CN113203724B - Single-layer close-packed nanoparticle hole array structure and preparation method and application thereof - Google Patents
Single-layer close-packed nanoparticle hole array structure and preparation method and application thereof Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
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Abstract
The invention provides a single-layer close-packed nanoparticle hole array structure, and a preparation method and application thereof, and belongs to the technical field of nanophotonics. The self-assembly method of the single-layer close-packed nano particle hole array structure provided by the invention comprises the following steps: coating the nano particles by adopting hydrophobic molecules, and dispersing the coated nano particles in an organic solvent to obtain nano particle dispersion liquid; and (3) dripping the nanoparticle dispersion liquid on the surface of a water film formed by the high-molecular hydrophilic polymer aqueous solution for self-assembly, and then removing the water film to obtain the single-layer close-packed nanoparticle hole array structure. The self-assembly method provided by the invention is suitable for nano particles with the particle size of 10-500 nm, and the pore size of the single-layer close-packed nano particle pore array structure can be adjusted within the range of 0.1-5 mu m by adjusting the concentration of the modified nano particle dispersion liquid and the high molecular hydrophilic polymer aqueous solution; the self-assembly method has the advantages of good universality, simple operation, large array area and low cost.
Description
Technical Field
The invention relates to the technical field of nano photonics, in particular to a single-layer close-packed nano particle hole array structure, a preparation method and application thereof.
Background
Nanoparticle pore array structures have attracted considerable attention due to their unique optical transmission phenomena coupled with the nanoparticles. The pore size of the nanoparticle pore array structure plays a decisive role in tuning the optical transmission phenomenon and the coupling between the nanoparticles.
At present, the preparation method of the nanoparticle hole array structure mainly comprises a physical etching method (such as electron beam etching and ion beam etching) and a traditional block copolymer self-assembly method. Although physical etching methods can accurately prepare nanoparticle pore array structures, it is difficult to prepare pore array systems composed of closely-spaced nanoparticles. The traditional block copolymer self-assembly method also realizes the preparation of the nano particle hole array structure, but the size of the nano particles suitable for the method is smaller than 10nm, and the pore size of the prepared nano particle hole array structure can only reach the nano level.
Disclosure of Invention
In view of the above, the present invention aims to provide a single-layer close-packed nanoparticle pore array structure, and a preparation method and application thereof, wherein the self-assembly method provided by the present invention can obtain a close-packed nanoparticle pore array structure, the applicable nanoparticle particle diameter is 10-500 nm, the applicable nanoparticle size range is wide, and the aperture of the single-layer close-packed nanoparticle pore array structure is adjustable within the range of 0.1-10 μm.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a self-assembly method of a single-layer close-packed nano particle hole array structure, which comprises the following steps:
coating the nano particles by adopting hydrophobic molecules, and dispersing the coated nano particles in an organic solvent to obtain a coated nano particle dispersion liquid; the granularity of the nano particles is 10-500 nm; the concentration of the modified nanoparticle dispersion liquid is 5-100 mg/mL;
dripping a high molecular hydrophilic polymer aqueous solution on a hydrophobic substrate to form a water film, dripping the modified nanoparticle dispersion liquid on the surface of the water film, and performing self-assembly to obtain a single-layer close-packed nanoparticle pore array structure; the concentration of the high molecular hydrophilic polymer aqueous solution is 0.0001-50 mg/mL; the high molecular hydrophilic polymer comprises one or more of bovine serum albumin, cellulose and sucrose.
Preferably, the shape of the nanoparticle includes a sphere, a cube, a rod, a cone, or an arrow.
Preferably, the hydrophobic molecule comprises one or more of polystyrene, polyvinylpyrrolidone, polytetrafluoroethylene, polydimethylsiloxane, polyvinylidene fluoride, polypropylene, polyethylene, polymethyl methacrylate, polyolefin, polyamide, polyacrylonitrile, polycarbonate, fluorosilicone resin, molten paraffin and organosilicon wax emulsion.
Preferably, the temperature of the coating is room temperature and the time is 12-36 h.
Preferably, the thickness of the water film is 0.1-100 mm.
Preferably, the volume of the modified nanoparticle dispersion liquid dropwise added to the surface of the water film is 0.5 to 10. Mu.L.
Preferably, the organic solvent includes chloroform, toluene or tetrahydrofuran.
Preferably, the self-assembly temperature is room temperature and the self-assembly time is 0.5-2 s.
The invention provides the monolayer close-packed nanoparticle pore array structure obtained by the self-assembly method in the technical scheme, wherein the granularity of nanoparticles of the monolayer close-packed nanoparticle pore array structure is 10-500 nm, and the aperture of the monolayer close-packed nanoparticle pore array structure is 0.1-10 mu m.
The invention also provides application of the single-layer close-packed nano-particle hole array structure in nonlinear effect, surface enhanced Raman scattering, biosensor or biomolecule detection.
The invention provides a self-assembly method of a single-layer close-packed nano particle hole array structure, which comprises the following steps: coating the nano particles by adopting hydrophobic molecules, and dispersing the coated nano particles in an organic solvent to obtain a coated nano particle dispersion liquid; the granularity of the nano particles is 10-500 nm; the concentration of the modified nanoparticle dispersion liquid is 5-100 mg/mL; dripping a high molecular hydrophilic polymer aqueous solution on a hydrophobic substrate to form a water film, dripping the modified nanoparticle dispersion liquid on the surface of the water film, and performing self-assembly to obtain a single-layer close-packed nanoparticle pore array structure; the concentration of the high molecular hydrophilic polymer aqueous solution is 0.0001-50 mg/mL; the high molecular hydrophilic polymer comprises one or more of bovine serum albumin, cellulose and sucrose. The self-assembly method provided by the invention is innovation based on a gas-liquid self-assembly method, is suitable for nano particles with the particle size of 10-500 nm, and can realize the adjustment of the pore size of round holes of a single-layer close-packed nano particle pore array structure within the range of 100 nm-5 mu m by adjusting the concentration of modified nano particle dispersion liquid and high-molecular hydrophilic polymer aqueous solution; the self-assembly method provided by the invention has good universality, can be used for preparing a single-layer close-packed nano particle hole array structure on any hydrophobic substrate, and is suitable for nano particles with different materials, sizes and shapes; in addition, the self-assembly method provided by the invention is simple to operate, large in array area and low in cost.
The invention provides the monolayer close-packed nanoparticle pore array structure obtained by the self-assembly method, wherein the granularity of nanoparticles of the monolayer close-packed nanoparticle pore array structure is 10-500 nm, and the aperture of the monolayer close-packed nanoparticle pore array structure is 0.1-10 mu m. The single-layer close-packed nanoparticle hole array structure provided by the invention can realize the combination of surface plasmon coupling and optical abnormal transmission phenomenon, is hopeful to realize resonance coupling among different local resonance modes, excites excellent optical effect, and has good application prospect in nonlinear effect, surface enhanced Raman scattering, biosensor or biomolecule detection.
Drawings
FIG. 1 is a transmission diagram of a single-layer closely-spaced nanoparticle pore array structure prepared in example 1 under a 10-fold optical microscope;
FIG. 2 is a transmission diagram of a 40-fold optical microscope of the single-layer closely-spaced nanoparticle pore array structure prepared in example 1;
FIG. 3 is an SEM scanning image of a monolayer closely-spaced nanoparticle pore array structure prepared in example 1;
FIG. 4 is a transmission diagram under a 40-fold optical microscope of the structure prepared in comparative example 1;
FIG. 5 is a transmission diagram of the nanoparticle structures prepared in example 1, examples 4 to 5, and comparative examples 2 to 3 under a 40-fold optical microscope, wherein a is comparative example 2, b is example 1, c is example 4, d is example 5,e, and d is comparative example 3.
Detailed Description
The invention provides a self-assembly method of a single-layer close-packed nano particle hole array structure, which comprises the following steps:
coating the nano particles by adopting hydrophobic molecules, and dispersing the coated nano particles in an organic solvent to obtain a coated nano particle dispersion liquid; the granularity of the nano particles is 10-500 nm; the concentration of the modified nanoparticle dispersion liquid is 5-100 mg/mL;
dripping a high molecular hydrophilic polymer aqueous solution on a hydrophobic substrate to form a water film, dripping the modified nanoparticle dispersion liquid on the surface of the water film, and performing self-assembly to obtain a single-layer close-packed nanoparticle pore array structure; the concentration of the high molecular hydrophilic polymer aqueous solution is 0.0001-50 mg/mL; the high molecular hydrophilic polymer comprises one or more of bovine serum albumin, cellulose and sucrose.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
The invention adopts hydrophobic molecules to coat nano particles and then disperse the nano particles in an organic solvent to obtain a coated nano particle dispersion liquid; the granularity of the nano particles is 10-500 nm; the concentration of the modified nanoparticle dispersion liquid is 5-100 mg/mL.
In the present invention, the particle size of the nanoparticle is 10 to 500nm, preferably 100 to 400nm, more preferably 200 to 300nm. In the present invention, the shape of the nanoparticles in the nanoparticle aqueous dispersion preferably includes a sphere, a cube, a rod, a cone, or an arrow; the nanoparticles are preferably metal nanoparticles, more preferably noble metal nanoparticles, most preferably gold nanoparticles. In the present invention, the hydrophobic molecule preferably includes one or more of polystyrene, polyvinylpyrrolidone, polytetrafluoroethylene, polydimethylsiloxane, polyvinylidene fluoride, polypropylene, polyethylene, polymethyl methacrylate, polyolefin, polyamide, polyacrylonitrile, polycarbonate, fluorosilicone resin, molten paraffin and silicone wax emulsion. In the present invention, the hydrophobic molecule solution is preferably obtained by dissolving a hydrophobic molecule in an organic solvent; the number average molecular weight of the hydrophobic molecule is preferably 1000 to 50000, more preferably 10000 to 40000, and most preferably 20000 to 30000. In the present invention, the mass ratio of the hydrophobic molecule to the nanoparticle is preferably 1 (1-3), more preferably 1 (1.5-2.5), and most preferably 1:2.
in the invention, the coating of the nano-particles by the hydrophobic molecules is preferably carried out by dissolving the hydrophobic molecules in an amphiphilic solvent to obtain a hydrophobic molecule solution; dispersing the nano particles in water to obtain nano particle aqueous dispersion; and mixing the hydrophobic molecule solution and the nanoparticle aqueous dispersion solution, and coating to obtain the modified nanoparticle. In the present invention, the amphiphilic solvent preferably includes chloroform, ethanol, toluene or tetrahydrofuran. In the present invention, the concentration of the hydrophobic molecular solution is preferably 0.1 to 5mg/mL, more preferably 0.5 to 4mg/mL, and most preferably 1 to 3mg/mL. In the present invention, the concentration of the nanoparticle aqueous dispersion is preferably 6 to 90mg/mL, more preferably 70 to 80mg/mL, and most preferably 75 to 80mg/mL. In the present invention, the mixing method is preferably stirring mixing, and the speed of the stirring mixing is not particularly limited, and the raw materials can be uniformly mixed; the mixing time is preferably 5 to 30 minutes, more preferably 10 to 25 minutes, and most preferably 15 to 20 minutes. In the present invention, the coating is preferably performed under a standing condition, and the time of the coating is preferably 12 to 48 hours, more preferably 18 to 24 hours, and most preferably 24 hours; the temperature of the coating is preferably room temperature; the coating is preferably carried out under a protective atmosphere; the protective atmosphere is not particularly limited, and protective atmospheres well known to those skilled in the art, such as nitrogen, helium or argon, are used. In the coating process, the hydrophobic molecules are combined with the nanoparticles, so that the hydrophobic molecules are coated on the surfaces of the nanoparticles to form the nanoparticles capped by the hydrophobic molecules.
After the coating, the present invention preferably further comprises washing the coated product to obtain modified nanoparticles. In the present invention, the solvent used for the washing is preferably chloroform, toluene or tetrahydrofuran; the number of times of washing is preferably 2 to 3 times; the washing mode is preferably centrifugal washing, and the centrifugal rate of the centrifugal washing is preferably 3000-5000 r/min, more preferably 4000r/min.
After the coating, the present invention preferably further comprises washing the coated product to obtain modified nanoparticles. In the present invention, the solvent used for the washing is preferably chloroform, toluene or tetrahydrofuran; the number of times of washing is preferably 2 to 3 times; the washing mode is preferably centrifugal washing, and the centrifugal rate of the centrifugal washing is preferably 3000-5000 r/min, more preferably 4000r/min.
In the present invention, the organic solvent preferably includes chloroform, toluene or tetrahydrofuran. In the present invention, the concentration of the modified nanoparticle dispersion is 5 to 100mg/mL, preferably 10 to 50mg/mL, more preferably 15 to 30mg/mL. In the invention, the concentration of the modified nanoparticle dispersion liquid is too large or too small to form a pore array, and the concentration of the modified nanoparticle dispersion liquid is controlled within the range, so that a single-layer close-packed nanoparticle pore array structure with the pore diameter of 0.1-10 mu m can be obtained.
After modified nanoparticle dispersion liquid is obtained, a macromolecular hydrophilic polymer aqueous solution is dripped on a hydrophobic substrate to form a water film, the modified nanoparticle dispersion liquid is dripped on the surface of the water film, and self-assembly is carried out to obtain a single-layer close-packed nanoparticle pore array structure; the concentration of the high molecular hydrophilic polymer aqueous solution is 0.0001-50 mg/mL.
In the present invention, the concentration of the aqueous solution of the high molecular weight hydrophilic polymer is 0.0001 to 10wt%, more preferably 0.1 to 5wt%, most preferably 0.5 to 2wt%.
The present invention is not particularly limited to the hydrophobic substrate, and may be any hydrophobic substrate known to those skilled in the art, such as a glass sheet, a silicon wafer, or Polydimethylsiloxane (PDMS); in a specific embodiment of the invention, the hydrophobic substrate is preferably a soda lime glass sheet; the hydrophobic substrate is preferably pretreated with trimethylsilane before use, and the pretreatment time is preferably 1-2 min. The hydrophobic substrate pretreated by the trimethylsilane is better in hydrophobicity, and the water film formed on the hydrophobic substrate by the high-molecular hydrophilic polymer aqueous solution can be ensured.
In the present invention, the thickness of the water film is preferably 0.1 to 100mm, more preferably 1 to 80mm, and most preferably 40 to 50mm; the radius of the water film is preferably 1 to 5cm, more preferably 2 to 4cm, most preferably 2 to 3cm.
In the present invention, the self-assembly temperature is preferably room temperature, and the time is preferably 0.5 to 2s, more preferably 1 to 1.5s. In the self-assembly process, the modified nano particles are used as basic structural units, spontaneous and automatic diffusion and assembly occur on the surface of the bovine serum albumin water film, and a single-layer close-packed nano particle hole array structure is formed on the surface of the water film. According to the invention, self-assembly is carried out on the surface of the water film, so that uniform self-diffusion of dispersed droplets of modified nanoparticles can be prevented, and a single-layer close-packed nanoparticle hole array structure cannot be obtained at an aqueous phase interface formed by a container. The invention can realize that the circular aperture of the single-layer close-packed nano particle hole array structure is adjustable within the range of 0.1-10 mu m by adjusting the concentration of the modified nano particle dispersion liquid and the high molecular hydrophilic polymer aqueous solution. In the present invention, the pore diameter is preferably 1 to 8. Mu.m, more preferably 3 to 6. Mu.m, most preferably 4 to 5. Mu.m.
After the self-assembly, the invention preferably further comprises the step of standing and evaporating the self-assembly system to form a single-layer close-packed nano particle hole array structure on the surface of the hydrophobic substrate. In the present invention, the temperature of the stationary evaporation is preferably room temperature, and the time of the stationary evaporation is not particularly limited, and the water may be evaporated.
The invention provides the monolayer close-packed nanoparticle pore array structure obtained by the self-assembly method, wherein the granularity of nanoparticles of the monolayer close-packed nanoparticle pore array structure is 10-500 nm, and the aperture of the monolayer close-packed nanoparticle pore array structure is 0.1-10 mu m. In the present invention, the pore diameter of the monolayer closely-spaced nanoparticle pore array structure is preferably 1 to 8 μm, more preferably 3 to 6 μm, and most preferably 4 to 5 μm. In the present invention, the single layer close packed sodiumThe gaps between the nano particles in the nano particle hole array structure are 1-10 nm, more preferably 3-8 nm, and most preferably 4-5 nm. In the present invention, the thickness of the monolayer closely-spaced nanoparticle pore array structure is preferably 10 to 500nm, more preferably 50 to 400nm, and most preferably 100 to 200nm. In the invention, the array structure size of the single-layer close-packed nano particle hole array structure is preferably 1-4 cm 2 More preferably 2 to 3cm 2 。
The invention also provides application of the single-layer close-packed nano-particle hole array structure in nonlinear effect, surface enhanced Raman scattering, biosensor or biomolecule detection. In the invention, the single-layer close-packed nanoparticle hole array structure can realize the combination of surface plasmon coupling and optical abnormal transmission phenomenon, is hopeful to realize resonance coupling among different local resonance modes, excites excellent optical effect, and has good application prospect in nonlinear effect, surface enhanced Raman scattering, biosensor or biomolecule detection.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Gold nanosphere particles with the diameter of 60nm are placed in water to obtain gold nanosphere particle dispersion with the concentration of 0.5 mg/mL; under the nitrogen environment, adding 4mg of thiolated polystyrene into 4mL of tetrahydrofuran under the stirring condition to obtain thiolated polystyrene solution; under the conditions of room temperature and stirring speed of 500r/min, 100 mu L of gold nanosphere particles are dispersed and dripped into a thiolated polystyrene solution, the solution is stood for 12h, and then the obtained solid product is centrifugally washed for 2 times at the speed of 4000r/min by using chloroform to obtain modified nano particles;
(2) Dispersing the modified nanoparticles in chloroform to obtain a modified nanoparticle dispersion liquid with the concentration of 35 mg/mL;
(3) Pretreating a soda-lime glass sheet by trimethyl silane for 2min to obtain a hydrophobic substrate; preparing a 1wt% concentration bovine serum albumin aqueous solution, dripping 750 mu L of bovine serum albumin aqueous solution on the hydrophobic substrate to form a water film with the radius of 1cm, dripping 2 mu L of modified nanoparticle solution in the middle of the water film by using a micropipette at the temperature of 30 ℃, self-assembling for 1s, standing and evaporating to obtain a single-layer close-packed nanoparticle pore array structure (gold nanosphere particles are spaced at 2nm, the diameter of round holes in the array structure of the single-layer close-packed nanoparticle pore array structure is 1 mu m, the thickness is 60nm, and the size is 1 cm) 2 )。
Comparative example 1
A monolayer closely packed nanoparticle pore array structure was prepared according to the method of example 1, differing from example 1 in that no bovine serum albumin was added.
The transmission diagram of the single-layer close-packed nanoparticle pore array structure prepared in example 1 under a 10-fold optical microscope is shown in fig. 1, the transmission diagram under a 40-fold optical microscope is shown in fig. 2, the scanning electron microscope is shown in fig. 3, and the transmission diagram of the pore array structure prepared in comparative example 1 under a 40-fold optical microscope is shown in fig. 4. The addition of bovine serum albumin from FIGS. 1-4 is a key factor in the formation of the pore structure.
Comparative example 2
A monolayer closely-spaced nanoparticle pore array structure was prepared as in example 1, differing from example 1 in that the concentration of the modified nanoparticle dispersion was 60mg/ml.
Comparative example 3
A monolayer closely-spaced nanoparticle pore array structure was prepared as in example 1, differing from example 1 in that the concentration of the modified nanoparticle dispersion was 10mg/ml.
Example 2
A single-layer close-packed nanoparticle pore array structure was prepared according to the method of example 1, differing from example 1 in that gold nanosphere particles were replaced with gold nanorod particles having a length of 120nm and a diameter of 30 nm.
Example 3
A monolayer closely packed nanoparticle pore array structure was prepared according to the method of example 1, differing from example 1 in that gold nanosphere particles were replaced with gold nanoarrow particles prepared in example 1, with gold arrow concentration of 20mg/mL.
Example 4
A monolayer closely-spaced nanoparticle pore array structure was prepared as in example 1, differing from example 1 in that the concentration of the modified nanoparticle dispersion in step (2) was 30mg/mL.
Example 5
A monolayer closely-spaced nanoparticle pore array structure was prepared as in example 1, differing from example 1 in that the concentration of the modified nanoparticle dispersion in step (2) was 20mg/mL.
The transmission diagrams of the single-layer closely-spaced nanoparticle pore array structures prepared in examples 1, 4-5 and comparative examples 2-3 under a 40-fold optical microscope are shown in fig. 5, where a is comparative example 2, b is example 1, c is example 4, d is example 5,e and comparative example 3. As can be seen from fig. 5, the concentration of the suitable modified nanoparticle dispersion is an important factor in the formation of a monolayer closely packed nanoparticle pore array structure.
From examples 1, 4 and 5, the size of the pore size can be adjusted by controlling the nanoparticle concentration.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A self-assembly method of a single-layer close-packed nanoparticle hole array structure comprises the following steps:
coating the nano particles by adopting hydrophobic molecules, and dispersing the coated nano particles in an organic solvent to obtain modified nano particle dispersion liquid; the granularity of the nano particles is 10-500 nm; the concentration of the modified nanoparticle dispersion liquid is 15-50 mg/mL; the hydrophobic molecule is thiolated polystyrene;
dripping a high molecular hydrophilic polymer aqueous solution on a hydrophobic substrate to form a water film, dripping the modified nanoparticle dispersion liquid on the surface of the water film, and performing self-assembly to obtain a single-layer close-packed nanoparticle pore array structure; the concentration of the high molecular hydrophilic polymer aqueous solution is 0.0001-50 mg/mL; the high molecular hydrophilic polymer is bovine serum albumin.
2. The self-assembly method of claim 1, wherein the nanoparticle shape comprises a sphere, cube, rod, cone, or arrow.
3. The self-assembly method according to any one of claims 1 to 2, wherein the temperature of the coating is room temperature for 12 to 36 hours.
4. The self-assembly method according to claim 1, wherein the thickness of the water film is 0.1-100 mm.
5. The self-assembly method according to claim 1 or 4, wherein the volume of the modified nanoparticle dispersion liquid added dropwise to the surface of the water film is 0.5 to 10 μl.
6. The self-assembly method according to claim 1, wherein the organic solvent comprises chloroform, toluene or tetrahydrofuran.
7. The self-assembly method according to claim 1, wherein the self-assembly temperature is room temperature for 0.5 to 2 seconds.
8. The monolayer closely-spaced nanoparticle pore array structure obtained by the self-assembly method according to any one of claims 1 to 7, wherein the particle size of the nanoparticles of the monolayer closely-spaced nanoparticle pore array structure is 10 to 500nm, and the pore diameter of the monolayer closely-spaced nanoparticle pore array structure is 0.1 to 10 μm.
9. Use of the monolayer closely packed nanoparticle pore array structure of claim 8 in nonlinear effects, surface enhanced raman scattering, biosensors or biomolecular detection.
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