEG o C。
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