CN111483971B - Biaxial symmetrical porous cavity-shaped array structure and preparation method thereof - Google Patents
Biaxial symmetrical porous cavity-shaped array structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of micro-machining of nano composite materials, and discloses a biaxial symmetrical porous cavity-shaped array structure and a preparation method thereof. The porous cavity-shaped array structure comprises a plurality of gold nano bowls, wherein 6 gold nano bowls are uniformly distributed around each gold nano bowl; the side surface of each gold nano bowl is provided with a plurality of 4 small holes; the small holes are arranged on the adjacent part of each gold nano bowl and the other gold nano bowl, and the 4 small holes on each gold nano bowl are opposite to each other; and the adjacent positions of the two gold nanobowls are respectively provided with small holes or are not provided with small holes, and the porous cavity-shaped array structure is in biaxial symmetry. The porous cavity-shaped array structure expands the range of hot spots, is in biaxial symmetry, and is favorable for application of the nano-structure array.
Description
Technical Field
The invention relates to the technical field of micro-machining of nano composite materials, in particular to a biaxial symmetrical porous cavity-shaped array structure and a preparation method thereof.
Background
The use of periodic nanostructure arrays with specific dimensions and morphology has attracted considerable attention in energy conversion and energy storage during the last decades. Because of their unique optical properties, noble metal nanostructure arrays are widely used in the fields of nanophotonics, optical sensing, nanoreactors, surface Enhanced Raman Scattering (SERS), and the like.
Controlling the morphology of the nanostructures plays an important role in modulating localized surface plasmon resonance. Because of the wide range of applications of symmetric metal nanoparticles, most research has focused on preparing symmetric metal nanoparticles. The damage of symmetry can lead the nano particles to have special optical activity due to the shape of anisotropy. Recently, a number of nano structures with reduced symmetry have been prepared, for example, chinese patent document No. CN201310656174.9 discloses a method for preparing a nano metal ball bowl array structure, which includes the following steps: (1) subjecting the substrate to a hydrophilic treatment; (2) Selecting a nano emulsion solution with uniform diameter and size, and utilizing a spin coating method or a pulling method to self-assemble a single-layer closely arranged nano ball array on the pole piece subjected to hydrophilic treatment in the step (1); (3) Plating a metal film on the nanosphere array obtained in the step (2); (4) Peeling the nano array with the surface plated with the metal film in the step (3) from the substrate by using a material with viscosity, easy solidification and molding or easy operation and low cost; (5) And (3) removing the nanospheres stripped in the step (4) by using a corrosive organic solvent or a reactive ion etching technology, so as to obtain the nano metal ball bowl array structure. The nano bowl structure with reduced symmetry prepared by the invention exhibits many interesting features due to the tunable surface plasmon resonance, for example, it not only has highly tunable optical characteristics, but also its optical activity depends on the angle of incidence and polarization. However, the hot spot of the nano bowl array structure is limited to the gap between the adjacent nano bowls, which can affect the application of the nano metal spherical bowl array structure, such as limiting the sensitivity of SERS detection when the nano metal spherical bowl array structure is used as a SERS substrate; in addition, symmetry of the nanostructure array has an important effect on the optical performance of the nanostructure array, and the nanostructure array prepared by the prior art, including the nano metal spherical bowl array structure, is mostly a six-axis symmetrical (i.e. each nanoparticle in the array has six symmetry axes) structure, but not a two-axis symmetrical (i.e. each nanoparticle in the array has two symmetry axes) structure, which has a limitation on the application of the nanostructure array.
Disclosure of Invention
In order to solve the technical problems, the invention provides a biaxial symmetrical porous cavity-shaped array structure and a preparation method thereof. The biaxial symmetry porous cavity-shaped array structure expands the hot spot range and is biaxial symmetry, thereby being beneficial to the application of the nanostructure array.
The specific technical scheme of the invention is as follows:
a biaxial symmetrical porous cavity-shaped array structure comprises a plurality of gold nano bowls, wherein 6 gold nano bowls are uniformly distributed around each gold nano bowl; 4 small holes are formed in the side face of each gold nano bowl; the small holes are arranged on the adjacent part of each gold nano bowl and the other gold nano bowl, and the 4 small holes on each gold nano bowl are opposite to each other; and two gold nanobowls adjacent to each other are provided with small holes or are not provided with small holes at the adjacent positions.
In the existing nano bowl array structure, hot spots of the plasma resonance effect are only distributed in gaps between adjacent nano bowls; the porous cavity-shaped array structure of the invention ensures that hot spots are distributed in gaps between adjacent nano bowls and around each small hole by arranging small holes on the side surface of each nano bowl, thereby expanding the distribution range of the hot spots, being beneficial to the application of the array structure, for example, when the array structure is applied as a SERS substrate, the sensitivity of SERS detection can be increased.
In addition, the porous cavity-shaped array structure is in biaxial symmetry, and the optical performance of the porous cavity-shaped array structure is different from that of the existing six-axis symmetry nano bowl array structure, so that the porous cavity-shaped array structure has different applications, and the application range of the nano bowl array structure is widened.
Preferably, the inner diameter of each gold nano bowl is 300-400 nm, and the diameter of each small hole is 50-100 nm.
Preferably, the inner diameter of each gold nano bowl is 150-200 nm, and the diameter of each small hole is 25-50 nm.
A preparation method of a biaxial symmetrical porous cavity array structure comprises the following steps:
(1) Preparing a highly ordered monolayer polystyrene microsphere array by a self-assembly method;
(2) Etching the polystyrene microsphere array prepared in the step (1) to reduce the diameter of the polystyrene microsphere;
(3) Vertically sputtering gold on the surface of the polystyrene small ball array subjected to the etching in the step (2) to obtain a spherical coated nano bowl;
(4) Adhering an adhesive tape to the upper surface of the nano bowl prepared in the step (3), so that the polystyrene beads and the nano bowl are transferred to the adhesive tape;
(5) Placing the adhesive tape obtained in the step (4) and polystyrene beads and nano bowls stuck on the adhesive tape into an organic solvent to dissolve the polystyrene beads;
(6) Etching the nano bowl structure stuck on the adhesive tape to enable small holes to appear on the adjacent part of each nano bowl and the other nano bowl, wherein each nano bowl is provided with 6 small holes;
(7) Obliquely sputtering gold on the sample obtained in the step (6) to fill 2 holes opposite to each nano bowl with gold, wherein small holes adjacent to the two nano bowls are filled or not filled;
(8) And (3) etching the sample prepared in the step (7) to obtain a perfect gold nano bowl with 4 small holes and a biaxial symmetrical porous cavity-like array structure formed by orderly arranging the gold nano bowls.
In the step (1), self-assembling to obtain a highly ordered single-layer polystyrene microsphere array, wherein the array has a six-axis symmetrical structure, namely six polystyrene microspheres are arranged around each polystyrene microsphere. In the step (2), the polystyrene pellets are etched to reduce the volume of the polystyrene pellets, so that a space is reserved for sputtering of subsequent metals. In the step (3), gold is covered on the whole outer surface of the upper half polystyrene sphere and part of the outer surface of the lower half polystyrene sphere by vertical sputtering to form spherically-covered nano bowls, and at the moment, the gold film is thinner on the adjacent part of each nano bowl and the other nano bowl due to the masking effect between the adjacent polystyrene spheres; in addition, gold is sputtered into the gap between the two pellets, forming a gold film on the substrate (typically a silicon wafer). In step (4), during the process of adhering the sputtered sample to the surface of the adhesive tape, the gold film on the substrate is left on the substrate, and thus transferred to the adhesive tape are the nano bowl and the polystyrene beads therein. In the step (6), in the etching process, the thin part of the gold film is firstly penetrated, so that six small holes are formed on each nano bowl and are respectively positioned on the adjacent parts of the nano bowl and six nano bowls around the nano bowl. In the step (7), 2 small holes on the side face of each nano bowl in the sputtering direction are filled with gold in the inclined sputtering process, and the other 4 small holes are not filled due to shielding between adjacent nano bowls, so that the whole array structure is changed from six-axis symmetry to two-axis symmetry; at this time, there may be problems that the periphery of the small holes is rough, some small holes are half-filled, and the like, and the defects can be solved by etching in the step (8), so that a perfect gold nano bowl with 4 small holes is obtained.
Preferably, in the step (1), the diameter of the polystyrene beads is 400-600 nm; and/or in the step (2), the diameter of the etched polystyrene beads is 300-400 nm, and the gap between adjacent polystyrene beads is 100-200 nm; and/or in the step (3), the thickness of the sputtered gold is 100-150 nm; and/or in the step (7), the thickness of the sputtered gold is 20-50 nm.
In the step (3), the thickness of sputtered gold is 100-150 nm, namely the thickest part of the formed nano bowl is 100-150 nm; in the step (7), the thickness of sputtered gold is 20-50 nm, namely, the thickness of the thickest part in the small hole filled with gold is 20-50 nm.
Preferably, in the step (2), the etching method is plasma etching, the etching power is 10-40W, and the etching time is 1-2 min; and/or in the step (3), the method for sputtering gold is magnetron sputtering, the sputtering power is 50-70W, and the sputtering time is 10-30 min; and/or in the step (6), the etching method is plasma etching, the etching power is 10-40W, and the etching time is 1-2 min; and/or in the step (7), the method for sputtering gold is magnetron sputtering, the sputtering power is 50-70W, and the sputtering time is 5-15 s; and/or in the step (8), the etching method is plasma etching, the etching power is 5-15W, and the etching time is 0.5-1 min.
Preferably, in the step (1), the diameter of the polystyrene beads is 200-300 nm; and/or in the step (2), the diameter of the etched polystyrene beads is 150-200 nm, and the gap between adjacent polystyrene beads is 50-100 nm; and/or in the step (3), the thickness of the sputtered gold is 50-75 nm; and/or in the step (7), the thickness of the sputtered gold is 10-25 nm.
Preferably, in the step (2), the etching method is plasma etching, the etching power is 10-40W, and the etching time is 0.5-1 min; and/or in the step (3), the method for sputtering gold is magnetron sputtering, the sputtering power is 50-70W, and the sputtering time is 5-15 min; and/or in the step (6), the etching method is plasma etching, the etching power is 10-40W, and the etching time is 0.5-1 min; and/or in the step (7), the method for sputtering gold is magnetron sputtering, the sputtering power is 50-70W, and the sputtering time is 2.5-7.5 s; and/or in the step (8), the etching method is plasma etching, the etching power is 5-15W, and the etching time is 15-30 s.
Preferably, in step (5), the organic solvent is at least one of dichloromethane, chloroform, toluene, and dimethylformamide.
Preferably, in the step (7), the inclination angle of the inclined sputtering is 65 ° to 75 ° relative to the vertical direction.
The inclined sputtering angle of 65-75 degrees can enable 2 small holes on the side face of each nano bowl in the sputtering direction to be filled, and the other 4 small holes cannot be filled due to shielding between adjacent nano bowls.
Compared with the prior art, the invention has the following advantages:
(1) The porous cavity-shaped array structure can expand the distribution of heat points, and is beneficial to the application of the array structure;
(2) The porous cavity-shaped array structure is in biaxial symmetry, so that the application range of the nano bowl array structure is widened;
(3) The preparation method of the biaxial symmetrical porous cavity-shaped array structure is simple in operation, short in time consumption and low in cost.
Drawings
FIG. 1 is a main process flow diagram of the preparation method of the present invention; the left side is a front view, and the right side is a top view;
FIG. 2 is a schematic diagram of the oblique sputtering in step (7) in the production method of the present invention; the left side is a top view, and the right side is a left view;
FIG. 3 is a scanning electron microscope image of the porous cavity array prepared in example 1.
Detailed Description
The invention is further described below with reference to examples.
Examples
As shown in fig. 1 (the left side is a front view, and the right side is a top view), a preparation method of a biaxial symmetrical porous cavity array comprises the following steps:
(1) Highly ordered monolayer polystyrene bead arrays were prepared by a self-assembly method:
mixing polystyrene microspheres with ethanol solution according to the volume ratio of 1:1, dripping a proper amount of solution onto a hydrophilic silicon wafer by using a liquid-transferring gun, and slowly placing the silicon wafer into a container filled with deionized water; polystyrene microspheres on the water surface form a single-layer film in disordered arrangement, and then 2% sodium dodecyl sulfate solution is dripped to drive the surface of the single-layer film to form a single-layer film in highly ordered arrangement; and finally, slowly taking out the monolayer film by using a hydrophilic silicon chip, sucking redundant water by using filter paper, standing and naturally drying in air to form a hexagonal close-packed polystyrene template which is highly orderly arranged on the silicon chip, wherein six polystyrene pellets are arranged around each polystyrene pellet.
(2) Etching the polystyrene microsphere array prepared in the step (1) by using a plasma etching machine to reduce the diameter of the polystyrene microsphere:
the etching gas is a mixed gas of 80% of oxygen and 20% of argon, and the etching power is 10-40W.
(3) And (3) vertically sputtering gold on the surface of the polystyrene small ball array etched in the step (2) by utilizing magnetron sputtering to obtain a spherical coated nano bowl:
and loading a gold target on a magnetic target position in a magnetron sputtering cavity, wherein the distance between the target and a sample substrate is kept at 20cm, the background air pressure is 5.0x10 < -5 > to 1.0x10 < -4 > Pa before starting, and the sputtering power is 50-70W.
(4) And (3) sticking the adhesive tape on the upper surface of the nano bowl prepared in the step (3), so that the polystyrene beads and the nano bowl are transferred onto the adhesive tape from the silicon chip.
(5) And (3) putting the adhesive tape obtained in the step (4) and the polystyrene beads and the nano bowl stuck on the adhesive tape into tetrahydrofuran to dissolve the polystyrene beads.
(6) And (3) etching the nano bowl structure stuck on the adhesive tape by using a plasma etching machine, so that small holes appear at the positions adjacent to the other nano bowl on each nano bowl, and each nano bowl is provided with 6 small holes:
the etching power of the mixed gas of the etching gas of 80% oxygen and 20% argon is 10-40W.
(7) And (3) obliquely sputtering gold on the sample obtained in the step (6) by utilizing magnetron sputtering, so that 2 holes opposite to each nano bowl are filled with gold, and small holes adjacent to two nano bowls are filled or not filled:
loading a gold target on a magnetic target position in a magnetron sputtering cavity, keeping the distance between the target and a sample substrate at 20cm, wherein the background air pressure is 5.0x10 < -5 > to 1.0x10 < -4 > Pa before starting, and the sputtering power is 50-70W;
and performing twice inclined sputtering from two directions successively, wherein the sputtering direction is shown in fig. 2, the left side is a top view, the right side is a left side view, and the inclined angles of the twice inclined sputtering are 65-75 degrees relative to the vertical direction.
(8) Etching the sample prepared in the step (7) to obtain a perfect gold nano bowl with 4 small holes and a biaxial symmetrical porous cavity-like array structure formed by orderly arranging the gold nano bowls:
the etching power of the mixed gas of the etching gas of 80% oxygen and 20% argon is 5-15W.
Through the above process, the two-axis symmetrical porous cavity array structure can be manufactured. The porous cavity-shaped array structure comprises a plurality of gold nano bowls, wherein 6 gold nano bowls are uniformly distributed around each gold nano bowl; 4 small holes are formed in the side face of each gold nano bowl; the small holes are positioned at the adjacent part of each gold nano bowl and the other gold nano bowl, and the 4 small holes on each gold nano bowl are opposite to each other; two gold nanobowls adjacent to each other have small holes or have no small holes in the vicinity.
In the step (1), self-assembling to obtain a highly ordered single-layer polystyrene microsphere array, wherein the array has a six-axis symmetrical structure, namely six polystyrene microspheres are arranged around each polystyrene microsphere. In the step (2), the polystyrene pellets are etched to reduce the volume of the polystyrene pellets, so that a space is reserved for sputtering of subsequent metals. In the step (3), gold is covered on the whole outer surface of the upper half polystyrene sphere and part of the outer surface of the lower half polystyrene sphere by vertical sputtering to form spherically-covered nano bowls, and at the moment, the gold film is thinner on the adjacent part of each nano bowl and the other nano bowl due to the masking effect between the adjacent polystyrene spheres; in addition, gold is sputtered into the gap between the two pellets, forming a gold film on the substrate (typically a silicon wafer). In step (4), during the process of adhering the sputtered sample to the surface of the adhesive tape, the gold film on the substrate is left on the substrate, and thus transferred to the adhesive tape are the nano bowl and the polystyrene beads therein. In the step (6), in the etching process, the thin part of the gold film is firstly penetrated, so that six small holes are formed on each nano bowl and are respectively positioned on the adjacent parts of the nano bowl and six nano bowls around the nano bowl. In the step (7), as shown in fig. 2, 2 small holes on the side surface of each nano bowl in the sputtering direction are filled with gold in the inclined sputtering process, and the other 4 small holes are not filled due to shielding between adjacent nano bowls, so that the whole array structure is changed from six-axis symmetry to two-axis symmetry; at this time, there may be problems that the periphery of the small holes is rough, some small holes are half-filled, and the like, and the defects can be solved by etching in the step (8), so that a perfect gold nano bowl with 4 small holes is obtained.
Example 1
A method of preparing a porous cavity array comprising the steps of:
(1) Highly ordered monolayer polystyrene bead arrays were prepared by a self-assembly method:
mixing polystyrene microspheres with the diameter of 500nm with ethanol solution according to the volume ratio of 1:1, dripping a proper amount of solution onto a hydrophilic silicon wafer by using a liquid-transferring gun, and slowly placing the silicon wafer into a container filled with deionized water; polystyrene microspheres on the water surface form a single-layer film in disordered arrangement, and then 2% sodium dodecyl sulfate solution is dripped to drive the surface of the single-layer film to form a single-layer film in highly ordered arrangement; and finally, slowly taking out the monolayer film by using a hydrophilic silicon chip, sucking redundant water by using filter paper, standing and naturally drying in air to form a hexagonal close-packed polystyrene template which is highly orderly arranged on the silicon chip, wherein six polystyrene pellets are arranged around each polystyrene pellet.
(2) Etching the polystyrene microsphere array prepared in the step (1) by using a plasma etching machine to reduce the diameter of the polystyrene microsphere:
the etching gas is a mixed gas of 80% oxygen and 20% argon, the etching power is 25W, the etching time is 1.5min, and the diameter of the polystyrene beads after etching is 300nm.
(3) And (3) vertically sputtering gold on the surface of the polystyrene small ball array etched in the step (2) by utilizing magnetron sputtering to obtain a spherical coated nano bowl:
and loading a gold target on a magnetic target position in a magnetron sputtering cavity, wherein the distance between the target and a sample substrate is kept at 20cm, the background air pressure is 7.0 multiplied by 10 < -5 > Pa before starting, the sputtering power is 60W, the sputtering time is 20min, and the sputtering thickness is 100nm.
(4) And (3) sticking the adhesive tape on the upper surface of the nano bowl prepared in the step (3), so that the polystyrene beads and the nano bowl are transferred onto the adhesive tape from the silicon chip.
(5) And (3) putting the adhesive tape obtained in the step (4) and the polystyrene beads and the nano bowl stuck on the adhesive tape into tetrahydrofuran to dissolve the polystyrene beads.
(6) And (3) etching the nano bowl structure stuck on the adhesive tape by using a plasma etching machine, so that small holes appear at the positions adjacent to the other nano bowl on each nano bowl, and each nano bowl is provided with 6 small holes:
the etching power of the mixed gas of the etching gas of 80% oxygen and 20% argon is 25W, and the etching time is 1.5min.
(7) And (3) obliquely sputtering gold on the sample obtained in the step (6) by utilizing magnetron sputtering, so that 2 holes opposite to each nano bowl are filled with gold, and small holes adjacent to two nano bowls are filled or not filled:
loading a gold target on a magnetic target position in a magnetron sputtering cavity, keeping the distance between the target and a sample substrate at 20cm, wherein the background air pressure is 7.0 multiplied by 10 < -5 > Pa before starting, the sputtering power is 60W, the sputtering time is 10s, and the sputtering thickness is 40nm;
and performing twice inclined sputtering from two directions successively, wherein the sputtering direction is shown in fig. 2, the left side is a top view, the right side is a left side view, and the inclined angles of the two inclined sputtering are 70 degrees relative to the vertical direction.
(8) Etching the sample prepared in the step (7) to obtain a perfect gold nano bowl with 4 small holes and a biaxial symmetrical porous cavity-like array structure formed by orderly arranging the gold nano bowls:
the etching power of the mixed gas of the etching gas of 80% oxygen and 20% argon is 10W, and the etching time is 45s.
Through the above process, a two-axis symmetrical porous cavity array structure can be obtained, and a scanning electron microscope picture of the array structure is shown in fig. 3. The porous cavity-shaped array structure comprises a plurality of gold nanobowls with the inner diameter of 260nm, and 6 gold nanobowls are uniformly distributed around each gold nanobowl; 4 small holes with the diameter of 100nm are formed in the side face of each gold nano bowl; the small holes are positioned at the adjacent part of each gold nano bowl and the other gold nano bowl, and the 4 small holes on each gold nano bowl are opposite to each other; two gold nanobowls adjacent to each other have small holes or have no small holes in the vicinity.
Example 2
A method of preparing a porous cavity array comprising the steps of:
(1) Highly ordered monolayer polystyrene bead arrays were prepared by a self-assembly method:
mixing polystyrene microspheres with the diameter of 250nm with ethanol solution according to the volume ratio of 1:1, dripping a proper amount of solution onto a hydrophilic silicon wafer by using a liquid-transferring gun, and slowly placing the silicon wafer into a container filled with deionized water; polystyrene microspheres on the water surface form a single-layer film in disordered arrangement, and then 2% sodium dodecyl sulfate solution is dripped to drive the surface of the single-layer film to form a single-layer film in highly ordered arrangement; and finally, slowly taking out the monolayer film by using a hydrophilic silicon chip, sucking redundant water by using filter paper, standing and naturally drying in air to form a hexagonal close-packed polystyrene template which is highly orderly arranged on the silicon chip, wherein six polystyrene pellets are arranged around each polystyrene pellet.
(2) Etching the polystyrene microsphere array prepared in the step (1) by using a plasma etching machine to reduce the diameter of the polystyrene microsphere:
the etching gas is a mixed gas of 80% oxygen and 20% argon, the etching power is 25W, the etching time is 45s, and the diameter of the etched polystyrene beads is 150nm.
(3) And (3) vertically sputtering gold on the surface of the polystyrene small ball array etched in the step (2) by utilizing magnetron sputtering to obtain a spherical coated nano bowl:
and loading a gold target on a magnetic target position in a magnetron sputtering cavity, wherein the distance between the target and a sample substrate is kept at 20cm, the background air pressure is 7.0 multiplied by 10 < -5 > Pa before starting, the sputtering power is 60W, the sputtering time is 10min, and the sputtering thickness is 50nm.
(4) And (3) sticking the adhesive tape on the upper surface of the nano bowl prepared in the step (3), so that the polystyrene beads and the nano bowl are transferred onto the adhesive tape from the silicon chip.
(5) And (3) putting the adhesive tape obtained in the step (4) and the polystyrene beads and the nano bowl stuck on the adhesive tape into tetrahydrofuran to dissolve the polystyrene beads.
(6) And (3) etching the nano bowl structure stuck on the adhesive tape by using a plasma etching machine, so that small holes appear at the positions adjacent to the other nano bowl on each nano bowl, and each nano bowl is provided with 6 small holes:
the etching power of the mixed gas of the etching gas of 80% oxygen and 20% argon is 25W, and the etching time is 45s.
(7) And (3) obliquely sputtering gold on the sample obtained in the step (6) by utilizing magnetron sputtering, so that 2 holes opposite to each nano bowl are filled with gold, and small holes adjacent to two nano bowls are filled or not filled:
loading a gold target on a magnetic target position in a magnetron sputtering cavity, keeping the distance between the target and a sample substrate at 20cm, wherein the background air pressure is 7.0 multiplied by 10 < -5 > Pa before starting, the sputtering power is 60W, the sputtering time is 5s, and the sputtering thickness is 20nm;
and performing twice inclined sputtering from two directions successively, wherein the inclined angles of the two inclined sputtering are 70 degrees relative to the vertical direction.
(8) Etching the sample prepared in the step (7) by using a plasma etching machine to obtain a perfect gold nano bowl with 4 small holes and a two-axis symmetrical porous cavity-like array structure formed by orderly arranging the gold nano bowls:
the etching power of the mixed gas of the etching gas of 80% oxygen and 20% argon is 10W, and the etching time is 20s.
Through the above process, the two-axis symmetrical porous cavity array structure can be manufactured. The porous cavity-shaped array structure comprises a plurality of gold nanobowls with the inner diameter of 130nm, and 6 gold nanobowls are uniformly distributed around each gold nanobowl; 4 small holes with the diameter of 50nm are formed in the side face of each gold nano bowl; the small holes are positioned at the adjacent part of each gold nano bowl and the other gold nano bowl, and the 4 small holes on each gold nano bowl are opposite to each other; two gold nanobowls adjacent to each other have small holes or have no small holes in the vicinity.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (9)
1. The two-axis symmetrical porous cavity-shaped array structure comprises a plurality of gold nano bowls, wherein 6 gold nano bowls are uniformly distributed around each gold nano bowl, and the structure is characterized in that 4 small holes are formed in the side face of each gold nano bowl; the small holes are arranged on the adjacent part of each gold nano bowl and the other gold nano bowl, and the 4 small holes on each gold nano bowl are opposite to each other; two gold nano bowls adjacent to each other are provided with small holes or are not provided with small holes at the adjacent positions; the preparation method of the biaxial symmetrical porous cavity-shaped array structure comprises the following steps:
(1) Preparing a highly ordered monolayer polystyrene microsphere array by a self-assembly method;
(2) Etching the polystyrene microsphere array prepared in the step (1) to reduce the diameter of the polystyrene microsphere;
(3) Vertically sputtering gold on the surface of the polystyrene small ball array subjected to the etching in the step (2) to obtain a spherical coated nano bowl;
(4) Adhering an adhesive tape to the upper surface of the nano bowl prepared in the step (3), so that the polystyrene beads and the nano bowl are transferred to the adhesive tape;
(5) Placing the adhesive tape obtained in the step (4) and polystyrene beads and nano bowls stuck on the adhesive tape into an organic solvent to dissolve the polystyrene beads;
(6) Etching the nano bowl structure stuck on the adhesive tape to enable small holes to appear on the adjacent part of each nano bowl and the other nano bowl, wherein each nano bowl is provided with 6 small holes;
(7) Obliquely sputtering gold on the sample obtained in the step (6) to fill 2 holes opposite to each nano bowl with gold, wherein small holes adjacent to the two nano bowls are filled or not filled;
(8) And (3) etching the sample prepared in the step (7) to obtain a perfect gold nano bowl with 4 small holes and a biaxial symmetrical porous cavity-like array structure formed by orderly arranging the gold nano bowls.
2. The two-axis symmetrical porous cavity array structure of claim 1, wherein the inner diameter of each gold nano bowl is 300-400 nm, and the diameter of each small hole is 50-100 nm.
3. The two-axis symmetrical porous cavity array structure according to claim 1, wherein the inner diameter of each gold nano bowl is 150-200 nm, and the diameter of each small hole is 25-50 nm.
4. A two-axis symmetrical multi-cavity array structure as defined in claim 1, wherein:
in the step (1), the diameter of the polystyrene beads is 400-600 nm; and/or
In the step (2), the diameter of the etched polystyrene beads is 300-400 nm, and the gap between adjacent polystyrene beads is 100-200 nm; and/or
In the step (3), the thickness of sputtered gold is 100-150 nm; and/or
In the step (7), the thickness of the sputtered gold is 20-50 nm.
5. A two-axis symmetrical multi-cavity array structure as defined in claim 4, wherein:
in the step (2), the etching method is plasma etching, the etching power is 10-40W, and the etching time is 1-2 min; and/or
In the step (3), the method of sputtering gold is magnetron sputtering, the sputtering power is 50-70W, and the sputtering time is 10-30 min; and/or
In the step (6), the etching method is plasma etching, the etching power is 10-40W, and the etching time is 1-2 min; and/or
In the step (7), the method for sputtering gold is magnetron sputtering, the sputtering power is 50-70W, and the sputtering time is 5-15 s; and/or
In the step (8), the etching method is plasma etching, the etching power is 5-15W, and the etching time is 0.5-1 min.
6. A two-axis symmetrical multi-cavity array structure as defined in claim 1, wherein:
in the step (1), the diameter of the polystyrene beads is 200-300 nm; and/or
In the step (2), the diameter of the etched polystyrene beads is 150-200 nm, and the gap between adjacent polystyrene beads is 50-100 nm; and/or
In the step (3), the thickness of sputtered gold is 50-75 nm; and/or
In the step (7), the thickness of the sputtered gold is 10-25 nm.
7. A two-axis symmetrical multi-cavity array structure as defined in claim 6, wherein:
in the step (2), the etching method is plasma etching, the etching power is 10-40W, and the etching time is 0.5-1 min; and/or
In the step (3), the method for sputtering gold is magnetron sputtering, the sputtering power is 50-70W, and the sputtering time is 5-15 min; and/or
In the step (6), the etching method is plasma etching, the etching power is 10-40W, and the etching time is 0.5-1 min; and/or
In the step (7), the method of sputtering gold is magnetron sputtering, the sputtering power is 50-70W, and the sputtering time is 2.5-7.5 s; and/or
In the step (8), the etching method is plasma etching, the etching power is 5-15W, and the etching time is 15-30 s.
8. The two-axis symmetrical porous cavity array structure according to claim 1, wherein in the step (5), the organic solvent is at least one of dichloromethane, chloroform, toluene and dimethylformamide.
9. The two-axis symmetrical porous cavity array structure of claim 1, wherein in the step (7), the inclined angle of the inclined sputtering is 65 ° to 75 ° with respect to the vertical direction.
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