1. The visible light photochromic lens based on surface plasmon resonance is characterized by comprising a lens substrate, wherein a visible light full-bandwidth antireflection film layer, a two-dimensional nano U-shaped metal silver film periodic array film layer and a silicon dioxide priming layer are sequentially arranged on the surface of the lens substrate from top to bottom.

2. The visible light photochromic lens based on surface plasmon resonance as claimed in claim 1, wherein the thickness of the two-dimensional nano U-shaped metal silver thin film periodic array film layer is 10 nm-30 nm.

3. The visible light photochromic lens based on surface plasmon resonance of claim 1 wherein the thickness of the silica primer layer is 2nm to 10 nm.

4. A preparation method of a visible light photochromic lens based on surface plasmon resonance is characterized by comprising the following steps:

step S1: carrying out ion-assisted bombardment electron beam evaporation deposition on the lens substrate to deposit a silicon dioxide priming layer;

step S2: each lens substrate is clamped with a mask plate, and an electron beam evaporation deposition is carried out on the silicon dioxide base layer to deposit a two-dimensional nano U-shaped metal silver film array film layer structure;

step S3: and finally, taking off the mask plate, and then carrying out ion beam assisted deposition and electron beam evaporation on the visible light full-bandwidth antireflection film layer.

5. The method for preparing the visible light photochromic lens based on the surface plasmon resonance as claimed in claim 4, wherein the optical central area of the mask plate adopts a hollow structure of U-shaped nanometer open area with the sub-wavelength scale of laser interference direct writing.

6. The method for preparing the visible light photochromic lens based on the surface plasmon resonance as claimed in claim 5, wherein the open-area hollow D of the mask plate is in the range of 50nm to 80nm, the L is in the range of 50nm to 80nm, the H is in the range of 1 μm to 3 μm, and the unit period is in the range of 300nm to 480 nm.

7. The method for preparing a visible light photochromic lens based on surface plasmon resonance according to claim 4, wherein the vapor deposition rate of the two-dimensional nanometer U-shaped metal silver film periodic array film layer in step S2 is 0.1 nm/S-1.0 nm/S.

8. The method for preparing a visible light photochromic lens based on surface plasmon resonance according to claim 4, wherein the visible light full-bandwidth antireflection film layer in step S3 comprises a trititanium pentoxide film layer and a silica film layer, the deposition rate of the silica film layer is 0.2 nm/S-3.0 nm/S, and the deposition rate of the trititanium pentoxide film layer is 0.3 nm/S-5.0 nm/S.

Background

Surface Plasmons (SPs) are near-field waves excited by incident light at a metal surface, and have the properties of enhanced field strength, highly localized optical field distribution, and being transmissible along the metal surface. Among many metal materials, the metal silver-based material has a small absorption coefficient, has the minimum absorption loss in a visible light band, has a negative dielectric constant in a real part of a visible light region, and is an ideal material for realizing a resonance phenomenon when a surface plasmon is the same as an incident light frequency. Surface Plasmon Resonance (SPR) has very unique optical properties of metallic nanostructures, such as surface optical electric field enhancement, surface enhanced spectroscopy, enhanced raman scattering, light transmission enhancement, surface plasmon nano-waveguiding, optical force enhancement, surface plasmon photocatalysis, surface enhanced energy transfer, selective light absorption, and the like. When the incident light intensity generates total internal reflection at the interface of the medium and the metal film, the evanescent wave permeating into the metal film triggers free electrons in the metal to generate surface plasma, when the frequency of the surface plasma is equal to that of the evanescent wave, the surface plasma and the evanescent wave resonate, the total reflection condition at the interface is destroyed, the phenomenon of attenuated total reflection is presented, the incident light is absorbed by the free electrons on the metal surface, and the energy of the reflected light is rapidly reduced.

Surface Plasmon Resonance (SPR) is a phenomenon in which when light waves are incident on the interface between a metal and a medium, free electrons on the surface of the metal oscillate in collective resonance to generate Surface Plasmon Polariton (SPP) waves which can propagate around metal nanoparticles or on a flat metal surface, the light waves couple with the free electrons on the surface of the metal to form a near-field electromagnetic wave propagating along the surface of the metal, and when the oscillation frequency of the free electrons is consistent with the frequency of the incident light, resonance occurs, and the energy of an electromagnetic field is effectively converted into collective vibrational energy of the free electrons on the surface of the metal in the resonance state, so that a special electromagnetic mode is formed, i.e., the electromagnetic field is confined to a small range on the surface of the metal and enhanced, and the phenomenon is called Surface Plasmon Resonance (SPR).

The international market does not produce the spectacle lenses based on the surface plasmon resonance visible light color changing, and particularly the surface plasmon resonance technology is not used for the visible light color changing on the spectacle lenses. No glasses lens based on surface plasmon resonance visible light color changing is developed in the international market, so that any glasses lens in the market does not have the dual function of simultaneously realizing visible light color changing based on surface plasmon resonance and high transmission visual field in the full bandwidth of visible light.

Disclosure of Invention

In order to solve the problems in the prior art, the application provides a visible light photochromic lens based on surface plasmon resonance and a preparation method thereof.

In a first aspect, an embodiment of the invention provides a visible light photochromic lens based on surface plasmon resonance, which comprises a lens substrate, wherein a visible light full-bandwidth antireflection film layer, a two-dimensional nano U-shaped metal silver film periodic array film layer and a silicon dioxide priming layer are sequentially arranged on the surface of the lens substrate from top to bottom.

In a preferred embodiment, the thickness of the two-dimensional U-shaped metal silver film periodic array film layer is 10 nm-30 nm.

In a preferred embodiment, the thickness of the bottom layer of silicon dioxide is between 2nm and 10 nm.

In a second aspect, an embodiment of the present invention provides a method for preparing a visible light photochromic lens based on surface plasmon resonance, including the following steps:

step S1: carrying out ion-assisted bombardment electron beam evaporation deposition on the lens substrate to deposit a silicon dioxide priming layer;

step S2: clamping a mask plate on each lens substrate, and performing electron beam evaporation deposition on the silicon dioxide base layer to deposit a two-dimensional nano U-shaped metal silver film periodic array film structure;

step S3: and finally, taking off the mask plate, and then carrying out ion beam assisted deposition and electron beam evaporation on the visible light full-bandwidth antireflection film layer.

In a preferred embodiment, the optical central area of the mask plate adopts a laser interference direct writing sub-wavelength scale U-shaped nanometer open area hollow structure.

In a preferred embodiment, the open-area hollow D (width) of the mask plate ranges from 50nm to 80nm, the L (length) ranges from 50nm to 80nm, the H (height) ranges from 1 μm to 3 μm, and the unit period ranges from 300nm to 480 nm.

In a preferred embodiment, the vapor deposition rate of the two-dimensional nanometer U-shaped metal silver film periodic array film layer in the step S2 is 0.1 nm/S-1.0 nm/S.

In a preferred embodiment, the visible light full-bandwidth antireflection film layer in step S3 includes a trititanium pentoxide film layer and a silicon dioxide film layer, where the deposition rate of the silicon dioxide film layer is 0.2 nm/S-3.0 nm/S, and the deposition rate of the trititanium pentoxide film layer is 0.3 nm/S-5.0 nm/S.

The invention relates to a visible light photochromic glasses lens based on surface plasmon resonance, wherein a two-dimensional nano U-shaped silver metal film array structure is designed in the structure of the visible light photochromic glasses lens for surface plasmon resonance, and the total structure of an integral film layer comprises the following three layers from top to bottom: a visible light full-bandwidth antireflection film layer, a two-dimensional nano U-shaped metal silver film periodic array film layer and a silicon dioxide priming coat. According to the preparation method of the glasses lens based on the surface plasmon resonance visible light color changing, a U-shaped open area hollow structure with a sub-wavelength scale is designed on a mask plate, namely the mask plate is subjected to laser interference in advance to directly write the U-shaped open area hollow structure with the sub-wavelength scale. After a silicon dioxide bottoming layer is deposited on the lens substrate, each lens is clamped with the special mask plate to carry out electron beam evaporation deposition on a two-dimensional nano U-shaped silver metal film array periodic structure film layer, and then an Ion Beam Assisted Deposition (IBAD) electron beam evaporation visible light full-bandwidth antireflection film layer is carried out on the outermost layer. In the process of evaporating the film layer, the adjustment of the optical equivalent admittance value is introduced, and a strict coupled wave method is adopted to optimize a visible light full-bandwidth antireflection film system and a surface plasmon resonance two-dimensional nano U-shaped silver metal film array film system. The method is used for developing a surface plasmon generating interface in a form of insulator-Metal-insulator (D-M-D), and the manufacturing process comprises the steps of performing evaporation deposition on a two-dimensional nano U-shaped Metal silver film periodic array film layer by using a mask plate method to regulate and control the Fermi level of a Metal electrode through electric potential under the action of an external optical field, so that the regulation and control of Surface Plasmon Resonance (SPR) energy are realized, the energy of thermal electrons and thermal holes generated by relaxation of the Surface Plasmon Resonance (SPR) is regulated, the photoelectric synergistic mechanism of the Surface Plasmon Resonance (SPR) chemical reaction is enhanced, and the selectivity and the efficiency of the Metal Nano Structure (NPs) photoelectrochemical interface reaction are regulated and controlled.

Drawings

The accompanying drawings are included to provide a further understanding of the embodiments and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments and together with the description serve to explain the principles of the invention. Other embodiments and many of the intended advantages of embodiments will be readily appreciated as they become better understood by reference to the following detailed description. The elements of the drawings are not necessarily to scale relative to each other. Like reference numerals designate corresponding similar parts.

FIG. 1 is a schematic diagram of the overall film morphology structure of a visible light photochromic lens based on surface plasmon resonance according to an embodiment of the present invention;

fig. 2 is a schematic diagram of a size structure of a U-shaped nano hollow area on a mask plate in a visible light photochromic lens manufacturing method based on surface plasmon resonance according to an embodiment of the present invention;

FIG. 3 is a flowchart of a method for manufacturing a visible light photochromic lens based on surface plasmon resonance according to an embodiment of the present invention;

FIG. 4 is an optical micrograph and a partial enlarged view of a two-dimensional nano metal silver film U-shaped nano array film structure deposited on a visible light photochromic lens based on surface plasmon resonance according to an embodiment of the invention;

FIG. 5 is a schematic diagram of the resonant diffraction field enhancement efficiency curve of visible light in the visible light waveband of the visible light photochromic lens based on surface plasmon resonance according to the embodiment of the invention;

fig. 6 is a graph showing the relationship between the coupling efficiency and the incident light field angle of the two-dimensional nano U-shaped metal silver thin film periodic array film layer of the visible light photochromic lens based on surface plasmon resonance in the embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to the accompanying drawings, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention is described in detail with reference to the accompanying drawing 1, and the visible light photochromic lens based on surface plasmon resonance comprises a lens substrate, wherein a visible light full-bandwidth antireflection film layer, a two-dimensional nano U-shaped metal silver film periodic array film layer and a silicon dioxide priming coat are sequentially arranged on the surface of the lens substrate from top to bottom.

The working principle of the visible light photochromic lens based on surface plasmon resonance is as follows: when light waves are incident on the surface of the metal material nano array, the interaction between the light and free electrons in the metal nano film layer can enhance the collective vibration of the free electrons, if the vibration frequency of the free electrons is consistent with the frequency of the incident waves, an external light field can be captured by the free electrons of the collective vibration, the extinction efficiency can be greatly increased, so that the free electrons on the surface of the metal material nano array are coupled with external photoelectrons to form a special electromagnetic mode, local surface plasmon resonance peaks can appear in corresponding wave bands, and the effect of radiation enhancement is further generated. When the frequency of the optical wave is matched with the frequency and wave number of the plasmon, Surface Plasmon Resonance (SPR) can be excited, the intensity of the incident light wave is sharply attenuated and shows a resonance absorption peak, and when the frequency and wave vector of the surface plasmon resonance and the frequency and wave vector of the incident light wave are equal, the surface plasmon resonance is excited, and the surface plasmon resonance and the incident light wave are subjected to energy coupling and resonance.

Surface Plasmon Resonance (SPR) is a phenomenon that when light waves enter a boundary surface between metal and a medium, free electrons on the surface of the metal oscillate collectively, the light waves and the free electrons on the surface of the metal are coupled to form near-field electromagnetic waves propagating along the surface of the metal, resonance is generated when the oscillation frequency of the free electrons is consistent with the frequency of incident light waves, the energy of an electromagnetic field is effectively converted into collective vibration energy of the free electrons on the surface of the metal in a resonance state, and a special electromagnetic mode is formed, namely the electromagnetic field is limited in a small range of the surface of the metal and enhanced, and the phenomenon is called Surface Plasmon Resonance (SPR), and the Surface Plasmon Resonance (SPR) effect is used for regulating and controlling surface reaction, so that the reaction efficiency and selectivity can be further improved.

Fig. 2 is a schematic diagram of a size structure of a U-shaped nano hollowed-out area on a mask plate in a visible light photochromic lens manufacturing method based on surface plasmon resonance, and as shown in fig. 2, a laser interference direct writing sub-wavelength scale U-shaped nano open area hollowed-out structure is adopted in an optical central area of the mask plate. The range of the open area hollow D (width) of the mask plate is 50 nm-80 nm, the range of the L (length) is 50 nm-80 nm, the range of the H (height) is 1 mu m-3 mu m, the range of the unit period is 300 nm-480 nm, and the white area is the hollow area of the mask template.

In particular embodiments, the lens substrate includes, but is not limited to, the following: any one of an optical lens, a glass substrate of a sunglass lens, a polycarbonate PC substrate, a nylon PA substrate, a CR-39 substrate, a PMMA substrate, an AC acrylic substrate, an MR-7 substrate, an MR-8 substrate, an MR-10 substrate, an MR-174 substrate and a TAC polarizer substrate.

Fig. 3 is a flowchart of a method for manufacturing a visible light photochromic lens based on surface plasmon resonance, and as shown in fig. 3, the present invention further provides a method for manufacturing a visible light photochromic lens based on surface plasmon resonance, which comprises the following steps:

step S1: depositing a silicon dioxide priming coat on the lens substrate by ion-assisted bombardment electron beam evaporation, wherein the thickness of the silicon dioxide priming coat is 2 nm-10 nm, the ion bombardment time is 1 min-5 min, and the background vacuum degree is 1 multiplied by 10^-3Pa～9×10^-3Pa, oxygen pressure 1X 10^-2Pa～8×10^-2Pa；

Step S2: the method comprises the following steps of clamping a mask plate on each lens substrate by adopting a mask plate technical method, and depositing a two-dimensional nano U-shaped metal silver film periodic array film structure on a silicon dioxide priming layer after a film material silver metal vapor flow penetrates through a sub-wavelength U-shaped hollow area on the mask plate when an electron beam vapor deposition is carried out, wherein the film thickness of the two-dimensional nano U-shaped metal silver film array film structure is 10-30 nm, the vapor flow deposition rate is 0.1-1.0 nm/s, and an optical micrograph and a local enlarged view of the deposited two-dimensional U-shaped nano metal silver film structure are shown in FIG. 4;

step S3: and finally, taking out the mask plate, carrying out ion beam assisted deposition and electron beam evaporation on the visible light full-bandwidth antireflection film layer, wherein the thickness of the visible light full-bandwidth antireflection film layer is 83-664 nm, the visible light full-bandwidth antireflection film layer comprises a low-refractive-index silicon dioxide film layer and a high-refractive-index trititanium pentoxide film layer which are periodically arranged from top to bottom, the deposition rate of the silicon dioxide film layer is 0.2-3.0 nm/s, the deposition rate of the trititanium pentoxide film layer is 0.3-5.0 nm/s, the film period number range of the visible light full-bandwidth antireflection film layer is 1-8, cooling for half an hour after the plating is stopped, and inflating the vacuum chamber to take out the lens.

In a specific embodiment, the center wavelength of the visible light full-bandwidth antireflection film layer is 550nm, the working wavelength range is 420nm to 780nm, the average reflectivity in the working wavelength range of 420nm to 780nm is less than 0.5%, and the transmittance is greater than 90%.

In a specific embodiment, the distance between the lens substrate and the evaporation source is 40-90 cm, the crystal growth temperature of the lens substrate is 40-80 ℃, the beam current density is 100-120 mA, and the vacuum degree is 1 multiplied by 10 when the lens substrate works^-3Pa～9×10^-3Pa, the power of the electron gun is 50-80%, the anode voltage of the electron gun is 100-130V, the anode current is 3-10A, the cathode voltage is 20-50V and the cathode current is 12-20A.

Fig. 5 is a schematic diagram of a resonant diffraction field enhancement efficiency curve of visible light in a visible light waveband of a visible light photochromic lens based on surface plasmon resonance along with a change of an incident wavelength, as shown in fig. 5, the resonant diffraction field enhancement efficiency of the spectacle lens based on surface plasmon resonance visible light photochromic also changes along with a change of the incident wavelength of the visible light, and a main reason for the change is that a transverse nanorod part is added in a two-dimensional nano U-shaped metal silver thin film array film layer structure, and the added transverse nanorod part has three main functions: firstly, connecting two longitudinal nanorods to enable transverse Surface Plasmas (SPs) excited on the longitudinal nanorods to be in bridging propagation through the two longitudinal nanorods to generate interference of the Surface Plasmas (SPs); secondly, incident light vertically irradiates on the transverse nanorods and directly excites longitudinal Surface Plasmons (SPs) on the transverse nanorods, so that a longitudinal Surface Plasmon Resonance (SPR) mode is added to the U-shaped nanostructure compared with a pure parallel nanorod, a resonance peak is increased, and the addition of the transverse part of the nanorods formed in the U-shaped nanostructure plays a leading role in exciting the Surface Plasmons (SPs); thirdly, when the Surface Plasmas (SPs) are transmitted to the horizontal part of the nano-rods, the Surface Plasmas (SPs) are transmitted upwards due to the connection and reflection action of the horizontal part of the nano-rods, so that the Surface Plasmas (SPs) which repeatedly come and go are interfered to form standing waves, a nano micro-cavity is formed by the two-dimensional U-shaped metal silver film structure and a medium interface filled in the opening area, the energy of the focused evanescent field repeatedly vibrates and is superposed in the micro-cavity, and the U-shaped nano-structure is utilized to transmit the focused evanescent field in a long distance under the condition of keeping enough strength.

In a specific embodiment, when light with an incident light field angle theta larger than a total reflection angle is incident on the surface of the two-dimensional U-shaped metal silver film periodic array film layer, evanescent waves tunneling through a medium-metal interface are generated and propagate along the inner interface of the two-dimensional U-shaped metal silver film periodic array film layer, when the wave vector of the evanescent waves is matched with the wave vector of the surface plasmon polariton wave, a Surface Plasmon Resonance (SPR) phenomenon can be excited, so that energy of light with specific wavelength is coupled to the surface plasmon polariton, and strong interaction is generated between the two waves. Fig. 6 is a graph showing the relationship between the coupling efficiency and the incident light field angle of the two-dimensional nano U-shaped metal silver film periodic array film layer of the visible light photochromic lens based on surface plasmon resonance, and as shown in fig. 6, when the evanescent wave vector of the metal surface is equal to the surface plasmon wave vector, the two components are subjected to energy coupling, surface plasmon resonance, that is, SPR absorption, is generated, and the reflected light intensity at the wavelength is sharply reduced.

The invention relates to a pair of glasses lens based on surface plasmon resonance visible light discoloration, wherein a two-dimensional nano U-shaped silver metal film array structure is designed in the structure of the glasses lens for surface plasmon resonance visible light discoloration, and the total structure of an integral film layer comprises the following three layers from top to bottom: the film comprises a visible light full-bandwidth antireflection film layer, a two-dimensional nano U-shaped metal silver film periodic array film layer and a silicon dioxide priming layer, wherein the thickness of the total film stack film layer ranges from 100nm to 700 nm. According to the preparation method of the glasses lens based on the surface plasmon resonance visible light color changing, a U-shaped open area hollow structure with a sub-wavelength scale is designed on a mask plate, namely the mask plate is subjected to laser interference in advance to directly write the U-shaped open area hollow structure with the sub-wavelength scale. After a silicon dioxide bottoming layer is deposited on the lens substrate, each lens is clamped with the special mask plate to carry out electron beam evaporation deposition on a two-dimensional nano U-shaped silver metal film array periodic structure film layer, and then an Ion Beam Assisted Deposition (IBAD) electron beam evaporation visible light full-bandwidth antireflection film layer is carried out on the outermost layer. In the process of evaporating the film layer, the adjustment of the optical equivalent admittance value is introduced, and a strict coupled wave method is adopted to optimize a visible light full-bandwidth antireflection film system and a surface plasmon resonance two-dimensional nano U-shaped silver metal film array film system. The method is used for developing a surface plasmon generating interface in a form of insulator-Metal-insulator (D-M-D), and the manufacturing process comprises the steps of performing evaporation deposition on a two-dimensional nano U-shaped Metal silver film periodic array film layer by using a mask plate method to regulate and control the Fermi level of a Metal electrode through electric potential under the action of an external optical field, so that the regulation and control of Surface Plasmon Resonance (SPR) energy are realized, the energy of thermal electrons and thermal holes generated by relaxation of the Surface Plasmon Resonance (SPR) is regulated, the photoelectric synergistic mechanism of the Surface Plasmon Resonance (SPR) chemical reaction is enhanced, and the selectivity and the efficiency of the Metal Nano Structure (NPs) photoelectrochemical interface reaction are regulated and controlled.

While the principles of the invention have been described in detail in connection with the preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing embodiments are merely illustrative of exemplary implementations of the invention and are not limiting of the scope of the invention. The details of the embodiments are not to be interpreted as limiting the scope of the invention, and any obvious changes, such as equivalent alterations, simple substitutions and the like, based on the technical solution of the invention, can be interpreted without departing from the spirit and scope of the invention.