CN114252952A - Double-layer chiral micro-nano structure and preparation method thereof - Google Patents
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- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3058—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state comprising electrically conductive elements, e.g. wire grids, conductive particles
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Abstract
The invention relates to the field of chiral micro-nano structure preparation, in particular to a double-layer chiral micro-nano structure and a preparation method thereof. In the invention, the double-layer chiral micro-nano structure can be prepared only by performing electron beam etching once and evaporating the noble metal material once, so that the material and time are saved, and the preparation process steps are simplified. In addition, dynamic regulation and control of circular dichroism can be realized, secondary evaporation can be performed on the basis of the structure, regulation and control of the thickness of the structural film and the thickness of the nanorod are realized, the application is flexible and convenient, and the method has a good application prospect in the field of chiral micro-nano structure preparation.
Description
Technical Field
The invention relates to the field of chiral micro-nano structure preparation, in particular to a double-layer chiral micro-nano structure and a preparation method thereof.
Background
The artificial chiral surface plasmon micro-nano structure has stronger interaction with light, and has important application in the fields of analytical chemistry, biosensing, circular polarization devices and the like.
At present, the technologies for preparing the artificial chiral surface plasmon micro-nano structure mainly comprise an electron beam etching method, a laser direct writing method and a molecular self-assembly method. The electron beam etching method can be used for preparing the plane artificial chiral surface plasmon micro-nano structure with high precision and size. The laser direct writing method can be used for preparing a micrometer-level three-dimensional artificial chiral surface plasmon micro-nano structure, such as a spiral or a conical metal spiral. The molecule self-assembly method links molecules and metal nanostructures through chemical bonds to form a chiral surface plasmon micro-nano structure, for example, researchers use a DNA double helix as a template to assemble a plurality of gold nanospheres into an artificial chiral surface plasmon micro-nano structure arranged in a double helix.
Compared with a single-layer chiral micro-nano structure, the double-layer chiral micro-nano structure has stronger circular dichroism. For example, the circular dichroism of a double-layer greek cross nanostructure is much greater than that of a single-layer greek cross nanostructure. The double-layer chiral micro-nano structure is generally concerned by researchers.
In the preparation of the double-layer chiral micro-nano structure, a molecular self-assembly method cannot be completed, and a laser direct writing method cannot prepare a nano-sized structure characteristic, because the laser wavelength of the laser direct writing method determines the set size of the artificial chiral surface plasmon micro-nano structure, but the laser wavelength is limited by optical diffraction, so that the preparation of the nano-level artificial chiral surface plasmon structure is difficult. In the traditional electron beam etching method, two times of electron beam etching are needed, and alignment is needed, so that the preparation difficulty is high, the required time is long, and the cost is high. Therefore, exploring a double-layer structure with a strong signal and a preparation method thereof are important research contents in the field.
Disclosure of Invention
In order to solve the problems, the invention provides a double-layer chiral micro-nano structure and a preparation method thereof.
On one hand, the invention provides a double-layer chiral micro-nano structure which comprises a substrate, a second noble metal layer, a transparent medium layer and a first noble metal layer, wherein the transparent medium layer is arranged on the substrate, the first noble metal layer is arranged on the transparent medium layer, L-shaped through holes are formed in the first noble metal layer and the transparent medium layer and are periodically arranged, each L-shaped hole comprises a first arm with a hole and a second arm with a hole, the second noble metal layer comprises nanorods which are periodically arranged, and the nanorods are arranged in the second arms with holes on the substrate.
Further, the material of the substrate is conductive glass.
Furthermore, the L-shaped hole is in a right-angle L shape.
Further, the material of the first noble metal layer and the second noble metal layer is gold or silver.
Furthermore, the thickness of the nano-rod is smaller than that of the transparent medium layer.
Furthermore, the material of the transparent medium layer is PMMA.
Furthermore, the period of the L-shaped holes is a rectangular period.
Further, the first arm of the aperture and the second arm of the aperture are oriented parallel to the sides of the rectangular period.
On the other hand, the invention also provides a preparation method of the double-layer chiral micro-nano structure, which comprises the following steps:
step 6, coating a film: before coating, the substrate is attached to a sample disk in an electron beam evaporation coating instrument and then vacuumized, and when the pressure in the cavity reaches 4 x 10-6Coating can be started by the torr; the deposition direction is 89.3 degrees and phi is 0 degree or 90 degrees, wherein theta represents a polarization angle and refers to an included angle between the normal direction of the sample table and the noble metal evaporation beam current; phi represents an azimuth angle and refers to an included angle between the projection of the noble metal evaporation beam on the sample table and a horizontal coordinate axis.
The invention has the beneficial effects that: the invention provides a double-layer chiral micro-nano structure and a preparation method thereof, wherein the upper layer is a first noble metal layer provided with L-shaped holes, the lower layer is a second noble metal layer provided with nano rods, and different couplings are generated between the L-shaped holes and the nano rods when different circularly polarized light is irradiated, so that different resonance intensities and different transmittances are caused, and strong circular dichroism is generated. In the invention, the double-layer chiral micro-nano structure can be prepared only by performing electron beam etching once and evaporating the noble metal material once, so that the material and time are saved, and the preparation process steps are simplified. In addition, dynamic regulation of circular dichroism can be achieved: generally, after the micro-nano structure is prepared, the parameters of the prepared micro-nano structure can not be changed, particularly the parameters of the lower layer, but secondary evaporation can be performed on the basis of the structure of the invention, so that the regulation and control of the thickness of the structural film and the thickness of the nanorod are realized, the application is flexible and convenient, and the method has good application prospect in the field of chiral micro-nano structure preparation.
The present invention will be described in further detail below with reference to the accompanying drawings.
Drawings
Fig. 1 is a schematic diagram of a double-layer chiral micro-nano structure.
Fig. 2 is a schematic structural view of the first noble metal layer.
FIG. 3 is a graph of transmission spectrum and circular dichroism spectrum of a double-layer chiral micro-nano structure.
Fig. 4 is a diagram of electric field and charge distribution at a resonance mode.
FIG. 5 is a schematic diagram of a deposition angle of another double-layer chiral micro-nano structure.
In the figure: 1. a substrate; 2. a second noble metal layer; 3. a transparent dielectric layer; 4. a first noble metal layer; 5. an L-shaped hole; 6. a triangular shaped annular hole; 51. a bore first arm; 52. a second arm of the aperture; 61. a triangular first arm; 62. a triangular second arm; 63. a triangular third arm.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail below by referring to the accompanying drawings and examples.
Example 1
The invention provides a double-layer chiral micro-nano structure, which comprises a substrate, a second noble metal layer, a transparent medium layer and a first noble metal layer as shown in figure 1. The transparent medium layer is arranged on the substrate, the substrate is made of conductive glass, so that the substrate is conductive during electron beam etching, and the phenomenon that an etched sample is irregular due to charge accumulation can be avoided. The transparent medium layer is made of PMMA. The first noble metal layer is arranged on the transparent medium layer, and the material of the first noble metal layer is silver or gold. As shown in fig. 2, the first noble metal layer and the transparent dielectric layer are provided with L-shaped through holes, that is, the L-shaped through holes penetrate through the first noble metal layer and the transparent dielectric layer to reach the surface of the substrate. The L-shaped holes are periodically arranged, and the period of the L-shaped holes is a rectangular period. The L-shaped hole is right-angled and L-shaped and comprises a hole first arm and a hole second arm. The second noble metal layer comprises nanorods which are periodically arranged, and the nanorods are arranged in the second arm with the holes on the substrate. The nano rod is made of gold or silver. The directions of the first arm of the hole and the second arm of the hole are parallel to both sides of the rectangular period, so that when surface plasmon polaritons are formed on the first noble metal layer, the directions of the surface plasmon polaritons are along the directions of the period, thereby forming charge accumulation on both sides of the first arm of the hole and the second arm of the hole, not only enhancing the charge vibration intensity on both sides of the first arm of the hole and the second arm of the hole, but also enhancing the coupling between the first noble metal layer and the nanorod.
In the invention, the upper layer is a first noble metal layer provided with L-shaped holes, the lower layer is a second noble metal layer provided with nano-rods, and different couplings are generated between the L-shaped holes and the nano-rods when different circularly polarized light is irradiated, so that different resonance intensities and different transmittances are generated, and strong circular dichroism is generated. In the invention, the double-layer chiral micro-nano structure can be prepared only by performing electron beam etching once and evaporating the noble metal material once, so that the material and time are saved, and the preparation process steps are simplified. In addition, dynamic regulation of circular dichroism can be achieved: generally, after the micro-nano structure is prepared, the parameters of the prepared micro-nano structure can not be changed, particularly the parameters of the lower layer, but secondary evaporation can be performed on the basis of the structure of the invention, so that the regulation and control of the thickness of the structural film and the thickness of the nanorod are realized, in addition, the change of the thickness of the film and the thickness of the nanorod directly influences the coupling strength between the film and the nanorod, the sensitivity of dynamic regulation and control is very high, the application is flexible and convenient, and the method has good application prospect in the field of chiral micro-nano structure preparation.
Example 2
On the basis of example 1, the thickness of the nanorods is smaller than that of the transparent dielectric layer, so that there is a certain distance between the lower surface of the first noble metal layer and the upper surface of the nanorods, and circular dichroism of transmitted light is generated using coupling between the first noble metal layer and the nanorods. Preferably, the distance between the lower surface of the first noble metal layer and the upper surface of the nanorods is greater than 10 nm and less than 240 nm, so that coupling between the thin film and the nanorods can be achieved.
Example 3
On the basis of the embodiment 2, a double-layer chiral micro-nano structure with specific morphological parameters is designed, and COMSOL finite element software is applied to calculate the transmission spectrum, circular dichroism spectrum and charge distribution at a resonance mode of the double-layer chiral micro-nano structure, so as to illustrate and explain the core principle of the invention.
The material of the first noble metal layer and the second noble metal layer is silver. The transparent medium layer is PMMA. The substrate is made of conductive glass and has a refractive index of 1.45. The thickness of the first noble metal layer was 60 nm. The first arm of the hole has a length of 260 nm and a width of 80 nm. The second arm of the aperture has a length of 320 nm and a width of 80 nm. The period of the L-shaped holes is 600 nanometers and 600 nanometers. The thickness of the transparent dielectric layer is 60 nanometers. The thickness of the nanorods is the same as that of the first noble metal layer. The length and width of the nanorod are the same as those of the second arm of the hole.
FIG. 3 is a transmission spectrum and circular dichroism spectrum of the double-layer chiral micro-nano structure. As can be seen, the transmission spectra under illumination with left-right circularly polarized light at wavelengths of 800 nm and 1380 nm differ, producing a circular dichroic effect. Wherein. The circular dichroism signal at the wavelength of 800 nanometers is obvious and reaches 20 percent. Fig. 4(a) is the electric field distribution of the resonance mode at a wavelength of 800 nm, and it can be seen from the figure that when left-handed circularly polarized light is incident, strong resonance coupling is generated between the double-layer chiral micro-nano structures; when right-handed circularly polarized light is incident, weak resonance coupling is generated between the double-layer chiral micro-nano structures. Mainly, whether the nano-rod is arranged right below the L-shaped hole or not results in different coupling strengths between the two L-shaped holes and the lower layer. Fig. 4(b) shows the electric field distribution of the resonance mode at a wavelength of 800 nm, and it can also be seen from the figure that the electric field intensity in the first arm of the hole is weaker when the left-handed circularly polarized light is incident, and the electric field intensity in the first arm of the hole is stronger when the right-handed circularly polarized light is incident, further proving the different coupling strengths between the two layers. Since the coupling between the nanorods and the first noble metal layer is different when left-handed circularly polarized light is incident and when right-handed circularly polarized light is incident, a strong Circular Dichroism (CD) signal is generated.
Example 4
The invention also provides a preparation method of the double-layer chiral micro-nano structure, which comprises the following steps:
step 6, coating a film: before coating, the substrate is attached to a sample disk in an electron beam evaporation coating instrument and then vacuumized, and when the pressure in the cavity reaches 4 x 10-6Coating can be started by the torr; the deposition direction is theta to 0 DEG and phi to 89.3 DEG, wherein theta represents a polarization angle and refers to an included angle between the normal direction of the sample table and the noble metal evaporation beam; phi represents an azimuth angle and refers to an included angle between the projection of the noble metal evaporation beam on the sample table and a horizontal coordinate axis. Thus, only in the second arm of the hole due to shadowing effectsThe product metal does not product the metal in the first arm of the hole, so that a double-layer chiral structure of the L-shaped hole and the metal rod is formed.
Example 5
Based on example 4, in step 4, the exposure pattern is a triangular ring hole, as shown in FIG. 5. The triangular ring hole is formed by a triangular first arm, a triangular second arm and a triangular third arm in a surrounding mode. In "step 6", the deposition direction is θ equal to 89.3 ° and Φ equal to 0 °. Therefore, nanorods are formed under the triangular first arm, the triangular second arm and the triangular third arm, the three nanorods are not connected with each other, and the distances between every two three nanorods are different due to the difference of angles between three angles of the triangular structure. Because the three nanorods are coupled with each other, a stronger electric field is gathered, and then stronger coupling is generated between the nanorods and the upper metal film, so that the difference of the transmissivity under the excitation of the left and right optical rotations is larger, and the structure prepared in the embodiment can generate strong circular dichroism. In addition, due to the fact that the angles of three angles of the triangle are different, the distances between every two three nanorods are different, the coupling strength between the nanorods is different, different couplings are generated between the nanorods and an upper metal film at different positions, coupling asymmetry is increased, the difference of transmittance under the excitation of left and right optical rotation is larger, and a circular dichroism signal is stronger. Compared with the structure in the embodiment 2, the structure has the characteristics of stronger coupling between double-layer metals and higher coupling asymmetry, so that the generated circular dichroism signal is larger.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the scope of protection of the present application.
Claims (9)
1. The double-layer chiral micro-nano structure is characterized by comprising a substrate, a second noble metal layer, a transparent medium layer and a first noble metal layer, wherein the transparent medium layer is arranged on the substrate, the first noble metal layer is arranged on the transparent medium layer, the first noble metal layer and the transparent medium layer are internally provided with L-shaped through holes, the L-shaped through holes are periodically arranged, each L-shaped through hole comprises a first hole arm and a second hole arm, the second noble metal layer comprises nanorods which are periodically arranged, and the nanorods are arranged on the substrate in the second hole arm.
2. The double-layer chiral micro-nano structure of claim 1, wherein: the substrate is made of conductive glass.
3. The double-layer chiral micro-nano structure of claim 1, wherein: the L-shaped hole is in a right-angle L shape.
4. The double-layer chiral micro-nano structure of claim 1, wherein: the first noble metal layer and the second noble metal layer are made of gold or silver.
5. The double-layer chiral micro-nano structure of claim 1, wherein: the thickness of the nano rod is smaller than that of the transparent medium layer.
6. The double-layer chiral micro-nano structure of claim 1, wherein: the transparent medium layer is made of PMMA.
7. The double-layer chiral micro-nano structure of claim 1, wherein: the period of the L-shaped holes is a rectangular period.
8. The double-layer chiral micro-nano structure of claim 1, wherein: the directions of the first arm of the hole and the second arm of the hole are parallel to two sides of the rectangular period.
9. The method for preparing a double-layer chiral micro-nano structure according to any one of claims 1 to 8, wherein the method comprises the following steps: the preparation method comprises the following steps:
step 1, preparing the substrate: according to actual needs, cutting the conductive glass into small squares with the side length of 1cm by using a glass cutter, and keeping the integrity of the corners of each small square; cleaning the substrate, namely ultrasonically cleaning the substrate by using acetone and alcohol for 15 minutes, ultrasonically cleaning the substrate by using deionized water for 3 minutes, and finally drying the cleaned substrate by using nitrogen for later use;
step 2, whirl coating: turning on a power supply of the spin coater, setting the time to be 60s and the rotating speed to be 4000rpm, measuring the front and back surfaces of the substrate by using a universal meter, and adsorbing the front surface of the substrate upwards on a sample disc of the spin coater; taking out the PMMA (AR-P672.03) from the refrigerator, sucking a drop of PMMA by a suction pipe, dripping the drop of PMMA at the center of the substrate, and opening a switch of a spin coater to spin the glue;
step 3, heating: turning on a heating plate power supply, setting the temperature to 150 ℃, taking out the substrate spun with PMMA from a spin coater, placing the substrate on the heating plate, heating, and mainly drying the PMMA on the substrate, taking out the substrate after 3min, and placing the substrate in a sample box;
step 4, electron beam exposure: spot was set to 3, HV was set to 15KV, and exposure dose was set to 100. mu.C/cm2Adjusting astigmatism, well calibrating, selecting an exposure position, and starting to expose a pre-designed L-shaped hole pattern;
step 5, development and fixation: putting the exposed sample into a developing solution, and staying for 60 s; then, fixing solution is put in, the fixing solution stays for 30s, and then the fixing solution is taken out and placed in a sample box;
step 6, coating a film: before coating, the substrate is attached to a sample disk in an electron beam evaporation coating instrument and then vacuumized, and when the pressure in the cavity reaches 4 x 10-6Coating can be started by the torr; the deposition direction is theta (89.3 degrees) and phi (0 degrees), wherein theta represents a polarization angle and refers to an included angle between the normal direction of the sample table and the noble metal evaporation beam;
the azimuth angle is the included angle between the projection of the noble metal evaporation beam on the sample table and the horizontal coordinate axis.
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