LU500721B1 - Anti-blue light protective film based on plasmonic particles and preparation method thereof - Google Patents

Abstract

A preparation method for an anti-blue light protective film based on plasmonic particles, which includes the following steps: coat a layer of silver film on the transparent substrate; annealing treatment, silver nanoparticles are obtained on the surface of the transparent substrate; using the atomic layer deposition method to wrap a layer of alumina transparent dielectric layer outside the silver nanoparticles to form a silver-alumina core-shell structure; annealing treatment, obtaining gold nanoparticles; using atomic layer to wrap a layer of titanium dioxide transparent dielectric layer on the outside of gold nanoparticles to form a gold-titanium dioxide core-shell structure; plating a layer of silica transparent film on the titanium dioxide transparent dielectric layer. Through a simple coating and annealing process, the present invention can form nanoparticles with a regular shape and a size and a controllable resonance band, thereby effectively absorbing blue light and reducing the yellowing of the film.

Description

DESCRIPTION LUS00721 ANTI-BLUE LIGHT PROTECTIVE FILM BASED ON PLASMONIC

PARTICLES AND PREPARATION METHOD THEREOF Technical Field The present invention belongs to the technical field of anti-blue light, and specifically relates to a method for preparing an anti-blue light protective film based on plasmonic particles.

Background Electronic products have now become indispensable and important tools for people’s life and study. Electronic products such as mobile phones, computers, TVs, etc. radiate blue light (wavelength of 400 nm-500 nm) to human eyes through the display screen, among which short-wave blue light with a wavelength of 425-450nm is harmful to humans eyes. Working in an environment with a lot of blue light radiation, people may often feel eye pain, eye swelling, suffer from worsening myopia and other ophthalmic problems. Long-term exposure to blue light can damage the visual cells of the human eye and the relative high energy blue light can result increased amounts of toxins in the macular area of the eyes, induces blindness and seriously affects the health of young people and the elderly.

As people pay more and more attention to health issues, the hazards brought out by the blue light will inevitably become a conspicuous obstacle to people's health. Therefore, reducing the amount of blue light radiation has gradually become a hot spot in current research, and will become an important indicator of the excellent performance of electronic products in the future, and has a broad market prospect.

In order to reduce the hazard resulted from blue light, a protective film is usually attached onto the top of the electronic product screen to reduce the amount of blue light radiation. There are generally two types of preparation methods for such a film that reduces the amount of blue light radiation: One is to coat or spray an absorber with blue light absorption function (such as

CN105353436A, etc.) on the substrate, use a strengthening liquid to crosslink the absorber HUs00721 (such as CN103992672A, etc.), and use an anti-blue film film-forming liquid (such as : CN109320969A) to realize the anti-blue light function. This kind of film preparation process has many shortcomings, such as complicated process, many articles to be used, and long preparation cycle.

Another way to reduce blue light radiation is to use nanoparticle absorbing layers. In CN106154384A, CN108047981 A a coating method is used to plate a nano-particle layer of titanium dioxide, or indium trioxide, or iron oxide or cadmium sulfide, or cadmium selenide with a certain thickness on the top of the substrate to enhance the absorption of blue light, but the disadvantage lies in that the shapes and sizes of the nanoparticles are difficult to control, and the thickness of the nanoparticle layer is required to be large and the cost is high; in CN111522080A photonic crystal materials formed by core-shell structure microspheres are used to prepare anti-blue light protective film, but the process used for preparing the core-shell structure is cumbersome, and it is difficult to ensure a uniform particle distribution. The film will turn yellow after being placed for a period of time, it, which will affect its light transmission effect.

Therefore, it is necessary to develop a technology that is simple in respect of technology itself, can effectively absorb harmful blue light, and can reduce the yellowing of the film.

The surface plasmon resonance of metal micro-nano structures has gradually become a research hotspot in the current physics, chemistry, materials, information science and other disciplines and their interdisciplinary fields. Plasmonic particles with wavelength selectivity can enhance the absorption rate of visible light in a certain wavelength band, and adjust it to fall into the blue wavelength band, through which the blue light hazard can be reduced. On the other hand, using different kinds of metal nanoparticles can absorb blue light while effectively absorbing yellow light. Compared with the above-mentioned materials, granular materials are simpler and easier to manufacture and are expected to solve current problems. Summary of the Invention In order to solve the deficiencies in the prior art, a method for preparing an anti-blue light protective film based on plasmonic particles is provided, which has the effects of simple HUs00721 process, low cost, uniform distribution of metal particles, and good anti-blue light effect.

In order to solve the above technical problems, the present invention adopts the following technical solution: a preparation method for an anti-blue light protective film based on plasmonic particles, comprises the following steps: (1) Using sputter coating or evaporation coating to coat a layer of silver film on the transparent substrate, the material of which may be glass, plastic, resin or polymer; (2) Putting the silver-plated transparent substrate into an annealing device for annealing treatment; (3) After annealing treatment, silver nanoparticles are obtained on the surface of the transparent substrate, and the size of the silver nanoparticles is related to the film thickness; the particle size is calculated according to the Mie scattering theory; (4) Using the atomic layer deposition method to wrap a layer of alumina transparent dielectric layer outside the silver nanoparticles to form a silver-alumina core-shell structure; (5) Using sputtering or evaporation coating method to coat a layer of transparent silica film on the transparent dielectric layer of alumina; (6) Plating a layer of gold film on the surface of the silica transparent film using the method as in step (1); (7) Putting the gold-plated transparent substrate into an annealing device for annealing treatment as in step (2); (8) Obtaining gold nanoparticles after annealing treatment, the size of which is related to the thickness of the film and is calculated according to the Mie scattering theory; (9) Using atomic layer deposition as in step (4) to wrap a layer of titanium dioxide transparent dielectric layer on the outside of gold nanoparticles to form a gold-titanium dioxide core-shell structure; (10) Plating a layer of silica transparent film on the titanium dioxide transparent dielectric layer in the manner as in step (5).

In step (1), an electron beam thermal evaporation coater is used to coat a silver film on the glass surface, and the specific steps are as follows: putting the cleaned optical glass with a HUs00721 dimension of 8cmx8cm into the substrate holder of the electron beam thermal evaporation coater, and putting the silver particles with a purity of 99.99% into the tungsten crucible for evaporation, and drawing the vacuum below 5x10“Pa to start coating; during the coating process, the coating rate can be controlled by controlling the magnitude of electron beam current, and the film thickness can be controlled by adjusting the coating rate and time.

In step (1), an argon ion sputtering coater is used to plate silver on the glass surface, and the specific steps are as follows: putting the cleaned optical glass with a dimension of 8cmx8cm into the sample rod stage of the argon ion sputtering coater, and pushing the sample rod stage into the argon ion sputtering coater, vacuuming, and when the vacuum degree reaches 5x10™*Pa or below, starting the sputtering coating; adjusting the working voltage and current of the electron gun, wherein the recommended parameter is 7kv/300uA, and the coating rate of silver is 8nm/min; the size of the silver particles finally obtained is related to the coating time, and the time is respectively controlled to be 15s, 30s, 45s, 60s, and 75s to obtain a film-like structure, and the silver particles after treatment for 30s-75s are island-shaped.

The annealing device in step (2) comprises a base, on which a cylindrical box is arranged. A number of heating tubes are evenly arranged along the circumference of the cylindrical box, the center line of which is horizontally arranged along the left and right direction. A hollow shaft is rotated between the center of the left side panel and the center of the right side panel of the cylindrical box. A hollow suction cup is fixed respectively on each of the opposite side outside the hollow shaft. The left end of the hollow shaft protrudes outside the left side panel of the cylindrical box and is connected to a vacuum tube through a rotary joint. The vacuum tube is connected to a vacuum pump, and the right side of the right side panel cylindrical box is provided with a motor, the main shaft of the motor is coaxially drivingly connected with the right end of the hollow shaft, and a box door is provided on the left side panel of the cylindrical box. The upper part of the right side panel of the cylindrical box is provided with an air inlet pipe.

Each heating tube is parallel to the center line of the cylindrical box, and the right end of HUS00721 each heating tube extends out of the right side panel of the cylindrical box and is fixedly connected with a terminal and all terminals are connected in series through wires, which is connected with a power line. A temperature sensor is provided in the cylindrical box. In the cylindrical box, a cylindrical isolation net is fixed on the inner side of all the heating tubes. Both the outside of the cylindrical box and the outside of the box door are provided with an insulating material layer. The hollow suction cup has a rectangular plate structure. The center of the hollow suction cup has a rectangular cavity. A plurality of first suction ports are spaced arranged along the length direction of the hollow shaft on the side of the hollow suction cup which is fixedly connected with the hollow shaft. The other side of the hollow suction cup is evenly provided with a plurality of second suction ports. Two box doors are arranged on the left side panel of the cylindrical box, and the two box doors are symmetrical about the center line of the cylindrical box.

In step (2), the specific process of annealing treatment is: opening the two box doors, first rotating the two hollow suction cups to the vertical state, and then putting the two silver-plated glass into the cylindrical box, wherein, the side surface of the glass without silver coating is in contact with the surface of the hollow suction cup; turning on the vacuum pump, which makes the two pieces of glass attached onto the hollow suction cup firmly through the vacuum tube, the hollow shaft, the first suction port and the second suction port; then closing the two box doors, starting the motor and the power supply of the heating tube, through which the heating tube heats the inner space of the closed cylindrical box, the motor drives the hollow shaft to rotate, and the hollow shaft drives the two hollow suction cups to rotate, and the two pieces of coated glass adsorbed on the hollow suction cup also rotate accordingly, and at the same time the protective nitrogen with 0.01MPa is filled and forced to pass into the cylinder box through the air inlet pipe and will be mixed with reducing hydrogen. Since there will be gas-permeable gaps between the glass and the hollow suction cup, the air inside the cylindrical box is replaced with protective nitrogen and reducing hydrogen while the hollow suction cup is adsorbed, then the temperature of the heating tube is raised to 300°C at a heating rate of 5°C/min. The temperature monitoring is transmitted to the PLC controller HUs00721 through the temperature sensor, the PLC controller regulates the power supply to supply current for the heating tube, after maintaining at 300°C for 30 minutes, first turn off the power of the motor and the heat tube, then open the door, turn off the vacuum pump, take out the two pieces of glass, therefore the annealing process is completed.

In step (3), the silver nanoparticles are uniformly arranged on the glass on the surface of the transparent substrate, and the radius size of the annealed silver nanoparticles is 10 nm; in step (4), the thickness of the alumina transparent dielectric layer is 10 nm, the refractive index of the transparent dielectric layer is 1.59.

The specific process of step (4) is: using trimethylaluminum and high-purity water as the reaction source, high-purity No as the purge gas, and growing an alumina transparent dielectric on the outside of the metal nanoparticles, the deposition temperature: 120°C, the trimethylaluminum pulse time: 0.2-0.6s; high-purity water pulse time: 0.3s; purge time: 10s; cycle period: 25 times.

The thickness of the silica transparent film in steps (5) and (10) is 120-200 nm, and the refractive index of the transparent silica film 1s 1.45.

In step (8), the gold nanoparticles are uniformly arranged on the glass, and the radius size of the annealed gold nanoparticles is 15 nm; in step (9), the thickness of the titanium dioxide transparent dielectric layer is 5 nm, and the refractive index of the titanium dioxide transparent dielectric layer is 2.45.

With the above technical solution, the thickness of the metal film depends on the growth rate and time of the plating film, and the metal can be silver, gold or aluminum. If the structure of the metal particles is required to be a core-shell structure, after the metal particles are formed, an atomic layer deposition (ALD) method is used to grow a transparent medium layer on the outside of the metal particles. Finally, a layer of transparent film is plated on the metal particles, which process can prevent the metal particles from oxidizing in the air, and can also adjust the resonance position. The film material is transparent and not unique. The uniform distribution of metal particles is achieved by coating. The metal in the present invention is not limited to silver, and it can also be other metals such as gold or aluminum, for 10500781 example, gold which can effectively absorb yellow light in a medium environment with a certain refractive index.

The annealing device uses a vacuum pump to suck the hollow suction cup to absorb the coated glass, and the motor drives the hollow suction cup and two pieces of coated glass to rotate slowly, which not only increases the temperature of the heated surface but also make the temperature to be consistent, in addition the coating and protective nitrogen gas are made to be in dynamic contact with the reducing hydrogen, thereby improving the processing quality of the annealing process.

Several heating tubes are evenly arranged along the circumferential direction of the cylindrical box, which can also improve the uniformity for heating the coating.

The isolation net not only has good heat permeability, but also prevents the glass from touching the heating tube when the glass is being taken and placed.

The thermal insulation material layer (polyurethane thermal insulation material can be used) can avoid heat loss and improve heating efficiency.

The annealing device adopts the cylindrical box with the characteristics of small size and compact structure. The entire annealing treatment process is also convenient to operate. The vacuum adsorption method not only ensures a firm and reliable fixation, but also can make it possible to be rotated during the treatment process, which improves the consistency of the coating surface temperature and greatly improve product quality.

In summary, as a whole, the present invention has the following beneficial effects: (1) In the present invention there is provided a new method for preparing an anti-blue light protective film based on plasmonic particles. Specially, using an argon ion sputtering coater and an electron beam thermal evaporation coater, a layer of silver film is plated on the transparent substrate, and then after annealing treatment, silver nanoparticles with strong wavelength selective optical antenna function are obtained. A layer of alumina transparent dielectric is wrapped on silver nanoparticals by ALD method, and different resonance wavelengths are adjusted, so as to achieve effective absorption of blue light. Plating a layer of silica environmental dielectric on the top not only can adjust the resonance position of the HUs00721 silver nanoparticles, but also can effectively prevent the silver nanoparticles from oxidizing. The preparation process of the invention is simple, the metal particles are evenly distributed, and the size of the metal particles can be controlled by controlling the coating time.

(2) The price of the metal target material used for coating is much lower than the metal particles obtained by other methods, the cost is low, and the market prospect is broad.

(3) In the invention the experimental period for preparing the anti-blue light protective film is short, thereby saving time and cost, and improving efficiency.

(4) Like the preparation method for the blue light absorbing particle layer (silver-plated film), a layer of gold film is plated on the substrate by sputtering or evaporation, and then annealed in a protective gas to obtain gold nanoparticles with the required size. ALD and other physical vapor deposition methods is used to grow titanium dioxide dielectric on the prepared particles, the thickness of the titanium dioxide dielectric layer is controlled by controlling the instrument parameters, and finally a layer of silica environment dielectric is plated on the top, so as to finally realize the absorption of yellow light.

(5) Through a simple coating and annealing process, the present invention can form nanoparticles with a regular shape and a size and a controllable resonance band, thereby effectively absorbing blue light and reducing the yellowing of the film, which has important application value.

Brief Description of Drawings Fig. 1 is a schematic diagram of the structure of the annealing device of the present invention; Fig. 2 is a right side view of Fig. 1.

Figure 3 is a left side view of Fig. 1; Fig. 4 shows the extinction, scattering and absorption spectra of plasmonic particles that achieves blue light (420-450nm) absorption in a quartz environment; Fig. 5 shows the extinction, scattering and absorption spectra of plasmonic particles that achieve yellow light absorption (570-600nm) in a quartz environment;

Fig. 6 is the SEM morphology of the silver film plated on the optical glass substrate by HUs00721 the electron beam thermal evaporation coater before and after annealing; Fig. 7 is the reflection, transmission and absorption spectra of a transparent display screen obtained by using an electron beam thermal evaporation coater; Fig. 8 is the layered structure of the anti-blue light protective film of the present invention.

Detailed Description of Preferred Embodiments As shown in Figure 8, a preparation method for an anti-blue light protective film based on plasmonic particles described in the present invention, comprises the following steps: (1) Using sputter coating or evaporation coating to coat a layer of silver film on the transparent substrate 23, the material of which may be glass, plastic, resin or polymer; (2) Putting the silver-plated transparent substrate 23 into an annealing device for annealing treatment; (3) After annealing treatment, silver nanoparticles are obtained on the surface of the transparent substrate 23, and the size of the silver nanoparticles is related to the film thickness; the particle size is calculated according to the Mie scattering theory; (4) Using the atomic layer deposition method to wrap a layer of alumina transparent dielectric layer outside the silver nanoparticles to form a silver-alumina core-shell structure; (5) Using sputtering or evaporation coating method to coat a layer of transparent silica film on the transparent dielectric layer of alumina, to form a blue light-resistant plasmonic structure layer 24; (6) Plating a layer of gold film on the surface of the silica transparent film using the method as in step (1); (7) Putting the gold-plated transparent substrate 23 into an annealing device for annealing treatment as in step (2); (8) Obtaining gold nanoparticles after annealing treatment, the size of which is related to the thickness of the film and is calculated according to the Mie scattering theory; (9) Using atomic layer deposition as in step (4) to wrap a layer of titanium dioxide transparent dielectric layer on the outside of gold nanoparticles to form a gold-titanium HUs00721 dioxide core-shell structure; (10) Plating a layer of silica transparent film on the titanium dioxide transparent dielectric layer in the manner as in step (5), to form a yellow light absorption plasmonic structure layer 25.

In step (1), an electron beam thermal evaporation coater is used to coat a silver film on the glass surface, and the specific steps are as follows: putting the cleaned optical glass with a dimension of 8cmx8cm into the substrate holder of the electron beam thermal evaporation coater, and putting the silver particles with a purity of 99.99% into the tungsten crucible for evaporation, and drawing the vacuum below 5x10*Pa to start coating; during the coating process, the coating rate can be controlled by controlling the magnitude of electron beam current, and the film thickness can be controlled by adjusting the coating rate and time. .

In step (1), an argon ion sputtering coater is used to plate silver on the glass surface, and the specific steps are as follows: putting the cleaned optical glass with a dimension of 8cmx8cm into the sample rod stage of the argon ion sputtering coater, and pushing the sample rod stage into the argon ion sputtering coater, vacuuming, and when the vacuum degree reaches 5x10™*Pa or below, starting the sputtering coating; adjusting the working voltage and current of the electron gun, wherein the recommended parameter is 7kv/300uA, and the coating rate of silver is 8nm/min; the size of the silver particles finally obtained is related to the coating time, and the time is respectively controlled to be 15s, 30s, 45s, 60s, and 75s to obtain a film-like structure, and the silver particles after treatment for 30s-75s are island-shaped.

As shown in Fig. 1 to Fig. 3, the annealing device in step (2) comprises a base 1, on which a cylindrical box 2 is arranged. A number of heating tubes 3 are evenly arranged along the circumference of the cylindrical box 2, the center line of which is horizontally arranged along the left and right direction. A hollow shaft 4 is rotated between the center of the left side panel and the center of the right side panel of the cylindrical box 2, and the right end of the hollow shaft 4 is blocked. A hollow suction cup 5 is fixed respectively on each of the opposite side outside the hollow shaft 4. The left end of the hollow shaft 4 protrudes outside the left HUs00721 side panel of the cylindrical box 2 and is connected to a vacuum tube 7 through a rotary joint

6. The vacuum tube 7 is connected to a vacuum pump 8, and the right side of the right side panel cylindrical box 2 is provided with a motor 9 (connected by a connecting plate 10 and a bolt 11), the main shaft of the motor 9 is coaxially drivingly connected with the right end of the hollow shaft 4, and a box door 12 is provided on the left side panel of the cylindrical box 2.

The upper part of the right side panel of the cylindrical box 2 is provided with an air inlet pipe

13.

Each heating tube 3 is parallel to the center line of the cylindrical box 2, and the right end of each heating tube 3 extends out of the right side panel of the cylindrical box 2 and is fixedly connected with a terminal 14 and all terminals 14 are connected in series through wires 15, which is connected with a power line 16. A temperature sensor 17 is provided in the cylindrical box 2. In the cylindrical box 2, a cylindrical isolation net 18 is fixed on the inner side of all the heating tubes 3. Both the outside of the cylindrical box 2 and the outside of the box door 12 are provided with an insulating material layer 19. The hollow suction cup 5 has a rectangular plate structure. The center of the hollow suction cup 5 has a rectangular cavity 20. A plurality of first suction ports 21 are spaced arranged along the length direction of the hollow shaft 4 on the side of the hollow suction cup 5 which is fixedly connected with the hollow shaft 4. The other side of the hollow suction cup 5 is evenly provided with a plurality of second suction ports 22. Two box doors 12 are arranged on the left side panel of the cylindrical box 2, and the two box doors 12 are symmetrical about the center line of the cylindrical box 2.

In step (2), the specific process of annealing treatment is: opening the two box doors 12, first rotating the two hollow suction cups 5 to the vertical state, and then putting the two silver-plated glass into the cylindrical box 2, wherein, the side surface of the glass without silver coating is in contact with the surface of the hollow suction cup 5; turning on the vacuum pump 8, which makes the two pieces of glass attached onto the hollow suction cup 5 firmly through the vacuum tube 7, the hollow shaft 4, the first suction port 21 and the second suction port 22; then closing the two box doors 12, starting the motor 9 and the power supply HUs00721 of the heating tube 3, through which the heating tube 3 heats the inner space of the closed cylindrical box 2, the motor 9 drives the hollow shaft 4 to rotate, and the hollow shaft 4 drives the two hollow suction cups 5 to rotate (the vacuum tube 7 does not move due to the setting of the rotary joint 6), and the two pieces of coated glass adsorbed on the hollow suction cup 5 also rotate accordingly, and at the same time the protective nitrogen with 0.01MPa is filled and forced to pass into the cylinder box 2 through the air inlet pipe 13 and will be mixed with reducing hydrogen. Since there will be gas-permeable gaps between the glass and the hollow suction cup 5, the air inside the cylindrical box 2 is replaced with protective nitrogen and reducing hydrogen while the hollow suction cup 5 is adsorbed, then the temperature of the heating tube 3 is raised to 300°C at a heating rate of 5°C/min. The temperature monitoring is transmitted to the PLC controller through the temperature sensor 17, the PLC controller regulates the power supply to supply current for the heating tube 3, after maintaining at 300°C for 30 minutes, first turn off the power of the motor 9 and the heat tube 3, then open the door 12, turn off the vacuum pump 8, take out the two pieces of glass, therefore the annealing process is completed.

In step (3), the silver nanoparticles are uniformly arranged on the glass on the surface of the transparent substrate 23, and the radius size of the annealed silver nanoparticles is 10 nm; in step (4), the thickness of the alumina transparent dielectric layer is 10 nm, the refractive index of the transparent dielectric layer is 1.59.

The specific process of step (4) is: using trimethylaluminum and high-purity water as the reaction source, high-purity No as the purge gas, and growing an alumina transparent dielectric on the outside of the metal nanoparticles, the deposition temperature: 120°C, the trimethylaluminum pulse time: 0.2-0.6s; high-purity water pulse time: 0.3s; purge time: 10s; cycle period: 25 times.

The thickness of the silica transparent film in steps (5) and (10) is 120-200 nm, and the refractive index of the transparent silica film 1s 1.45.

In step (8), the gold nanoparticles are uniformly arranged on the glass, and the radius size of the annealed gold nanoparticles is 15 nm; in step (9), the thickness of the titanium HUs00721 dioxide transparent dielectric layer is 5 nm, and the refractive index of the titanium dioxide transparent dielectric layer is 2.45.

The thickness of the metal film depends on the growth rate and time of the plating film, and the metal can be silver, gold or aluminum. If the structure of the metal particles is required to be a core-shell structure, after the metal particles are formed, an atomic layer deposition (ALD) method is used to grow a transparent dielectric layer on the outside of the metal particles. Finally, a layer of transparent film is plated on the metal particles, which process can prevent the metal particles from oxidizing in the air, and can also adjust the resonance position. The film material is transparent and not unique. The uniform distribution of metal particles is achieved by coating. The metal in the present invention is not limited to silver, and it can also be other metals such as gold or aluminum, for example, gold which can effectively absorb yellow light in a dielectric environment with a certain refractive index.

The annealing device uses a vacuum pump 8 to suck the hollow suction cup 5 to absorb the coated glass, and the motor 9 drives the hollow suction cup 5 and two pieces of coated glass to rotate slowly, which not only increases the temperature of the heated surface but also make the temperature to be consistent, in addition the coating and protective nitrogen gas are made to be in dynamic contact with the reducing hydrogen, thereby improving the processing quality of the annealing process.

Several heating tubes 3 are evenly arranged along the circumferential direction of the cylindrical box 2, which can also improve the uniformity for heating the coating.

The isolation net 18 not only has good heat permeability, but also prevents the glass from touching the heating tube 3 when the glass is being taken and placed.

The thermal insulation material layer 19 (polyurethane thermal insulation material can be used) can avoid heat loss and improve heating efficiency.

The annealing device adopts the cylindrical box 2 with the characteristics of small size and compact structure. The entire annealing treatment process is also convenient to operate. The vacuum adsorption method not only ensures a firm and reliable fixation, but also can make it possible to be rotated during the treatment process, which improves the consistency of HUs00721 the coating surface temperature and greatly improve product quality.

Fig. 4 is the extinction, scattering and absorption spectra of plasmonic particles with blue light absorption (420-450nm) realized by the anti-blue light plasmonic structure layer 24 in a quartz (transparent substrate 23) environment. The particles used are silver-alumina core-shell structure, wherein the radius of the inner silver particles can be any size between 10 and 15nm, and the thickness of the shell dielectric alumina can be any size between 10 and 15nm. In addition, the particles can also be pure silver particles with a radius of 10-20nm and the refractive index of the environment dielectric n,=1.7; pure aluminum particles with a radius of 10-15nm and the refractive index of the environmental dielectric n,=2.45.

Fig. 5 shows the extinction, scattering and absorption spectra of plasmonic particles with yellow light absorption (570-600nm) realized by the yellow light absorption plasmonic structure layer 25 in a quartz environment. The particles used are of gold-titanium dioxide core-shell structure, wherein the radius of the inner silver particles can be any size between 15 and 20 nm, and the thickness of the shell dielectric titanium dioxide can be any size between 5 and 10 nm. In addition, the particles can also be pure gold particles, with a radius of 15-20nm, and the refractive index of the environment dielectric 7,=1.7.

Fig. 6 shows the SEM morphology of the silver film coated on the optical glass substrate by the electron beam thermal evaporation coater before and after annealing. On the left is the SEM morphology after coating, the film thickness is Snm, and on the right is the corresponding SEM morphology after annealing, the sizes of the obtained silver particles are mostly below 20nm.

Fig. 7 shows the reflection, transmission, and absorption spectra of an anti-blue light protective film obtained by using an electron beam thermal evaporation coater, wherein A=1-R-T. Reflection refers to reflectivity, the obtained anti-blue protective film has the strongest reflectivity, which is between 0.18-0.24, in the blue band around 420nm-470nm, while its reflectivity falls below 0.12 in most other visible light bands. Transmittance refers to the transmittance rate, and the blue light band around 420nm-470nm has the weakest transmittance, which 1s between 0.5-0.7, while most other bands have a transmittance above 10500781

0.8. Absorption refers to the absorption rate, the blue light around 420nm-470nm has the strongest absorption rate, which is between 0.15-0.28, and for most of the other bands it is below 0.05.

Those skilled in the art should understand that the present invention is not limited by the above-mentioned embodiment. The above-mentioned embodiment and the specification only illustrate the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various aspects. Variations and improvements, these changes and improvements fall within the scope of the claimed invention.

Claims (11)

CLAIMS LU500721

1. A preparation method for an anti-blue light protective film based on plasmonic particles, comprising the following steps: (1) using sputter coating or evaporation coating to coat a layer of silver film on the transparent substrate, the material of which may be glass, plastic, resin or polymer; (2) putting the silver-plated transparent substrate into an annealing device for annealing treatment; (3) after annealing treatment, silver nanoparticles are obtained on the surface of the transparent substrate, and the size of the silver nanoparticles is related to the film thickness; the particle size is calculated according to the Mie theory; (4) using the atomic layer deposition method to wrap a layer of alumina transparent dielectric layer outside the silver nanoparticle to form a silver-alumina core-shell structure; (5) using sputtering or evaporation coating method to coat a layer of transparent silica film on the transparent dielectric layer of alumina; (6) plating a layer of gold film on the surface of the silica transparent film using the method as in step (1); (7) putting the gold-plated transparent substrate into an annealing device for annealing treatment as in step (2); (8) obtaining gold nanoparticles after annealing treatment, the size of which is related to the thickness of the film and is calculated according to the Mie theory; (9) using atomic layer deposition as in step (4) to wrap a layer of titanium dioxide transparent dielectric layer on the outside of gold nanoparticles to form a gold-titanium dioxide core-shell structure; (10) plating a layer of silica transparent film on the titanium dioxide transparent dielectric layer in the manner as in step (5).

2. The preparation method for an anti-blue light protective film based on plasmonic particles according to claim 1, wherein in step (1), an electron beam thermal evaporation coater is used to coat a silver film on the glass surface, and the specific steps are as follows: putting the cleaned optical glass with a dimension of 8cm*8cm into the substrate holder of the electron beam thermal evaporation coater, and putting the silver particles with a purity HUs00721 of 99.99% into the tungsten crucible for evaporation, and drawing the vacuum below 5x10*Pa to start coating; during the coating process, the coating rate can be controlled by controlling the magnitude of electron beam current, and the film thickness can be controlled by adjusting the coating rate and time.

3. The preparation method for an anti-blue light protective film based on plasmonic particles according to claim 1, wherein in step (1), an argon ion sputtering coater is used to plate silver on the glass surface, and the specific steps are as follows: putting the cleaned optical glass with a dimension of 8cmx8cm into the sample rod stage of the argon ion sputtering coater, and pushing the sample rod stage into the argon ion sputtering coater, vacuuming, and when the vacuum degree reaches 5x10*Pa or below, starting the sputtering coating; adjusting the working voltage and current of the electron gun, wherein the recommended parameter is 7kv/300uA, and the coating rate of silver is 8nm/min; the size of the silver particles finally obtained is related to the coating time, and the time is respectively controlled to be 15s, 30s, 45s, 60s, and 75s to obtain a film-like structure, and the silver particles after treatment for 30s-75s are island-shaped.

4. The preparation method for an anti-blue light protective film based on plasmonic particles according to claim 2 or 3, wherein the annealing device in step (2) comprises a base, on which a cylindrical box is arranged, a number of heating tubes are evenly arranged along the circumference of the cylindrical box, the center line of which is horizontally arranged along the left and right direction, a hollow shaft is rotated between the center of the left side panel and the center of the right side panel of the cylindrical box, a hollow suction cup is fixed respectively on each of the opposite side outside the hollow shaft, the left end of the hollow shaft protrudes outside the left side panel of the cylindrical box and is connected to a vacuum tube through a rotary joint, the vacuum tube is connected to a vacuum pump, and the right side of the right side panel cylindrical box is provided with a motor, the main shaft of the motor is coaxially drivingly connected with the right end of the hollow shaft, and a box door HUS00721 is provided on the left side panel of the cylindrical box, the upper part of the right side panel of the cylindrical box is provided with an air inlet pipe.

5. The preparation method for an anti-blue light protective film based on plasmonic particles according to claim 4, wherein each heating tube is parallel to the center line of the cylindrical box, and the right end of each heating tube extends out of the right side panel of the cylindrical box and is fixedly connected with a terminal and all terminals are connected in series through wires, which is connected with a power line, a temperature sensor is provided in the cylindrical box, in the cylindrical box, a cylindrical isolation net is fixed on the inner side of all the heating tubes, both the outside of the cylindrical box and the outside of the box door are provided with an insulating material layer, the hollow suction cup has a rectangular plate structure, the center of the hollow suction cup has a rectangular cavity, a plurality of first suction ports are spaced arranged along the length direction of the hollow shaft on the side of the hollow suction cup which is fixedly connected with the hollow shaft, the other side of the hollow suction cup is evenly provided with a plurality of second suction ports, two box doors are arranged on the left side panel of the cylindrical box, and the two box doors are symmetrical about the center line of the cylindrical box.

6. The preparation method for an anti-blue light protective film based on plasmonic particles according to claim 5, wherein in step (2), the specific process of annealing treatment is: opening the two box doors, first rotating the two hollow suction cups to the vertical state, and then putting the two silver-plated glass into the cylindrical box, wherein, the side surface of the glass without silver coating is in contact with the surface of the hollow suction cup; turning on the vacuum pump, which makes the two pieces of glass attached onto the hollow suction cup firmly through the vacuum tube, the hollow shaft, the first suction port and the second suction port; then closing the two box doors, starting the motor and the power supply of the heating tube, through which the heating tube heats the inner space of the closed cylindrical box, the motor drives the hollow shaft to rotate, and the hollow shaft drives the two hollow suction cups to rotate, and the two pieces of coated glass adsorbed on the hollow HUs00721 suction cup also rotate accordingly, and at the same time the protective nitrogen with

0.01MPa is filled and forced to pass into the cylinder box through the air inlet pipe and will be mixed with reducing hydrogen; since there will be gas-permeable gaps between the glass and the hollow suction cup, the air inside the cylindrical box is replaced with protective nitrogen and reducing hydrogen while the hollow suction cup is adsorbed, then the temperature of the heating tube is raised to 300°C at a heating rate of 5'C/min, the temperature monitoring is transmitted to the PLC controller through the temperature sensor, the PLC controller regulates the power supply to supply current for the heating tube, after maintaining at 300°C for 30 minutes, first turn off the power of the motor and the heat tube, then open the door, turn off the vacuum pump, take out the two pieces of glass, therefore the annealing process is completed.

7. The preparation method for an anti-blue light protective film based on plasmonic particles according to claim 6, wherein in step (3), the silver nanoparticles are uniformly arranged on the glass on the surface of the transparent substrate, and the radius size of the annealed silver nanoparticles is 10 nm; in step (4), the thickness of the alumina transparent dielectric layer is 10 nm, the refractive index of the transparent dielectric layer is 1.59.

8. The preparation method for an anti-blue light protective film based on plasmonic particles according to claim 7, wherein the specific process of step (4) is: using trimethylaluminum and high-purity water as the reaction source, high-purity N» as the purge gas, and growing an alumina transparent dielectric on the outside of the metal nanoparticles, the deposition temperature: 120°C, the trimethylaluminum pulse time: 0.2-0.6s; high-purity water pulse time: 0.3s; purge time: 10s; cycle period: 25 times.

9. The preparation method for an anti-blue light protective film based on plasmonic particles according to claim 8, wherein the thickness of the silica transparent film in steps (5) and (10) is 120-200 nm, and the refractive index of the transparent silica film is 1.45.

10. The preparation method for an anti-blue light protective film based on plasmonic particles according to claim 8, wherein in step (8), the gold nanoparticles are uniformly HUS00721 arranged on the glass, and the radius size of the annealed gold nanoparticles is 15 nm; in step (9), the thickness of the titanium dioxide transparent dielectric layer is 5 nm, and the refractive index of the titanium dioxide transparent dielectric layer is 2.45.

11. An anti-blue light protective film based on plasmonic particles prepared by the preparation method for an anti-blue light protective film based on plasmonic particles according to claims 1-10.