CN-118047544-B - Double-metal co-doped laminated oxide film, preparation method and holographic encryption application

CN118047544BCN 118047544 BCN118047544 BCN 118047544BCN-118047544-B

Abstract

The invention provides a bimetal co-doped laminated oxide film which comprises a mesoporous TiO 2 film positioned on a glass substrate, au-Ag blending nano particles deposited on the mesoporous TiO 2 film, an amorphous TaO x film layer positioned on the Au-Ag blending nano particles, wherein x is a positive number, and a silver film positioned on the amorphous TaO x film layer. The invention also provides an encryption holographic storage method which comprises the steps of exposing a first area and exposing a second area on the bimetal co-doped laminated oxide film twice by using pulse laser, carrying out holographic storage, brushing by using NaCl solution, and reading the first area or the second area to carry out holographic storage data. The preparation process of the laminated oxide film is simple and easy to operate, and the invention creatively provides an encryption holographic storage method, and the film can also be used in the field of color printing, so that the application range and the field of the composite film of metal and TiO 2 are widened.

Inventors

FU SHENCHENG
QI XIUPING
TAO YUXIN
ZHANG XINTONG
LIU YICHUN

Assignees

东北师范大学

Dates

Publication Date: 20260508
Application Date: 20240202

Claims (10)

1. A bi-metal co-doped layered oxide film comprising: A glass substrate; a mesoporous TiO 2 film positioned on the glass substrate; Au-Ag blending nano particles deposited on the mesoporous TiO 2 film; An amorphous TaO x film layer positioned on the Au-Ag blending nano-particles, wherein x is a positive number; And a silver film positioned on the amorphous TaO x film layer.
2. The bi-metal co-doped stacked oxide film according to claim 1, wherein the thickness of the amorphous TaO x film layer is 35-45 nm, and the thickness of the silver film is 15-20 nm.
3. A bi-metal co-doped layered oxide film according to claim 1, wherein said amorphous TaO x film layer has a thickness of 40nm and said silver film has a thickness of 17nm.
4. A method for producing a double metal co-doped layered oxide film according to any one of claims 1 to 3, comprising: S1, coating a layer of TiO 2 slurry on a glass substrate by adopting a screen printing method, and performing thermal annealing treatment to remove organic components to obtain the mesoporous TiO 2 film; S2, depositing a layer of gold nanoparticles on the surface of the mesoporous TiO 2 film by magnetron sputtering; S3, immersing the TiO 2 film deposited with the gold nanoparticles into a silver nitrate solution, and irradiating with ultraviolet light to deposit the silver nanoparticles, so as to form the Au-Ag blending nanoparticle layer; S4, coating an amorphous TaO x layer on the Au-Ag blending nano particle layer by using a pulling method, and performing heat treatment to obtain an amorphous TaO x film layer; s5, performing magnetron sputtering on the amorphous TaO x film layer to form a continuous silver film.
5. The preparation method of the bimetal codoped laminated oxide film according to claim 4, wherein the specific process of S1 is that a glass substrate is placed under a screen printer screen plate, a layer of TiO 2 slurry is scraped on the upper surface of the glass substrate through a scraper, then the glass substrate is placed in a muffle furnace for annealing, and the polymer in the TiO 2 slurry is removed to obtain the mesoporous TiO 2 film; Opening a gas cylinder argon main valve, adjusting a decompression air valve to enable output gas pressure to be 0.035-0.045MPa, loading a gold target, placing the mesoporous TiO 2 film obtained in the step S1 into a magnetron sputtering instrument, sputtering gold, and depositing a layer of gold nano particles on the surface of the mesoporous TiO 2 film to obtain a mesoporous TiO 2 film deposited with gold nano particles; soaking the mesoporous TiO 2 film deposited with the gold nanoparticles by using 0.5mol/L silver nitrate solution, wherein the liquid level of the silver nitrate solution is higher than that of the mesoporous TiO 2 film which is soaked in the silver nitrate solution and deposited with the gold nanoparticles, and irradiating the silver nitrate solution for 5min by using ultraviolet light to realize the deposition of the silver nanoparticles, so as to obtain the Au-Ag blended nanoparticles; The specific process of the S4 is that the Au-Ag blending nano particles obtained in the S3 are placed in TaO x precursor sol, a TaO x film is prepared on the Au-Ag blending nano particle layer by a pulling and dipping method, the rising and falling speeds of the glass substrate in the pulling and dipping process are 0.35cm/S, the dipping time of the glass substrate in the TaO x precursor sol is 6S, the glass substrate is hung for 3min perpendicular to the ground after the dipping is completed, and then the glass substrate is subjected to 160 ℃ heat treatment for 30min; The specific process of the S5 is that a gas steel cylinder argon main valve is opened, a decompression air valve is regulated to enable the output gas pressure to be 0.035-0.045MPa, a silver target is loaded, the film obtained in the S4 is placed into a magnetron sputtering instrument by using tweezers, silver is sputtered, a continuous silver film is obtained, and the preparation of the bimetal co-doped laminated oxide film is completed.
6. The method for preparing a bimetal co-doped laminated oxide film according to claim 5, wherein the annealing of the glass substrate in a muffle furnace is specifically that the glass substrate is annealed at 500 ℃ for 1h in the muffle furnace, the gold sputtering time is 5s, the silver sputtering time is 20s, and the magnetron sputtering current is 30mA.
7. Use of a bi-metallic co-doped layered oxide film according to any of claims 1 to 3 as an encrypted holographic storage material.
8. An encrypted holographic storage method, comprising: Obtaining a bi-metal co-doped layered oxide film as described in any one of claims 1 to 3; Performing one exposure and two exposures on N first areas and M second areas on the bimetal co-doped laminated oxide film by using pulse laser, wherein the first areas and the second areas are not overlapped, and N and M are integers larger than 0; Dividing the information to be stored in an encryption manner into M parts, storing the information in the M second areas in a one-to-one correspondence manner, and storing the interference information in the first areas, or dividing the information to be stored in an encryption manner into N parts, storing the information in the N first areas in a one-to-one correspondence manner, and storing the interference information in the second areas; brushing the bimetal co-doped laminated oxide film by using NaCl solution to distinguish a first area from a second area, wherein the color of the first area coated with the NaCl solution is different from that of the second area coated with the NaCl solution; Reading the first area or the second area to carry out holographic storage data; and splicing the information read in the first area or the second area.
9. The encrypted holographic storage method of claim 8, wherein the first region and the second region are identical in shape.
10. The encrypted holographic storage method of claim 8, wherein the pulsed laser is an infrared laser with power of 10W, laser moving line speed of 1000mm/s, spacing between two adjacent laser lines of 0.1mm, and pulse repetition frequency of 20kHz.

Description

Double-metal co-doped laminated oxide film, preparation method and holographic encryption application Technical Field The invention relates to the technical field of optical data storage and encryption, in particular to a bimetal co-doped laminated oxide film, a preparation method and holographic encryption application. Background The holographic technology can record and reproduce all information of the object, so that an observer can acquire the outline and depth information of the real object under the naked eye condition, and the holographic information recording method has wide application prospect in entertainment, education and medical treatment, especially in the information anti-counterfeiting field, and is widely focused in the industry. Meanwhile, with the development of the digital industry, the demands of people on personal information security are also becoming stronger, information privacy protection is becoming more and more important in modern society, data encryption is crucial for information protection, and development of novel encryption technology has become a key force for promoting progress of the information society. Therefore, it is particularly important to realize the holographic technology and the encryption technology on the same system, and in recent years, the composite film of the metal and the TiO 2 gradually realizes stable and rapid holographic storage, but the application range is difficult to expand because of the single photoelectric characteristic, and the encryption storage application of the system is not researched at present. In view of this, there is a need to design a composite film that can be used for encrypted holographic storage, a method of manufacturing the same, and a holographic encrypted storage method based thereon. Disclosure of Invention In order to solve the problems, the invention provides a bimetal co-doped laminated oxide film, a preparation method and holographic encryption application. The technical scheme adopted by the invention for solving the technical problems is as follows: in a first aspect, the present invention provides a bi-metal co-doped stacked oxide film comprising: A glass substrate; a mesoporous TiO 2 film positioned on the glass substrate; Au-Ag blending nano particles deposited on the mesoporous TiO 2 film; An amorphous TaO x film layer positioned on the Au-Ag blending nano-particles, wherein x is a positive number; And a silver film positioned on the amorphous TaO x film layer. In a preferred embodiment, the thickness of the amorphous TaO x film layer is 35-45 nm, and the thickness of the silver film is 15-20 nm. In a second aspect, the present invention provides a method for preparing the bimetal co-doped stacked oxide film according to the first aspect, which includes: S1, coating a layer of TiO 2 slurry on a glass substrate by adopting a screen printing method, and performing thermal annealing treatment to remove organic components to obtain the mesoporous TiO 2 film; S2, depositing a layer of gold nanoparticles on the surface of the mesoporous TiO 2 film by magnetron sputtering; S3, immersing the TiO 2 film deposited with the gold nanoparticles into a silver nitrate solution, and irradiating with ultraviolet light to deposit the silver nanoparticles, so as to form the Au-Ag blending nanoparticle layer; S4, coating an amorphous TaO x layer on the Au-Ag blending nano particle layer by using a pulling method, and performing heat treatment to obtain an amorphous TaO x film layer; s5, performing magnetron sputtering on the amorphous TaO x film layer to form a continuous silver film. In a preferred embodiment, the specific process of the S1 is that a glass substrate is placed under a screen plate of a screen printer, a layer of TiO 2 slurry is coated on the upper surface of the glass substrate through a scraper, then the glass substrate is placed in a muffle furnace for annealing, and the polymer in the TiO 2 slurry is removed to obtain the mesoporous TiO 2 film; Opening a gas cylinder argon main valve, adjusting a decompression air valve to enable output air pressure to be 0.035-0.045Mpa, loading a gold target, placing the mesoporous TiO 2 film obtained in the step S1 into a magnetron sputtering instrument by using tweezers, sputtering gold, and depositing a layer of gold nano particles on the surface of the mesoporous TiO 2 film to obtain a mesoporous TiO 2 film deposited with gold nano particles; soaking the mesoporous TiO 2 film deposited with the gold nanoparticles by using 0.5mol/L silver nitrate solution, wherein the liquid level of the silver nitrate solution is higher than that of the mesoporous TiO 2 film which is soaked in the silver nitrate solution and deposited with the gold nanoparticles, and irradiating the silver nitrate solution for 5min by using ultraviolet light to realize the deposition of the silver nanoparticles, so as to obtain the Au-Ag blended nanoparticles; The specific process of the S4 is that the Au